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CN113614123B - Transition metal bis (phenoxide) complexes and their use as olefin polymerization catalysts - Google Patents

Transition metal bis (phenoxide) complexes and their use as olefin polymerization catalysts Download PDF

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CN113614123B
CN113614123B CN202080023077.4A CN202080023077A CN113614123B CN 113614123 B CN113614123 B CN 113614123B CN 202080023077 A CN202080023077 A CN 202080023077A CN 113614123 B CN113614123 B CN 113614123B
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tetrakis
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CN113614123A (en
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G·P·戈于诺夫
M·I·夏利科夫
V·A·波波夫
D·V·乌博斯基
A·Z·沃斯科宾尼科夫
J·R·哈格多恩
M·E·蒂东尼
A·E·卡彭特
C·A·菲勒
J·A·M·卡尼奇
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ExxonMobil Chemical Patents Inc
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Abstract

The present invention relates to transition metal complexes of dianionic tridentate ligands characterized by a central neutral heterocyclic lewis base and two phenoxide donors, wherein the tridentate ligand coordinates to the metal center to form two octamembered rings. Preferably, the bis (phenoxide) complex is represented by the following formula (I):m, L, X, m, n, E, E', Q, R therein 1 、R 2 、R 3 、R 4 、R 1 '、R 2 '、R 3 '、R 4 '、A 1 、A 1 '、Andas defined herein, wherein A 1 QA 1 ' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms which will A via a 3-atom bridge 2 To A 2 ' wherein Q is the central atom of a 3-atom bridge.

Description

Transition metal bis (phenoxide) complexes and their use as olefin polymerization catalysts
The inventors: georgy P.Goryunov, mikhail I.Sharikov, vlatslav A.Popov, dm ithry V.Uborsky, alexander Z.Voskoboynyikov, john R.Hagadorn, michelle E.Titone, alex E.Carpenter, catherine A.Faler, joan M.Canch
Priority
The present invention claims the benefits and priorities of USSN 62/804,372 filed on month 2 and 12 of 2019 and EP search report application number 19179811.5 filed on month 6 and 12 of 2019, the disclosures of which are incorporated herein in their entirety.
Technical Field
The present invention relates to novel catalyst compounds comprising group 4 bis (phenolate) complexes, catalyst systems comprising the same and uses thereof.
Background
Olefin polymerization catalysts have important applications in industry. Accordingly, there is a benefit in finding new catalyst systems that improve the commercial utility of the catalysts and allow for the preparation of polymers with improved properties.
Catalysts for the polymerization of olefins may be based on bis (phenoxide) complexes as catalyst precursors, which are generally activated by aluminoxanes or activators containing non-coordinating anions.
KR 2018022137 (LG chem.) describes transition metal complexes of bis (methylphenoxy) pyridine.
U.S. Pat. No. 7,030,256 B2 (Symyx Technologies, inc.) describes bridged bis-aromatic ligands, catalysts, polymerization processes and polymers derived therefrom.
US 6,825,296 (University of Hong Kong) describes transition metal complexes of bis (phenoxide) ligands which coordinate to the metal with two 6 membered rings.
US 7,847,099 (California Institute of Technology) describes transition metal complexes of bis (phenoxide) ligands which coordinate to the metal with two 6-membered rings.
WO 2016/172110- (Univation Technologies) describes complexes of tridentate bis (phenoxide) ligands, which are characterized by acyclic ether or thioether donors.
Other references of interest include: baier, m.c. (2014) "Post-Metallocenes in the Industrial Production of Polyolefins," angel. Chem. Int. Ed.2014, v.53, pp.9722-9744; and Golisz, S.et al ((2009) "Synthesis of Early Transition Metal Bisphenolate Complexes and Their Use as Olefin Polymerization Catalysts," Macromolecules, v.42 (22), pp.8751-8762).
New catalysts capable of polymerizing olefins at high process temperatures to produce high molecular weight and/or high stereoregularity polymers are desirable for the industrial production of polyolefins. There remains a need in the art for new and improved catalyst systems for olefin polymerization in order to achieve specific polymer properties, such as high molecular weight and/or high tacticity polymers, preferably at high process temperatures.
It is therefore an object of the present invention to provide novel catalyst compounds, catalyst systems comprising such compounds and methods of polymerizing olefins using such compounds and systems.
Disclosure of Invention
The present invention relates to transition metal complexes of dianionic tridentate ligands characterized by a central neutral heterocyclic lewis base and two phenoxide donors, wherein the tridentate ligand coordinates to the metal center to form two octamembered rings.
The present invention relates to bis (phenoxide) complexes represented by the following formula (I):
wherein:
m is a group 3-6 transition metal or lanthanide;
e and E' are each independently O, S or NR 9 Wherein R is 9 Independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl or heteroatom-containing groups;
q is a group 14, 15 or 16 atom forming a coordination bond with the metal M;
A 1 QA 1' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms which will A via a 3-atom bridge 2 To A 2' Wherein Q is the central atom of the 3-atom bridge, A 1 And A 1 ' independently is C, N or C (R) 22 ) Wherein R is 22 Selected from hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 A substituted hydrocarbyl group;
is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom bridge 1 An aryl group attached to the E bond;
is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom bridge 1' An aryl group attached to the E' linkage;
l is a neutral Lewis base;
x is an anionic ligand;
n is 1, 2 or 3;
m is 0, 1 or 2;
n+m is not more than 4;
R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' and R is 4' Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings;
Any two L groups may be joined together to form a bidentate lewis base;
the X group may be joined to the L group to form a monoanionic bidentate group;
any two X groups can be joined together to form a dianionic ligand group.
The present invention also relates to a process for polymerizing olefins comprising contacting the catalyst compound described herein with an activator and one or more monomers. The invention also relates to a polymer composition prepared by the method described herein.
Definition of the definition
For the purposes of the present invention and of the claims, the following definitions shall be used.
The novel numbering scheme for the groups of the periodic Table of the elements is used as described in Chemical and Engineering News, v.63 (5), pg.27 (1985). Thus, a "group 4 metal" is an element selected from group 4 of the periodic table, such as Hf, ti or Zr.
"catalyst productivity" is a measure of the quality of polymer produced using a known amount of polymerization catalyst. In general, "catalyst productivity" is expressed in units of (g polymer)/(g catalyst) or (g polymer)/(mmol catalyst) and the like. If no units are specified, the "catalyst productivity" is in units of (g polymer)/(g catalyst). For calculation of catalyst productivity, only the weight of the transition metal component of the catalyst was used (i.e., the activator and/or cocatalyst was omitted). "catalyst activity" is a measure of the mass of polymer produced per unit time for batch and semi-batch polymerizations using a known amount of polymerization catalyst. For calculation of catalyst productivity, only the weight of the transition metal component of the catalyst was used (i.e., the activator and/or cocatalyst was omitted). In general, "catalyst activity" is expressed in units of (g polymer)/(mmol catalyst)/hour or (kg polymer)/(mmol catalyst)/hour, etc. If no units are specified, the unit of "catalyst activity" is (g polymer)/(mmol catalyst)/hour.
"conversion" is the percentage of monomer converted to polymer product in polymerization and is reported as% and calculated based on polymer yield, polymer composition, and amount of monomer fed to the reactor.
"olefins," or "olefinic hydrocarbons," are linear, branched, or cyclic compounds of carbon and hydrogen having at least one double bond. For the purposes of this specification and the claims appended hereto, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35wt% to 55wt%, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction and that the derived units are present at 35wt% to 55wt% based on the weight of the copolymer. "Polymer" has two or more monomer units that are the same or different. "homopolymer" is a polymer containing the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. "terpolymer" is a polymer having three monomer units that differ from one another. Accordingly, the definition of copolymer as used herein includes terpolymers and the like. "different" as used in reference to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mole% ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mole% propylene derived units, and the like.
Ethylene should be considered an alpha-olefin.
The term "Cn" refers to hydrocarbons having n carbon atom(s) per molecule, where n is a positive integer, unless otherwise specified.
The term "hydrocarbon" refers to a class of compounds containing carbon-bonded hydrogen and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different n values. Similarly, "C m -C y "group or compound" refers to a group or compound containing carbon atoms in the total number of m to y. Thus C 1 -C 50 Alkyl refers to alkyl groups containing carbon atoms in a total of 1 to 50.
The terms "group", "group" and "substituent" may be used interchangeably.
The terms "hydrocarbyl (hydrocarbyl radical)", "hydrocarbyl (hydrocarbyl group)" or "hydrocarbyls" are used interchangeably and are defined to mean groups consisting of only hydrogen and carbon atoms. Preferred hydrocarbyl groups are C 1 -C 100 The groups, which may be linear, branched or cyclic, and when cyclic, may be aromatic or non-aromatic. Examples of such groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, aryl groups such as phenyl, benzyl, naphthyl, and the like.
Unless otherwise indicated (e.g., definition of "substituted hydrocarbyl", etc.), the term "substituted" means that at least one hydrogen atom has been substituted with at least one non-hydrogen group, e.g., a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, e.g., halogen (e.g., br, cl, F, or I) or at least one functional group, e.g., -NR: 2 ，-OR*，-SeR*，-TeR*，-PR* 2 ，-AsR* 2 ，-SbR* 2 ，-SR*，-BR* 2 ，-SiR* 3 ，-GeR* 3 ，-SnR* 3 ，-PbR* 3 ，-(CH 2 ) q -SiR* 3 and the like, wherein q is 1 to 10, each R is independently hydrogen, hydrocarbyl or halocarbyl (halocarbyl), and two or more R may join together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted within the hydrocarbyl ring.
The term "substituted hydrocarbyl" refers to a group (e.g., a functional group, such as-NR:, in which at least one hydrogen atom of the hydrocarbyl group has been replaced with at least one heteroatom (e.g., halogen, such as Br, cl, F, or I) or heteroatom-containing group (e.g., a functional group 2 、-OR*、-SeR*、-TeR*、-PR* 2 、-AsR* 2 、-SbR* 2 、-SR*、-BR* 2 、-SiR* 3 、-GeR* 3 、-SnR* 3 、-PbR* 3 、-(CH 2 ) q -SiR* 3 And the like, wherein q is 1 to 10 and each R is independently hydrogen, hydrocarbyl or halocarbyl, and two or more R may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted within the hydrocarbyl ring.
The term "aryl" or "aryl group" refers to aromatic rings (typically composed of 6 carbon atoms) and substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O or S. The term "aromatic" as used herein also refers to pseudo-aromatic heterocycles, which are heterocyclic substituents having similar properties and structure (nearly planar) as aromatic heterocyclic ligands, but are not aromatic by definition.
The term "substituted aromatic" refers to an aromatic group having 1 or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.
"substituted phenoxide (substituted phenolate)" is a phenoxide group in which at least one, two, three, four or five hydrogen atoms in the 2, 3, 4, 5 and/or 6 positions have been substituted by at least one non-hydrogen group, e.g. a hydrocarbon group, a heteroatom or a heteroatom-containing groupRadicals of a sub-group, e.g. halogen (e.g. Br, cl, F or I) or at least one functional group, e.g. -NR 2 、-OR*、-SeR*、-TeR*、-PR* 2 、-AsR* 2 、-SbR* 2 、-SR*、-BR* 2 、-SiR* 3 、-GeR* 3 、-SnR* 3 、-PbR* 3 、-(CH 2 ) q -SiR* 3 And the like, wherein q is 1 to 10 and each R is independently hydrogen, hydrocarbyl or halocarbyl, and two or more R may join together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, wherein the 1-position is phenolate (Ph-O-, ph-S-and Ph-N (R-yl), wherein R-is hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl, heteroatom or heteroatom-containing group). Preferably, the "substituted phenoxide" group in the catalyst compounds described herein is represented by the formula:
wherein R is 18 Is hydrogen, C 1 -C 40 Hydrocarbyl radicals (e.g. C 1 -C 40 Alkyl) or C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, E 17 Is oxygen, sulfur or NR 17 And R is 17 、R 18 、R 19 、R 20 And R is 21 Each of which is independently selected from hydrogen, C 1 -C 40 Hydrocarbyl radicals (e.g. C 1 -C 40 Alkyl) or C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 18 、R 19 、R 20 And R is 21 Two or more of (C) are joined together to form C 4 -C 62 A cyclic or polycyclic ring structure, or a combination thereof, and the wavy line shows the position of the substituted phenoxide group to form a bond with the remainder of the catalyst compound.
"alkyl-substituted phenoxide" is a phenoxide group in which at least one, two, three, four or five of the positions 2, 3, 4, 5 and/or 6 are presentHaving at least one hydrogen atom substituted by at least one alkyl group, e.g. C 1 -C 40 Or C 2 -C 20 Or C 3 -C 12 Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl (adamantanyl), and the like, including substituted analogs thereof.
"aryl-substituted phenoxide" is a phenoxide in which at least one, two, three, four or five hydrogen atoms in the 2, 3, 4, 5 and/or 6 positions have been substituted by at least one aryl group, for example C 1 -C 40 Or C 2 -C 20 Or C 3 -C 12 Aryl groups such as phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2, 6-dimethylphenyl, mesityl (mesityl), 2-ethylphenyl, naphthyl and the like, including substituted analogs thereof.
The term "ring atom" refers to an atom that is part of a cyclic ring structure. According to this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms.
A heterocycle, also known as a heterocycle, is a ring having a heteroatom in the ring structure, as opposed to a "heteroatom-substituted ring" in which a hydrogen on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N, N-dimethylamino-phenyl is a heteroatom-substituted ring. Substituted heterocycle means a heterocycle having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group.
A substituted hydrocarbyl ring refers to a ring made up of carbon and hydrogen atoms wherein 1 or more hydrogen groups are replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom-containing group.
For the purposes of this disclosure, with respect to catalyst compounds (e.g., substituted bis (phenoxide) catalyst compounds), the term "substituted" refers to a hydrogen group that has been substituted with a hydrocarbyl, heteroatom, or heteroatom-containing group, such as a halogen (e.g., br, cl, F, or I) or at least one functional group such as-NR: 2 、-OR*、-SeR*、-TeR*、-PR* 2 、-AsR* 2 、-SbR* 2 、-SR*、-BR* 2 、-SiR* 3 、-GeR* 3 、-SnR* 3 、-PbR* 3 、-(CH 2 ) q -SiR* 3 and the like, wherein q is 1-10 and each R is independently hydrogen, hydrocarbyl or halocarbyl, and two or more R may be joined together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted within the hydrocarbyl ring.
The tertiary hydrocarbyl group has carbon atoms bonded to three other carbon atoms. When the hydrocarbyl group is an alkyl group, the tertiary hydrocarbyl group is also referred to as a tertiary alkyl group. Examples of tertiary hydrocarbyl groups include tert-butyl, 2-methylbutan-2-yl, 2-methylhexane-2-yl, 2-phenylpropane-2-yl, 2-cyclohexylpropan-2-yl, 1-methylcyclohexyl, 1-adamantyl, bicyclo [2.2.1] heptan-1-yl, and the like. The tertiary hydrocarbyl group may be represented by formula a:
wherein R is A 、R B And R is C Is a hydrocarbon group or a substituted hydrocarbon group which may be optionally bonded to each other, and the wavy line shows the position at which the tertiary hydrocarbon group forms a bond with other groups.
A cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group that forms at least one cycloaliphatic (non-aromatic) ring. The cyclic tertiary hydrocarbyl group is also referred to as a cycloaliphatic tertiary hydrocarbyl group. When the hydrocarbyl is alkyl, the cyclic tertiary hydrocarbyl is also referred to as cyclic tertiary alkyl or alicyclic tertiary alkyl. Examples of the cyclic tertiary hydrocarbon group include 1-adamantyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo [3.3.1] nonan-1-yl, bicyclo [2.2.1] heptan-1-yl, bicyclo [2.3.3] hexan-1-yl, bicyclo [1.1.1] pentan-1-yl, bicyclo [2.2.2] octan-1-yl and the like. The cyclic tertiary hydrocarbyl group may be represented by formula B:
Wherein R is A Is a hydrocarbyl or substituted hydrocarbyl group, each R D Independently is hydrogen or hydrocarbyl or substituted hydrocarbyl, w is an integer from 1 to about 30, R A And one or more R D And/or two or more R D May optionally be bonded to each other to form additional loops.
When the cyclic tertiary hydrocarbyl group contains more than one alicyclic ring, it may be referred to as a polycyclic tertiary hydrocarbyl group, or if the hydrocarbyl group is an alkyl group, it may be referred to as a polycyclic tertiary alkyl group.
The terms "alkyl group" and "alkyl" are used interchangeably throughout this disclosure. For purposes of this disclosure, "alkyl" is defined as C, which may be linear, branched, or cyclic 1 -C 100 An alkyl group. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including substituted analogs thereof. Substituted alkyl is where at least one hydrogen atom of the alkyl has been replaced by at least one non-hydrogen group such as a hydrocarbon group, a heteroatom or a heteroatom-containing group such as halogen (e.g. Br, cl, F or I) or at least one functional group such as-NR 2 、-OR*、-SeR*、-TeR*、-PR* 2 、-AsR* 2 、-SbR* 2 、-SR*、-BR* 2 、-SiR* 3 、-GeR* 3 、-SnR* 3 、-PbR* 3 、-(CH 2 ) q -SiR* 3 An isosubstituted group wherein q is 1 to 10 and each R is independently hydrogen, hydrocarbyl or halocarbyl. And two or more R may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted within the hydrocarbyl ring.
Where isomers of the alkyl, alkenyl, alkoxy, or aryl groups are present (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), mention of one member of the group (e.g., n-butyl) should explicitly disclose the remaining isomers of the family (e.g., isobutyl, sec-butyl, and tert-butyl). Likewise, references to alkyl, alkenyl, alkoxy, or aryl groups without specifying a particular isomer (e.g., butyl) explicitly disclose all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).
Mn as used herein is the number average molecular weight, mw is the weight average molecular weight, mz is the z average molecular weight, wt% is the weight percent, and mol% is the mole percent. Molecular Weight Distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., mw, mn, mz) are g/mol (gmol) -1 )。
The following abbreviations may be used herein: me is methyl, et is ethyl, pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, bu is butyl, nBu is n-butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, oct is octyl, ph is phenyl, MAO is methylaluminoxane, dme is 1, 2-dimethoxyethane, p-tBu is p-tert-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOA and TNOAL are tri (n-octyl) aluminum, p-Me is p-methyl, bn is benzyl (i.e., CH) 2 Ph), THF (also known as THF) is tetrahydrofuran, RT is room temperature (and 23 ℃ unless otherwise indicated), tol is toluene, etOAc is ethyl acetate, cbz is carbazole, cy is cyclohexyl.
A "catalyst system" is a combination comprising at least one catalyst compound and at least one activator. When "catalyst system" is used to describe such pairing prior to activation, it refers to the unactivated catalyst complex (procatalyst) along with the activator and optionally the co-activator. When it is used to describe such pairing after activation, it refers to the activated complex and the activator or other charge balancing moiety. The transition metal compound may be neutral, as in a procatalyst, or a charged species with a counter ion, as in an activated catalyst system. For the purposes of the present invention and the claims thereto, when the catalyst system is described as comprising components in neutral stable form, it is well understood by those of ordinary skill in the art that the components in ionic form are in a form that reacts with the monomer to produce a polymer. Polymerization catalyst systems are catalyst systems that can polymerize monomers into polymers.
In the description herein, a catalyst may be described as a catalyst, a catalyst precursor, a procatalyst compound, a catalyst compound, or a transition metal compound, and these terms are used interchangeably.
An "anionic ligand" is a negatively charged ligand that contributes one or more electron pairs to a metal ion. The term "anion donor" is used interchangeably with "anionic ligand". In the context of the present invention, examples of anion donors include, but are not limited to, methyl, chloride, fluoride, alkoxy, aryloxy, alkyl, alkenyl, alkylthio (thio), carboxylate, amino (amido), methyl, benzyl, hydride (hydro), amidinate, amidate (amidate), and phenyl. The two anion donors may be joined to form a dianionic group.
A "neutral lewis base" or "neutral donor group" is an uncharged (i.e., neutral) group that provides one or more pairs of electrons to a metal ion. Non-limiting examples of neutral lewis bases include ethers, thioethers, amines, phosphines, diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkenes, alkynes, allenes, and carbenes. The lewis bases may be joined together to form a bidentate or tridentate lewis base.
For purposes of the present invention and the appended claims, phenoxide donors include Ph-O-, ph-S-, and Ph-N (R-A) -groups, where R-A is hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl, heteroatom or heteroatom-containing group, ph is optionally substituted phenyl.
Detailed Description
The present invention relates to a novel catalyst family comprising a transition metal complex of a dianionic tridentate ligand characterized by a central neutral donor group and two phenoxide donors, wherein the tridentate ligand coordinates to the metal center to form two octamembered rings. In this type of complex, it is advantageous for the central neutral donor to be a heterocyclic group. The heterocyclic group is particularly advantageous in that it lacks hydrogen in the alpha position of the heteroatom. In this type of complex it is also advantageous for the phenoxide to be substituted by one or more cyclic tertiary alkyl substituents. The use of cyclic tertiary alkyl substituted phenoxides has been shown to improve the ability of these catalysts to prepare high molecular weight polymers.
Complexes of substituted bis (phenoxide) ligands, such as adamantyl substituted bis (phenoxide) ligands, have been prepared and characterized herein. These complexes form active olefin polymerization catalysts when combined with an activator such as a non-coordinating anion or an alumoxane activator. Useful bis (arylphenoxide) pyridine complexes include tridentate bis (arylphenoxide) pyridine ligands coordinated to the group 4 transition metal to form two octamembered rings.
The invention also relates to a metal complex comprising: a metal selected from the group consisting of group 3-6 or lanthanide metals, and a tridentate dianionic ligand containing two anionic donor groups and a neutral lewis base donor, wherein the neutral lewis base donor is covalently bonded between the two anionic donors, and wherein the metal-ligand complex is characterized by a pair of 8-membered metal cyclized (metallocycle) rings.
The present invention relates to catalyst systems comprising an activator and one or more of the catalyst compounds described herein.
The present invention also relates to a process for polymerizing olefins using the catalyst compounds described herein, comprising contacting one or more olefins with a catalyst system comprising an activator and the catalyst compounds described herein.
The present disclosure also relates to catalyst systems comprising the transition metal compounds and activator compounds described herein, to the use of such activator compounds for activating transition metal compounds in catalyst systems for polymerizing olefins, and to methods for polymerizing olefins comprising contacting one or more olefins under polymerization conditions with a catalyst system comprising a transition metal compound and an activator compound, wherein no aromatic solvent, such as toluene, is present (at zero mol% relative to the moles of activator, or at less than 1mol%, preferably the catalyst system, polymerization reaction, and/or polymer produced is free of "detectable aromatic hydrocarbon solvents", such as toluene). For the purposes of this disclosure, "detectable aromatic hydrocarbon solvent" refers to 0.1mg/m as determined by gas chromatography 2 Or more. For the purposes of this disclosure, "detectable toluene" refers to 0.1mg/m as determined by gas chromatography 2 Or more.
The polyalphaolefins produced herein preferably contain 0ppm (or less than 1ppm, or less than 2ppm, or less than 5 ppm) of residual aromatic hydrocarbons. Preferably, the polyalphaolefins produced herein contain 0ppm (or less than 1 ppm) of residual toluene.
The catalyst system used herein preferably contains 0ppm (or less than 1 ppm) of residual aromatic hydrocarbons. Preferably, the catalyst system used herein contains 0ppm (or less than 1 ppm) of residual toluene.
The polyalphaolefins produced herein preferably contain 5wt% or less of aromatic hydrocarbons, such as toluene, (or, 4wt% or less, or, 3wt% or less, or, 2wt% or less, or, 1wt% or less, or, 0.5wt% or less, or, less than 50ppm, or, less than 5 ppm) of residual aromatic hydrocarbons, such as toluene.
Catalyst compound
The terms "catalyst", "compound", "catalyst compound" and "complex" are used interchangeably to describe a transition metal or lanthanide metal complex that when combined with a suitable activator forms an olefin polymerization catalyst.
The catalyst complex of the present invention comprises a metal selected from group 3, 4, 5 or 6 or lanthanide metals of the periodic table of the elements, a tridentate dianionic ligand containing two anionic donor groups, and a neutral heterocyclic lewis base donor, wherein the heterocyclic donor is covalently bonded between the two anionic donors. Preferably, the dianionic tridentate ligand is characterized by a central heterocyclic donor group and two phenoxide donors, and the tridentate ligand coordinates to the metal center to form two eight membered rings.
The metal is preferably selected from group 3, 4, 5 or 6 elements. Preferably, the metal M is a group 4 metal. Most preferably, the metal M is zirconium or hafnium.
Preferably, the heterocyclic lewis base donor is characterized by a nitrogen or oxygen donor atom. Preferred heterocyclic groups include pyridine, pyrazine, pyrimidine, triazine, thiazole,Imidazole, thiophene,Derivatives of oxazole, thiazole, furan and substituted variants thereof. Preferably, the heterocyclic lewis base lacks hydrogen(s) in the alpha position of the donor atom. Particularly preferred heterocyclic lewis base donors include pyridine, 3-substituted pyridine and 4-substituted pyridine.
The anion donor of the tridentate dianion ligand may be an arylhydrocarbon sulfide (arylsulfide), a phenoxide (phenolate) or an anilide (anilide). The preferred anion donor is a phenoxide. Preferably, the tridentate dianionic ligand coordinates to the metal center to form a complex lacking a symmetrical mirror surface. Preferably, the tridentate dianionic ligand coordinates to the metal center to form a complex having two axes of symmetry; when determining the symmetry of the bis (phenoxide) complex, only the metal and the dianionic tridentate ligand are considered (i.e. the remaining ligands are ignored).
The bis (phenoxide) ligands useful in the present invention are preferably tridentate dianionic ligands which coordinate to the metal M in such a way as to form a pair of 8-membered metallocycle rings. The bis (phenoxide) ligand is entangled around the metal to form a complex with 2-fold axis of rotation, giving the complex a C 2 Symmetry. C (C) 2 The geometry and 8-membered metallocycle rings are characteristic of these complexes, which makes them effective catalyst components for the production of polyolefins, in particular isotactic poly (alpha-olefins). If the ligand has a mirror surface (C) s ) The symmetry pattern coordinates to the metal and the catalyst is expected to produce only atactic poly (alpha-olefins); these symmetry-reactivity rules are summarized by Bercaw, j.e. (2009) in Macromolecules, v.42, pp.8751-8762. The said pair of 8-membered metallocycle rings of the complexes of the invention is also a significant feature advantageous for catalyst activity, temperature stability and the isoselectivity (isoselectiity) of monomer linkages. Related group 4 complexes (Macromolecules 2009, 42, 8751-8762) characterized by smaller 6-membered metallocycle rings are known to form C when used in olefin polymerization 2 And C s Mixtures of symmetrical complexes and are therefore less suitable for productionHighly isotactic poly (alpha-olefins).
The bis (phenoxide) ligands containing an oxygen donor group (i.e. e=e' =oxygen in formula (I)) in the present invention are preferably substituted with alkyl, substituted alkyl, aryl or other groups. Advantageously, each phenolic salt group is substituted at a ring position adjacent to the oxygen donor atom. Preferably the substitution at a position adjacent to the oxygen donor atom is an alkyl group containing 1 to 20 carbon atoms. Preferably, the substitution at a position immediately adjacent to the oxygen donor atom is a non-aromatic cyclic alkyl group having one or more five-or six-membered rings. Preferably, the substitution at a position immediately adjacent to the oxygen donor atom is a cyclic tertiary alkyl group. It is highly preferred that the substitution at a position immediately adjacent to the oxygen donor atom is adamantan-1-yl or substituted adamantan-1-yl.
The neutral heterocyclic lewis base donor is covalently bonded between the two anion donors via a "linking group" that links the heterocyclic lewis base to the phenolic salt group. In formula (I), the "linker" is represented by (A) 3 A 2 ) And (A) 2' A 3' ) And (3) representing. The choice of each linking group can affect catalyst properties such as the stereoregularity of the poly (alpha-olefin) produced. Each linking group is typically C of two atoms in length 2 -C 40 Divalent groups. One or both of the linking groups may independently be phenylene, substituted phenylene, heteroaryl, vinylidene, or an acyclic two carbon-length linking group. When one or both of the linking groups is phenylene, the alkyl substituent on the phenylene group can be selected to optimize catalyst performance. In general, one or both phenylene groups may be unsubstituted or may be independently substituted with C 1 -C 20 Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl or isomers thereof such as isopropyl and the like.
The invention also relates to catalyst compounds represented by formula (I) and catalyst systems comprising such compounds:
Wherein:
m is a group 3, 4, 5 or 6 transition metal or lanthanide (e.g., hf, zr or Ti);
e and E' are each independently O, S or NR 9 Wherein R is 9 Independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 A substituted hydrocarbyl or heteroatom-containing group, preferably O, preferably both E and E' are O;
q is a group 14, 15 or 16 atom forming a coordination bond with the metal M, preferably Q is C, O, S or N, more preferably Q is C, N or O, most preferably Q is N;
A 1 QA 1' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms which will A via a 3-atom bridge 2 To A 2' Wherein Q is the central atom (A) of a 3-atom bridge 1 QA 1' With connection A 1 And A 1' The combination of curves representing heterocyclic lewis bases), a 1 And A 1' Is independently C, N or C (R) 22 ) Wherein R is 22 Selected from hydrogen, C 1 -C 20 Hydrocarbyl and C 1 -C 20 Substituted hydrocarbyl groups. Preferably A 1 And A 1' Is C;
is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom bridge 1 To E-linked aryl groups, e.g. o-phenylene, substituted o-phenylene, ortho-aromatics, indolene (indoene), substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene (pyrrolene), substituted pyrrolene, thiophene, substituted thiophene, 1, 2-ethylene (-CH) 2 CH 2 (-), substituted 1, 2-ethylene, 1, 2-ethenylene (-hc=ch-) or substituted 1, 2-ethenylene, preferably +. >Is a divalent hydrocarbon group;
is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom bridge 1' Aryl groups attached to E' linkages, e.g. o-phenylene, substituted o-phenylene, ortho-aromatics, indolene, substituted indolene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1, 2-ethylene (-CH) 2 CH 2 (-), substituted 1, 2-ethylene, 1, 2-ethenylene (-hc=ch-) or substituted 1, 2-ethenylene, preferably +.>Is a divalent hydrocarbon group;
each L is independently a lewis base;
each X is independently an anionic ligand;
n is 1,2 or 3;
m is 0, 1 or 2;
n+m is not more than 4;
R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' and R is 4' Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals (preferably R 1' And R is 1 Independently a cyclic group, e.g., cyclic tertiary alkyl), or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings;
Any two L groups may be joined together to form a bidentate lewis base;
the X group may be joined to the L group to form a monoanionic bidentate group;
any two X groups can be joined together to form a dianionic ligand group.
The invention further relates to catalyst compounds represented by formula (II) and catalyst systems comprising such compounds:
wherein:
m is a group 3, 4, 5 or 6 transition metal or lanthanide (e.g., hf, zr or Ti);
e and E' are each independently O, S or NR 9 Wherein R is 9 Independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 A substituted hydrocarbyl or heteroatom-containing group, preferably O, preferably both E and E' are O;
each L is independently a lewis base;
each X is independently an anionic ligand;
n is 1, 2 or 3;
m is 0, 1 or 2;
n+m is not more than 4;
R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' and R is 4' Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings;
Any two L groups may be joined together to form a bidentate lewis base;
the X group may be joined to the L group to form a monoanionic bidentate group;
any two X groups can be joined together to form a dianionic ligand group;
R 5 、R 6 、R 7 、R 8 、R 5' 、R 6' 、R 7' 、R 8' 、R 10 、R 11 and R is 12 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 5 And R is 6 、R 6 And R is 7 、R 7 And R is 8 、R 5' And R is 6' 、R 6' And R is 7' 、R 7' And R is 8' 、R 10 And R is 11 Or R is 11 And R is 12 May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings.
The metal M is preferably selected from group 3, 4, 5 or 6 elements, more preferably group 4. Most preferably, the metal M is zirconium or hafnium.
The donor atom Q of the neutral heterocyclic Lewis base (in formula (I)) is preferably nitrogen, carbon or oxygen. Preferably Q is nitrogen.
Non-limiting examples of neutral heterocyclic Lewis base groups include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene,Derivatives of oxazole, thiazole, furan and substituted variants thereof. Preferred heterocyclic lewis bases include derivatives of pyridine, pyrazine, thiazole, and imidazole.
Each A of a heterocyclic Lewis base (in formula I) 1 And A 1' Is independently C, N or C (R) 22 ) Wherein R is 22 Selected from hydrogen, C 1 -C 20 Hydrocarbyl and C 1 -C 20 Substituted hydrocarbyl groups. Preferably A 1 And A 1′ Is carbon. When Q is carbon, it is preferred that A 1 And A 1′ Selected from nitrogen and C (R) 22 ). When Q is nitrogen, A is preferred 1 And A 1′ Is carbon. Preferably q=nitrogen, a 1 ＝A 1′ =carbon. When Q is nitrogen or oxygen, it is preferred that the heterocyclic Lewis base of formula (I) does not have any groups with A 1 Or A 1' An atomically bonded hydrogen atom. This is preferred because it is believed that hydrogen at those positions may undergo undesirable decomposition reactions that reduce the stability of the catalytically active species.
From A 1 QA 1' With connection A 1 And A 1' The heterocyclic Lewis base (of formula I) represented by the combination of curves of (I) is preferably selected from the group consisting of 23 The radicals being selected from hydrogen, hetero atoms, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Amino (amide) and C 1 -C 20 Substituted alkyl.
In some embodiments, the method of A 1 QA 1' With connection A 1 And A 1' The heterocyclic lewis base (of formula (I)) represented by the combination of curves (I) is a six-membered ring containing one ring heteroatom, wherein Q is a ring heteroatom, or a five-membered ring containing one or two ring heteroatoms, but wherein Q is a ring carbon. Alternatively, from A 1 QA 1' With connection A 1 And A 1' The heterocyclic lewis base (of formula (I)) represented by the combination of curves (I) is not a five membered ring containing one or more ring heteroatoms, wherein Q is a ring heteroatom.
In formula (I) or (II), E and E' are each selected from oxygen or NR 9 Wherein R is 9 Independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl or heteroatom-containing groups. Preferably E and E' are oxygen. When E and/or E' is NR 9 When R is preferred 9 Selected from C 1 -C 20 Hydrocarbyl, alkyl, or aryl. In one embodiment E and E' are each selected from O, S or N (alkyl) or N (aryl), wherein alkyl is preferably C 1 To C 20 Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, and aryl is C 6 To C 40 Aryl groups such as phenyl, naphthyl, benzyl, methylphenyl, and the like.
In the context of an embodiment of the present invention,and->Independently a divalent hydrocarbon group, e.g. C 1 -C 12 A hydrocarbon group.
In the complexes of the formula (I) or (II), when E and E' are oxygen, it is advantageous for each phenolate group to be in a position immediately adjacent to the oxygen atom (i.e., R in the formula (I) or (II) 1 And R is 1' ) Is substituted. Thus, when E and E' are oxygen, R is preferred 1 And R is 1' Each of which is independently C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, more preferably R 1 And R is 1' Independently a non-aromatic cyclic alkyl group (e.g., cyclohexyl, cyclooctyl, adamantyl or 1-methylcyclohexyl or substituted adamantyl) having one or more five-or six-membered rings, most preferably a non-aromatic cyclic tertiary alkyl group (e.g., 1-methylcyclohexyl, adamantyl or substituted adamantyl).
In some embodiments of the invention of formula (I) or (II), R 1 And R is 1' Independently is a tertiary hydrocarbyl group. In other embodiments of formula (I) or (II) of the invention, R 1 And R is 1' Independently a cyclic tertiary hydrocarbyl group. In other embodiments of formula (I) or (II) of the invention, R 1 And R is 1' Independently is a polycyclic tertiary hydrocarbyl group.
In the formula of the invention(I) Or (II) in some embodiments, R 1 And R is 1' Independently is a tertiary hydrocarbyl group. In other embodiments of formula (I) or (II) of the invention, R 1 And R is 1' Independently a cyclic tertiary hydrocarbyl group. In other embodiments of formula (I) or (II) of the invention, R 1 And R is 1' Independently is a polycyclic tertiary hydrocarbyl group.
A linker (i.e. of formula (I)And->) Each is preferably an ortho-phenylene group, preferably a portion of a substituted ortho-phenylene group. R of the formula (II) is preferably 7 And R is 7' The position being hydrogen, or C 1 -C 20 Alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or isomers thereof such as isopropyl and the like. For applications targeting polymers with high tacticity, R of formula (II) is preferred 7 And R is 7' Position C 1 -C 20 Alkyl, most preferably R 7 And R is 7' Are all C 1 -C 3 An alkyl group.
In embodiments of formula (I) herein, Q is C, N or O, preferably Q is N.
In embodiments of formula (I) herein, A 1 And A 1' Independently is carbon, nitrogen or C (R) 22 ) Wherein R is 22 Selected from hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 Substituted hydrocarbyl groups. Preferably A 1 And A 1′ Is carbon.
In embodiments of formula (I) herein, A in formula (I) 1 QA 1 ' is a heterocyclic Lewis base such as pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene,An azole, thiazole, furan or a substituted variant thereof.
In embodiments of formula (I) herein, A 1 QA 1' Is part of a heterocyclic Lewis base containing 2 to 20 non-hydrogen atoms which will A via a 3-atom bridge 2 To A 2' Wherein Q is the central atom of a 3-atom bridge. Preferably, each A 1 And A 1' Is a carbon atom, and A 1 QA 1' The fragments are formed into pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene,An azole, thiazole, furan or substituted variant of a group thereof or a part of a substituted variant thereof.
In one embodiment of formula (I) herein, Q is carbon and each A 1 And A 1' Is N or C (R) 22 ) Wherein R is 22 Selected from hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 Substituted hydrocarbyl, heteroatom or heteroatom-containing group. In this embodiment, A 1 QA 1' The fragment forms a cyclic carbene, an N-heterocyclic carbene, a substituted variant of a cyclic aminoalkyl carbene or a group thereof, or a part of a substituted variant thereof.
In the embodiments of formula (I) herein,is a divalent radical containing 2 to 20 non-hydrogen atoms which bridges A via a 2-atom bridge 1 To E-bonded aryl, wherein +.>Is a linear alkyl group or forms part of a cyclic group (e.g., an optionally substituted ortho-phenylene or ortho-arylene group) or substituted variant thereof.
Is a divalent radical containing 2 to 20 non-hydrogen atoms which bridges A via a 2-atom bridge 1' An aryl group linked to E' wherein +.>Is a linear alkyl group or forms part of a cyclic group (e.g., an optionally substituted ortho-phenylene or ortho-arylene group) or substituted variant thereof.
In embodiments of the invention herein, in formulas (I) and (II), M is a group 4 metal, such as Hf or Zr.
In embodiments of the invention herein, in formulas (I) and (II), E and E' are O.
In embodiments of the invention herein, in formulas (I) and (II), R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' And R is 4' Independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof.
In embodiments of the invention herein, in formulas (I) and (II), R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' 、R 4' And R is 9 Independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecylEicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.
In embodiments of the invention herein, in formulas (I) and (II), R 4 And R is 4' Independently hydrogen or C 1 -C 3 Hydrocarbyl groups such as methyl, ethyl or propyl.
In embodiments of the invention herein, in formulas (I) and (II), R 9 Is hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl or heteroatom-containing groups are preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof. Preferably, R 9 Is methyl, ethyl, propyl, butyl, C 1 -C 6 Alkyl, phenyl, 2-methylphenyl, 2, 6-dimethylphenyl or 2,4, 6-trimethylphenyl.
In embodiments of the invention herein, in formulas (I) and (II), each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms (e.g., alkyl or aryl), hydride, amide, alkoxy (alkoxide), thio (sulfa), phospho (phospho), halo (halide), alkylsulfonate (alky-sulfonate), and combinations thereof (two or more X may form part of a fused or cyclic ring system), preferably, each X is independently selected from the group consisting of halo, aryl, and C 1 -C 5 Alkyl, preferably each X is independently hydrogen, dimethylamino, diethylamino, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, pentyl. Fluoro, iodo, bromo or chloro.
Alternatively, each X may independently be halo, hydrogen, alkyl, alkenyl, or aralkyl.
In embodiments of the invention herein, in formulas (I) and (II), each L is a lewis base independently selected from ethers, sulfides, amines, nitriles, imines, pyridines, halogenated hydrocarbons and phosphines, preferably ethers and sulfides, and combinations thereof, optionally, two or more L may form part of a fused ring or ring system, preferably, each L is independently selected from ether and sulfide groups, preferably, each L is an diethyl ether, tetrahydrofuran, dibutyl ether or dimethyl sulfide group.
In embodiments of the invention herein, in formulas (I) and (II), R 1 And R is 1' Independently a cyclic tertiary alkyl group.
In embodiments of the invention herein, in formulas (I) and (II), n is 1, 2 or 3, typically 2.
In embodiments of the invention herein, in formulas (I) and (II), m is 0, 1 or 2, typically 0.
In embodiments of the invention herein, in formulas (I) and (II), R 1 And R is 1' Not hydrogen.
In embodiments of the invention herein, in formulas (I) and (II), M is Hf or Zr, and E' are O; r is R 1 And R is 1' Each of which is independently C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, each R 2 、R 3 、R 4 、R 2' 、R 3' And R is 4' Independently hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles, each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings; each X is independently selected from the group consisting of hydrocarbyl groups (e.g., alkyl or aryl groups) having from 1 to 20 carbon atoms, hydrogen groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halo groups, and combinations thereof (two or more X's may form a fused ring or ring system Part of (2); each L is independently selected from ether, thioether, and halocarbon (two or more L may form part of a fused ring or ring system).
In an embodiment of the invention herein, in formula (II), R 5 、R 6 、R 7 、R 8 、R 5' 、R 6' 、R 7' 、R 8' 、R 10 、R 11 And R is 12 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 A substituted hydrocarbyl, heteroatom, or heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl, unsubstituted hydrocarbyl, substituted heterocycle, or unsubstituted heterocycle, each having 5, 6, 7, or 8 ring atoms, and wherein the substituents on the rings may join to form additional rings.
In an embodiment of the invention herein, in formula (II), R 5 、R 6 、R 7 、R 8 、R 5' 、R 6' 、R 7' 、R 8' 、R 10 、R 11 And R is 12 Each independently is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.
In an embodiment of the invention herein, in formula (II), R 5 、R 6 、R 7 、R 8 、R 5' 、R 6' 、R 7' 、R 8' 、R 10 、R 11 And R is 12 Each of (a) is independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexene A group, methylcyclohexyl, and isomers thereof.
In an embodiment of the invention herein, in formula (II), M is Hf or Zr, E and E' are O; r is R 1 And R is 1' Each of which is independently C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, each R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' And R is 4' Independently hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings; r is R 9 Is hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 Substituted hydrocarbyl or heteroatom-containing groups such as hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or isomers thereof;
each X is independently selected from the group consisting of hydrocarbyl groups (e.g., alkyl or aryl groups) having from 1 to 20 carbon atoms, hydrogen groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halogen groups, dienes, amines, phosphines, ethers, and combinations thereof (two or more X may form part of a fused ring or ring system); n is 2; m is 0; and R is 5 、R 6 、R 7 、R 8 、R 5' 、R 6' 、R 7' 、R 8' 、R 10 、R 11 And R is 12 Each of which is independently hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 Substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups may be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstitutedHeterocycles, each having 5, 6, 7 or 8 ring atoms, and wherein the substituents on the ring may join to form additional rings, e.g. R 5 、R 6 、R 7 、R 8 、R 5' 、R 6' 、R 7' 、R 8' 、R 10 、R 11 And R is 12 Independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (e.g., methylphenyl and dimethylphenyl), benzyl, substituted benzyl (e.g., methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, and isomers thereof.
A preferred embodiment of formula (I) is that M is Zr or Hf, Q is nitrogen, A 1 And A 1' Are all carbon, E and E' are both oxygen, and R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl groups.
A preferred embodiment of formula (I) is that M is Zr or Hf, Q is nitrogen, A 1 And A 1' Are all carbon, E and E' are both oxygen, and R 1 And R is 1' Are adamantan-1-yl or substituted adamantan-1-yl.
Preferred embodiments of formula (I) are that M is Zr or Hf, Q is nitrogen, A 1 And A 1' Both are carbon, E and E' are oxygen, and R 1 And R is 1' Both are C 6 -C 20 Aryl groups.
A preferred embodiment of formula (II) is that M is Zr or Hf, E and E' are both oxygen, and R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl groups.
A preferred embodiment of formula (II) is that M is Zr or Hf, E and E' are both oxygen, and R 1 And R is 1' Are adamantan-1-yl or substituted adamantan-1-yl.
A preferred embodiment of formula (II) is that M is Zr or Hf, E and E' are both oxygen, and R 1 、R 1' 、R 3 And R is 3' Is adamantan-1-yl or substituted adamantan-1-yl.
A preferred embodiment of formula (II) is that M is Zr or Hf, E and E' are both oxygen, R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl, and R 7 And R is 7' Are all C 1 -C 20 An alkyl group.
Catalyst compounds particularly suitable for use in the present invention include one or more of the following: zirconium dimethyl [2', 2' "- (pyridin-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1 '-biphenyl ] -2-phenoxide) ], hafnium dimethyl [2',2 '" - (pyridin-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenoxide) ], zirconium dimethyl [6,6'- (pyridin-2, 6-diylbis (benzo [ b ] thiophen-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenoxide) ], hafnium dimethyl [6,6' - (pyridin-2, 6-diyl) bis (benzo [ b ] thiophen-3, 2-diyl) ] bis (2-adamantan-1-yl) -4-methylphenoxide ], zirconium dimethyl [2', 2' "- (pyridin-2, 6-diyl) bis (3- ((3 r,5 r) -1-adamantan-3, 2-diyl) bis (1- ((3 r,5 r) -1-methyl) biphenyl ] -2, 5-dimethylphenoxide) ], 7R) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ], zirconium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3R, 5R, 7R) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-phenoxide) ], hafnium dimethyl [2',2 '" - (pyridine-2, 6-diyl) bis (3- ((3R, 5R, 7R) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-phenoxide) ].
Catalyst compounds particularly useful in the present invention include those represented by one or more of the following formulas:
in some embodiments, two or more different catalyst compounds are present in the catalyst system used herein. In some embodiments, two or more different catalyst compounds are present in the reaction zone, wherein the process(s) described herein are performed. When two transition metal compound-based catalysts are used as a mixed catalyst system in one reactor, the two transition metal compounds are preferably selected so that the two are compatible. Simple screening methods known to those of ordinary skill in the art are, for example, by 1 H or 13 C NMR can be used to determine which transition metal compounds are compatible. The same activator is preferably used for the transition metal compound, however, two different activators, for example, a non-coordinating anion activator and an alumoxane, may be used in combination. If one or more of the transition metal compounds contains an X group that is not a hydrogen group, a hydrocarbyl group, or a substituted hydrocarbyl group, the aluminoxane may be contacted with the transition metal compound prior to the addition of the non-coordinating anion activator.
The two transition metal compounds (procatalysts) may be used in any ratio. (A) The preferred molar ratio of transition metal compound to (B) transition metal compound is in the range of 1:1000 to 1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1, alternatively 1:1 to 100:1, alternatively 1:1 to 75:1, alternatively 5:1 to 50:1 (A: B). The specific ratio selected will depend on the exact procatalyst, activation process, and desired end product selected. In a particular embodiment, when two procatalysts are used, where both are activated with the same activator, useful mole% is 10 to 99.9% A and 0.1 to 90% B, or 25 to 99% A and 0.5 to 50% B, or 50 to 99% A and 1 to 25% B, or 75 to 99% A and 1 to 10% B, based on the molecular weight of the procatalyst.
Process for preparing catalyst compounds
Ligand synthesis
The bis (phenol) ligands can be prepared using the general procedure shown in scheme 1. The formation of the bis (phenol) ligand by coupling of compound a with compound B (method 1) can be accomplished by known Pd-and Ni-catalyzed couplings, such as Negishi, suzuki or Kumada couplings. The formation of the bis (phenol) ligand by coupling of compound C with compound D (method 2) can be accomplished by known Pd-and Ni-catalyzed couplings, such as Negishi, suzuki or Kumada couplings. Compound D can be prepared from compound E as follows: reacting compound E with an organolithium reagent or magnesium metal, and then optionally with a main group metal halide (e.g., znCl 2 ) Or boron-based reagents (e.g. B (O) i Pr) 3 、 i PrOB (pin)). Compound E can be prepared in a non-catalytic reaction by reaction of an aryl lithium or aryl grignard reagent (compound F) with a dihaloaromatic hydrocarbon (compound G) such as 1-bromo-2-chlorobenzene. Compound E can also be prepared in a Pd-or Ni-catalyzed reaction by reacting an arylzinc or aryl-boron reagent (compound F) with a dihaloaromatic hydrocarbon (compound G).
Scheme 1
Wherein M' is a group 1, 2, 12 or 13 element or a substituted element, e.g., li, mgCl, mgBr, znCl, B (OH) 2 B (pinacol), P is a protecting group, e.g., methoxymethyl (MOM), tetrahydropyranyl (THP), t-butyl, allyl, ethoxymethyl, trialkylsilyl, t-butyldimethylsilyl or benzyl, R is C 1 -C 40 Alkyl, substituted alkyl, aryl, tertiary alkyl, cyclic tertiary alkyl, adamantyl or substituted adamantyl, and each of X 'and X' is halogen, such as Cl, br, F or I.
Preferably, the bis (phenol) ligand and intermediates used in the preparation of the bis (phenol) ligand are prepared and purified without the use of column chromatography. This can be accomplished by a variety of methods including distillation, precipitation and washing, formation of insoluble salts (e.g., by reaction of pyridine derivatives with organic acids), and liquid-liquid extraction. Preferred methods include those described in Neal c.anderson Practical Process Research and Development-A Guide for Organic Chemists (ISBN: 1493300125X).
Synthesis of carbene bis (phenol) ligands
The general synthetic method for preparing carbene bis (phenol) ligands is shown in scheme 2. The substituted phenol may be ortho-brominated and then protected with known phenol protecting groups such as MOM, THP, t-butyldimethylsilyl (TBDMS), benzyl (Bn), and the like. The bromide is then converted to a borate (compound I) or boric acid, which can be used for Suzuki coupling with bromoaniline. The biphenylamine (compound J) can be bridged by reaction with dibromoethane or by condensation with oxalaldehyde and then deprotected (compound K). Reaction with triethyl orthoformate forms an imine salt which is deprotonated to carbene.
Scheme 2
To a substituted phenol (compound H) dissolved in methylene chloride was added 1 equivalent of N-bromosuccinimide and 0.1 equivalent of diisopropylamine. After stirring at ambient temperature until completion, the reaction was quenched with 10% hcl solution. The organic portion was washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to afford bromophenol as a generally solid. The substituted bromophenol, methoxymethyl chloride and potassium carbonate were dissolved in anhydrous acetone and stirred at ambient temperature until the reaction was complete. The solution was filtered and the filtrate was concentrated to give the protected phenol (compound I). Alternatively, the substituted bromophenol and one equivalent of dihydropyran are dissolved in dichloromethane and cooled to 0 ℃. Catalytic amounts of p-toluene sulfonic acid were added and the reaction stirred for 10 minutes and then quenched with trimethylamine. The mixture was washed with water and brine, then dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give a tetrahydropyran protected phenol.
The aryl bromide (compound I) was dissolved in THF and cooled to-78 ℃. Slowly adding n-butyllithium, howeverTrimethoxyborate was then added. The reaction was stirred at ambient temperature until completion. The solvent was removed and the solid borate was washed with pentane. Boric acid can be prepared from borates by treatment with HCl. The borate or boric acid is dissolved in toluene along with an equivalent amount of o-bromoaniline and a catalytic amount of tetrakis (triphenylphosphine) palladium. An aqueous solution of sodium carbonate was added and the reaction was heated to reflux overnight. After cooling, the layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic portions were washed with brine, dried (MgSO 4 ) Filtered, and concentrated under reduced pressure. The coupled product (compound J) is typically purified using column chromatography.
Aniline (compound J) and dibromoethane (0.5 eq) were dissolved in acetonitrile and heated at 60 ℃ overnight. The reaction was filtered and concentrated to give ethylene-bridged diphenylamine. The protected phenol was deprotected by reaction with HCl to give the bridged bis (biphenyl) alcohol (compound K).
The diamine (compound K) was dissolved in triethyl orthoformate. Ammonium chloride was added and the reaction was heated to reflux overnight. A precipitate formed, which was collected by filtration and washed with diethyl ether to give an imine salt. The ammonium chloride was suspended in THF and treated with lithium or sodium hexamethyldisilylamide. After completion, the reaction was filtered and the filtrate was concentrated to give the carbene ligand.
Preparation of bis (phenolate) complexes
Transition metal or lanthanide metal bis (phenoxide) complexes are used in the present invention as catalyst components for the polymerization of olefins. The terms "catalyst" and "catalyst complex" are used interchangeably. The preparation of transition metal or lanthanide metal bis (phenoxide) complexes can be accomplished by reaction of the bis (phenolic) ligand with a metal reactant containing an anionic basic leaving group. Typical anionic basic leaving groups include dialkylamino, benzyl, phenyl, hydrogen, and methyl. In this reaction, the basic leaving group functions to deprotonate the bis (phenol) ligand. Suitable metal reactants for this type of reaction include, but are not limited to, hfBn 4 (Bn＝CH 2 Ph)、ZrBn 4 、TiBn 4 、ZrBn 2 Cl 2 (OEt 2 )、HfBn 2 Cl 2 (OEt 2 ) 2 、Zr(NMe 2 ) 2 Cl 2 (dimethoxyethane), hf (NMe) 2 ) 2 Cl 2 (dimethoxyethane), hf (NMe) 2 ) 4 、Zr(NMe 2 ) 4 And Hf (NEt) 2 ) 4 . Suitable metal reactants also include ZrMe 4 、HfMe 4 And other group 4 alkylates which may be formed in situ and used without isolation.
A second method for preparing transition metal or lanthanide bis (phenoxide) complexes is to react the bis (phenolic) ligand with an alkali or alkaline earth metal base (e.g., na, buLi, i PrMgBr) to produce a deprotonated ligand, then with a metal halide (e.g., hfCl 4 、ZrCl 4 ) To form a bis (phenolate) complex. Bis (phenoxide) metal complexes containing metal halides, alkoxides or amino leaving groups can be alkylated by reaction with organolithium, grignard reagents and organoaluminum reactants. In the alkylation reaction, the alkyl group is transferred into the bis (phenoxide) metal center and the leaving group is removed. Reagents commonly used in alkylation reactions include, but are not limited to MeLi, meMgBr, alMe 3 、Al( i Bu) 3 、AlOct 3 And PhCH (Ph CH) 2 MgCl. Typically 2 to 20 molar equivalents of alkylating reagent are added to the bis (phenoxide) complex. The alkylation is generally carried out in an ether or hydrocarbon solvent or solvent mixture at a temperature typically from-80 ℃ to 120 ℃.
Activating agent
The terms "cocatalyst" and "activator" are used interchangeably herein.
The catalyst systems described herein generally comprise a catalyst complex, such as the transition metal or lanthanide bis (phenoxide) complex described above, and an activator, such as an alumoxane or a non-coordinating anion. These catalyst systems may be formed by combining the catalyst components described herein with an activator in any manner known from the literature. The catalyst system may also be added to or result from solution polymerization or bulk polymerization (in monomers). The catalyst systems of the present disclosure may have one or more activators and one, two, or more catalyst components. An activator is defined as any compound that can activate any of the above-described catalyst compounds by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators include, for example, alumoxane, aluminum alkyls, ionizing activators (which may be neutral or ionic), and cocatalysts of conventional type. Preferred activators generally include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds that abstract reactive metal ligands, cationize metal compounds, and provide charge-balancing non-coordinating or weakly coordinating anions, such as non-coordinating anions.
Aluminoxane activator
Aluminoxane activators are useful as activators in the catalyst systems described herein. Aluminoxanes generally contain-Al (R) 1 ) Oligomer compounds of the O-subunit, wherein R 1 Is an alkyl group. Examples of alumoxanes include Methylalumoxane (MAO), modified Methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylaluminoxanes and modified alkylaluminoxane are suitable as catalyst activators, especially when the abstractable ligand is alkyl, halogen, alkoxy or amino. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. Visually transparent methylaluminoxane may preferably be used. The cloudy or gel aluminoxane can be filtered to prepare a clear solution or the clear aluminoxane can be decanted from the cloudy solution. Useful aluminoxanes are Modified Methylaluminoxane (MMAO) co-catalyst type 3A (commercially available under the trade name modified methylaluminoxane type 3A from Akzo Chemicals, inc.) covered by U.S. Pat. No. 5,041,584. Another useful alumoxane is US 9,340,630; solid polymethylaluminoxanes described in US 8,404,880 and US 8,975,209.
When the activator is an alumoxane (modified or unmodified), the maximum amount of activator is typically at most 5,000-fold molar excess of Al/M relative to the catalyst compound (per metal catalytic site). The minimum activator to catalyst compound ratio is 1:1 molar ratio. Alternative preferred ranges include 1:1 to 500:1, or 1:1 to 200:1, or 1:1 to 100:1, or 1:1 to 50:1.
In an alternative embodiment, little or no aluminoxane is used in the polymerization process described herein. Preferably, the aluminoxane is present in a molar ratio of aluminium to catalyst compound transition metal of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1.
Ionizing/non-coordinating anion activators
The term "non-coordinating anion" (NCA) refers to an anion that is not or only weakly coordinated to the cation, and thus remains sufficiently labile to be displaced by a neutral lewis base. In addition, the anion does not transfer an anionic substituent or fragment to the cation, allowing it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions that can be used in accordance with the present invention are those that are compatible in the sense that they stabilize the transition metal cation at +1 in the sense that their ionic charge is balanced, yet remain sufficiently labile to allow for displacement during polymerization. The term NCA is also defined as including multicomponent NCA-containing activators comprising an acidic cationic group and a non-coordinating anion, such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. The term NCA is also defined to include neutral lewis acids, such as tris (pentafluorophenyl) boron, which can react with catalysts to form activated radicals by extraction of anionic groups. Any metal or metalloid that can form a compatible, weakly coordinating complex can be used or included in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.
The use of ionizing activators (neutral or ionic) is within the scope of the present invention. It is also within the scope of the invention to use a neutral or ionic activator alone or in combination with an alumoxane or modified alumoxane activator.
In an embodiment of the invention, the activator is represented by formula (III):
(Z) d + (A d- ) (III)
wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; h is hydrogen; (L-H) + Is a Bronsted acid; a is that d- Is a non-coordinating anion having a charge d-; d is an integer of 1 to 3 (e.g., 1, 2 or 3), preferably Z is (Ar) 3 C + ) Wherein Ar is aryl or is heteroatom, C 1 To C 40 Hydrocarbyl or substituted C 1 To C 40 Hydrocarbyl-substituted aryl groups. Anionic component A d- Comprising a compound having the formula [ M ] k+ Q n ] d- Wherein k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4); n-k=d; m is an element selected from group 13 of the periodic Table of the elements, preferably boron or aluminum, Q is independently hydrogen, a bridged or unbridged dialkylamino group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halohydrocarbyl group, a substituted halohydrocarbyl group, and a halocarbyl group, said Q having up to 40 carbon atoms (with the proviso that Q is a halo group no more than 1 time). Preferably, each Q is a fluorinated hydrocarbyl group having from 1 to 40 (e.g., 1 to 20) carbon atoms, more preferably each Q is a fluorinated aryl group, such as a perfluorinated aryl group, most preferably each Q is a pentafluoroaryl group or a perfluoronaphthyl group. Suitable A d- Also included are diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is incorporated herein by reference in its entirety.
When Z is an activating cation (L-H), it may be a Bronsted acid capable of donating a proton to the transition metal catalyst precursor to produce a transition metal cation, including ammonium, oxygenSulfonium and mixtures thereof, such as ammonium of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, N-methyl-4-nonadecyl-N-octadecylaniline, N-methyl-4-octadecyl-N-octadecylaniline, diphenylamine, trimethylamine, triethylamine, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, dioctadecyl methylamine; phosphorus from triethylphosphine, triphenylphosphine and diphenylphosphine->From ethers such as dimethyl ether, diethyl ether, tetraHydrofuran and di->Alkoxy->Sulfonium from sulfides such as diethyl sulfide, tetrahydrothiophene, and mixtures thereof.
In particularly useful embodiments of the invention, the activator is soluble in a non-aromatic hydrocarbon solvent, such as an aliphatic solvent.
In one or more embodiments, a 20wt% mixture of activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25 ℃, preferably a 30wt% mixture of activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25 ℃.
In embodiments of the invention, the activators described herein have a solubility in methylcyclohexane of greater than 10mM (or greater than 20mM, or greater than 50 mM) at 25deg.C (2 hours of agitation).
In an embodiment of the invention, the activator described herein has a solubility in isohexane of greater than 1mM (or greater than 10mM, or greater than 20 mM) at 25 ℃ (stirring for 2 hours).
In an embodiment of the invention, the activators described herein have a solubility in methylcyclohexane of greater than 10mM (or greater than 20mM, or greater than 50 mM) at 25 ℃ (stirring for 2 hours), and a solubility in isohexane of greater than 1mM (or greater than 10mM, or greater than 20 mM) at 25 ℃ (stirring for 2 hours).
In a preferred embodiment, the activator is a non-aromatic hydrocarbon soluble activator compound.
Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (V):
wherein:
e is nitrogen or phosphorus;
d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6; n-k=d (preferably d is 1, 2 or 3;k is 3; n is 4, 5 or 6);
R 1′ 、R 2′ and R is 3′ Independently is a C1-C50 hydrocarbon group optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups,
Wherein R is 1′ 、R 2′ And R is 3′ Together comprising 15 or more carbon atoms;
mt is an element selected from group 13 of the periodic table, such as B or Al;
each Q is independently hydrogen, a bridged or unbridged dialkylamino group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group, or a halo-substituted hydrocarbyl group.
Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VI):
[R 1′ R 2′ R 3′ EH] + [BR 4′ R 5′ R 6′ R 7′ ] - (VI)
wherein: e is nitrogen or phosphorus; r is R 1′ Is methyl; r is R 2′ And R is 3′ Independently C optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups 4 -C 50 Hydrocarbyl radicals, wherein R 2′ And R is 3′ Together containing 14 or more carbon atoms; b is boron; and R is 4′ 、R 5′ 、R 6′ And R is 7′ Independently is hydrogen, a bridged or unbridged dialkylamido (dialkylamido), halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halocarbyl (halocarbyl), substituted halocarbyl or halosubstituted hydrocarbyl (halosubstituted-hydrocarbylaryl).
Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by formula (VII) or formula (VIII):
and
wherein:
n is nitrogen;
R 2′ and R is 3′ Independently C optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups 6 -C 40 Hydrocarbyl radicals, wherein R 2′ And R is 3′ Together (if present) contain 14 or more carbon atoms;
R 8′ 、R 9′ and R is 10′ Independently C 4 -C 30 Hydrocarbyl or substituted C4-C30 hydrocarbyl;
b is boron;
R 4′ 、R 5′ 、R 6′ and R is 7′ Independently is a hydrogen group, a bridged or unbridged dialkylamido group, a halogen group, an alkoxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, or a halogen substituted hydrocarbon group.
Optionally, in any of formulae (V), (VI), (VII) or (VIII) herein, R 4′ 、R 5′ 、R 6′ And R is 7′ Is pentafluorophenyl.
Optionally, in any of formulae (V), (VI), (VII) or (VIII) herein, R 4′ 、R 5′ 、R 6′ And R is 7′ Is a pentafluoronaphthyl group.
Optionally, in any embodiment of formula (VIII) herein, R 8′ And R is 10′ Is a hydrogen atom, R 9′ Is optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups C 4 -C 30 A hydrocarbon group.
Optionally, at this pointIn any embodiment of formula (VIII), R 9′ Is optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups C 8 -C 22 A hydrocarbon group.
Optionally, in any embodiment of formulas (VII) or (VIII) herein, R 2′ And R is 3′ Independently C 12 -C 22 A hydrocarbon group.
Optionally R 1′ 、R 2′ And R is 3′ Together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 38 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 15 to 100 carbon atoms, e.g., 25 to 75 carbon atoms).
Optionally R 2′ And R is 3′ ' together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).
Optionally R 8′ 、R 9′ And R is 10′ Together contain 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 38 or more carbon atoms, e.g., 40 or more carbon atoms, e.g., 15 to 100 carbon atoms, e.g., 25 to 75 carbon atoms).
Optionally, when Q is fluorophenyl, then R 2′ Not C 1 -C 40 Linear alkyl (or R) 2′ C not being optionally substituted 1 -C 40 Linear alkyl).
Optionally R 4′ 、R 5′ 、R 6′ And R is 7′ Each of which is aryl (e.g., phenyl or naphthyl), wherein R 4′ 、R 5′ 、R 6′ And R is 7′ At least one of which is substituted with at least one fluorine atom, preferably R 4′ 、R 5′ 、R 6′ And R is 7′ Is a perfluoroaryl group (e.g., perfluorophenyl or perfluoronaphthyl).
Optionally, each Q is aryl (e.g., phenyl or naphthyl), wherein at least one of Q is substituted with at least one fluorine atom, preferably each Q is perfluoroaryl (e.g., perfluorophenyl or perfluoronaphthyl).
Optionally R 1′ Is methyl; r is R 2′ Is C 6 -C 50 An aryl group; r is R 3′ Independently C 1 -C 40 Linear alkyl or C 5 -C 50 Aryl groups.
Optionally R 2′ And R is 3′ Each of which is independently unsubstituted or substituted with halo, C 1 -C 35 Alkyl, C 5 -C 15 Aryl, C 6 -C 35 Aralkyl, C 6 -C 35 At least one of alkylaryl groups, wherein R 2 And R is 3 Together containing 20 or more carbon atoms.
Optionally, each Q is independently hydrogen, a bridged or unbridged dialkylamino group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group, or a halo-substituted hydrocarbyl group, provided that when Q is fluorophenyl, then R 2′ Not C 1 -C 40 Linear alkyl, preferably R 2′ C not being optionally substituted 1 -C 40 Linear alkyl (or R when Q is substituted phenyl) 2′ Not C 1 -C 40 Linear alkyl, preferably R 2′ C not being optionally substituted 1 -C 40 Linear alkyl). Optionally, when Q is fluorophenyl (or when Q is substituted phenyl), then R 2′ Is meta-and/or para-substituted phenyl, whereinThe meta and para substituents are independently optionally substituted C 1 To C 40 Hydrocarbyl radicals (e.g. C 6 To C 40 Aryl or linear alkyl, C 12 To C 30 Aryl or linear alkyl, or C 10 To C 20 Aryl or linear alkyl), optionally substituted alkoxy or optionally substituted silyl. Optionally, each Q is a fluorinated hydrocarbon group containing 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl group (e.g., phenyl or naphthyl), and most preferably each Q is a fluorinated aryl group (e.g., phenyl or naphthyl). Suitable [ Mt k+ Q n ] d- Also included are diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is incorporated herein by reference in its entirety. Optionally, at least one Q is not substituted phenyl. Optionally, all Q are not substituted phenyl. Optionally, at least one Q is not a perfluorophenyl group. Optionally, all Q are not perfluorophenyl.
In some embodiments of the invention, R 1′ Not methyl, R 2′ Not C 18 Alkyl, R 3′ Not C 18 Alkyl, or R 1′ Not methyl, R 2′ Not C 18 Alkyl, R 3′ Not C 18 Alkyl, and at least one Q is not substituted phenyl, optionally all Q are not substituted phenyl.
Useful cationic components in formulas (III) and (V) through (VIII) include those represented by the following formulas:
useful cationic components in formulas (III) and (V) through (VIII) include those represented by the following formulas:
the anionic component of the activators described herein includes a compound represented by the formula [ Mt ] k+ Q n ] - Those represented, wherein k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4), (preferably k is 3; n is 4, 5 or 6, preferably when M is B, n is 4); mt is an element selected from group 13 of the periodic table of elements, preferably boron or aluminum, and Q is independently hydrogen, a bridged and unbridged dialkylamido group, a halo group, an alkoxy group, an aryloxy group, a hydrocarbyl group, a substituted hydrocarbyl group, a halocarbyl group, a substituted halocarbyl group and a halo-substituted hydrocarbyl group, with the proviso that Q has up to 20 carbon atoms, with no more than 1 occurrence of halo. Preferably, each Q is a fluorinated hydrocarbyl group, optionally containing 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, most preferably each Q is a perfluorinated aryl group. Preferably, at least one Q is not a substituted phenyl group, such as a perfluorophenyl group, preferably all Q are not substituted phenyl groups, such as perfluorophenyl groups.
In one embodiment, the borate activator comprises tetrakis (heptafluoronaphthalen-2-yl) borate.
In one embodiment, the borate activator comprises tetrakis (pentafluorophenyl) borate.
Anions useful in the non-coordinating anion activators described herein also include those represented by formula 7 below:
wherein:
m is a group 13 atom, preferably B or Al, preferably B;
each R 11 Independently halo, preferably fluoro;
each R 12 Independently halo, C 6 -C 20 Substituted aromatic hydrocarbon radicals or of the formula-O-Si-R a Wherein R is a Is C 1 -C 20 Hydrocarbyl or hydrocarbylsilyl radicals, preferably R 12 Is fluoro or perfluorinated phenyl;
each of which isR 13 Is halo, C 6 -C 20 Substituted aromatic hydrocarbon radicals or of the formula-O-Si-R a Wherein R is a Is C 1 -C 20 Hydrocarbyl or hydrocarbylsilyl radicals, preferably R 13 Is a fluoro group or a C6 perfluorinated aromatic hydrocarbon group;
wherein R is 12 And R is 13 May form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R 12 And R is 13 Forming perfluorinated benzene rings. Preferably the anion has a molecular weight of more than 700g/mol and preferably at least three of the substituents on the M atoms each have a molecular weight of more than 180 cubicMolecular volume of (2).
"molecular volume" is used herein as an approximation of the spatial steric bulk of the activator molecule in solution. Comparison of substituents having different molecular volumes allows substituents having smaller molecular volumes to be considered "smaller volumes" than substituents having larger molecular volumes. In contrast, substituents having a larger molecular volume may be considered to be "more bulky" than substituents having a smaller molecular volume.
The molecular volume can be calculated as reported in "A Simple" Back of the Envelope "Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, v.71 (11), november 1994, pp.962-964. Molecular Volume (MV) (in units of) Calculated using the formula mv=8.3v s Wherein V is s Is the scaled volume. V (V) s Is the sum of the relative volumes of the constituent atoms and is calculated from the formula of the substituents using the relative volumes of table a below. For fused rings, V of each fused ring s The reduction is 7.5 percent. Calculation of anions the total MV is the sum of MVs per substituent, e.g.the MV of the perfluorophenyl group is +.>Calculation of tetrakis (perfluorophenyl) borate Total MV is +.>Four times or +.>
Table A
Element(s) Relative volume
H 1
First short term, li-F 2
Second short term, na-Cl 4
First long term, K-Br 5
Second long term, rb-I 7.5
Third long term, cs-Bi 9
Exemplary anions useful herein and their respective scaled volumes and molecular volumes are shown in table B below. The dashed bond represents a bond with boron.
Table B
The activator may be, for example, [ M2HTH ]] + [NCA] - Added to the polymerization as ion pairs, wherein the bis (hydrogenated tallow) methylamine ("M2 HTH") cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [ NCA ] ] - . Alternatively, the transition metal complex may be reacted with a neutral NCA precursor, e.g., B (C 6 F 5 ) 3 And reacting, which extracts anionic groups from the complex to form an activated species. Useful activators include [ tetrakis (pentafluorophenyl) borate]Di (hydrogenated tallow) methyl ammonium (i.e. [ M ] 2 HTH]B(C 6 F 5 ) 4 ) And [ tetrakis (pentafluorophenyl) borate]Dioctadecyl tolylammonium (i.e. [ DOdTH ]]B(C 6 F 5 ) 4 )。
Activator compounds particularly useful in the present invention include one or more of the following:
[ N, N-bis (hydrogenated tallow) methyl ammonium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-hexadecyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-tetradecyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-dodecyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-decyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate ],
[ N-methyl-4-octyl-N-octadecyl anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-hexyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-butyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-octadecyl-N-decylphenylammonium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-nonadecyl-N-dodecylanilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-nonadecyl-N-tetradecyl anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-4-nonadecyl-N-hexadecyl-anilinium tetrakis (perfluorophenyl) borate,
[ N-ethyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate,
[ N-methyl-N, N-dioctadecyl ammonium tetrakis (perfluorophenyl) borate ],
[ N-methyl-N, N-dicetyl ammonium tetrakis (perfluorophenyl) borate ],
[ N-methyl-N, N-ditetradecylammonium ] tetrakis (perfluorophenyl) borate,
[ N-methyl-N, N-didodecyl ammonium tetrakis (perfluorophenyl) borate ],
[ N-methyl-N, N-didecyl ammonium tetrakis (perfluorophenyl) borate ],
[ N-methyl-N, N-dioctyl ammonium tetrakis (perfluorophenyl) borate ],
[ N-ethyl-N, N-dioctadecyl ammonium tetrakis (perfluorophenyl) borate ],
[ N, N-dioctadecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N, N-di (hexadecyl) tolylammonium tetrakis (perfluorophenyl) borate ],
[ N, N-ditetradecyl ] tolylammonium tetrakis (perfluorophenyl) borate,
[ N, N-didodecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-octadecyl-N-hexadecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-octadecyl-N-hexadecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-octadecyl-N-tetradecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-octadecyl-N-dodecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-octadecyl-N-decyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-hexadecyl-N-tetradecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-hexadecyl-N-dodecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-hexadecyl-N-decyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-tetradecyl-N-dodecyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-tetradecyl-N-decyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-dodecyl-N-decyl-tolylammonium tetrakis (perfluorophenyl) borate ],
[ N-methyl-N-octadecyl-anilinium tetrakis (perfluorophenyl) borate ],
[ N-methyl-N-hexadecyl anilinium tetrakis (perfluorophenyl) borate ],
[ N-methyl-N-tetradecyl anilinium tetrakis (perfluorophenyl) borate ],
[ N-methyl-N-dodecylanilinium tetrakis (perfluorophenyl) borate ],
[ tetrakis (perfluorophenyl) borate ] N-methyl-N-decylammonium benzene, and
[ N-methyl-N-octylanilinium tetrakis (perfluorophenyl) borate ].
Other useful activators and synthetic non-aromatic hydrocarbon soluble activators are described in USSN 16/394,166 submitted at 25 of 2019, USSN 16/394,186 submitted at 25 of 2019, and USSN 16/394,197 submitted at 25 of 2019, which are incorporated herein by reference.
Also, particularly useful activators include dimethylanilinium tetrakis (pentafluorophenyl) borate and dimethylanilinium tetrakis (heptafluoro-2-naphthyl) borate. For a more detailed description of useful activators, see WO 2004/026921, pages 72 to 81. A list of further particularly useful activators that can be used in the practice of the present invention can be found in page 72, paragraph 74 to page 72, paragraph 74 of WO 2004/046214.
For a description of useful activators, see US 8,658,556 and US 6,211,105.
Preferred activators for use herein also include N-methyl-4-nonadecyl-N-octadecyl anilinium tetrakis (pentafluorophenyl) borate, N-methyl-4-nonadecyl-N-octadecyl anilinium tetrakis (perfluoronaphthyl) borate, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N-dimethylanilinium tetrakis (perfluorophenyl) borate, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, triphenylcarbon tetrakis (perfluoronaphthyl) borateTriphenylcarbon tetrakis (perfluorobiphenyl) borate>Triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borateTriphenylcarbon tetrakis (perfluorophenyl) borate>[Me 3 NH + ][B(C 6 F 5 ) 4 -]The method comprises the steps of carrying out a first treatment on the surface of the 1- (4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluorophenyl) pyrrolidine +. >And tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluoropyridine.
In a preferred embodiment, the activator comprises a triaryl carbon(e.g. triphenylcarbon tetraphenylborate)Tris (pentafluorophenyl) boratePhenyl carbon->Triphenylcarbon tetrakis (2, 3,4, 6-tetrafluorophenyl) borate +.>Triphenylcarbon tetrakis (perfluoronaphthyl) borate>Triphenylcarbon tetrakis (perfluorobiphenyl) borate>Triphenylcarbon +.4-bis (trifluoromethyl) phenyl) borate>)。
In another embodiment, the activator comprises one or more of the following: trialkylammonium tetrakis (pentafluorophenyl) borate, N-dialkylanilinium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (perfluoronaphthyl) borate, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate, N-dialkylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate, trialkylammonium tetrakis (perfluoronaphthyl) borate, N-tetrakis (perfluoronaphthyl) borate, N-dialkylanilinium borate, trialkylammonium tetrakis (perfluorobiphenyl) borate, N-dialkylanilinium tetrakis (perfluorobiphenyl) borate, trialkylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dialkylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dialkyl- (2, 4, 6-trimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate (wherein alkyl is methyl, ethyl, propyl, N-butyl, sec-butyl or tert-butyl).
Typical activator to catalyst ratios, for example, all NCA activators to catalyst ratios are about 1:1 molar ratio. Alternative preferred ranges include 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1, or 1:1 to 1000:1. Particularly useful ranges are 0.5:1 to 10:1, preferably 1:1 to 5:1.
It is also within the scope of the present disclosure that the catalyst compounds may be combined with a combination of aluminoxane and NCA (see, e.g., U.S. Pat. No. 3,979/007928; and WO 1995/014044 (the disclosures of which are incorporated herein by reference in their entirety), which discuss the use of aluminoxane in combination with an ionizing activator.
Optional scavenger, coactivator, chain transfer agent
In addition to the activator compounds, scavengers or coactivators may be used. Scavengers are compounds that are typically added to promote polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. Co-activators (not scavengers) may also be used in combination with the activators to form active catalysts. In some embodiments, the coactivator may be premixed with the transition metal compound to form the alkylated transition metal compound.
The coactivator may include an alumoxane such as methylalumoxane, a modified alumoxane such as modified methylalumoxane and an alkyl aluminum such as trimethylaluminum, tri-isobutylaluminum, triethylaluminum and tri-isopropylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum or tri-n-dodecylaluminum. When the procatalyst is not a dihydrocarbyl or dihydride complex, the coactivator is typically used in combination with a Lewis acid activator and an ionic activator. Co-activators are also sometimes used as scavengers to deactivate impurities in the feed or reactor.
Alkyl aluminum or organoaluminum compounds that can be used as scavengers or coactivators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and dialkylzinc, diethylzinc.
Chain transfer agents may be used in the compositions and/or methods described herein. Useful chain transfer agents are typically hydrogen, alkylaluminoxane, a chain transfer agent of the formula AlR 3 、ZnR 2 A compound of formula (wherein each R is independently C 1 -C 8 Aliphatic groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexylOctyl or an isomer thereof) or a combination thereof, such as diethyl zinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum or a combination thereof.
Polymerization process
For the polymerization processes described herein, the term "continuous" refers to a system that operates without interruption or stopping. For example, a continuous process for preparing a polymer will be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.
Solution polymerization refers to a polymerization process in which the polymer is dissolved in a liquid phase polymerization medium, such as an inert solvent or monomer or blend thereof. Solution polymerization is generally homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Such a system is preferably not turbid, as described in J.Vladimir Oliveira et al (2000) Ind.chem.Res., v.29, p.4627.
Bulk polymerization refers to a polymerization process in which the monomer and/or comonomer being polymerized is used as a solvent or diluent with little use of an inert solvent as a solvent or diluent. A small portion of the inert solvent may serve as a support for the catalyst and scavenger. The bulk polymerization system contains less than 25wt% of an inert solvent or diluent, preferably less than 10wt%, preferably less than 1wt%, preferably 0wt%.
In embodiments herein, the present invention relates to polymerization processes wherein a monomer (e.g., propylene) and optionally a comonomer are contacted with a catalyst system comprising an activator and at least one of the above-described catalyst compounds. The catalyst compound and activator may be combined in any order and are typically combined prior to contact with the monomer.
Monomers useful herein include substituted or unsubstituted C 2 -C 40 Alpha-olefins, preferably C 2 -C 20 Alpha-olefins, preferably C 2 -C 12 Alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In a preferred embodiment of the invention, the monomers include propylene and optionally a comonomer comprisingComprising one or more ethylene or C 4 -C 40 Olefins, preferably C 4 -C 20 Olefins, or preferably C 6 -C 12 An olefin. C (C) 4 -C 40 The olefin monomers may be linear, branched or cyclic. C (C) 4 -C 40 The cyclic olefin may be strained (strained) or unstrained (unstrained), monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups. In another preferred embodiment, the monomers include ethylene and optionally a comonomer comprising one or more C 3 -C 40 Olefins, preferably C 4 -C 20 Olefins, or preferably C 6 -C 12 An olefin. The C is 3 -C 40 The olefin monomers may be linear, branched or cyclic. The C is 3 -C 40 The cyclic olefin may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.
Exemplary C 2 -C 40 Olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, substituted derivatives thereof and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 5-methylcyclopentene, cyclopentene, norbornene, 5-ethylidene-2-norbornene and corresponding homologs and derivatives thereof.
In a preferred embodiment, the diene(s) is/are present in the polymer prepared herein in an amount of up to 10% by weight, preferably from 0.00001 to 1.0% by weight, preferably from 0.002 to 0.5% by weight, even more preferably from 0.003 to 0.2% by weight, based on the total weight of the composition. In some embodiments, 500ppm or less diene, preferably 400ppm or less, preferably 300ppm or less diene, is added to the polymerization. In other embodiments, at least 50ppm diene, or 100ppm or more, or 150ppm or more, is added to the polymerization.
Preferred diene monomers useful in the present invention include those having at least two non-monomersAny hydrocarbon structure of saturated bonds, preferably C 5 -C 30 Wherein at least two of the unsaturated bonds are readily incorporated into the polymer by a stereospecific or non-stereospecific catalyst. It is further preferred that the diene monomer is selected from non-conjugated diene monomers. More preferably, the diene monomers are linear divinyl monomers, most preferably those having from 5 to 30 carbon atoms. Examples of preferred dienes include pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, eicosadiene, heneicosanadiene, docosyl diene, tricosyl diene, tetracosyl diene, pentacosyl diene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene, 1, 9-decadiene, 1, 10-undecadiene, 1, 11-dodecadiene, 1, 12-tridecadiene, 1, 13-tetradecadiene, divinylbenzene, and low molecular weight polybutadiene (Mw less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, vinyl norbornene, norbornadiene, and dicyclopentadiene.
The polymerization process of the present invention may be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry or gas phase polymerization process known in the art may be used. These methods may be tested in batch, semi-batch or continuous modes. Homogeneous polymerization processes and slurry processes are preferred. (the homogeneous polymerization process is preferably one in which at least 90% by weight of the product is soluble in the reaction medium). Particularly preferred is a bulk homogeneous process. (bulk processes are preferably processes in which the monomer concentration in all the feed to the reactor is 70% by volume or more.) or, the solvent or diluent is not present or added to the reaction medium (except in small amounts used as a support for the catalyst system or other additives, or in amounts typically used in combination with monomers, such as propane in propylene). In another embodiment, the process is a slurry process. The term "slurry polymerization process" as used herein refers to a polymerization process wherein a supported catalyst is used and monomers are polymerized on the supported catalyst particles. At least 95wt% of the polymer product derived from the supported catalyst is in the form of solid particles (insoluble in the diluent).
Suitable diluents/solvents for the polymerization include non-coordinating inert liquids. Examples include linear and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof such as those commercially available (Isopar TM A fluid); perhalogenated hydrocarbons, e.g. perfluorinated C 4-10 Alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins that may act as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof. In another embodiment, the solvent is a non-aromatic solvent, preferably the aromatic compound is present in the solvent at less than 1wt%, preferably less than 0.5wt%, preferably less than 0wt%, based on the weight of the solvent.
In a preferred embodiment, the feed concentration of the monomers and comonomers used in the polymerization is 60vol% solvent or less, preferably 40vol% or less, preferably 20vol% or less, based on the total volume of the feed stream. Preferably, the polymerization is tested in a bulk process.
The preferred polymerization may be tested at any temperature and/or pressure suitable to obtain the desired ethylene polymer. Typical temperatures and/or pressures include temperatures from about 0 ℃ to about 300 ℃, preferably from about 20 ℃ to about 200 ℃, preferably from about 35 ℃ to about 150 ℃, preferably from about 40 ℃ to about 120 ℃, preferably from about 45 ℃ to about 80 ℃; and a pressure of from about 0.35MPa to about 10MPa, preferably from about 0.45MPa to about 6MPa, or preferably from about 0.5MPa to about 4 MPa.
In a typical polymerization, the run time of the reaction is up to 300 minutes, preferably about 5 to 250 minutes, or preferably about 10 to 120 minutes.
In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of from 0.001 to 50psig (0.007 to 345 kPa), preferably from 0.01 to 25psig (0.07 to 172 kPa), more preferably from 0.1 to 10psig (0.7 to 70 kPa).
In an alternative embodiment, the catalyst activity is at least 10,000 g/mmol/hr, preferably 100,000 g/mmol/hr or more, preferably 500,000g/mmol/hr or more, preferably 1,000,000g/mmol/hr or more, preferably 2,000,000g/mmol/hr or more, preferably 5,000,000g/mmol/hr or more. In an alternative embodiment, the conversion of olefin monomer is at least 10%, preferably 20% or more, preferably 30% or more, preferably 50% or more, preferably 80% or more, based on the polymer yield and the weight of monomer entering the reaction zone.
In a preferred embodiment, little or no aluminoxane is used in the process for preparing the polymer. Preferably, the aluminoxane is present in a zero mole percent or the aluminoxane is present in an aluminum to transition metal mole ratio of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1.
In a preferred embodiment, little or no scavenger is used in the process for preparing the ethylene polymer. Preferably, the scavenger (e.g., trialkylaluminum) is present at zero mole percent, or the scavenger is present at a scavenger metal to transition metal mole ratio of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1.
In a preferred embodiment, the polymerization: 1) At a temperature of 0-300 ℃ (preferably 25-150 ℃, preferably 40-120 ℃, preferably 45-80 ℃, preferably 60-160 ℃); 2) At a pressure of from atmospheric pressure to 10MPa (preferably 0.35-10MPa, preferably 0.45-6MPa, preferably 0.5-4 MPa); 3) In an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably wherein the aromatic compound is present in the solvent in less than 1wt%, preferably less than 0.5wt%, preferably in 0wt%, based on the weight of the solvent); 4) Wherein the catalyst system for polymerization comprises less than 0.5 mole%, preferably 0 mole% of an aluminoxane or said aluminoxane is present in an aluminum to transition metal mole ratio of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1; 5) The polymerization is preferably carried out in one reaction zone; 6) The catalyst activity is at least 10,000g/mmol/hr (preferably at least 100,000g/mmol/hr, preferably at least 200,000g/mmol/hr, preferably at least 500,000g/mmol/hr, preferably at least 1,000,000g/mmol/hr, preferably at least 2,000,000g/mmol/hr, preferably at least 5,000,000 g/mmol/hr); 7) Optionally, a scavenger (e.g., a trialkylaluminum compound) is not present (e.g., present at zero mole percent, or the scavenger is present at a scavenger metal to transition metal mole ratio of less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1); and 8) optionally, hydrogen is present in the polymerization reactor at a partial pressure of from 0.001 to 50psig (0.007 to 345 kPa), preferably from 0.01 to 25psig (0.07 to 172 kPa), more preferably from 0.1 to 10psig (0.7 to 70 kPa). In a preferred embodiment, the catalyst system used in the polymerization comprises at most one catalyst compound. "reaction zone" also referred to as "polymerization zone" is a vessel in which polymerization is conducted, such as a batch reactor. When multiple reactors are used in a series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerization in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, the polymerization is carried out in one reaction zone. Room temperature is 23 ℃, unless otherwise indicated.
Other additives may also be used in the polymerization, as desired, such as one or more scavengers, hydrogen, alkylaluminum, silane or chain transfer agent (e.g., alkylaluminoxane, represented by the formula AlR 3 Or ZnR 2 A compound of formula (wherein each R is independently C 1 -C 8 Aliphatic groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or isomers thereof) or combinations thereof, such as diethyl zinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.
Polyolefin products
The invention also relates to a composition of matter prepared by the method described herein. The process described herein can be used to prepare polymers of olefins or olefin mixtures. Polymers which may be prepared include polyethylene, polypropylene, C 4 -C 20 Homopolymers of olefins, C 4 -C 20 Copolymers of olefins, ethylene and C 3 -C 20 Copolymers of olefins, propylene and C 4 -C 20 Copolymers of olefins, C 4 -C 20 Olefin terpolymer, ethylene and propylene with C 4 -C 20 Olefin terpolymers, and terpolymers of ethylene and propylene with 5-ethylidene-2-norbornene.
In a preferred embodiment, the process described herein produces a propylene homopolymer or propylene copolymer, such as a propylene-ethylene and/or propylene-alpha-olefin (preferably C) having a Mw/Mn of from 1 to 10 (preferably from 2 to 5, preferably from 2 to 4, preferably from 2 to 3) 4 -C 20 ) Copolymers (e.g., propylene-hexene copolymers or propylene-octene copolymers).
In a preferred embodiment, the polymers prepared herein are preferably polymers having 0 to 25 mole% (or 0.5 to 20 mole%, or 1 to 15 mole%, preferably 3 to 10 mole%) of one or more C' s 3 -C 20 Olefin comonomer (preferably C) 3 -C 12 Ethylene copolymers of alpha-olefins, preferably propylene, butene, hexene, octene, decene, dodecene, preferably propylene, butene, hexene, octene, or preferably having from 0 to 25 mol% (or from 0.5 to 20 mol%, or from 1 to 15 mol%, preferably from 3 to 10 mol%) of one or more C 2 Or C 4 -C 20 Olefin comonomer (preferably ethylene or C 4 -C 12 Alpha-olefins, preferably ethylene, butene, hexene, octene, decene, dodecene, preferably ethylene, butene, hexene, octene).
In a preferred embodiment, the monomer is ethylene and the comonomer is hexene, preferably 1 to 15 mole% hexene, or 1 to 10 mole%.
Typically, the polymers prepared herein have Mw of 5,000 to 1,000,000g/mol (preferably 25,000 to 750,000g/mol, preferably 50,000 to 500,000 g/mol), and/or Mw/Mn of greater than 1 to 40 (or 1.2 to 20, or 1.3 to 10, or 1.4 to 5,1.5 to 4, or 1.5 to 3).
In a preferred embodiment, the polymers prepared herein have a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC). By "unimodal" is meant that the GPC trace has one peak or inflection point. By "multimodal" is meant that the GPC trace has at least two peaks or inflection points. An inflection point is a point where the sign of the second derivative of the curve changes (e.g., from negative to positive, or vice versa).
Blends of
In another embodiment, the polymer (preferably polyethylene or polypropylene) prepared herein is combined with one or more additional polymers prior to forming the film, molded part or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene and ethylene and/or butene and/or hexene, polybutene, ethylene-vinyl acetate, LDPE, LLDPE, HDPE, ethylene-vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate or any other polymer polymerizable by high pressure free radical processes, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrenic block copolymers, polyamino, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidene fluoride, polyethylene glycol and/or polyisobutylene.
In a preferred embodiment, the polymer (preferably polyethylene or polypropylene) is present in the above blend in an amount of 10 to 99wt%, preferably 20 to 95wt%, even more preferably at least 30 to 90wt%, even more preferably at least 40 to 90wt%, even more preferably at least 50 to 90wt%, even more preferably at least 60 to 90wt%, even more preferably at least 70 to 90wt%, based on the weight of the polymer in the blend.
The above blend can be prepared as follows: the polymers of the present invention are mixed with one or more polymers (as described above), the reactors are connected together in series to produce a reactor blend or more than one catalyst is used in the same reactor to produce multiple polymer materials. The polymers may be mixed together prior to being fed into the extruder or may be mixed in the extruder.
The blend may be formed using conventional equipment and methods, such as dry blending the components and then melt mixing in a mixer, or mixing the components together directly in a mixer such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder, which may include a compounding extruder and a side arm extruder used directly downstream of the polymerization process, which may include blending powders or pellets of the resin at the hopper of the film extruder. Further, additives may be included in the blend, in one or more components of the blend, and/or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art and may include, for example: a filler; antioxidants (e.g. sterically hindered phenols such as IRGANOX available from Ciba-Geigy TM 1010 or IRGANOX TM 1076 A) is provided; phosphites (e.g., IRGAFOS available from Ciba-Geigy) TM 168 A) is provided; an anti-blocking additive; tackifiers such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates and hydrogenated rosins; a UV stabilizer; a heat stabilizer; an antiblocking agent; an anti-sticking agent; an antistatic agent; a pigment; a colorant; a dye; a wax; silicon oxide; a filler; talc, and the like.
Any of the above polymers and compositions in combination with optional additives (see, e.g., U.S. patent application publication 2016/0060430, paragraph) may be used in a variety of end-use applications. Such end uses may be prepared by methods known in the art. End uses include polymer products and products having a particular end use. Exemplary end uses may include, but are not limited to, films, film-based products, diaper backsheets, industrial filter cloths, wire and cable coating compositions, articles formed by molding techniques such as injection or blow molding, extrusion coating, foaming, casting, and combinations thereof. End uses also include products made from films, such as bags, packages, and personal care films, pouches, medical products, such as medical films and Intravenous (IV) bags.
Film and method for producing the same
In particular, any of the above polymers, such as the polypropylene described above or blends thereof, may be used in a variety of end use applications. Such applications include, for example, single or multilayer blown, extruded and/or shrink films. These films may be formed by a number of well known extrusion or coextrusion techniques, such as blown film processing techniques, wherein the composition may be extruded in the molten state through an annular die and then expanded to form a uniaxially or biaxially oriented melt, then cooled to form a tube, blown film, and then may be axially cut and stretched to form a flat film. The film may then be unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the film layers may be oriented in the transverse and/or longitudinal directions to the same or different extents. The uniaxial orientation may be performed using typical cold stretching or hot stretching methods. Biaxial orientation may be performed using a tenter frame apparatus or a double bubble process and may be performed before or after the individual layers are assembled. For example, a polyethylene layer may be extrusion coated or laminated to an oriented polypropylene layer or polyethylene and polypropylene may be co-extruded together into a film and then oriented. Also, the oriented polypropylene may be laminated to the oriented polyethylene or the oriented polyethylene may be coated onto the polypropylene and then the combination may be oriented even further, if desired. Typically, the film is oriented in the Machine Direction (MD) in a proportion of up to 15, preferably 5-7, and in the Transverse Direction (TD) in a proportion of up to 15, preferably 7-9. However, in another embodiment, the film is oriented in both the MD and TD directions to the same extent.
The thickness of the film may vary depending on the intended application; however, films of thickness from 1 μm to 50 μm are generally suitable. Films intended for packaging are typically 10-50 μm thick. The thickness of the sealing layer is typically 0.2-50 μm. The sealing layer may be present on both the inner and outer surfaces of the film or the sealing layer may be present only on the inner or outer surfaces.
In another embodiment, one or more of the layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwaves. In a preferred embodiment, one or both of the surface layers are modified by corona treatment.
In another embodiment, the invention relates to:
1. a catalyst compound represented by the following formula (I):
wherein:
m is a group 3, 4, 5 or 6 transition metal or lanthanide;
e and E' are each independently O, S or NR 9 Wherein R is 9 Independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl or heteroatom-containing groups;
q is a group 14, 15 or 16 atom forming a coordination bond with the metal M;
A 1 QA 1' is part of a heterocyclic Lewis base containing 4 to 40 non-hydrogen atoms which will A via a 3-atom bridge 2 To A 2' Wherein Q is the central atom of the 3-atom bridge, A 1 And A 1' Is independently C, N or C (R) 22 ) Wherein R is 22 Selected from hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 A substituted hydrocarbyl group;
is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom bridge 1 An aryl group attached to the E bond;
is a divalent radical containing 2 to 40 non-hydrogen atoms which bridges A via a 2-atom bridge 1' An aryl group attached to the E' linkage;
l is a Lewis base;
x is an anionic ligand;
n is 1, 2 or 3;
m is 0, 1 or 2;
n+m is not more than 4;
R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' and R is 4' Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl, heteroatom or heteroatom-containing group,
and R is 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings;
any two L groups may be joined together to form a bidentate lewis base;
the X group may be joined to the L group to form a monoanionic bidentate group;
any two X groups can be joined together to form a dianionic ligand group.
2. A catalyst compound of formula 1, wherein the catalyst compound is represented by formula (II):
Wherein:
m is a group 3, 4, 5 or 6 transition metal or lanthanide;
e and E' are each independently O, S or NR 9 Wherein R is 9 Independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl or heteroatom-containing groups;
each L is independently a lewis base;
each X is independently an anionic ligand;
n is 1, 2 or 3;
m is 0, 1 or 2;
n+m is not more than 4;
R 1 、R 2 、R 3 、R 4 、R 1' 、R 2' 、R 3' and R is 4' Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings;
any two L groups may be joined together to form a bidentate lewis base;
the X group may be joined to the L group to form a monoanionic bidentate group;
any two X groups can be joined together to form a dianionic ligand group;
R 5 、R 6 、R 7 、R 8 、R 5' 、R 6' 、R 7' 、R 8' 、R 10 、R 11 and R is 12 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 5 And R is 6 、R 6 And R is 7 、R 7 And R is 8 、R 5' And R is 6' 、R 6' And R is 7' 、R 7' And R is 8' 、R 10 And R is 11 Or R is 11 And R is 12 May be joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings may be joined to form additional rings.
3. The catalyst compound of paragraph 1 or 2, wherein M is Hf, zr or Ti.
4. The catalyst compound of paragraph 1, 2 or 3, wherein E and E' are each O.
5. The catalyst compound of paragraph 1, 2, 3 or 4 wherein R 1 And R is 1' Independently C 4 -C 40 And a tertiary hydrocarbon group.
6. The catalyst compound of paragraph 1, 2, 3, 4 or 5 wherein R 1 And R is 1' Independently C 4 -C 40 Cyclic tertiary hydrocarbyl groups.
7. The catalyst compound of paragraph 1, 2, 3, 4, 5 or 6 wherein R 1 And R is 1' Independently C 4 -C 40 Polycyclic tertiary hydrocarbon groups.
8. The catalyst compound of any one of paragraphs 1-7, wherein each X is independently selected from the group consisting of: substituted or unsubstituted hydrocarbyl groups containing 1 to 20 carbon atoms, hydrogen groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halogen groups, and combinations thereof (two X's may form part of a fused ring or ring system).
9. The catalyst compound of any one of paragraphs 1-8, wherein each L is independently selected from the group consisting of: ethers, thioethers, amines, phosphines, diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, pyridine, alkene, alkyne, allene, and carbene, and combinations thereof, optionally, two or more L may form part of a fused ring or ring system).
10. The catalyst compound of paragraph 1, wherein M is Zr or Hf, Q is nitrogen, A 1 And A 1' Are all carbon, E and E' are both oxygen, and R 1 And R is 1' Are all C 4 -C 20 Annular ringAnd a tertiary alkyl group.
11. The catalyst compound of paragraph 1, wherein M is Zr or Hf, Q is nitrogen, A 1 And A 1' Are all carbon, E and E' are both oxygen, and R 1 And R is 1' Are adamantan-1-yl or substituted adamantan-1-yl.
12. The catalyst compound of paragraph 1, wherein M is Zr or Hf, Q is nitrogen, A 1 And A 1' Are all carbon, E and E' are both oxygen, and R 1 And R is 1' Are all C 6 -C 20 Aryl groups.
13. The catalyst compound of paragraph 1, wherein Q is nitrogen, A 1 And A 1' Are all carbon, R 1 And R is 1' Are all hydrogen, E and E' are both NR 9 Wherein R is 9 Selected from C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbyl or heteroatom-containing groups.
14. The catalyst compound of paragraph 1 wherein Q is carbon, A 1 And A 1' Are both nitrogen and E' are both oxygen.
15. The catalyst compound of paragraph 1, wherein Q is carbon, A 1 Is nitrogen, A 1' Is C (R) 22 ) And E' are both oxygen, wherein R 22 Selected from hydrogen, C 1 -C 20 Hydrocarbon radicals, C 1 -C 20 Substituted hydrocarbyl groups.
16. The catalyst compound of paragraph 1, wherein the heterocyclic lewis base is selected from the group represented by the following formula:
wherein each R is 23 Independently selected from hydrogen, C 1 -C 20 Alkyl and C 1 -C 20 Substituted alkyl.
17. The catalyst compound of paragraph 2, wherein M is Zr or Hf, E and E' are both oxygen, and R 1 And R is 1' Are all C4-C20 cyclic tertiary alkyl groups.
18. The catalyst compound of paragraph 2, wherein M is Zr or Hf, E and E' are both oxygen, R 1 And R is 1' Are allAdamantan-1-yl or substituted adamantan-1-yl.
19. The catalyst compound of paragraph 2, wherein M is Zr or Hf, E and E' are both oxygen, and R 1 、R 1' 、R 3 And R is 3' Is adamantan-1-yl or substituted adamantan-1-yl.
20. The catalyst compound of paragraph 2, wherein M is Zr or Hf, E and E' are both oxygen, R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl, and R 7 And R is 7' Are all C 1 -C 20 An alkyl group.
21. The catalyst compound of paragraph 2, wherein M is Zr or Hf, E and E' are both O, R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl, and R 7 And R is 7' Are all C 1 -C 20 An alkyl group.
22. The catalyst compound of paragraph 2, wherein M is Zr or Hf, E and E' are both O, R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl, and R 7 And R is 7' Are all C 1 -C 3 An alkyl group.
23. The catalyst compound of paragraph 1, wherein the catalyst compound is represented by one or more of the following formulas:
24. a catalyst system comprising an activator and a catalyst compound of any of paragraphs 1-23.
25. The catalyst system of paragraph 24, wherein the activator comprises an alumoxane or a non-coordinating anion.
26. The catalyst system of paragraph 24, wherein the activator is soluble in a non-aromatic hydrocarbon solvent.
27. The catalyst system of section 24, wherein the catalyst system is free of aromatic solvents.
28. The catalyst system of paragraph 24, wherein the activator is represented by the formula:
(Z) d + (A d- )
wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; h is hydrogen; (L-H) + Is a Bronsted acid; a is that d- Is a non-coordinating anion having a charge d-; d is an integer from 1 to 3.
29. The catalyst system of paragraph 24, wherein the activator is represented by the formula:
wherein: e is nitrogen or phosphorus; d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6;
n-k＝d；R 1′ 、R 2′ and R is 3′ Independently C optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups 1 -C 50 Hydrocarbyl radicals, wherein R 1′ 、R 2′ And R is 3′ Together comprising 15 or more carbon atoms; mt is an element selected from group 13 of the periodic table; and each Q is independently hydrogen, a bridged or unbridged dialkylamido, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halo-substituted hydrocarbyl.
30. The catalyst system of paragraph 24, wherein the activator is represented by the formula:
(Z) d + (A d- )
wherein A is d- Is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, (Z) d + Represented by one or more of the following formulas:
31. the catalyst system of paragraph 24, wherein the activator is one or more of the following:
N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (pentafluorophenyl) borate,
N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluoronaphthyl) borate,
dioctadecyl methyl ammonium tetrakis (pentafluorophenyl) borate,
dioctadecyl methyl ammonium tetra (perfluoronaphthyl) borate,
n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
triphenylcarbon tetrakis (pentafluorophenyl) borate
Trimethyl ammonium tetrakis (perfluoronaphthyl) borate,
triethylammonium tetrakis (perfluoronaphthyl) borate,
tripropylammonium tetrakis (perfluoronaphthyl) borate,
tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate,
tri (tert-butyl) ammonium tetrakis (perfluoronaphthyl) borate,
n, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate,
n, N-diethylanilinium tetrakis (perfluoronaphthyl) borate,
n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (perfluoronaphthyl) borate),
tetra (perfluoronaphthyl) boronic acid(tropylium)，
Triphenylcarbon tetrakis (perfluoronaphthyl) borate
Triphenylphosphine tetrakis (perfluoronaphthyl) borate
Triethylsilane tetra (perfluoronaphthyl) borate
Benzene tetra (perfluoronaphthyl) borate (diazonium))，
Trimethyl ammonium tetrakis (perfluorobiphenyl) borate,
Triethylammonium tetrakis (perfluorobiphenyl) borate,
Tripropylammonium tetrakis (perfluorobiphenyl) borate,
Tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate,
Tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate,
n, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate,
N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate,
N, N-dimethyl- (2, 4, 6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate,
Tetra (perfluorobiphenyl) boronic acid
Triphenylcarbon tetrakis (perfluorobiphenyl) borate
Triphenylphosphine tetrakis (perfluorobiphenyl) borate
Triethylsilane tetra (perfluorobiphenyl) borate
Benzene tetra (perfluorobiphenyl) borate (diazonium)，
[ 4-tert-butyl-PhNMe 2 H][(C 6 F 3 (C 6 F 5 ) 2 ) 4 B]，
The preparation method comprises the steps of carrying out trimethyl ammonium tetraphenyl borate,
triethylammonium tetraphenylborate,
Tripropylammonium tetraphenylborate is used as a catalyst,
tri (n-butyl) ammonium tetraphenylborate,
tri (tert-butyl) ammonium tetraphenyl borate,
tetraphenylboronic acid N, N-dimethylanilinium,
tetraphenylboronic acid N, N-diethylanilinium,
tetraphenylboronic acid N, N-dimethyl- (2, 4, 6-trimethylanilinium),
tetraphenylboronic acid
Triphenylcarbon tetraphenyl borate
Tetraphenylboronic acid triphenylphosphine
Triethylsilane tetraphenylborate
Tetraphenylboronic acid benzene (diazonium))，
Trimethyl ammonium tetrakis (pentafluorophenyl) borate,
triethylammonium tetrakis (pentafluorophenyl) borate,
Tripropylammonium tetrakis (pentafluorophenyl) borate,
tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,
tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate,
n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
n, N-diethylanilinium tetrakis (pentafluorophenyl) borate,
n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (pentafluorophenyl) borate,
tetrakis (pentafluorophenyl) borate
Triphenylcarbon tetrakis (pentafluorophenyl) borate
Triphenylphosphine tetrakis (pentafluorophenyl) borate
Triethylsilane tetra (pentafluorophenyl) borate
Benzene tetra (pentafluorophenyl) borate (diazonium)，
Trimethyl ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
triethylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
tripropylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
tri (n-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
dimethyl (tert-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
n, N-dimethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
n, N-diethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate),
tetrakis (2, 3,4, 6-tetrafluorophenyl) borate
Triphenylcarbon tetrakis (2, 3,4, 6-tetrafluorophenyl) borate
Triphenylphosphine tetrakis (2, 3,4, 6-tetrafluorophenyl) borate
Triethylsilane tetrakis (2, 3,4, 6-tetrafluorophenyl) borate
Benzene tetrakis (2, 3,4, 6-tetrafluorophenyl) borate (diazonium)，
Trimethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
triethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
tripropylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
tri (n-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
Tri (tert-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
n, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
N, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
N, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate
Triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate
Triphenylphosphine tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate
Triethylsilane tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate
Benzene tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (diazonium)，
Di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate,
dicyclohexylammonium tetrakis (pentafluorophenyl) borate,
tris (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate
Tris (2, 6-dimethylphenyl) phosphorus tetrakis (pentafluorophenyl) borate
Triphenylcarbon tetrakis (perfluorophenyl) borate
1- (4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluorophenyl) pyrrole Alkyl (C)
Tetra (pentafluorophenyl) borate,
4- (tris (pentafluorophenyl) boronic acid) -2,3,5, 6-tetrafluoropyridine, and
triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate
32. A process for polymerizing olefins comprising contacting one or more olefins with the catalyst system of any of stages 23-31.
33. The process of paragraph 32, wherein the process is conducted at a temperature of from about 0 ℃ to about 300 ℃, at a pressure of from about 0.35MPa to about 10MPa and for a time of up to 300 minutes.
34. The method of paragraph 32, further comprising obtaining the polymer.
35. The process of paragraph 32, wherein the olefin comprises one or more substituted or unsubstituted C 2 -C 40 Alpha-olefins.
Experiment
Shown in scheme 3 is a graph of catalyst complexes 1-32. Complexes 26 and 27 are prepared as described in U.S. patent application Ser. No. Lewis base catalysts and methods thereof (attorney docket No. 2019EM 043), filed concurrently herewith, which claims the priority and benefit of 62/804,372 filed on month 2 and 12 of 2019. Complex 28 (comparative) was prepared as described by Golisz et al (2009) Macromolecules, v.42, pp.8751-8762, and was the comparative complex. Complexes 31 and 32 were prepared using procedures similar to those described for complex 29. 2- (adamantan-1-yl) -4- (tert-butyl) phenol was prepared from 4-tert-butylphenol (Merck) and adamantanol-1 (Aldrich) as described in Organic Letters 2015, v.17, pp.2242-2245.
Scheme 3
Scheme 3 (subsequent)
Scheme 3 (subsequent)
Scheme 3 (subsequent)
2- (adamantan-1-yl) -6-bromo-4- (tert-butyl) phenol
To a solution of 57.6g (203 mmol) 2- (adamantan-1-yl) -4- (tert-butyl) phenol in 400mL chloroform was added dropwise a solution of 10.4mL (203 mmol) bromine in 200mL chloroform at room temperature for 30 minutes. The resulting mixture was diluted with 400mL of water. The resulting mixture was extracted with dichloromethane (3X 100 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 71.6g (97%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.32(d,J＝2.3Hz,1H),7.19(d,J＝2.3Hz,1H),5.65(s,1H),2.18-2.03(m,9H),1.78(m,6H),1.29(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ148.07,143.75,137.00,126.04,123.62,112.11,40.24,37.67,37.01,34.46,31.47,29.03。
(1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantane
At room temperature toTo a solution of 71.6g (197 mmol) 2- (adamantan-1-yl) -6-bromo-4- (tert-butyl) phenol in 1,000mL THF was added 8.28g (207 mmol,60% by weight in mineral oil) sodium hydride in portions. To the resulting suspension was added dropwise 16.5mL (217 mmol) of methoxymethyl chloride at room temperature over 10 minutes. The resulting mixture was stirred overnight and then poured into 1,000ml of water. The resulting mixture was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 80.3g (quantitative) of white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.39(d,J＝2.4Hz,1H),7.27(d,J＝2.4Hz,1H),5.23(s,2H),3.71(s,3H),2.20-2.04(m,9H),1.82-1.74(m,6H),1.29(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ150.88,147.47,144.42,128.46,123.72,117.46,99.53,57.74,41.31,38.05,36.85,34.58,31.30,29.08。
2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan (dioxaborolan)
To a solution of 22.5g (55.0 mmol) (1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantane in 300mL of anhydrous THF was added dropwise 23.2mL (57.9 mmol, 2.5M) nBuLi in hexane for 20 min at-80℃the reaction mixture was stirred at this temperature for 1 h, then 14.5mL (71.7 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan. The suspension obtained was stirred at room temperature for 1 h and then poured into 300mL of water, the mixture obtained was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 25.0g (quantitative) of colorless viscous oil was obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.54(d,J＝2.5Hz,1H),7.43(d,J＝2.6Hz,1H),5.18(s,2H),3.60(s,3H),2.24-2.13(m,6H),2.09(br.s.,3H),1.85-1.75(m,6H),1.37(s,12H),1.33(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ159.64,144.48,140.55,130.58,127.47,100.81,83.48,57.63,41.24,37.29,37.05,34.40,31.50,29.16,24.79。
1- (2 '-bromo-5- (tert-butyl) -2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane
To 25.0g (55.0 mmol) of 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 200mL of twoTo the solution in the alkane was added, in order, 15.6g (55.0 mmol) of 2-bromoiodobenzene, 19.0g (137 mmol) of potassium carbonate and 100mL of water. The resulting mixture was purged with argon for 10 minutes, then 3.20g (2.75 mmol) of Pd (PPh) was added 3 ) 4 . The mixture thus obtained was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The resulting mixture was extracted with dichloromethane (3X 100 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 23.5g (88%) of a white solid was obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.68(dd,J＝1.0,8.0Hz,1H),7.42(dd,J＝1.7,7.6Hz,1H),7.37-7.32(m,2H),7.20(dt,J＝1.8,7.7Hz,1H),7.08(d,J＝2.5Hz,1H),4.53(d,J＝4.6Hz,1H),4.40(d,J＝4.6Hz,1H),3.20(s,3H),2.23-2.14(m,6H),2.10(br.s.,3H),1.86-1.70(m,6H),1.33(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ151.28,145.09,142.09,141.47,133.90,132.93,132.41,128.55,127.06,126.81,124.18,123.87,98.83,57.07,41.31,37.55,37.01,34.60,31.49,29.17。
2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
30.0g (62.1 mmol) of 1- (2 '-bromo-5- (tert-butyl) -2- (methoxymethoxy) - [1,1' -biphenyl) are introduced at-80 ℃]To a solution of 3-yl) adamantane in 500mL anhydrous THF was added dropwise 25.6mL (63.9 mmol, 2.5M) of a solution of nBuLi in hexane for 20 min. The reaction mixture was stirred at this temperature for 1 hour, then 16.5mL (80.7 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The resulting mixture was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 32.9g (quantitative) of a colorless glassy solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.75(d,J＝7.3Hz,1H),7.44-7.36(m,1H),7.36-7.30(m,2H),7.30-7.26(m,1H),6.96(d,J＝2.4Hz,1H),4.53(d,J＝4.7Hz,1H),4.37(d,J＝4.7Hz,1H),3.22(s,3H),2.26-2.14(m,6H),2.09(br.s.,3H),1.85-1.71(m,6H),1.30(s,9H),1.15(s,6H),1.10(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.35,146.48,144.32,141.26,136.15,134.38,130.44,129.78,126.75,126.04,123.13,98.60,83.32,57.08,41.50,37.51,37.09,34.49,31.57,29.26,24.92,24.21。
2', 2' "- (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-ol
To 32.9g (62.0 mmol) of 2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 140ml of diTo the solution in alkane was added 7.35g (31.0 mmol) of 2, 6-dibromopyridine, 50.5g (155 mmol) of cesium carbonate and 70ml of water in this order. The resulting mixture was purged with argon for 10 minutes, then 3.50g (3.10 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil was then added 300mL THF, 300mL methanol, and 21mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 500mL of water. The resulting mixture was extracted with dichloromethane (3X 350 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). The glassy solid obtained was triturated with 70ml of n-pentane, the precipitate obtained was filtered off, washed with 2 x 20ml of n-pentane and dried in vacuo. 21.5g (87%) of a mixture of the two isomers are obtained as a white powder. 1 H NMR(CDCl 3 ,400MHz):δ8.10+6.59(2s,2H),7.53-7.38(m,10H),7.09+7.08(2d,J＝2.4Hz,2H),7.04+6.97(2d,J＝7.8Hz,2H),6.95+6.54(2d,J＝2.4Hz),2.03-1.79(m,18H),1.74-1.59(m,12H),1.16+1.01(2s,18H)。 13 C NMR(CDCl 3 The minor isomer shifts marked with x are δ 157.86,157.72, 150.01,149.23, 141.82, 141.77,139.65, 139.42,137.92,137.43,137.32, 136.80,136.67, 136.29, 131.98, 131.72,130.81,130.37, 129.80,129.09, 128.91,128.81, 127.82, 127.67,126.40,125.65, 122.99, 122.78,122.47,122.07, 40.48,40.37, 37.04,36.89, 34.19, 34.01,31.47,29.12,29.07.
Hafnium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenoxide) ] (complex 5)
At 0℃3.22g (10.05 mmol) of hafnium tetrachloride were introduced by syringe<0.05% zr) in 250mL of anhydrous toluene was added 14.6mL (42.2 mmol,2.9 m) of MeMgBr in diethyl ether in one portion. The resulting suspension was stirred for 1 minute and was stirred in the following8.00g (10.05 mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl were added in portions over 1 minute]-2-phenol). The reaction mixture was stirred at room temperature for 36 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 100mL of hot toluene and the combined organic extracts were filtered through a thin pad of Celite (Celite) 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 50mL of n-hexane, the precipitate obtained was filtered off (G3), washed with 20mL of n-hexane (2×20 mL) and then dried in vacuo. 6.66g (61%, 1:1 solvate with n-hexane) of a pale beige solid are produced. C (C) 59 H 69 HfNO 2 ×1.0(C 6 H 14 ) Is calculated by analysis of: c,71.70; h,7.68; n,1.29. Actual measurement value: c71.95; h,7.83; n1.18. 1 H NMR(C 6 D 6 ,400MHz):δ7.58(d,J＝2.6Hz,2H),7.22-7.17(m,2H),7.14-7.08(m,4H),7.07(d,J＝2.5Hz,2H),7.00-6.96(m,2H),6.48-6.33(m,3H),2.62-2.51(m,6H),2.47-2.35(m,6H),2.19(br.s,6H),2.06-1.95(m,6H),1.92-1.78(m,6H),1.34(s,18H),-0.12(s,6H)。 13 C NMR(C 6 D 6 ,100MHz):δ159.74,157.86,143.93,140.49,139.57,138.58,133.87,133.00,132.61,131.60,131.44,127.98,125.71,124.99,124.73,51.09,41.95,38.49,37.86,34.79,32.35,30.03。
Zirconium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenoxide) ] (complex 6)
To a suspension of 2.92g (12.56 mmol) zirconium tetrachloride in 300mL dry toluene was added 18.2mL (52.7 mmol, 2.9M) of MeMgBr in ether via syringe at 0deg.C. To the resulting suspension 10.00g (12.56 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3-adamant-1-yl) -5- (tert-butyl) - [1,1' -biphenyl were added in one portion immediately]-2-phenol). The reaction mixture was stirred at room temperature for 2 hours and then evaporated to near dryness. The solid obtained was extracted with 2X 100mL of hot toluene and the combined organic extracts were passed through tigerA thin pad of formula salt 503 is filtered. Next, the filtrate was evaporated to dryness. The residue was triturated with 50mL of n-hexane and the precipitate obtained was filtered off (G3), washed with n-hexane (2 x 20 mL) and then dried in vacuo. 8.95g (74%, 1:0.5 solvate with n-hexane) of beige solid are obtained. C (C) 59 H 69 ZrNO 2 ×0.5(C 6 H 14 ) Is calculated by analysis of: c,77.69; h,7.99; n,1.46. Found: c77.90; h,8.15; n1.36. 1 H NMR(C 6 D 6 ,400MHz):δ7.56(d,J＝2.6Hz,2H),7.20-7.17(m,2H),7.14-7.07(m,4H),7.07(d,J＝2.5Hz,2H),6.98-6.94(m,2H),6.52-6.34(m,3H),2.65-2.51(m,6H),2.49-2.36(m,6H),2.19(br.s.,6H),2.07-1.93(m,6H),1.92-1.78(m,6H),1.34(s,18H),0.09(s,6H)。 13 C NMR(C 6 D 6 ,100MHz):δ159.20,158.22,143.79,140.60,139.55,138.05,133.77,133.38,133.04,131.49,131.32,127.94,125.78,124.65,124.52,42.87,41.99,38.58,37.86,34.82,32.34,30.04。
1-adamantanol
To a stirred solution of 1-bromoadamantane (5.00 g,23.242 mmol) in dimethylmethylamino (25 ml) was added hydrochloric acid (8.7 ml of 0.67M HCl) followed by water (15 ml). The mixture was brought to 105 ℃ and stirred for 1 hour. After cooling to room temperature, water (150 mL) was added and the resulting precipitate was collected by vacuum filtration. The solid was dissolved in dichloromethane (200 ml) and washed with water (3X 100 ml). The organic layer was dried (MgSO 4 ) Filtration and concentration under vacuum gave 3.512g (23.069 mmol,99% yield).
2, 4-di (adamantan-1-yl) phenol
To a mixture of phenol (2.00 g,21.252 mmol) and 1-adamantanol (6.794 g,44.629mmol,2.10 eq.) in dichloromethane (20 mL) was added dropwise (via 10)Minute) concentrated sulfuric acid (2.5 mL). It was stirred at room temperature overnight. Water (15 ml) was added to the reaction mixture to give a pH of 9-10 (2M aqueous NaOH solution). The organics were extracted with dichloromethane (3×20 ml), washed with brine, dried (MgSO 4 ) Filtered and concentrated in vacuo. The residue was purified by column chromatography (5-10% ethyl acetate/hexane) to give 1.29g (17% yield) of a white solid.
1,1' - (4- (methoxymethoxy) -1, 3-phenylene) bis (adamantane)
To a mixture of 2, 4-bis (adamantyl) phenol (1.29 g, 3.578 mmol) in tetrahydrofuran (3 mL) was slowly added 60% sodium hydride in mineral oil (0.185 g,4.625mmol,1.30 eq). It was stirred at room temperature for 30 minutes, at which time chloromethyl methyl ether (0.459 ml,6.049mmol,1.70 eq.) was gradually added. The reaction was stirred at room temperature overnight. The reaction mixture was quenched with water (20 mL) and the pH was adjusted to 8-10 using potassium hydroxide. The product was extracted with diethyl ether (3X 30 ml) and dried (MgSO 4 ) Filtration and concentration in vacuo gave 1.330g (3.275 mmol,92% yield).
(3, 5-Diadamantan-1-yl) -2- (methoxymethoxy) phenyl) lithium (1, 2-dimethoxyethane)
Pentane (20 mL) was added to 1,1' - (4- (methoxymethoxy) -1, 3-phenylene) bis (adamantane) (1.38 g,3.40 mmol) to form a solution. 1.6M BuLi in hexane (2.13 mL,3.40 mmol) was added dropwise. 1, 2-Dimethoxyethane (DME) was then added dropwise. Within minutes, the yellow solution became cloudy and then began to form a precipitate. The mixture was stirred for 1.5 hours, then the precipitate was separated on a fritted disc, washed with pentane (3×15 mL) and dried under reduced pressure. The product was isolated as an off-white solid. Yield: 1.15g,67.2%.
1,1' - (2 ' -bromo-2- (methoxymethoxy) - [1,1' -biphenyl ] -3, 5-diyl) bis (adamantane)
Toluene (20 mL) was added to (3, 5-diadamantan-1-yl) -2- (methoxymethoxy) phenyl) lithium (1, 2-dimethoxyethane) (1.15 g,2.29 mmol) to form a suspension. A toluene solution (10 mL) of 1-bromo-2-chlorobenzene (0.482 g,2.52 mmol) was added dropwise over 1 hour to form a turbid solution. The mixture was stirred for an additional 1 hour, and then volatiles were removed under reduced pressure. The residue was taken up in CH 2 Cl 2 (8 mL) and filtered through Celite 503 on a Teflon filter. The volatiles were evaporated and pentane (3 mL) was added to the residue. The mixture was cooled to-20 ℃ overnight. The volatiles were evaporated and the residue was dried under reduced pressure at 60 ℃. Yield: 1.32g,98.9%.
2', 2' "- (pyridine-2, 6-diyl) bis ((3, 5-diamantan-1-yl) - [1,1' -biphenyl ] -2-ol)
Tetrahydrofuran (15 mL) was added to 1,1' - (2 ' -bromo-2- (methoxymethoxy) - [1,1' -biphenyl)]3, 5-diyl) bis (adamantane) (1.32 g,2.26 mmol) to form a solution. The mixture was cooled to-45℃and 1.6M BuLi in hexane (1.46 mL,2.33 mmol) was added dropwise over one minute. The mixture was allowed to slowly warm to-25 ℃ over 45 minutes. Adding solid ZnCl to the clear solution 2 (0.216 g,1.58 mmol). The mixture was allowed to slowly warm to ambient temperature over 30 minutes. After 30 min at ambient temperature, 2, 6-dibromopyridine (0.260 g,1.10 mmol) and Pd (P (tBu) 3 ) 2 (0.023 g,0.045 mmol) was added to the clear colorless solution. The mixture was heated overnight on a metal block maintained at 65 ℃. After stirring overnight, the volatiles were evaporated using a rotary evaporator. To the residue were added methanol (20 mL), THF (20 mL) and concentrated HCl (1 mL). The mixture was heated to 60 ℃ for 5 hours. Then use the screw The volatiles were evaporated by a rotary evaporator and the solvent was removed by CH 2 Cl 2 (60 mL) the residue was extracted. The organics were washed with water (3X 50 mL) and diluted NaHCO 3 The pH was adjusted to 7 (1X 50 mL) and then dried with brine (40 mL) and over MgSO 4 And (5) drying. The volatiles were filtered and removed to give 1.2g of crude product. Purified by column chromatography on silica gel using 2-8% etoac in isohexane. Evaporation of isohexane-EtOAc gives a white residue containing some insoluble in CH 2 Cl 2 Is a substance of (a). The solid was extracted with benzene (10 mL), filtered and evaporated. The residue was dried under reduced pressure at 60 ℃ to give a foamy solid. Yield: 0.322g,30.8%.
Dibenzyl zirconium [2', 2' "- (pyridine-2, 6-diyl) bis (3, 5-diamantan-1-yl) - [1,1' -biphenyl ] -2-phenoxide) ] (complex 22)
Benzene (15 mL) was added to 2', 2' "- (pyridine-2, 6-diyl) bis ((3, 5-diadamantan-1-yl) - [1,1' -biphenyl)]2-phenol) (0.315 g,0.331 mmol) to form a solution. Adding ZrBn 4 (0.151 g,0.331 mmol) and benzene (2 mL). The mixture was shaken to form a yellow-orange solution. After 30 minutes, the mixture was filtered and evaporated to 1mL. Hexane (3 mL) was added to form a cloudy mixture. The volatiles were evaporated to dryness. The yellowish orange solid was washed thoroughly with pentane (5 mL). The pentane extract was filtered and cooled to-20 ℃ for several hours. Some yellow solid was isolated from the pentane solution. The sample that had been washed with pentane was combined with methylcyclohexane (10 mL) and the mixture was heated to near boiling for several minutes. Some crystalline solid was isolated from the orange solution. The mixture was allowed to stand at ambient temperature for 2 hours, then the colorless solid was isolated and dried under reduced pressure. HNMR spectroscopy indicated that the product was co-crystallized with 1 equivalent of methylcyclohexane. Yield: 0.092g,21%.
1- (3-bromo-2- (methoxymethoxy) -5-methylphenyl) adamantane
A solution of 21.3g (66.4 mmol) of 2-bromo-6-adamantyl-4-methylphenol in 300mL of anhydrous THF was separated at room temperature2.79g (69.7 mmol,60% by weight in mineral oil) of sodium hydride are added in portions. Thereafter, 5.55mL (73.0 mmol) of MOMCl was added dropwise over 1 hour. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 300mL of cold water. The crude product was extracted with 3X 200mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. 24.3g (quantitative) of a colourless oil are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.24(d,J＝1.5Hz,1H),7.05(d,J＝1.8Hz,1H),5.22(s,2H),3.71(s,3H),2.27(s,3H),2.07-2.15(m,9H),1.78(m,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.01,144.92,134.34,131.80,127.44,117.57,99.56,57.75,41.27,37.71,36.82,29.03,20.68。
2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [ b ] thiophene
To 10.0g (74.5 mmol) of benzo [ b ] at-10 ℃]To a solution of thiophene in 250mL dry THF was added dropwise 29.8mL (74.5 mmol, 2.5M) of a hexane solution of nBuLi. The reaction mixture was stirred at 0deg.C for 1 hour, then 11.2g (82.0 mmol) of ZnCl was added 2 . Next, the resulting solution was warmed to room temperature, followed by the addition of 13.6g (37.3 mmol) of 1- (3-bromo-2- (methoxymethoxy) -5-methylphenyl) adamantane and 1.52g (2.98 mmol) of Pd [ P ] t Bu 3 ] 2 . The resulting mixture was stirred at 60 ℃ overnight and then poured into 250mL of water. The crude product was extracted with 3X 150mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography (40-63 μm; eluent: hexane-ethyl acetate=10:1, volume) on silica gel 60. 5.31g (34%) of a pale yellow solid are obtained. 1 HNMR(CDCl 3 ,400MHz):δ7.88(d,J＝7.7Hz,1H),7.81(d,J＝7.4Hz,1H),7.54(s,1H),7.32-7.42(m,2H),7.18-7.23(m,2H),4.79(s,2H),3.49(s,3H),2.38(s,3H),2.24(m,6H),2.16(m,3H),1.85(m,6H)。
3-bromo-2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [ b ] thiophene
To 5.31g (12.7 mmol) of 2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [ b ] at room temperature]To a solution of thiophene in 150ml of chloroform was added 2.26g (12.7 mmol) of N-bromosuccinimide. The reaction mixture was stirred at this temperature for 2 hours and then poured into 100mL of water. The crude product was extracted with 3X 50mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was recrystallized from 90mL of n-hexane at-30 ℃. 6.25g (98%) of a pale yellow solid are obtained. 1 HNMR(CDCl 3 ,400MHz):δ7.90(d,J＝7.8Hz,1H),7.84(d,J＝7.9Hz,1H),7.49(dt,J＝0.9,7.1Hz,1H),7.43(dt,J＝1.2,8.1Hz,1H),7.24(d,J＝2.0Hz,1H),7.12(d,J＝1.7Hz,1H),4.66(s,2H),3.33(s,3H),2.38(s,3H),2.22(m,6H),2.14(br.s,3H),1.83(m,6H)。 13 C NMR(CDCl 3 ,100MHz):δ153.19,143.13,138.54,138.19,137.38,132.48,130.68,129.30,126.06,125.38,125.03,123.42,122.19,107.76,99.33,57.38,41.17,37.30,36.97,29.10,20.98。
6,6' - (pyridine-2, 6-diylbis (benzo [ b ] thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenol
3.00g (6.03 mmol) of 3-bromo-2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [ b ] at-80 ℃]To a solution of thiophene in 120mL of anhydrous THF was added dropwise a solution of 2.41mL (6.03 mmol, 2.5M) of nBuLi in hexane. The reaction mixture was stirred at this temperature for 30 minutes, then 2.32g (17.1 mmol) of ZnCl was added 2 . The resulting mixture was warmed to room temperature, then 0.72g (3.02 mmol) of 2, 6-dibromopyridine and 245mg (0.48 mmol) of Pd [ P ] were added successively t Bu 3 ] 2 . The resulting mixture was stirred at 60℃overnight, poured into 100mL of water, and the mixture was stirred overnightThe crude product was extracted with dichloromethane (3X 50 mL). The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. To the resulting oil were then added 50mL THF, 50mL methanol, and 1mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine=100:10:1, volume). 0.78g (31%) of a white foam was obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.87-7.94(m,4H),7.67(t,J＝7.8Hz,1H),7.38-7.48(m,4H),7.28(d,J＝7.8Hz,2H),6.91-6.99(m,4H),2.23(s,6H),1.82(br.s,6H),1.67(br.s,9H),1.57-1.62(m,6H),1.42-1.50(m,6H)。 13 C NMR(CDCl 3 ,100MHz):δ153.56,150.70,140.51,139.91,138.86,138.50,137.87,131.91,129.49,128.68,128.49,124.92,124.77,123.71,122.82,122.00,40.02,36.81,36.60,28.98,20.73。
Hafnium dimethyl [6,6' - (pyridine-2, 6-diylbis (benzo [ b ])]Thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenolate](Complex 23). To a suspension of 155mg (0.485 mmol) hafnium tetrachloride in 50mL dry toluene was added 0.75mL (2.20 mmol, 2.9M) of MeMgBr in ether at room temperature. The resulting suspension was stirred for 1 min, and 400mg (0.485 mmol) of 6,6' - (pyridine-2, 6-diylbis (benzo [ b ]) was added dropwise over 1 min ]Thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenol) in 10mL of anhydrous toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 5mL of n-hexane and dried in vacuo. 303mg (60%) of an off-white solid are obtained as hexane solvate. C (C) 57 H 57 HfNO 2 S 2 ×2(C 6 H 14 ) Is calculated by analysis of: c,68.89; h,7.12; n,1.16. Actual measurement value: c69.07; h7.33; n1.11. 1 H NMR(C 6 D 6 ,400MHz):δ7.35(dd,J＝1.9,6.9Hz,2H),7.21(d,J＝2.1Hz,2H),7.12(d,J＝2.1Hz,2H),7.05-7.12(m,4H),6.92(dd,J＝2.0,6.5Hz,2H),6.69(t,J＝7.8Hz,1H),6.46(d,J＝7.8Hz,2H),2.20(s,6H),2.11-2.17(m,6H),1.99-2.07(m,6H),1.75-1.87(m,12H),1.63-1.70(m,6H),0.18(s,6H)。 13 C NMR(C 6 D 6 ,100MHz):δ160.12,154.44,150.43,149.60,147.46,143.70,141.40,140.26,134.21,131.01,130.32,129.66,127.31,126.59,125.59,125.45,124.83,124.64,122.98,122.68,114.02,52.62,41.19,38.05,37.67,32.30,29.73,23.39,14.69。
Zirconium dimethyl [6,6' - (pyridine-2, 6-diylbis (benzo [ b ] thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenolate) ] (complex 24)
To a suspension of 58mg (0.247 mmol) zirconium tetrachloride in 30mL dry toluene was added 0.38mL (1.11 mmol, 2.9M) of MeMgBr in ether at room temperature. The resulting suspension was stirred for 10 seconds and 204mg (0.247 mmol) of 6,6' - (pyridine-2, 6-diylbis (benzo [ b ]) was added dropwise over 30 seconds]Thiophene-3, 2-diyl)) bis (2-adamantan-1-yl) -4-methylphenol) in 10mL of anhydrous toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The solid obtained was extracted with 2×20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 5mL of n-hexane and then dried in vacuo. 140mg (60%) of an off-white solid was obtained. C (C) 57 H 57 ZrNO 2 S 2 Is calculated by analysis of: c,72.57; h,6.09; n,1.48. Actual measurement value: c72.78; h6.29; n1.31. 1 H NMR(C 6 D 6 ,400MHz):δ7.34(dd,J＝1.9,6.7Hz,2H),7.20(d,J＝2.2Hz,2H),7.12(d,J＝2.5Hz,2H),7.08(m,4H),7.02(m,2H),6.91(dd,J＝1.8,6.4Hz,2H),6.69(t,J＝7.6Hz,1H),6.45(d,J＝7.8Hz,2H),2.20(s,6H),2.15-2.21(m,6H),2.02-2.09(m,6H),1.75-1.85(m,12H),1.64-1.72(m,6H),0.40(s,6H)。 13 C NMR(C 6 D 6 ,100MHz):δ160.18,155.17,149.57,141.60,140.66,140.29,139.81,130.94,130.24,129.66,128.88,127.40,126.54,126.12,126.02,125.72,125.45,125.07,122.93,122.73,44.72,41.44,38.36,37.83,29.99,21.65,21.18。
2- (3, 5-Dimethyladamantan-1-yl) -4-fluorophenol
To a solution of 8.40g (75.0 mmol) of 4-fluorophenol and 13.5g (75.0 mmol) of 3, 5-dimethyladamantan-1-ol in 150mL of dichloromethane was added dropwise a solution of 4.90mL (75.0 mmol) of methanesulfonic acid and 5mL of acetic acid in 100mL of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then 300ml of 5% NaHCO was carefully poured in 3 Is a kind of medium. The resulting mixture was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified using a Kugelrohr apparatus (1 mbar, 70 ℃) to give 14.2g (68%) of the title product as a pale yellow oil. 1 H NMR(CDCl 3 ,400MHz):δ6.93(dd,J＝3.1,11.2Hz,1H),6.73(ddd,J＝3.1,7.4,8.6Hz,1H),6.55(dd,J＝4.9,8.6Hz),4.62(s,1H),2.16(dt,J＝3.1,6.3Hz,1H),1.91(m,2H),1.64-1.74(m,4H),1.35-1.45(m,4H),1.20(br.s,2H),0.87(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ158.49(J F ＝236Hz),150.19(J F ＝2.0Hz),137.69(J F ＝5.9Hz),117.12(J F ＝8.1Hz),114.13(J F ＝24.0Hz),112.57(J F ＝22.9Hz),50.92,46.44,43.05,38.70,38.48,31.38,30.84,29.90。
2-bromo-6- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol
To a solution of 14.2g (51.7 mmol) 2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol in 200mL dichloromethane was added dropwise a solution of 2.67mL (51.7 mmol) bromine in 100mL dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then 200mL of 5% NaHCO was carefully poured in 3 Is a kind of medium. The resulting mixture was extracted with dichloromethane (3X 50 mL) and the combined organics were combined The extract is Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 17.5g (96%) of a pale yellow solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.06(dd,J＝3.0,7.0Hz,1H),6.93(dd,J＝2.9,10.8Hz,1H),5.59(s,1H),2.16(m,1H),1.89(br.s,2H),1.63-1.73(m,4H),1.34-1.44(m,4H),1.19(br.s,2H),0.86(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ157.21(J F ＝241Hz),146.61(J F ＝2.8Hz),137.97(J F ＝6.1Hz),115.34(J F ＝25.8Hz),113.64(J F ＝23.6Hz),110.83(J F ＝10.9Hz),54.77,50.48,45.71,42.61,38.96,38.03,31.02,30.42,29.49。
1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5-dimethyladamantane
To a solution of 17.5g (49.5 mmol) 2-bromo-6- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol in 200mL anhydrous THF was added portionwise 2.17g (54.4 mmol,60% wt in mineral oil) sodium hydride at room temperature. Thereafter, 4.53mL (60.0 mmol) of MOMCl was added dropwise over 1 hour. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 300mL of cold water. The crude product was extracted with 3X 200mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. 19.6g (quantitative) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.13(dd,J＝3.1,6.8Hz,1H),6.98(dd,J＝3.1,10.9Hz,1H),5.19(s,2H),3.68(s,3H),2.16(m,1H),1.89(br.s,2H),1.64-1.74(m,4H),1.34-1.44(m,4H),1.19(br.s,2H),0.87(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ159.47(J F ＝245Hz),150.08(J F ＝3.3Hz),146.34(J F ＝6.4Hz),118.13(J F ＝25.4Hz),117.65(J F ＝10.7Hz),114.01(J F ＝23.4Hz),99.95,57.89,50.69,47.13,42.84,39.78,39.55,31.50,30.84,29.94。
2- (3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [ b ] thiophene
To 3.38g (25.2 mmol) of benzo [ b ] at-10 ℃]To a solution of thiophene in 200mL dry THF was added 9.50mL (23.9 mmol, 2.5M) of nBuLi in hexane dropwise. The reaction mixture was stirred at 0deg.C for 2 hours, then 3.30g (23.9 mmol) of ZnCl was added 2 . Next, the resulting solution was warmed to room temperature, followed by the addition of 5.00g (12.6 mmol) of 1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5-dimethyladamantane and 643mg (1.26 mmol) of Pd [ P ] t Bu 3 ] 2 . The resulting mixture was stirred at 60 ℃ overnight and then poured into 250mL of water. The crude product was extracted with 3X 150mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography (40-63 um; eluent: hexane-ethyl acetate=10:1, volume) on silica gel 60. 4.52g (80%) of a pale yellow oil are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.85(dd,J＝1.1,7.3Hz,1H),7.79(dd,J＝1.5,7.0Hz,1H),7.51(s,1H),7.35(qd,J＝5.7,7.2,7.2,7.2,2H),7.06(s,1H),7.04(m,1H),4.72(s,2H),3.45(s,3H),2.20(m,1H),1.98(br.s,2H),1.71-1.83(m,4H),1.37-1.47(m,4H),1.22(br.s,2H),0.90(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ159.72(J F ＝241Hz),150.30,150.28,145.71,140.51(J F ＝2.0Hz),140.29,139.92,129.86,129.78,124.51(J F ＝3.5Hz),123.64(J F ＝3.5Hz),122.15,115.46(J F ＝23.7Hz),114.68(J F ＝23.6Hz),99.29,57.73,50.84,47.25,42.97,39.59,39.47,31.54,30.92,30.03。
3-bromo-2- (3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [ b ] thiophene
4.50g (10.0 mmol) of 2- (3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [ b ] are reacted at room temperature]To a solution of thiophene in 150mL of chloroform was added 1.82g (10.2 mmol) of N-bromosuccinimide. The reaction mixture was stirred at this temperature for 12 hours and then poured into 100mL of water. The crude product was extracted with 3X 50mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was recrystallized from 110mL of n-hexane. 4.88g (92%) of an off-white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.87(d,J＝7.4Hz,1H),7.83(d,J＝8.0Hz,1H),7.49(dt,J＝1.1,7.1Hz,1H),7.43(dt,J＝1.3,7.3Hz,1H),7.11(dd,J＝3.2,10.9Hz,1H),6.99(dd,J＝3.2,7.6Hz,1H),4.59(s,2H),3.31(s,3H),2.19(m,1H),1.98(br.s,2H),1.70-1.83(m,4H),1.36-1.46(m,4H),1.21(br.s,2H),0.89(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ159.24(J F ＝242Hz),151.76(J F ＝2.9Hz),145.29(J F ＝6.4Hz),138.60,138.01,135.93,127.35(J F ＝9.0Hz),125.76,125.22,123.64,122.29,116.40(J F ＝23.4Hz),115.67(J F ＝23.6Hz),108.29,99.65,57.51,50.86,47.09,42.98,39.41,39.36,31.51,30.92,29.99。
6,6' - (pyridine-2, 6-diylbis (benzo [ b ] thiophen-3, 2-diyl)) bis (2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol)
4.00g (7.55 mmol) of 3-bromo-2- (3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [ b ] at-80 ℃ ]To a solution of thiophene in 50mL dry THF was added dropwise a solution of 3.08mL (7.70 mmol, 2.5M) nBuLi in hexane. The reaction mixture was stirred at this temperature for 30 minutes, then 1.02g (7.70 mmol) of ZnCl was added 2 . The resulting mixture was warmed to room temperature, then 0.86g (3.63 mmol) of 2, 6-dibromopyridine and 194mg (0.38 mmol) of Pd [ P ] were added successively t Bu 3 ] 2 . The resulting mixture was stirred overnight at 60 ℃, poured into 100mL of water, and the crude product was extracted with dichloromethane (3×50 mL). The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. And then to the obtainedTo the oil was added 50mL THF, 50mL methanol and 2mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine=100:10:1, volume). 1.80g (56% of rotamer mixture) of pale yellow foam are produced. 1 H NMR(CDCl 3 ,400MHz):δ7.85-7.91(m,4H),7.71(t,J＝7.8Hz,1H),7.43(m,4H),7.27(m,2H),6.82-6.87(m,4H),0.91-2.15(m,26H),0.69-0.87(m,12H)。 13 C NMR(CDCl 3 ,100MHz):δ157.34,154.97,153.27,148.98,140.47(J F ＝5.9Hz),140.03,138.96,138.56,138.09,132.36,125.19,124.00,122.91,122.19,119.08,115.02(J F ＝11.0Hz),114.79(J F ＝10.7Hz),50.73,46.35,46.14,43.07,42.71,38.59,37.57,31.39,31.15,30.87,30.74,30.03,29.93。
Hafnium dimethyl [6,6' - (pyridine-2, 6-diylbis (benzo [ b ] thiophene-3, 2-diyl)) bis (2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol salt ] (complex 25)
To 623mg (1.94 mmol) of hafnium tetrachloride at room temperature<0.05% zr) to a suspension in 70mL of anhydrous toluene was added 3.01mL (8.73 mmol,2.9 m) of MeMgBr in diethyl ether in one portion. The resulting suspension was stirred for 1 minute and 1.73g (1.94 mmol) of 6,6' - (pyridine-2, 6-diylbis (benzo [ b ]) was added dropwise over 1 minute]Thiophene-3, 2-diyl)) bis (2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol) in 20mL of anhydrous toluene. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The solid obtained was extracted with 2×50mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 15mL of n-hexane and then dried in vacuo. 1.40g (66%) of an off-white solid was obtained as hexane solvate. C (C) 59 H 59 F 2 HfNO 2 S 2 ×0.5(C 6 H 14 ) Is calculated by analysis of: c,65.45; h,5.85; n,1.23.Found:C 65.68; h6.07; n1.14. 1 H NMR(C 6 D 6 ,400MHz):δ7.31(m,2H),7.23(dd,J＝3.3,11.1Hz,2H),7.09(dd,J＝3.2,7.7Hz,2H),7.04(m,4H),6.83(m,2H),6.74(t,J＝7.8Hz,1H),6.35(d,J＝7.8Hz,2H),2.33(d,J＝12.1Hz,2H),2.05(d,J＝11.7Hz,2H),1.66(br.s,2H),1.03–1.50(m,20H),0.83(s,6H),0.76(s,6H),-0.10(s,6H)。 13 C NMR(CD 2 Cl 2 ,100MHz):δ158.62,156.35(J F ＝234Hz),154.17,147.34(J F ＝1.8Hz),141.61,141.52(J F ＝6.1Hz),141.02,139.98,127.11,126.43,126.18,126.01,124.23(J F ＝8.8Hz),122.81,115.91(J F ＝16.8Hz),115.68(J F ＝16.8Hz),52.36,51.64,48.47,45.29,43.61,42.34,39.67,37.98,31.91,31.44,31.38,30.79,29.98,27.47。
2, 6-bis (2-bromophenyl) pyridine
2, 6-dibromopyridine (3.73 g,15.7 mmol), 2-bromophenyl-boric acid (6.26 g,31.4 mmol), sodium carbonate (8.33 g,78.6 mmol), and Di-phenylpyridineAlkane (66 mL) and water (33 mL) were combined in a round bottom flask. The mixture was bubbled with nitrogen for 1 hour, then Pd (PPh 3 ) 4 (1.82 g,1.57 mmol). The mixture was bubbled for 30 minutes and then heated to 100 ℃ overnight. The next day, the mixture was poured into water (200 mL) and extracted with dichloromethane (4×60 mL). The combined organics were dried with brine then Na 2 SO 4 And (5) drying. Evaporation gave the crude product as a yellow-orange oily solid which was purified by crystallization from hot toluene. The yield was 3.42g,55.9%.
2- (3- (2, 3-dimethylbutan-2-yl) -2- (methoxymethoxy) -5-methylphenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
Tetrahydrofuran (20 mL) was added to 1-bromo-3- (2, 3-dimethylbutan-2-yl) -2- (methoxymethoxy) -5-methylbenzene (2.89 g,9.17 mmol) to form a light brown solution. A solution of BuLi (6.30 mL,10.1 mmol) in hexane was added dropwise over 5 minutes at-50℃to form a brown suspension. The mixture was stirred for 45 minutes, then 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan (2.22 g,11.9 mmol) was added to form a clear brown solution. The mixture was slowly warmed to ambient temperature. After stirring overnight, the mixture was poured into water (100 mL) and shaken. The mixture was extracted with dichloromethane (5X 50 mL). The combined organics were washed with water, brine and then dried over MgSO 4. Volatiles were removed to give the product as a brown oil. Yield: 2.45g,73.7%.
2', 2' "- (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbutan-2-yl) -5-methyl- [1,1' -biphenyl ] -2-ol)
A100 mL round bottom flask was charged with 1-bromo-3- (2, 3-dimethylbutan-2-yl) -2- (methoxymethoxy) -5-methylbenzene (2.45 g,6.76 mmol), 2, 6-bis (2-bromophenyl) pyridine (1.32 g,3.38 mmol), na 2 CO 3 (1.79 g,16.9 mmol), twoAlkane (20 mL) and water (10 mL). The mixture was bubbled with nitrogen for 30 min, then solid Pd (PPh 3 ) 4 (0.3991 g,0.340 mmol). The mixture was bubbled for another 15 minutes, then stirred and heated in an oil bath maintained at 100 ℃. After 17 hours, the brown mixture was combined with water (100 mL) in a separatory funnel. The mixture was treated with CH 2 Cl 2 (6X 25 mL) extraction. The combined organics were dried with brine then over MgSO 4 And (5) drying. The volatiles were removed to give 3.1g of a brown oil which was combined with tetrahydrofuran (20 mL), methanol (20 mL) and concentrated HCl (1.0 mL). The mixture was stirred and heated to 60 ℃ for 4 hours.The volatiles were then evaporated and the residue was taken up in CH 2 Cl 2 (100 mL) was extracted, washed with water (3X 50 mL), and dried with brine (20 mL). The mixture was dried over MgSO 4 The reaction mixture was dried, filtered and evaporated to give a crude product which was purified by column chromatography on silica gel eluting with 2-8% ethyl acetate in hexane. Yield: 0.87g,42%.
Dibenzyl zirconium [2', 2' "- (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbutan-2-yl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 29)
Toluene (5 mL) was added to 2', 2' - (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbutan-2-yl) -5-methyl- [1,1' -biphenyl ] -2-ol) (0.260 g,0.425 mmol) and zirconium tetrabenzyl (0.194 g,0.425 mmol) to form a slightly hazy orange solution. After stirring overnight, the mixture was evaporated and the residue was extracted with methylcyclohexane (5 mL). The cloudy orange solution was filtered and evaporated to a residue, and pentane (4 mL) was added. The mixture was triturated to form a separate yellow-orange solid. The mixture was cooled to-15 ℃ for 1 hour, and then the solids were collected on a sinter pan. The solid was washed with cold pentane (2X 5 mL) and dried under reduced pressure. The product was co-crystallized with 1 equivalent of hexane. Yield: 0.233g,56.5%.
Hafnium dibenzyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbutan-2-yl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 30)
Toluene (5 mL) was added to 2', 2' "- (pyridine-2, 6-diyl) bis (3- (2, 3-dimethylbutan-2-yl) -5-methyl- [1,1' -biphenyl ] -2-ol) (0.208 g,0.340 mmol) and hafnium tetrabenzyl (0.185 g,0.340 mmol) to form a clear yellow-orange solution. The mixture was stirred overnight. The mixture was filtered and evaporated to a residue. Pentane (3 mL) was added and the mixture was triturated until a dispersed solid formed. The mixture was cooled to-15 ℃ for 1 hour. The yellow solid was then collected on a fritted disc, washed with cold pentane (2 x 5 mL) and dried under reduced pressure. The product was co-crystallized with 1 equivalent of hexane. Yield: 0.160g,44.5%.
2- (adamantan-1-yl) -6-bromo-4-methylphenol
To a solution of 21.2g (87.0 mmol) 2- (adamantan-1-yl) -4-methylphenol in 200mL dichloromethane was added dropwise a solution of 4.50mL (87.0 mmol) bromine in 100mL dichloromethane at room temperature for 10 min. The resulting mixture was diluted with 400mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. 21.5g (77%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.17(s,1H),6.98(s,1H),5.65(s,1H),2.27(s,3H),2.10-2.13(m,9H),1.80(m,6H), 13 C NMR(CDCl 3 ,100MHz):δ148.18,137.38,130.24,129.32,127.26,112.08,40.18,37.32,36.98,28.99,20.55.
(1- (3-bromo-5-methyl-2- (methoxymethoxy) phenyl) adamantane
To a solution of 21.3g (66.4 mmol) 2- (adamantan-1-yl) -6-bromo-4-methylphenol in 400mL THF was added 2.79g (69.7 mmol,60% wt. in mineral oil) sodium hydride in portions at room temperature. To the resulting suspension was added dropwise 5.55mL (73.0 mmol) of methoxymethyl chloride at room temperature over 10 minutes. The resulting mixture was stirred overnight and then poured into 200mL of water. The mixture thus obtained was extracted with dichloromethane (3X 200 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 24.3g (quantitative) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.24(d,J＝1.5Hz,1H),7.05(d,J＝1.8Hz,1H),5.22(s,2H),3.71(s,3H),2.27(s,3H),2.05-2.12(m,9H),1.78(m,6H)。 13 CNMR(CDCl 3 ,100MHz):δ151.01,144.92,134.34,131.80,127.44,117.57,99.56,57.75,41.27,37.71,36.82,29.03,20.68。
2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
To a solution of 20.0g (55.0 mmol) (1- (3-bromo-5-methyl-2- (methoxymethoxy) phenyl) adamantane in 400mL anhydrous THF was added dropwise 22.5mL (56.4 mmol) of 2.5M nBuLi in hexane at-80℃for 20 min. The reaction mixture was stirred at this temperature for 1 h, then 16.7mL (82.2 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolane. The suspension obtained was stirred at room temperature for 1 h and then poured into 300mL water. The crude product was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 22.4g (99%) of a colorless viscous oil are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.35(d,J＝2.3Hz,1H),7.18(d,J＝2.3Hz,1H),5.14(s,2H),3.58(s,3H),2.28(s,3H),2.14(m,6H),2.06(m,3H),1.76(m,6H),1.35(s,12H)。 13 C NMR(CDCl 3 ,100MHz):δ159.68,141.34,134.58,131.69,131.14,100.96,83.61,57.75,41.25,37.04,29.14,24.79,20.83。
1- (2 '-bromo-5-methyl-2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane
To 10.0g (24.3 mmol) of 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 100mL of 1, 4-bisTo the solution in the alkane were added, in order, 7.22g (25.5 mmol) of 2-bromoiodobenzene, 8.38g (60.6 mmol) of potassium carbonate and 50mL of water. The resulting mixture was purged with argon for 10 minutes, then 1.40g (1.21 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 10.7g (quantitative) of a white solid are obtained. 1 HNMR(CDCl 3 ,400MHz):δ7.72(d,J＝7.9Hz,1H),7.35-7.44(m,3H),7.19-7.26(m,1H),6.94(m,1H),4.53(dd,J＝20.0,4.6Hz,2H),3.24(s,3H),2.38(s,3H),2.23(m,6H),2.15(m,3H),1.84(m,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.51,142.78,141.11,134.63,132.76,132.16,132.13,129.83,128.57,127.76,127.03,124.05,98.85,56.95,41.21,37.18,36.94,29.07,21.00。/>
2- (3 '- (adamantan-1-yl) -5' -methyl-2 '- (methoxymethoxy) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
To 10.7g (24.3 mmol) of 1- (2 '-bromo-5-methyl-2- (methoxymethoxy) - [1,1' -biphenyl) at-80 ℃]To a solution of 3-yl) adamantane in 250mL anhydrous THF was added dropwise 11.6mL (29.1 mmol) of a 2.5M nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 8.43mL (41.3 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-diethyl ether=10:1, volume). 8.60g (72%) of a colorless glassy solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.75(d,J＝7.4Hz,1H),7.33-7.44(m,2H),7.29-7.33(m,1H),7.07(br.s,1H),6.84(br.s,1H),4.50(d,J＝4.4Hz,1H),4.40(d,J＝4.4Hz,1H),3.27(s,3H),2.30(s,3H),2.21(br.s,6H),2.11(m,3H),1.80(m,6H),1.21(s,6H),1.15(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.52,145.68,142.04,136.74,134.30,131.47,130.51,130.23,129.79,126.69,126.06,98.73,83.39,57.22,41.47,37.20,37.04,29.19,25.00,24.16,20.97。
2', 2' "- (pyridine-2, 6-diyl) bis (3-adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-ol
To 4.00g (8.19 mmol) of 2- (3 '- (adamantan-1-yl) -5' -methyl-2 '- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of 1, 4-bisTo a solution in alkane was then added 969mg (4.09 mmol) of 2, 6-dibromopyridine, 6.68g (20.5 mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, then 470mg (0.41 mmol) of Pd (PPh 3) 4 was added. The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil were then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). The glassy solid obtained is triturated with 30mL of n-pentane, the precipitate thus obtained is filtered off (G3), washed with 2 x 10mL of n-pentane and dried in vacuo. 2.10g (72%) of a mixture of the two isomers was obtained as a white powder. 1 H NMR(CDCl 3 ,400MHz):δ7.64(s,1H),7.41-7.59(m,7H),7.33–7.38(m,2H),7.27(br.s,1H),7.02(d,J＝7.9Hz,1H),7.00(d,J＝7.8Hz,1H),6.87-6.92(m,3H),6.21(d,J＝1.7Hz,1H),2.26(s,3H),1.55-1.98(m,33H)。 13 C NMR(CDCl 3 ,100MHz)δ157.91,157.89,150.24,149.65,139.70,138.49,137.93,137.58,137.54,137.44,137.06,136.80,132.39,131.36,130.48,130.34,130.17,129.97,129.36,129.09,128.90,128.82,128.70,128.45,127.78,127.71,126.90,126.54,122.30,122.02,40.35,40.17,37.00,36.78,36.66,36.46,29.09,28.96,20.85,20.52。
(3 r,5r,7 r) -1- (2 ' -bromo-2- (methoxymethoxy) -4', 5-dimethyl- [1,1' -biphenyl ] -3-yl) adamantane
To 6.11g (14.8 mmol) of 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 100mL of 1, 4-bisTo a solution in alkane was then added 4.62g (15.6 mmol) of 2-bromo-4-methyl iodobenzene, 5.12g (37.0 mmol) of potassium carbonate and 50mL of water. The resulting mixture was purged with argon for 10 minutes, then 850mg (0.741 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 4.88g (73%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.53(s,1H),7.27(d,J＝7.8Hz,1H),7.16–7.19(m,2H),6.90(d,J＝1.7Hz,1H),4.40(m,2H),3.27(s,3H),2.40(s,3H),2.35(s,3H),2.20(m,6H),2.12(m,3H),1.81(m,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.72,142.67,138.73,138.09,134.43,133.20,132.02,131.82,130.08,127.94,127.61,123.70,98.79,57.06,41.21,37.19,36.98,29.11,21.03,20.75。
2- (3 '- ((3 r,5r,7 r) -adamantan-1-yl) -2' - (methoxymethoxy) -4,5 '-dimethyl- [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
4.88g (10.7 mmol) of (3 r,5r,7 r) -1- (2 ' -bromo-2- (methoxymethoxy) -4', 5-dimethyl- [1,1' -biphenyl are introduced at-80 ℃ ]3-yl) adamantane 5.20mL (12.8 mmol) of a 2.5M solution of nBuLi in hexane was added dropwise to a solution of 120mL of anhydrous THF for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 4.43mL (21.4 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-diethyl ether=10:1, volume). 3.04g (57%) of a colorless glassy solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.53(s,1H),7.19-7.23(m,2H),7.02(d,J＝2.1Hz,1H),6.79(d,J＝1.7Hz,1H),4.43(m,2H),3.27(s,3H),2.37(s,3H),2.26(s,3H),2.17(m,6H),2.08(m,6H),1.77(m,6H),1.18(s,6H),1.13(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.71,142.84,141.95,136.61,135.53,134.91,131.41,130.65,130.63,130.21,126.52,98.73,83.38,57.28,41.49,37.20,37.07,29.22,25.02,24.20,21.03,20.99。
2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-ol)
To 3.04g (6.05 mmol) of 2- (3 '- ((3 r,5r,7 r) -adamantan-1-yl) -2' - (methoxymethoxy) -4,5 '-dimethyl- [1,1' -biphenyl)]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of 1, 4-bisTo the solution in alkane was then added 716mg (3.02 mmol) of 2, 6-dibromopyridine, 4.92g (15.1 mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, then 350mg (0.30 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 0.74g (33%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 ,400MHz):δ7.66(s,1H),7.39-7.42(m,3H),7.22-7.35(m,5H),6.96-7.01(m,2H),6.85-6.91(m,3H),6.16(d,J＝1.5Hz,1H),2.49(s,3H),2.47(s,3H),2.26(s,3H),1.58-2.04(m,33H)。 13 C NMR(CDCl 3 ,100MHz)δ158.05,157.98,150.39,149.80,139.62,138.29,137.77,137.61,137.55,136.94,136.62,134.64,134.44,132.31,131.18,130.90,130.77,130.39,130.15,129.95,129.55,129.13,128.99,128.62,128.34,126.74,126.34,122.22,121.95,40.35,40.21,37.07,36.88,36.65,36.46,29.15,29.04,21.09,21.06,20.86,20.51。
(3 r,5r,7 r) -1- (2 ' -bromo-4 ' - (tert-butyl) -2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl ] -3-yl) adamantane
To 8.00g (19.4 mmol) of 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 50mL of 1, 4-bisTo the solution in the alkane were added 7.22g (21.3 mmol) of 2-bromo-4- (tert-butyl) iodobenzene, 6.70g (48.5 mmol) of potassium carbonate and 25mL of water in this order. The resulting mixture was purged with argon for 10 minutes, then 2.20g (1.90 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 5.20g (54%) of a white solid was obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.68(s,1H),7.30-7.38(m,2H),7.16(s,1H),6.92(s,1H),4.49(m,2H),3.18(s,3H),2.35(s,3H),2.19(m,6H),2.12(m,3H),1.81(m,6H),1.37(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ152.30,151.61,142.80,138.05,134.67,132.11,131.74,130.01,129.70,127.66,124.22,123.89,98.83,56.93,41.29,37.24,37.00,34.60,31.22,29.14,21.05。
2- (3 '- ((3 r,5r,7 r) -adamantan-1-yl) -4- (tert-butyl) -2' - (methoxymethoxy) -5 '-methyl- [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
To 5.12g (10.3 mmol) of (3 r,5r,7 r) -1- (2 ' -bromo-4 ' - (tert-butyl) -2- (methoxymethoxy) -5-methyl- [1,1' -biphenyl at-80 ℃]To a solution of 3-yl) adamantane in 120mL anhydrous THF was added dropwise 6.20mL (15.4 mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 5.23mL (25.6 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. Will beThe residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-diethyl ether=10:1, volume). 3.30g (59%) of a colorless glassy solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.72(d,J＝2.1Hz,1H),7.44(dd,J＝8.1,2.2Hz,1H),7.29(d,J＝8.1Hz,1H),7.05(d,J＝2.0Hz,1H),6.83(d,J＝1.7Hz,1H),4.45(m,2H),3.24(s,3H),2.28(s,3H),2.20(m,6H),2.10(m,3H),1.79(m,6H),1.37(s,9H),1.20(br.s,6H),1.14(br.s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.61,148.72,142.79,141.98,136.75,131.35,130.67,130.64,129.95,126.89,126.48,98.70,83.33,57.20,41.51,37.22,37.08,34.45,31.41,29.22,25.03,24.22,20.96。
2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl ] -2-ol)
To 1.75g (3.21 mmol) of 2- (3 '- ((3 r,5r,7 r) -adamantan-1-yl) -4- (tert-butyl) -2' - (methoxymethoxy) -5 '-methyl- [1,1' -biphenyl)]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of 1, 4-bisTo a solution in alkane was then added 381mg (1.61 mmol) of 2, 6-dibromopyridine, 2.62g (8.03 mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, then 180mg (0.16 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Drying at the topAnd evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 0.60g (45%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 Delta 7.72 and 7.08 (2 s, 2H), 7.40-7.53 (m, 5H), 7.21-7.26 (m, 2H), 6.94-7.00 (m, 2H), 6.80-6.86 and 6.09 (2 m, 4H), 1.53-1.95 (m, 30H), 1.39 and 1.40 (2 s, 18H). 13 C NMR(CDCl 3 ,100MHz)δ158.53,150.71,150.54,149.85,139.47,137.94,137.52,136.66,134.45,132.05,130.80,130.68,129.49,129.04,128.58,128.41,127.40,127.24,126.78,126.36,125.72,122.26,122.02,40.38,40.28,37.05,36.87,36.70,36.52,34.67,31.58,31.39,29.11,28.98,20.87,20.52。
2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl ] -2-ol)
To 1.50g (2.75 mmol) of 2- (3 '- ((3 r,5r,7 r) -adamantan-1-yl) -4- (tert-butyl) -2' - (methoxymethoxy) -5 '-methyl- [1,1' -biphenyl)]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of 1, 4-bisTo a solution in alkane, 367mg (1.38 mmol) of 2, 6-dibromo-4-methoxypyridine, 2.25g (6.90 mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 160mg (0.138 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were used5％NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.04g (89%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 Delta 7.88 and 7.31 (2 s, 2H), 7.46-7.57 (m, 4H), 7.21-7.27 (m, 2H), 6.83 (m, 2H), 6.46-6.48 (m, 2H), 6.12 and 6.88 (2 m, 2H), 3.50 and 3.41 (2 s, 3H), 1.57-1.95 (m, 30H), 1.40 and 1.41 (2 s, 18H). 13 C NMR(CDCl 3 ,100MHz)δ160.07,150.75,150.50,139.59,137.92,134.48,131.99,130.84,130.77,129.49,129.11,128.53,127.13,126.42,125.79,108.64,108.33,55.22,40.54,40.29,37.08,36.92,36.77,34.69,31.46,31.42,29.17,29.06,20.57。
2- (adamantan-1-yl) -6-bromo-4- (tert-butyl) phenol
To a solution of 236g (830 mmol) 2- (adamantan-1-yl) -4- (tert-butyl) phenol in 2000mL dichloromethane was added dropwise a solution of 132g (830 mmol) bromine in 400mL dichloromethane at room temperature for 1 hour. The resulting mixture was diluted with 2,000ml of water. The resulting mixture was extracted with dichloromethane (3X 500 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 299g (99%) of a white solid was obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.32(d,J＝2.3Hz,1H),7.19(d,J＝2.3Hz,1H),5.65(s,1H),2.18-2.03(m,9H),1.78(m,6H),1.29(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ148.07,143.75,137.00,126.04,123.62,112.11,40.24,37.67,37.01,34.46,31.47,29.03。
(1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantane
330g (9)To a solution of 10 mmol) 2- (adamantan-1-yl) -6-bromo-4- (tert-butyl) phenol in 3,000ml THF was added 40.0g (1.00 mol,60% wt. in mineral oil) sodium hydride in portions. To the resulting suspension was added dropwise 76.0mL (1.00 mol) of methoxymethyl chloride at room temperature over 40 minutes. The resulting mixture was stirred overnight and then poured into 2,000ml of water. The desired product was extracted with dichloromethane (3X 900 mL) and extracted with 5% NaHCO 3 The combined organic extracts were washed over Na 2 SO 4 Dried on, and then evaporated to dryness. 367g (99%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.39(d,J＝2.4Hz,1H),7.27(d,J＝2.4Hz,1H),5.23(s,2H),3.71(s,3H),2.20-2.04(m,9H),1.82-1.74(m,6H),1.29(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ150.88,147.47,144.42,128.46,123.72,117.46,99.53,57.74,41.31,38.05,36.85,34.58,31.30,29.08。
2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
To a solution of 183.5g (450 mmol) (1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantane in 2,500mL of anhydrous THF was added dropwise 190mL (473 mmol) of 2.5M nBuLi in hexane at-80℃for 20 min the reaction mixture was stirred at this temperature for 1 h, then 120mL (585 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan. The resulting suspension was stirred at room temperature for 1 h and then poured into 300mL of water. The resulting mixture was evaporated to about 1 l, the crude product was extracted with dichloromethane (3X 800 mL.) the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 204.7g (quantitative) of a colourless solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.54(d,J＝2.5Hz,1H),7.43(d,J＝2.6Hz,1H),5.18(s,2H),3.60(s,3H),2.24-2.13(m,6H),2.09(br.s.,3H),1.85-1.75(m,6H),1.37(s,12H),1.33(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ159.64,144.48,140.55,130.58,127.47,100.81,83.48,57.63,41.24,37.29,37.05,34.40,31.50,29.16,24.79。
1- (2 '-bromo-5- (tert-butyl) -2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane
150g (330 mmol) of 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan, 1000mL of di-are then introduced into a 2L pressure vesselAlkane, 93.4g (330 mmol) 2-bromoiodobenzene, 114g (825 mmol) potassium carbonate and 500mL water. The resulting mixture was purged with argon for 10 minutes, then 19.1g (17.0 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 115 ℃ for 12 hours, then cooled to room temperature and diluted with 500mL of water. The crude product was extracted with dichloromethane (3X 700 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 112g (70%) of a white solid were produced. 1 H NMR(CDCl 3 ,400MHz):δ7.68(dd,J＝1.0,8.0Hz,1H),7.42(dd,J＝1.7,7.6Hz,1H),7.37-7.32(m,2H),7.20(dt,J＝1.8,7.7Hz,1H),7.08(d,J＝2.5Hz,1H),4.53(d,J＝4.6Hz,1H),4.40(d,J＝4.6Hz,1H),3.20(s,3H),2.23-2.14(m,6H),2.10(br.s.,3H),1.86-1.70(m,6H),1.33(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ151.28,145.09,142.09,141.47,133.90,132.93,132.41,128.55,127.06,126.81,124.18,123.87,98.83,57.07,41.31,37.55,37.01,34.60,31.49,29.17。
2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
223g (462 mmol) of 1- (2 '-bromo-5- (tert-butyl) -2- (methoxymethoxy) - [1,1' -biphenyl) are introduced at-80 ℃ ]-3-yl) adamantane 194mL (485 mmol) of a 2.5M nBuLi solution in hexane was added dropwise to a solution of 3,000mL of anhydrous THF for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 122mL (600 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The resulting mixture was evaporated to about 1 liter and the crude product extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 240.9g (quantitative) of a white solid are produced. 1 H NMR(CDCl 3 ,400MHz):δ7.75(d,J＝7.3Hz,1H),7.44-7.36(m,1H),7.36-7.30(m,2H),7.30-7.26(m,1H),6.96(d,J＝2.4Hz,1H),4.53(d,J＝4.7Hz,1H),4.37(d,J＝4.7Hz,1H),3.22(s,3H),2.26-2.14(m,6H),2.09(br.s.,3H),1.85-1.71(m,6H),1.30(s,9H),1.15(s,6H),1.10(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.35,146.48,144.32,141.26,136.15,134.38,130.44,129.78,126.75,126.04,123.13,98.60,83.32,57.08,41.50,37.51,37.09,34.49,31.57,29.26,24.92,24.21。
2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-ol)
To 2.00g (3.77 mmol) of 2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of twoTo a solution in alkane, 503mg (1.88 mmol) of 2, 6-dibromo-4-methoxypyridine, 3.07g (9.42 mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 440mg (0.380 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12h, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were extracted over Na 2 SO 4 Dried and then evaporated to dryness. To the resulting oil were then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.33g (86%) of a mixture of the two isomers was produced as a white foam. 1 H NMR(CDCl 3 Delta 8.31 and 7.13 (2 s, 2H), 7.37-7.60 (m, 8H), 7.09-7.11 (m, 2H), 6.55 and 6.98 (2 m, 2H), 6.50 and 6.42 (2 s, 2H), 3.37 and +3.36 (2 s, 3H), 1.87-2.00 (m, 18H), 1.60-1.69 (m, 12H), 1.21 and 1.00 (2 s, 18H). 13 C NMR(CDCl 3 ,100MHz)δ165.87,159.18,149.98,141.89,139.42,137.80,137.42,131.50,130.81,129.86,129.05,127.75,126.53,122.80,108.97,55.12,40.57,40.32,37.07,37.01,34.02,31.58,31.46,29.11,29.02。
2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-ol)
To 2.00g (3.77 mmol) of 2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40ml of diTo a solution in alkane, 406mg (1.88 mmol) of 2, 6-dichloro-4-trifluoromethylpyridine, 3.07g (9.42 mmol) of cesium carbonate and 20ml of water were then added. The resulting mixture was purged with argon for 10 minutes, then 440mg (0.380 mmol) of Pd (PPh) was added 3 ) 4 . The method comprisesThe mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil were then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.31g (83%) of a mixture of the two isomers was produced as a white foam. 1 H NMR(CDCl 3 ,400MHz):δ7.40-7.55(m,8H),7.04-7.14+5.62(2m,6H),6.86+6.56(2d,J＝2.4Hz,2H),1.90-2.02(m,18H),1.60-1.74(m,12H),1.16+1.01(2s,18H)。 13 C NMR(CDCl 3 ,100MHz)δ159.29,159.09,149.57,148.84,142.43,142.33,139.45,138.78,138.45,137.60,137.22,136.72,136.24,131.62,131.51,130.76,130.52,129.76,129.71,128.53,128.39,128.16,127.42,126.03,125.28,123.46,123.34,118.20(q,Jc, F ＝3.5Hz),40.45,40.34,37.07,37.03,34.21,34.06,31.45,31.42,29.11,29.06。
(3 r,5r,7 r) -1- (2 ' -bromo-5- (tert-butyl) -2- (methoxymethoxy) -4' -methyl- [1,1' -biphenyl ] -3-yl) adamantane
To 10.0g (22.0 mmol) of 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 100mL of 1, 4-bisTo a solution in alkane was then added 6.83g (23.0 mmol) of 2-bromo-4-methyl iodobenzene, 7.60g (55.0 mmol) of potassium carbonate and 50mL of water. The resulting mixture was purged with argon for 10 minutes, then 1.27g (1.10 mmol) of Pd (P) was added Ph 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 8.77g (80%) of a white solid were produced. 1 H NMR(CDCl 3 ,400MHz):δ7.56(m,1H),7.32-7.39(m,2H),7.19(d,J＝7.8Hz,1H),7.11(d,J＝2.5Hz,1H),4.59(m,1H),4.47(m,1H),3.29(s,3H),2.41(s,3H),2.25(m,6H),2.15(m,3H),1.84(m,6H),1.37(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ151.48,144.93,141.94,138.66,138.46,133.66,133.32,132.02,127.90,127.02,123.82,123.66,98.75,57.09,41.30,37.53,37.04,34.56,31.48,29.19,20.76.
4- ((3 r,5r,7 r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [ c, e ] [1,2] oxyborone
8.75g (17.6 mmol) of (3 r,5r,7 r) -1- (2 ' -bromo-5- (tert-butyl) -2- (methoxymethoxy) -4' -methyl- [1,1' -biphenyl are introduced at-80 ℃]To a solution of 3-yl) adamantane in 120mL anhydrous THF was added dropwise 8.44mL (21.1 mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 6.12mL (30.0 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was recrystallized from 20mL of hot isopropanol, the crystalline material obtained was filtered off (G3), washed with 5mL of cold isopropanol and dried in vacuo. 4.90g (51%) of white crystals are obtained. 1 H NMR(CDCl 3 ,400MHz):δ8.07(d,J＝8.3Hz,1H),8.03(d,J＝2.0Hz,1H),7.87(m,1H),7.46(d,J＝8.2Hz,1H),7.40(d,J＝2.0Hz,1H),5.25(sept,J＝6.1Hz,1H),2.46(s,3H),2.30(m,6H),2.16(m,3H),1.85(m,6H),1.42(s,9H),1.42(d,J＝6.0Hz,6H)。 13 C NMR(CDCl 3 ,100MHz):δ147.99,143.84,138.75,138.38,136.14,133.08,132.97,123.55,122.32,121.59,117.90,65.66,40.77,37.45,37.19,34.75,31.67,29.17,24.74,21.21。
2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-ol)
To 1.60g (3.62 mmol) of 4- ((3 r,5r,7 r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [ c, e][1,2]1, 4-Di-oxolane in 40mLTo a solution in alkane was then added 429mg (1.81 mmol) of 2, 6-dibromopyridine, 2.95g (9.10 mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, then 210mg (0.180 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.11g (74%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 ,400MHz):δ8.15+6.81(2s,2H),7.31-7.40(m,3H),7.21-7.24(m,2H),6.90-7.03+6.49(2m,6H),2.42+2.41(2s,6H),1.73-2.06(m,18H),1.60-1.67(m,12H),1.13+0.97(2s,18H)。 13 C NMR(CDCl 3 ,100MHz)δ157.96,157.77,150.22,149.45,141.67,139.30,137.45,137.40,136.71,135.04,131.60,131.43,130.82,129.84,129.64,126.50,125.77,122.58,122.42,40.52,40.39,37.11,37.03,36.85,33.99,31.48,29.19,29.11,21.14。
2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-ol)
To 1.60g (3.62 mmol) 4- ((3 r,5r,7 r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [ c, e ][1,2]Oxoborocyclohexane in 40mL of 1, 4-DiTo a solution in alkane, 391mg (1.81 mmol) of 2, 6-dichloro-4-trifluoromethylpyridine, 2.95g (9.10 mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 210mg (0.180 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.01g (62%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 Delta 7.44 and 5.97 (2 s, 2H), 7.34-7.38 (m, 6H), 7.12 (d, j=2.4 hz, 2H), 7.07 (s, 2H), 6.92 and 6.56 (2 m, 2H), 2.49 and 2.48 (2 s, 6H), 1.85-2.04 (m, 18H), 1.65-1.75 (m, 12H), 1.18 and 1.03 (s, 18H). 13 C NMR(CDCl 3 ,100MHz)δ159.41,159.19,149.81,149.80,149.05,142.20,142.16,139.08,138.70,138.57,138.37,138.10,138.01,137.26,136.25,134.77,134.03,131.51,131.27,130.91,130.49,130.41,128.66,127.64,126.17,125.43,123.69,123.31,123.12,118.23(q,Jc, F ＝3.8Hz),117.88(q,Jc, F ＝3.8Hz),40.47,40.34,37.08,37.06,34.02,31.42,29.17,29.08,26.91,21.14。
2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-ol)
To 1.60g (3.62 mmol) 4- ((3 r,5r,7 r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [ c, e][1,2]Oxoborocyclohexane in 40mL of 1, 4-Di To a solution in alkane was then added 483mg (1.81 mmol) of 2, 6-dibromo-4-methoxypyridine, 2.95g (9.10 mmol) of cesium carbonate, and 20mL of water. The resulting mixture was purged with argon for 10 minutes, then 210mg (0.180 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 910mg (58%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 ,400MHz):δ8.39+6.52(2s,2H),7.25-7.45(m,7H),7.00-7.12(m,2H),6.42-6.56(m,3H),3.41+3.38(2s,3H),2.47(s,6H),1.87-2.02(m,18H),1.62-1.75(m,12H),1.24+1.02(2s,18H)。 13 C NMR(CDCl 3 ,100MHz)δ165.79,159.28,159.22,150.13,149.66,141.90,141.78,139.28,138.72,137.54,137.36,136.77,134.89,134.80,132.26,131.39,131.37,130.94,130.08,129.87,129.75,129.34,126.60,125.60,123.01,122.58,108.92,108.34,55.09,54.73,40.61,40.35,37.08,37.07,36.87,34.22,33.99,31.56,31.46,29.19,29.07,26.90,22.65,21.15。
(3 r,5r,7 r) -1- (2 ' -bromo-5- (tert-butyl) -4' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane
To 10.0g (22.0 mmol) of 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) 1, 4-Di-5, 5-tetramethyl-1, 3, 2-dioxaborolan in 100mLTo a solution in alkane was then added 6.83g (23.0 mmol) of 2-bromo-4-isopropyl iodobenzene, 7.60g (55.0 mmol) of potassium carbonate and 50mL of water. The resulting mixture was purged with argon for 10 minutes, then 1.27g (1.10 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 11.5g (95%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.53(d,J＝1.7Hz,1H),7.30-7.33(m,2H),7.19(dd,J＝8.0,1.7Hz,1H),7.08(d,J＝2.5Hz,1H),4.52(m,1H),4.39(m,1H),3.18(s,3H),2.92(sept,J＝6.9Hz,1H),2.14-2.20(m,6H),2.10(br.s,3H),1.74-1.84(m,6H),1.32(s,9H),1.28(d,J＝6.9Hz,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.35,149.85,145.03,142.04,138.73,133.91,132.21,130.79,126.96,125.33,124.02,123.71,98.76,57.03,41.35,37.57,37.04,33.63,31.50,29.20,24.83,23.90。
2- (3 '- ((3 r,5r,7 r) -adamantan-1-yl) -5' - (tert-butyl) -4-isopropyl-2 '- (methoxymethoxy) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
11.3g (21.5 mmol) of (3 r,5r,7 r) -1- (2 ' -bromo-5- (tert-butyl) -4' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl) are introduced at-80 ℃]9.00mL (22.6 mmol) of a 2.5M nBuLi in hexane was added dropwise to a solution of 3-yl) adamantane in 200mL of anhydrous THF for 20 min. The reaction mixture was stirred at this temperature for 1 hour, then 6.98mL (32.2 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. Will beThe resulting suspension was stirred at room temperature for 1 hour and then poured into 100mL of water. The resulting mixture was evaporated to about 150mL, and the crude product was extracted with dichloromethane (3×100 mL). The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-diethyl ether=10:1, volume). 6.80g (56%) of a white solid was produced. 1 H NMR(CDCl 3 ,400MHz):δ7.57(s,1H),7.24-7.28(m,3H),6.97(d,J＝2.4Hz,1H),4.52(m,1H),4.37(m,1H),3.20(s,3H),2.95(sept,J＝6.9Hz,1H),2.17–2.21(m,6H),2.09(br.s,3H),1.73-1.84(m,6H),1.29(s,9H),1.28(d,J＝6.9Hz,6H),1.15(s,6H),1.10(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ151.43,146.50,144.22,143.92,141.17,136.17,132.40,130.45,127.73,126.84,122.94,98.52,83.26,57.06,41.50,37.49,37.10,34.48,33.86,31.58,29.26,24.94,24.41,24.13,24.07。
2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-ol)
To 3.20g (5.66 mmol) of 2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of 1, 4-bisTo a solution in alkane, 609mg (2.83 mmol) of 2, 6-dibromopyridine, 5.00g (14.2 mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 300mg (0.260 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. Subsequently, 50mL of THF and 50mL of methanol were added to the obtained oilAnd 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.34g (54%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 ,400MHz):δ8.26+6.83(2s,2H),6.95-7.58+6.52(2m,13H),3.01(sept,J＝6.9Hz,2H),1.85-2.02(m,18H),1.62-1.68(m,12H),1.33(d,J＝6.9Hz,6H),1.32(d,J＝6.9Hz,6H),1.13+1.00(2s,18H)。 13 C NMR(CDCl 3 ,100MHz)δ158.28,157.98,150.28,149.48,148.14,148.02,141.61,141.46,139.28,137.50,136.74,136.20,135.43,135.13,132.10,131.67,130.07,129.29,128.97,128.07,127.18,126.90,126.58,125.77,122.74,122.50,122.44,122.20,40.51,40.30,37.08,37.05,36.81,34.17,34.00,33.84,33.78,31.50,31.40,29.15,29.10,24.14,23.81。
2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-ol)
To 1.77g (3.09 mmol) of 2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of twoTo a solution in alkane was then added 325mg (1.51 mmol) of 2, 6-dichloro-4-trifluoromethylpyridine, 3.00g (9.04 mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, then 200mg (0.190 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3X 50 mL) and combinedIs Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil were then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.17g (82%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 400 MHz) delta 7.35-7.46 and 5.99 (2 m, 8H), 7.06-7.13 (m, 4H), 6.95 and 6.56 (2 m, 2H), 3.05 (sept, j=6.9 hz, 2H), 1.86-2.04 (m, 18H), 1.63-1.71 (m, 12H), 1.36 (d, j=6.9 hz, 6H), 1.34 (d, j=6.9 hz, 6H), 1.15 and 1.01 (2 s, 18H). 13 C NMR(CDCl 3 ,100MHz)δ159.68,149.86,149.11,148.81,142.12,138.59,137.29,136.18,135.10,131.67,131.57,128.98,128.81,127.66,126.29,125.43,123.10,118.27(q,J C,F ＝3.5Hz),40.48,40.28,37.06,36.87,34.02,33.84,31.43,31.39,29.12,29.07,24.07,23.86。
2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-ol)
To 1.77g (3.09 mmol) of 2- (3 '- (adamantan-1-yl) -5' - (tert-butyl) -2'- (methoxymethoxy) - [1,1' -biphenyl]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of twoTo a solution in alkane, 400mg (1.51 mmol) of 2, 6-dibromo-4-methoxypyridine, 3.00g (9.04 mmol) of cesium carbonate and 20mL of water were then added. The resulting mixture was purged with argon for 10 minutes, then 200mg (0.190 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100deg.C for 12 hours, then cooled to room temperature, and usedDilute with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12NHCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.01g (74%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 Delta 8.40 and 7.02 (2 s, 2H), 7.23-7.44 (m, 6H), 7.07 (m, 2H), 6.56-6.58 (m, 2H), 6.41 (m, 2H), 3.50 and 3.37 (2 s, 3H), 3.02 (sept, J=6.9 Hz, 2H), 1.85-2.02 (m, 18H), 1.62-1.70 (m, 12H), 1.34 (d, J=6.9 Hz, 12H), 1.19+1.00 (2 s, 18H). 13 C NMR(CDCl 3 ,100MHz)δ165.74,159.62,150.20,148.30,141.73,139.35,137.37,135.18,131.38,129.99,129.03,127.34,127.03,126.71,125.71,122.56,108.94,55.12,40.61,37.08,37.06,34.01,33.76,31.48,29.13,24.12,23.83。
2- (adamantan-1-yl) -4-fluorophenol
To a solution of 30.0g (268 mmol) of 4-fluorophenol and 40.8g (268 mmol) of adamantan 1-ol in 300ml of dichloromethane was added dropwise a solution of 17.4ml (268 mmol) of methanesulfonic acid and 20ml of acetic acid in 100ml of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then 300mL of 5% NaHCO was carefully poured in 3 Is a kind of medium. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified using a Kugelrohr apparatus (0.3 mbar, 95 ℃) to give 49.3g (75%) of the title product as a pale yellow oil. 1 H NMR(CDCl 3 ,400MHz):δ6.92(dd,J＝11.2,3.1Hz,1H),6.73(ddd,J＝8.7,7.4,3.1Hz,1H),6.60(dd,J＝8.7,5.0Hz,1H),4.34(br.s,1H),2.08-2.11(m,9H),1.75-1.80(m,9H),1.58-1.67(m,3H), 13 C NMR(CDCl 3 ,100MHz):δ158.28(d,J C,F ＝236Hz),150.60(d,J C,F ＝2.0Hz),138.27(d,J C,F ＝5.9Hz),117.07(d,J C,F ＝8.1Hz),113.88(d,J C,F ＝23.9Hz),112.36(d,J C,F ＝23.0Hz),45.05,40.13,36.88,35.90,30.65,28.88。
2-bromo-6- (adamantan-1-yl) -4-fluorophenol
To a solution of 49.3g (200 mmol) 2- (adamantan-1-yl) -4-fluorophenol in 500mL dichloromethane was added dropwise a solution of 10.3mL (200 mmol) bromine in 100mL dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then 200mL of 5% NaHCO was carefully poured in 3 Is a kind of medium. The crude product was extracted with dichloromethane (3X 150 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 65.0g (quantitative) of a pale yellow solid was obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.07(dd,J＝7.0,3.0Hz,1H),6.92(dd,J＝10.8,3.0Hz,1H),5.60(s,1H),2.07(br.s,9H),1.77(br.s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ157.21(d,J C,F ＝241Hz),147.03(d,J C,F ＝3.0Hz),138.91(d,J C,F ＝5.9Hz),115.66(d,J C,F ＝25.8Hz),113.97(d,J C,F ＝23.6Hz),111.21(d,J C,F ＝10.9Hz),39.88,37.60,36.82,28.86。
(3 r,5r,7 r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) adamantane
To a solution of 48.4g (150 mmol) 2-bromo-6- (adamantan-1-yl) -4-fluorophenol in 500mL anhydrous THF at room temperature was added 6.30g (155 mmol,60% wt. in mineral oil) sodium hydride in portions.Thereafter, 13.7mL (180 mmol) of MOMCl was added dropwise over 1 hour. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 300mL of cold water. The crude product was extracted with 3X 200mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. 56.0g (quantitative) of a white solid is obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.12(dd,J＝6.9,3.1Hz,1H),6.98(dd,J＝10.9,3.1Hz,1H),5.20(s,2H),3.69(s,3H),2.07(br.s,9H),1.76(br.s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ159.51(d,J C,F ＝245Hz),149.86(d,J C,F ＝3.3Hz),146.93(d,J C,F ＝6.5Hz),118.09(d,J C,F ＝25.4Hz),117.67(d,J C,F ＝10.5Hz),113.99(d,J C,F ＝23.6Hz),99.72,57.83,40.99,38.06,36.67,28.92。
2- ((3 r,5r,7 r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
To a solution of 28.0g (75.8 mmol) of (1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) adamantane in 400mL of anhydrous THF was added dropwise 30.3mL (75.8 mmol) of a 2.5M nBuLi in hexane at-80℃for 20 min the reaction mixture was stirred at this temperature for 1 h, then 20.1mL (98.5 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan. The suspension obtained was stirred at room temperature for 1 h and then poured into 300mL of water the crude product was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was recrystallized from isopropanol. 27.8g (88%) of a white solid was produced. 1 H NMR(CDCl 3 ,400MHz):δ7.19(dd,J＝7.7,3.3Hz,1H),7.06(dd,J＝10.9,3.3Hz,1H),5.12(s,2H),3.57(s,3H),2.10(br.s,6H),2.06(br.s,3H),1.75(br.,s 6H),1.34(s,12H)。 13 C NMR(CDCl 3 ,100MHz):δ159.46(d,J C,F ＝241Hz),157.48(d,J C,F ＝2.0Hz),144.23(d,J C,F ＝5.7Hz),119.42(d,J C,F ＝21.0Hz),117.35(d,J C,F ＝24.0Hz),100.98,83.96,57.73,40.97,37.29,36.87,28.99,24.79。
(3 r,5r,7 r) -1- (2 ' -bromo-5-fluoro-4 ' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) adamantane
To 8.00g (19.21 mmol) of 2- ((3 r,5r,7 r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 60mL of 1, 4-dio To a solution in alkane was then added 6.24g (19.2 mmol) of 2-bromo-4-isopropyl iodobenzene, 6.63g (48.0 mmol) of potassium carbonate and 50mL of water. The resulting mixture was purged with argon for 10 minutes, then 1.10g (0.96 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 150 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 4.70g (50%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.53(d,J＝1.6Hz,1H),7.27(d,J＝7.9Hz,1H),7.20(dd,J＝7.9,1.6Hz,1H),7.03(dd,J＝11.0,3.2Hz,1H),6.79(dd,J＝7.9,3.2Hz,1H),4.48(m,1H),4.40(m,1H),3.16(s,3H),2.93(sept,J＝6.9Hz,1H),2.13(br.s,6H),2.10(br.s,3H),1.78(br.s,6H),1.28(d,J＝6.9Hz,6H)。 13 C NMR(CDCl 3 ,100MHz):δ159.33(d,J C,F ＝240Hz),150.47,145.50(d,J C,F ＝5.9Hz),137.28,136.00(d,J C,F ＝8.8Hz),131.87,130.86,125.47,123.65,115.67(d,J C,F ＝23.6Hz),113.95(d,J C,F ＝23.6Hz),98.98,57.03,41.03,37.57,36.85,33.66,29.03,23.84。
2- (3 '- ((3 r,5r,7 r) -adamantan-1-yl) -5' -fluoro-4-isopropyl-2 '- (methoxymethoxy) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
4.70g (9.64 mmol) of (3 r,5r,7 r) -1- (2 ' -bromo-5-fluoro-4 ' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl) are introduced at-80 ℃]3-yl) adamantane to a solution of 100mL of anhydrous THF was added dropwise 3.86mL (9.64 mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 2.33mL (12.5 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 300 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-diethyl ether=10:1, volume). 5.10g (99%) of a colorless glassy solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.59(d,J＝1.9Hz),7.29(dd,J＝7.9,1.9Hz,1H),7.24(d,J＝7.9Hz),6.95(dd,J＝11.2,3.2Hz,1H),6.71(dd,J＝8.0,3.2Hz,1H),4.30–4.42(m,2H),3.20(s,3H),2.95(sept,J＝6.9Hz,1H),2.14(br.s,6H),2.08(br.s,6H),1.74-1.80(m,6H),1.28(d,J＝6.9Hz,6H),1.17(br.s,12H)。 13 C NMR(CDCl 3 ,100MHz):δ159.31(d,J C,F ＝240Hz),149.77(d,J C,F ＝2.4Hz),147.17,144.55(d,J C,F ＝6.6Hz),142.17,138.49(d,J C,F ＝8.1Hz),132.80,130.14,128.01,115.90(d,J C,F ＝22.5Hz),112.61(d,J C,F =23.6 Hz), 98.69,83.48,57.23,41.26,37.52,36.91,33.86,29.09,25.07 (wide), 24.26 (wide), 24.04.
2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-ol
To 2.00g (3.74 mmol) of 2- (3 '- ((3 r,5r,7 r) -adamantan-1-yl) -5' -fluoro-4-isopropyl-2 '- (methoxymethoxy) - [1,1' -biphenyl)]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of 1, 4-bisTo a solution in alkane was then added 500mg (1.87 mmol) of 2, 6-dibromo-4-methoxypyridine, 3.04g (9.35 mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, then 216mg (0.187 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil were then added 50mL THF, 50mL methanol, and 3mL 12NHCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 1.31g (83%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 Delta 7.95 (s, 1H), 7.20-7.46 (m, 8H), 6.73-6.84 and 6.06-6.09 (2 m, 3H), 6.59 and 6.51 (2 s, 2H), 3.63 and 3.46 (2 s, 3H), 2.95-3.10 (2 sept, 2H), 1.57-2.15 (m, 30H), 1.28-1.37 (m, 12H). 13 C NMR(CDCl 3 ,100MHz)δ166.41,166.10,159.62,159.46,157.73(d,J C,F ＝237Hz),157.62(d,J C,F ＝237Hz),148.99,148.74,148.66,148.29,139.95,139.89,139.39,138.30,133.96,131.90,131.14,129.34,128.13,128.03,127.84,127.59,127.03,114.54(d,J C,F ＝22.7Hz),114.19(d,J C,F ＝22.9Hz),113.01(d,J C,F ＝23.2Hz),112.70(d,J C,F ＝24.1Hz),108.57,108.45,55.25,54.97,40.16,39.96,37.00,36.93,36.89,36.83,36.68,33.83,33.65,28.99,28.90,23.99,23.93,23.76。
2- (3, 5-Dimethyladamantan-1-yl) -4-fluorophenol
To a solution of 8.40g (75.0 mmol) of 4-fluorophenol and 13.5g (75.0 mmol) of 3, 5-dimethyladamantan-1-ol in 150mL of dichloromethane was added dropwise a solution of 4.90mL (75.0 mmol) of methanesulfonic acid and 5mL of acetic acid in 100mL of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then 300ml of 5% NaHCO was carefully poured in 3 Is a kind of medium. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified using a Kugelrohr apparatus (1 mbar, 70 ℃) to give 14.2g (68%) of the title product as a pale yellow oil. 1 HNMR(CDCl 3 ,400MHz):δ6.93(dd,J＝3.1,11.2Hz,1H),6.73(ddd,J＝3.1,7.4,8.6Hz,1H),6.55(dd,J＝4.9,8.6Hz),4.62(s,1H),2.16(dt,J＝3.1,6.3Hz,1H),1.91(m,2H),1.64-1.74(m,4H),1.35-1.45(m,4H),1.20(br.s,2H),0.87(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ158.49(J F ＝236Hz),150.19(J F ＝2.0Hz),137.69(J F ＝5.9Hz),117.12(J F ＝8.1Hz),114.13(J F ＝24.0Hz),112.57(J F ＝22.9Hz),50.92,46.44,43.05,38.70,38.48,31.38,30.84,29.90。
2-bromo-6- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol
To a solution of 14.2g (51.7 mmol) 2- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol in 200mL dichloromethane was added dropwise a solution of 2.67mL (51.7 mmol) bromine in 100mL dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then 200mL of 5% NaHCO was carefully poured in 3 Is a kind of medium. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 DryingDrying, and then evaporating to dryness. 17.5g (96%) of a pale yellow solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.06(dd,J＝3.0,7.0Hz,1H),6.93(dd,J＝2.9,10.8Hz,1H),5.59(s,1H),2.16(m,1H),1.89(br.s,2H),1.63-1.73(m,4H),1.34-1.44(m,4H),1.19(br.s,2H),0.86(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ157.21(J F ＝241Hz),146.61(J F ＝2.8Hz),137.97(J F ＝6.1Hz),115.34(J F ＝25.8Hz),113.64(J F ＝23.6Hz),110.83(J F ＝10.9Hz),54.77,50.48,45.71,42.61,38.96,38.03,31.02,30.42,29.49。
1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5-dimethyladamantane
To a solution of 17.5g (49.5 mmol) 2-bromo-6- (3, 5-dimethyladamantan-1-yl) -4-fluorophenol in 200mL anhydrous THF was added portionwise 2.17g (54.4 mmol,60% wt in mineral oil) sodium hydride at room temperature. Thereafter, 4.53mL (60.0 mmol) of MOMCl was added dropwise over 1 hour. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 300mL of cold water. The crude product was extracted with 3X 200mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. 19.6g (quantitative) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.13(dd,J＝3.1,6.8Hz,1H),6.98(dd,J＝3.1,10.9Hz,1H),5.19(s,2H),3.68(s,3H),2.16(m,1H),1.89(br.s,2H),1.64-1.74(m,4H),1.34-1.44(m,4H),1.19(br.s,2H),0.87(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ159.47(J F ＝245Hz),150.08(J F ＝3.3Hz),146.34(J F ＝6.4Hz),118.13(J F ＝25.4Hz),117.65(J F ＝10.7Hz),114.01(J F ＝23.4Hz),99.95,57.89,50.69,47.13,42.84,39.78,39.55,31.50,30.84,29.94。
2- (3- ((1 r,3r,5s,7 r) -3, 5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
To a solution of 14.0g (35.3 mmol) 1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3, 5-dimethyladamantane in 250mL anhydrous THF was added dropwise 16.9mL (42.3 mmol) 2.5M nBuLi in hexane at-80℃for 20 min. The reaction mixture was stirred at this temperature for 1 hour, then 11.0mL (52.9 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 100 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was recrystallized from isopropanol. 9.65g (62%) of a white solid was produced. 1 H NMR(CDCl 3 ,400MHz):δ7.19(dd,J＝7.7,3.3Hz,1H),7.08(dd,J＝11.0,3.3Hz,1H),5.11(s,2H),3.57(s,3H),2.13-2.16(m,1H),1.92(br.s,2H),1.66-1.77(m,4H),1.34(s,12H),1.33-1.44(m,4H),1.18(br.s,2H),0.85(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ159.41(d,J C,F ＝240Hz),157.64,143.65(d,J C,F ＝5.5Hz),119.53(d,J C,F ＝21.0Hz),117.42(d,J C,F ＝24.0Hz),101.19,84.00,57.86,50.91,47.15,43.03,39.51,39.03,31.48,30.90,30.00,24.78。
(1 r,3R,5S,7 r) -1- (2 ' -bromo-5-fluoro-4 ' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) -3, 5-dimethyladamantane
To 4.02g (9.09 mmol) of 2- ((3 r,5r,7 r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 20mL of 1, 4-dioTo the solution in the alkane was then added 3.55g (10.9 mmol) of 2-bromo-4-isopropyl iodobenzene, 740g (22.7 mmol) cesium carbonate and 10mL water. The resulting mixture was purged with argon for 10 minutes, then 525mg (0.48 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 4.00g (86%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.52(d,J＝1.5Hz,1H),7.26(d,J＝7.7Hz,1H),7.20(dd,J＝7.8,1.6Hz,1H),7.03(dd,J＝11.1,3.2Hz,1H),6.78(dd,J＝7.9,3.2Hz,1H),4.47(m,1H),4.36(m,1H),3.18(s,3H),2.92(sept,J＝6.9Hz,1H),2.15-2.20(m,1H),1.92-1.99(m,2H),1.77-1.83(m,2H),1.65-1.71(m,2H),1.34-1.47(m,4H),1.27(d,J＝6.9Hz,6H),1.20(br.s,2H),0.88(s,6H)。 13 C NMR(CDCl 3 ,100MHz):δ159.24(d,J C,F ＝240Hz),150.45,150.18(d,J C,F ＝2.6Hz),144.82(d,J C,F ＝6.5Hz),137.25,135.86(d,J C,F ＝8.7Hz),131.90,130.88,125.50,123.59,115.76(d,J C,F ＝22.9Hz),113.96(d,J C,F ＝23.8Hz),99.13,57.10,50.89,47.25,47.20,43.01,39.47,39.28,33.65,31.50,30.95,30.02,23.86,23.84。
2- (3 '- ((1 r,3r,5s,7 r) -3, 5-dimethyladamantan-1-yl) -5' -fluoro-4-isopropyl-2 '- (methoxymethoxy) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
4.00g (7.76 mmol) of (1 r,3R,5S,7 r) -1- (2 ' -bromo-5-fluoro-4 ' -isopropyl-2- (methoxymethoxy) - [1,1' -biphenyl were introduced at-80 ℃]3.17mL (7.91 mmol) of 2.5MnBuLi in hexane was added dropwise to a solution of 3-yl) -3, 5-dimethyladamantane in 50mL anhydrous THF for 20 min. The reaction mixture was stirred at this temperature for 1 hour, then 2.35mL (11.6 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxy was addedHeteroborolanes. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300ml of water. The crude product was extracted with dichloromethane (3X 100 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-diethyl ether=10:1, volume). 3.97g (91%) of a colorless glassy solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.59(d,J＝1.8Hz,1H),7.29(dd,J＝7.9,1.9Hz,1H),7.24(d,J＝7.9Hz,1H),6.95(dd,J＝11.2,3.2Hz,1H),6.72(dd,J＝8.1,3.2Hz,1H),4.34(s,2H),3.22(s,3H),2.95(sept,J＝6.9Hz,1H),2.14-2.19(m,1H),1.72-1.98(m,6H),1.31-1.45(m,4H),1.28(d,J＝6.9Hz,6H),1.13-1.22(m,14H)。 13 CNMR(CDCl 3 ,100MHz):δ159.29(d,J C,F ＝240Hz),150.01(d,J C,F ＝2.6Hz),147.15,143.88(d,J C,F ＝6.5Hz),142.10(d,J C,F ＝1.7Hz),132.85,130.16,128.06,115.85(d,J C,F ＝22.7Hz),112.63(d,J C,F =23.6 Hz), 98.83,83.46,57.24,50.90,47.44 (wide), 43.04,39.69,39.20,33.85,31.52,30.94,30.08,25.20 (wide), 24.17 (wide), 24.04.
2', 2' "- (pyridine-2, 6-diyl) bis (3- ((1 r,3r,5s,7 r) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-ol)
To 3.97g (7.76 mmol) of 2- (3 '- ((1 r,3R,5S,7 r) -3, 5-dimethyladamantan-1-yl) -5' -fluoro-4-isopropyl-2 '- (methoxymethoxy) - [1,1' -biphenyl) ]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 40mL of 1, 4-bisTo a solution in alkane were then added 880mg (3.72 mmol) of 2, 6-dibromopyridine, 6.40g (19.4 mmol) of cesium carbonate and 20mL of water. The resulting mixture was purged with argon for 10 minutes, then 400mg (0.380 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100deg.C for 12 hoursAt this point, it was then cooled to room temperature and diluted with 50mL of water. The mixture thus obtained was extracted with dichloromethane (3×50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil was then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 2.11g (66%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 Delta 7.87 and 7.04 (2 s, 2H), 7.63 and 7.42 (2 t, 1H), 7.21-7.38 (m, 7H), 7.15 and 6.98 (2 d, J=7.8 Hz, 2H), 6.80 (dd, J=11.0, 3.0Hz, 1H), 6.74 (dd, J=8.0, 3.0Hz, 1H), 6.69 (dd, J=11.1, 3.0Hz, 1H), 6.11 (dd, J=8.1, 3.1Hz, 1H), 2.94-3.06 (2 sept, 2H), 1.41-1.85 (m, 12H), 0.96-1.35 (m, 24H), 0.78 (s, 3H), 0.77 (s, 3H), 0.72 (s, 3H), 0.69 (s, 3H). 13 C NMR(CDCl 3 ,100MHz)δ157.65(d,J C,F ＝238Hz),149.11,148.67,148.01,140.28,139.20,138.29,137.09,134.11,133.64,132.05,131.61,128.58,127.93,122.28,114.60(d,J C,F ＝22.3Hz),114.13(d,J C,F ＝23.0Hz),113.22(d,J C,F ＝23.4Hz),51.07,50.72,47.18,46.97,46.09,46.03,43.18,42.89,42.68,42.63,38.59,38.47,37.89,33.85,33.73,31.45,31.27,31.20,31.09,31.01,30.89,30.82,30.70,30.01,29.96。
4-fluoro-2- ((3 r,5r,7 r) -3,5, 7-trimethyladamantan-1-yl) phenol
To a solution of 2.80g (25.0 mmol) of 4-fluorophenol and 4.40g (22.7 mmol) of 3,5, 7-trimethyladamantan-1-ol in 30mL of dichloromethane was added dropwise a solution of 1.60mL (25.0 mmol) of methanesulfonic acid and 2mL of acetic acid in 30mL of dichloromethane at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours, then carefullyPour 300ml of 5% NaHCO 3 Is a kind of medium. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified using a Kugelrohr apparatus (1 mbar, 80 ℃) to give 3.9g (60%) of the title product as a pale yellow oil. 1 H NMR(CDCl 3 ,400MHz):δ6.93(dd,J＝11.3,3.1Hz,1H),6.70-6.74(m,1H),6.55(dd,J＝8.6,5.0Hz,1H),4.87(br.s,1H),1.62(br.s,6H),1.00-1.18(m,6H),0.87(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ158.44(d,J C,F ＝237Hz),150.28(d,J C,F ＝2.0Hz),137.44(d,J C,F ＝5.9Hz),117.10(d,J C,F ＝8.3Hz),114.13(d,J C,F ＝24.0Hz),112.56(d,J C,F ＝23.0Hz),50.28,45.77,39.34,32.12,30.46。
2-bromo-4-fluoro-6- ((3 r,5r,7 r) -3,5, 7-trimethyladamantan-1-yl) phenol
To a solution of 3.60g (12.5 mmol) 4-fluoro-2- ((3 r,5r,7 r) -3,5, 7-trimethyladamantan-1-yl) phenol in 20mL DMF was added 2.22g (12.5 mmol) NBS in one portion at room temperature. The resulting mixture was stirred at room temperature for 48 hours, then 200mL of 5% NaHCO was carefully poured in 3 Is a kind of medium. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 3.00g (65%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.06(dd,J＝6.9,3.0Hz,1H),6.94(dd,J＝10.8,3.0Hz,1H),5.60(s,1H),1.61(br.s,6H),1.06-1.18(m,6H),0.87(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ157.20(d,J C,F ＝241Hz),146.99(d,J C,F ＝3.0Hz),138.10(d,J C,F ＝6.0Hz),115.76(d,J C,F ＝26.0Hz),114.06(d,J C,F ＝23.6Hz),111.22(d,J C,F ＝10.9Hz),50.20,45.45,40.19,32.14,30.42。
(3 r,5r,7 r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3,5, 7-trimethyladamantane
To a solution of 2.20g (6.00 mmol) 2-bromo-4-fluoro-6- ((3 r,5r,7 r) -3,5, 7-trimethyladamantan-1-yl) phenol in 20mL anhydrous THF was added 270mg (6.60 mmol,60% wt in mineral oil) sodium hydride at room temperature. After that, 630. Mu.L (7.80 mmol) of MOMCl was added in one portion. The reaction mixture was heated at 60 ℃ for 24 hours and then poured into 30mL of cold water. The crude product was extracted with 3X 20mL of dichloromethane. The combined organic extracts were taken up in Na 2 SO 4 Dried on, and then evaporated to dryness. 2.50g (97%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.14(dd,J＝6.9,3.1Hz,1H),6.99(dd,J＝10.9,3.1Hz,1H),5.19(s,2H),3.67(s,3H),1.62(br.s,6H),1.06-1.17(m,6H),0.88(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ159.50(d,J C,F ＝245Hz),150.15,146.11(d,J C,F ＝6.4Hz),118.17(d,J C,F ＝25.4Hz),117.67(d,J C,F ＝10.5Hz),114.05(d,J C,F ＝23.6Hz),100.08,57.93,50.07,46.53,40.65,32.25,30.46。
2- (5-fluoro-2- (methoxymethoxy) -3- ((3 r,5r,7 r) -3,5, 7-trimethyladamantan-1-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
To a solution of 2.50g (5.89 mmol) (3 r,5r,7 r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3,5, 7-trimethyladamantane in 30mL anhydrous THF was added dropwise 2.68mL (6.70 mmol) of 2.5M nBuLi in hexane at-80℃for 20 min. The reaction mixture was stirred at this temperature for 1 hour, then 1.84mL (7.12 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The suspension obtained is stirred at room temperature For 1 hour, then poured into 30mL of water. The crude product was extracted with dichloromethane (3X 40 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. 2.70g (96%) of a white solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.20(dd,J＝7.6,3.2Hz,1H),7.08(dd,J＝10.9,3.3Hz,1H),5.11(s,2H),3.57(s,3H),1.65(br.s,6H),1.34(s,12H),1.06-1.17(m,6H),0.86(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ159.39(d,J C,F ＝240Hz),157.71(d,J C,F ＝2.0Hz),143.38(d,J C,F ＝5.7Hz),119.59(d,J C,F ＝21.0Hz),117.46(d,J C,F ＝24.0Hz),101.29,84.01,57.92,50.24,46.51,39.88,32.20,30.52,24.77。
(3 r,5r,7 r) -1- (2 '-bromo-5-fluoro-2- (methoxymethoxy) - [1,1' -biphenyl ] -3-yl) -3,5, 7-trimethyladamantane
To 2.70g (5.89 mmol) of 2- (5-fluoro-2- (methoxymethoxy) -3- ((3 r,5r,7 r) -3,5, 7-trimethyladamant-1-yl) phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 20mL of 1, 4-bisTo a solution in alkane was then added 2.24g (7.90 mmol) of 2-bromoiodobenzene, 5.00g (15.2 mmol) of cesium carbonate and 10mL of water. The resulting mixture was purged with argon for 10 minutes, then 350mg (0.30 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 100mL of water. The crude product was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-dichloromethane=10:1, volume). 2.50g (85%) of a white solid was obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.73(d,J＝7.9Hz,1H),7.40-7.42(m,2H),7.26-7.30(m,1H),7.10(dd,J＝11.1,3.2Hz,1H),6.83(dd,J＝7.8,3.2Hz,1H),4.53(m,1H),4.42(m,1H),3.27(s,3H),1.73(s,6H),1.14–1.25(m,6H),0.95(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ159.22(d,J C,F ＝241Hz),150.23(d,J C,F ＝2.7Hz),140.01(d,J C,F ＝1.84Hz),135.75(d,J C,F ＝8.5Hz),133.03,132.12,129.11,127.24,123.75,115.69(d,J C,F ＝23.2Hz),114.14(d,J C,F ＝23.8Hz),99.24,57.16,50.21,46.52,40.13,32.21,30.55。
2- (5 '-fluoro-2' - (methoxymethoxy) -3'- ((3 r,5r,7 r) -3,5, 7-trimethyladamantan-1-yl) - [1,1' -biphenyl ] -2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan
To 2.34g (4.80 mmol) of (3 r,5r,7 r) -1- (2 '-bromo-5-fluoro-2- (methoxymethoxy) - [1,1' -biphenyl) at-80 ℃]To a solution of 3-yl) -3,5, 7-trimethyladamantane in 20mL anhydrous THF was added dropwise 2.00mL (5.04 mmol) of a 2.5M solution of nBuLi in hexane for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, then 1.34mL (7.21 mmol) of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 100mL of water. The crude product was extracted with dichloromethane (3X 100 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-diethyl ether=10:1, volume). 2.50g (97%) of a colorless glassy solid are obtained. 1 H NMR(CDCl 3 ,400MHz):δ7.76(d,J＝7.6Hz,1H),7.43(td,J＝7.5,1.5Hz,1H),7.31-7.35(m,2H),6.98(dd,J＝11.2,3.2Hz,1H),6.73(dd,J＝8.0,3.2Hz,1H),4.33(s,2H),3.25(s,3H),1.70(br.s,6H),1.08-1.21(m,18H),0.88(s,9H)。 13 C NMR(CDCl 3 ,100MHz):δ159.30(d,J C,F ＝240Hz),150.06(d,J C,F ＝2.4Hz),144.58,143.70(d,J C,F ＝6.6Hz),138.28(d,J C,F ＝8.3Hz),134.75,130.20,130.11,126.61,115.78(d,J C,F ＝22.7Hz),112.86(d,J C,F =23.6 Hz), 98.97,83.53,57.26,50.22,46.71,40.02,32.24,30.55,25.20 (wide), 24.12 (wide).
2', 2' "- (pyridine-2, 6-diyl) bis (5-fluoro-3- ((3 r,5r,7 r) -3,5, 7-trimethyladamant-1-yl) - [1,1' -biphenyl ] -2-ol)
To 2.50g (4.80 mmol) of 2- (5 '-fluoro-2' - (methoxymethoxy) -3'- ((3 r,5r,7 r) -3,5, 7-trimethyladamantan-1-yl) - [1,1' -biphenyl)]-2-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in 20mL of 1, 4-bis To a solution in alkane was then added 546mg (2.30 mmol) of 2, 6-dibromopyridine, 4.02g (12.0 mmol) of cesium carbonate and 10mL of water. The resulting mixture was purged with argon for 10 minutes, then 304mg (0.240 mmol) of Pd (PPh) was added 3 ) 4 . The mixture was stirred at 100 ℃ for 12 hours, then cooled to room temperature and diluted with 50mL of water. The resulting mixture was extracted with dichloromethane (3X 50 mL) and the combined organic extracts were taken up in Na 2 SO 4 Drying the mixture, and evaporating the mixture to dryness. To the resulting oil were then added 50mL THF, 50mL methanol, and 3mL 12N HCl. The reaction mixture was stirred at 60 ℃ overnight and then poured into 200mL of water. The crude product was extracted with dichloromethane (3X 70 mL) and the combined organic extracts were extracted with 5% NaHCO 3 Washing in Na 2 SO 4 Dried on, and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 μm, eluent: hexane-ethyl acetate=10:1, volume). 690mg (37%) of a mixture of the two isomers was obtained as a white foam. 1 H NMR(CDCl 3 400MHz for delta 7.37-7.54 (m, 8H), 6.65-7.04 and 6.29-6.32 (m, 9H), 1.43 (s, 6H), 1.22-1.40 (m, 6H), 0.95-1.15 (m, 12H), 0.78 (s, 9H), 0.72 (s, 9H). 13 C NMR(CDCl 3 ,100MHz)δ157.71(d,J C,F ＝240Hz),157.68(d,J C,F ＝240Hz),148.03,147.62(d,J C,F ＝2.0Hz),139.79,138.99,138.91,138.70,138.64,136.92,136.82,135.82,135.67,132.05,131.43,130.60,130.00,129.82,129.20,128.57,128.44,122.41,122.18,114.26(d,J C,F ＝22.7Hz),113.84(d,J C,F ＝23.0Hz),113.51(d,J C,F ＝23.4Hz),113.12(d,J C,F ＝23.7Hz),50.30,50.05,45.71,39.55,39.49,32.17,32.00,31.89,30.60,30.44。
Hafnium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 1)
225mg (0.702 mmol) of hafnium tetrachloride were introduced by syringe at 0deg.C<0.5% zr) to a suspension in 50mL of anhydrous toluene was added 1.10mL (3.16 mmol) of 2.9M MeMgBr in diethyl ether in one portion. To the resulting suspension 500mg (0.702 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl) were added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 473mg (73%) of a white-off-white solid are produced. C (C) 53 H 57 HfNO 2 Is calculated by analysis of: c,69.30; h,6.26; n,1.52. Actual measurement value: c69.58; h,6.39; n1.40. 1 H NMR(CDCl 3 ,400MHz):δ7.69(t,J＝7.8Hz,1H),7.54(td,J＝7.6,1.4Hz,2H),7.35(td,J＝7.5,1.3Hz,2H),7.30(dd,J＝7.8,1.2Hz,2H),7.10-7.14(m,4H),7.02(d,J＝2.3Hz,2H),6.69(dd,J＝2.3,0.6Hz,2H),2.23(s,6H),2.18-2.24(m,6H),2.04-2.14(m,12H),1.68-1.85(m,12H),-0.78(s,6H)。 13 C NMR(CDCl 3 ,100MHz)δ158.78,157.35,142.53,139.60,138.26,132.88,132.34,131.79,130.83,130.69,128.66,127.52,127.40,126.22,124.77,49.51,40.85,37.15,37.00,29.06,20.76。
Zirconium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 3)
To a suspension of 131mg (0.562 mmol) zirconium tetrachloride in 50mL anhydrous toluene was added 870uL (2.53 mmol) of 2.9MMeMgBr in diethyl ether in one portion via syringe at-30 ℃. To the resulting suspension 400mg (0.562 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5-methyl- [1,1' -biphenyl were added immediately in one portion ]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 318mg (68%) of an off-white solid was obtained. C (C) 53 H 57 ZrNO 2 Is calculated by analysis of: c,76.58; h,6.91; n,1.69. Actual measurement value: c76.89; h,7.06; n1.52. 1 H NMR(C 6 D 6 ,400MHz):7.11-7.20(m,8H),7.02-7.04(m,2H),6.76(d,J＝2.2Hz,2H),6.39-6.50(m,3H),2.45-2.54(m,6H),2.32-2.37(m,6H),2.23(s,6H),2.17(br.s,6H),1.94-2.03(m,6H),1.80-1.89(m,6H),-0.10(s,6H)。 13 C NMR(CDCl 3 ,100MHz)δ159.31,158.31,143.44,139.58,138.60,133.65,133.59,133.18,131.42,131.13,129.36,128.54,128.06,127.20,124.43,42.89,41.95,38.18,37.85,30.01,21.41。
Hafnium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 2)
118mg (0.369 mmol) of hafnium tetrachloride were introduced by syringe at 0 ℃(<0.5% zr) in 50mL of anhydrous toluene, 570 μl (1.66 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 273mg (0.369 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl are added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 240mg (69%) of a white-off-white solid are obtained. C (C) 55 H 61 HfNO 2 Is calculated by analysis of: c,69.79; h,6.50; n,1.48. Actual measurement value: c70.08; h,6.73; n1.35. 1 H NMR(C 6 D 6 ,400MHz):δ7.20(d,J＝2.4Hz,2H),7.12(d,J＝8.0Hz,2H),6.97(dd,J＝7.8,1.8Hz,2H),6.84(m,2H),6.74-6.76(m,2H),6.43-6.56(m,3H),2.45-2.53(m,6H),2.30-2.38(m,6H),2.23(s,6H),2.21(s,6H),2.15(br.s,6H),1.94-2.03(m,6H),1.76-1.84(m,6H),-0.03(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ159.99,158.16,140.99,139.42,139.03,137.75,133.71,133.23,133.14,132.44,131.03,129.60,128.29,126.99,125.20,51.24,41.67,38.04,37.81,30.04,21.41,21.39。
Zirconium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 4)
To a suspension of 83mg (0.354 mmol) zirconium tetrachloride in 30mL of anhydrous toluene was added 540. Mu.L (1.59 mmol) of 2.9MMeMgBr in diethyl ether via syringe at-30 ℃. To the resulting suspension 262mg (0.354 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -biphenyl) were added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated toNear drying. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 193mg (63%) of an off-white solid was produced. C (C) 55 H 61 ZrNO 2 Is calculated by analysis of: c,76.88; h,7.16; n,1.63. Actual measurement value: c77.06; h,7.43; n1.51. 1 H NMR(C 6 D 6 ,400MHz):δ7.19(d,J＝1.8Hz,2H),7.13(d,J＝7.8Hz,2H),6.96(ddd,J＝7.8,1.8,0.6Hz,2H),6.82(dd,J＝1.2,0.6Hz,2H),6.76(dd,J＝2.4,0.6Hz,2H),6.42-6.57(m,3H),2.48-2.55(m,6H),2.34-2.42(m,6H),2.22(s,6H),2.20(s,6H),2.15(br.s,6H),1.95-2.02(m,6H),1.77-1.84(m,6H),-0.20(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ159.46,158.49,140.84,139.40,138.49,137.69,133.62,133.59,133.51,132.31,130.93,129.66,128.89,128.22,127.09,126.03,124.74,42.91,41.72,38.14,37.80,30.04,21.42,21.38。
Hafnium dimethyl [2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenoxide) ] (complex 7)
155mg (0.484 mmol) of hafnium tetrachloride were introduced via syringe at 0℃C<0.5% zr) in 50mL of anhydrous toluene, 750 μl (2.18 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 400mg (0.484 mmol) of 2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl) are added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane, the precipitate obtained was filtered off (G4), washed with 2X 5mL of n-hexane, thenAnd drying in vacuum. 338mg (68%) of a white-off-white solid are obtained. C (C) 60 H 71 HfNO 3 Is calculated by analysis of: c,69.78; h,6.93; n,1.36. Found: c70.04; h,7.16; n1.24. 1 H NMR(C 6 D 6 ,400MHz):δ7.59(d,J＝2.6Hz,2H),7.19-7.21(m,2H),7.09-7.16(m,8H),6.08(s,2H),2.57-2.63(m,6H),2.55(s,3H),2.43-2.49(m,6H),2.21(br.s,6H),1.99-2.06(m,6H),1.83-1.90(m,6H),1.33(s,18H),-0.10(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ167.56,159.92,159.70,143.99,140.37,138.65,133.99,133.04,132.78,131.59,131.32,129.66,128.90,127.90,125.85,124.81,111.17,55.17,50.99,41.98,38.57,37.89,34.79,32.36,30.08。
Hafnium dimethyl [2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl ] -2-phenoxide) ] (complex 8)
148mg (0.463 mmol) of hafnium tetrachloride were introduced via syringe at 0℃<0.5% zr) in 50mL of anhydrous toluene, 720uL (2.10 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 400mg (0.463 mmol) of 2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) - [1,1' -biphenyl) are added immediately in one portion ]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 342mg (69%) of a yellow solid was produced. C (C) 60 H 68 F 3 HfNO 2 Is calculated by analysis of: c,67.31; h,6.40; n,1.31. Found: c67.65; h,6.66; n1.20. 1 H NMR(C 6 D 6 ,400MHz):δ7.55(d,J＝2.6Hz,2H),7.07-7.18(m,4H),7.03(td,J＝7.4,1.6Hz,2H),6.99(d,J＝2.5Hz,2H),6.91(dd,J＝7.4,1.1Hz,2H),6.82(s,2H),2.47-2.53(m,6H),2.32-2.39(m,6H),2.17(br.s,6H),1.94-2.01(m,6H),1.80-1.89(m,6H),1.30(s,18H),-0.13(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ160.03,159.46,143.80,141.05,138.65,133.82,132.47,132.08,131.72,131.25,125.67,124.93,121.29(q,Jc, F ＝3.1Hz),51.49,41.94,38.49,37.79,34.78,32.23,29.98。
Hafnium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 9)
155mg (0.485 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.5% zr) in 50mL of anhydrous toluene, 750 μl (2.20 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 400mg (0.485 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl were immediately added in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 287mg (57%) of a white-off-white solid are obtained. C (C) 61 H 73 HfNO 2 Is calculated by analysis of: c,71.08; h,7.14; n,1.36. Actual measurement value: c71.31; h,7.32; n1.24. 1 H NMR(C 6 D 6 ,400MHz):δ7.58(d,J＝2.6Hz,2H),7.12(d,J＝7.8Hz,2H),7.03(d,J＝2.6Hz,2H),6.95(dd,J＝7.9,1.3Hz,2H),6.75(d,J＝0.7Hz,2H),6.39-6.52(m,3H),2.55-2.62(m,6H),2.40-2.48(m,6H),2.19(s,6H),2.19(br.s,6H),1.98-2.05(m,6H),1.78-1.86(m,6H),1.33(s,18H),-0.02(s,6H)。 13 CNMR(C 6 D 6 ,100MHz)δ159.90,158.06,141.34,140.38,139.30,138.47,137.64,133.82,133.12,132.86,132.49,131.21,129.66,128.90,126.00,125.32,124.41,51.20,41.77,38.48,37.81,34.76,32.35,30.07,21.31。
Hafnium dimethyl [2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 10)
135mg (0.421 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.5% Zr) in 50mL of anhydrous toluene 650. Mu.L (1.89 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 400mg (0.421 mmol) of 2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl) are added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 356mg (73%) of a yellow solid was produced. C (C) 66 H 80 F 3 HfNO 2 Is calculated by analysis of: c,68.64; h,6.98; n,1.21. Actual measurement value: c68.88; h,7.16; n1.13. 1 H NMR(C 6 D 6 ,400MHz):δ7.57(d,J＝2.6Hz,2H),7.19-7.22(m,4H),7.02(s,2H),6.98(d,J＝2.5Hz,2H),6.93(d,J＝1.7Hz,2H),2.91(sept,J＝6.9Hz,2H),2.53-2.60(m,6H),2.40-2.47(m,6H),2.15(br.s,6H),1.96-2.03(m,6H),1.77-1.85(m,6H),1.28(s,18H),1.23(d,J＝6.9Hz,6H),1.07(d,J＝6.9Hz,6H),0.00(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ160.39,159.75,149.13,141.82,140.98,138.51,134.19,132.28,129.29,125.96,124.61,121.84(q,Jc, F ＝3.0Hz),51.54,41.81,38.53,37.78,34.77,33.85,32.24,29.95,26.57,22.32。
Hafnium dimethyl [2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 11)
140mg (0.440 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.5% Zr) in 50mL of anhydrous toluene was added 680. Mu.L (1.98 mmol) of 2.9mM MgBr in diethyl ether. To the resulting suspension 400mg (0.440 mmol) of 2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl) are added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 310mg (63%) of a white solid are obtained. C (C) 66 H 83 HfNO 3 Is calculated by analysis of: c,70.98; h,7.49; n,1.25. Found: c71.24; h,7.52; n1.14. 1 H NMR(C 6 D 6 ,400MHz):δ7.60(d,J＝2.6Hz,2H),7.25(d,J＝8.1Hz,2H),7.18(m,2H),7.07(d,J＝2.5Hz,2H),7.02(d,J＝1.8Hz,2H),6.21(s,2H),2.98(sept,J＝6.8Hz,2H),2.60-2.67(m,6H),2.61(s,3H),2.48-2.56(m,6H),2.18(br.s,6H),2.01-2.08(m,6H),1.80-1.87(m,6H),1.31(s,18H),1.25(d,J＝6.8Hz,6H),1.12(d,J＝6.8Hz,6H),-0.02(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ167.36,160.15,160.03,148.56,141.83,140.28,138.50,134.24,133.36,132.93,129.58,128.24,126.19,124.50,111.80,55.16,51.06,41.85,38.60,37.87,34.79,33.77,32.38,30.03,26.54,22.31。
Hafnium dimethyl [2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 12)
144mg (0.448 mmol) of hafnium tetrachloride were introduced via syringe at 0℃C<0.5% zr) in 50mL of anhydrous toluene 695 μl (2.02 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 400mg (0.448 mmol) of 2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl) are added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 398mg (81%) of a yellow solid were produced. C (C) 62 H 72 F 3 HfNO 2 Is calculated by analysis of: c,67.78; h,6.61; n,1.27. Found: c68.03; h,6.74; n1.15. 1 H NMR(C 6 D 6 ,400MHz):δ7.55(d,J＝2.6Hz,2H),7.07(d,J＝7.9Hz,2H),6.95(d,J＝2.6Hz,2H),6.93(dd,J＝7.8,1.2Hz,2H),6.84(s,2H),6.69(d,J＝0.7Hz,2H),2.50-2.57(m,6H),2.37-2.45(m,6H),2.16(s,6H),2.15(br.s,6H),1.96-2.04(m,6H),1.78-1.86(m,6H),1.30(s,18H),-0.03(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ160.17,159.61,141.22,140.90,138.47,137.94,133.72,132.95,132.29,132.16,130.86,129.66,128.90,126.03,125.92,124.58,121.56(q,J F ＝3.5Hz),51.51,41.74,38.48,37.76,34.76,32.25,30.04,21.27。
Zirconium dimethyl [2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 13)
A suspension of 105mg (0.448 mmol) zirconium tetrachloride in 50mL dry toluene was introduced via syringe at-30 ℃ 695 μl (2.02 mmol) of 2.9 mmenmgbr in diethyl ether was added in portions. To the resulting suspension 400mg (0.448 mmol) of 2', 2' "- (4- (trifluoromethyl) pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl) are added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 330mg (73%) of a yellow solid was produced. C (C) 62 H 72 F 3 ZrNO 2 Is calculated by analysis of: c,73.62; h,7.18; n,1.38. Actual measurement value: c73.90; h,7.32; n1.21. 1 H NMR(C 6 D 6 ,400MHz):δ7.54(d,J＝2.6Hz,2H),7.07(d,J＝7.8Hz,2H),6.95(d,J＝2.5Hz,2H),6.91(dd,J＝7.8,1.2Hz,2H),6.83(s,2H),6.67(m,2H),2.52-2.59(m,6H),2.39-2.47(m,6H),2.15(s,6H),2.15(br.s,6H),1.96-2.04(m,6H),1.79-1.86(m,6H),1.30(s,18H),-0.20(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ160.53,159.08,141.06,141.00,137.91,137.88,133.60,132.81,132.64,132.55,130.76,129.66,128.90,125.99,124.49,121.05(q,J F ＝3.0Hz),43.38,41.78,38.58,37.75,34.79,32.24,30.04,21.25。
Hafnium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 14)
145mg (0.454 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.5% zr) to a suspension in 50mL of anhydrous toluene was added 704 μl (2.04 mmol) of 2.9M MeMgBr in diethyl ether in one portion. To the resulting suspension 400mg (0.454 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-isopropyl- [1,1' -biphenyl) are added immediately in one portion ]-2-phenol). The reaction is carried outThe mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 333mg (67%) of a white solid were produced. C (C) 65 H 81 HfNO 2 Is calculated by analysis of: c,71.83; h,7.51; n,1.29. Actual measurement value: c72.09; h,7.67; n1.20. 1 H NMR(C 6 D 6 ,400MHz):δ7.58(d,J＝2.6Hz,2H),7.25(d,J＝8.1Hz,2H),7.17–7.19(m,2H),7.04(d,J＝2.6Hz,2H),6.92(d,J＝1.8Hz,2H),6.43-6.55(m,3H),2.95(sept,J＝6.9Hz,2H),2.56-2.63(m,6H),2.44-2.50(m,6H),2.17(br.s,6H),1.99-2.06(m,6H),1.78-1.86(m,6H),1.31(s,18H),1.25(d,J＝6.9Hz,6H),1.10(d,J＝6.9Hz,6H),0.00(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ158.67,157.62,147.92,140.68,139.28,138.93,137.17,133.04,132.32,131.59,128.97,127.37,125.20,125.15,123.24,49.62,40.65,37.42,37.04,34.15,33.03,31.72,29.08,26.02,21.86。
Hafnium dimethyl [2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl ] -2-phenolate) ] (complex 15)
112mg (0.351 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.5% zr) in 50mL of anhydrous toluene 544 μl (1.56 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 300mg (0.351 mmol) of 2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5- (tert-butyl) -4 '-methyl- [1,1' -biphenyl were added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Then, the filtrate was evaporated to dryness . The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 284mg (76%) of a white solid was produced. C (C) 62 H 75 HfNO 3 Is calculated by analysis of: c,70.20; h,7.13; n,1.32. Actual measurement value: c70.45; h,7.33; n1.23. 1 H NMR(C 6 D 6 ,400MHz):δ7.59(d,J＝2.6Hz,2H),7.12-7.14(m,2H),7.05(d,J＝2.6Hz,2H),6.95(dd,J＝7.9,1.2Hz,2H),6.85(m,2H),6.09(s,2H),2.63(s,3H),2.59-2.65(m,6H),2.44-2.53(m,6H),2.22(s,6H),2.19(br.s,6H),2.01-2.08(m,6H),1.80-1.87(m,6H),1.33(s,18H),0.00(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ166.82,159.09,158.73,140.36,139.21,137.23,137.08,132.94,132.42,131.61,131.51,130.47,123.29,110.90,55.69,49.23,40.68,37.47,37.02,34.15,31.72,29.16,21.01。
Hafnium dimethyl [2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 16)
153mg (0.479 mmol) of hafnium tetrachloride were introduced via syringe at 0℃C<0.05% zr) in 50mL of anhydrous toluene, 743 μl (2.16 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 400mg (0.479 mmol) of 2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl) are added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 286mg (57%) of a white solid was produced. C (C) 58 H 65 F 2 HfNO 3 Is calculated by analysis of: c,66.94; h,6.30; n,1.35. Found: c67.23；H,6.51；N 1.25。 1 H NMR(C 6 D 6 ,400MHz):δ7.11-7.20(m,6H),7.02(m,2H),6.72(dd,J＝7.8,3.2Hz,2H),6.21(s,2H),2.94(sept,J＝6.8Hz,2H),2.52(s,3H),2.33-2.42(m,6H),2.20-2.30(m,6H),2.07(br.s,6H),1.87-1.95(m,6H),1.72-1.80(m,6H),1.24(d,J＝6.8Hz,6H),1.14(d,J＝6.8Hz,6H),-0.05(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ167.75,159.75,158.49,157.28(d,Jc, F ＝235Hz),149.31,141.11(d,Jc, F ＝5.7Hz),140.05(d,Jc, F ＝1.7Hz),133.81,133.47(d,Jc, F ＝7.7Hz),133.28,129.32,128.51,115.00(d,Jc, F ＝22.3Hz),114.58(d,Jc, F ＝23.0Hz),111.65,55.26,51.57,41.18,38.28,37.59,33.99,29.77,26.37,22.34。
Hafnium dimethyl [2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl ] -2-phenolate) ] (complex 17)
165mg (0.515 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.05% zr) in 50mL of anhydrous toluene 800 μl (2.32 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 440mg (0.515 mmol) of 2', 2' "- (4-methoxypyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl were added immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 380mg (70%) of a white solid are obtained. C (C) 62 H 75 HfNO 3 Is calculated by analysis of: c,70.20; h,7.13; n,1.32. Actual measurement value: c70.46; h,7.29; n1.25. 1 H NMR(C 6 D 6 ,400MHz):δ7.36(dd,J＝8.3,2.0Hz,2H),7.24(m,4H),7.20(d,J＝2.0Hz,2H),6.70(d,J＝2.0Hz,2H),6.26(s,2H),2.52-2.59(m,6H),2.47(s,3H),2.41-2.48(m,6H),2.19(s,6H),2.17(br.s,6H),1.98-2.06(m,6H),1.76-1.84(m,6H),1.34(s,18H),-0.06(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ167.46,160.77,160.29,151.37,141.42,139.12,134.02,133.98,133.05,129.71,129.56,126.86,125.47,112.05,55.00,51.36,41.67,38.26,37.81,35.15,31.74,29.98,21.34。
Hafnium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl ] -2-phenolate) ] (complex 18)
124mg (0.388 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.05% zr) in 50mL of anhydrous toluene 600 μl (1.75 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. 320mg (0.388 mmol) of 2', 2' - (pyridine-2, 6-diyl) bis (3- ((3 r,5r,7 r) -adamantan-1-yl) -4'- (tert-butyl) -5-methyl- [1,1' -biphenyl) are added to the resulting suspension in one portion immediately]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 301mg (75%) of a white solid are produced. C (C) 61 H 73 HfNO 2 Is calculated by analysis of: c,71.08; h,7.14; n,1.32. Actual measurement value: c71.39; h,7.27; n1.22. 1 H NMR(C 6 D 6 ,400MHz):δ7.35(dd,J＝8.3,2.0Hz,2H),7.22(d,J＝8.3Hz,2H),7.19(d,J＝2.0Hz,2H),7.14(d,J＝2.0Hz,2H),6.66(d,J＝1.7Hz,2H),6.45-6.53(m,3H),2.48-2.56(m,6H),2.37-2.45(m,6H),2.19(s,6H),2.16(br.s,6H),1.96-2.05(m,6H),1.75-1.84(m,6H),1.32(s,18H),0.07(s,6H)。 13 C NMR(C 6 D 6 ,100MHz)δ160.12,158.83,151.36,141.36,139.48,139.01,133.84,132.99,129.65,129.57,126.93,125.76,125.54,51.54,41.59,38.17,37.75,35.12,31.69,29.92,21.33。
Hafnium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((1 r,3r,5s,7 r) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 19)
210mg (0.654 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.05% zr) in 50mL of anhydrous toluene, 900 μl (2.61 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension 562mg (0.654 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3- ((1 r,3r,5s,7 r) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl) are added in one portion immediately]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 530mg (76%) of a white solid were produced. C (C) 61 H 71 F 2 HfNO 2 Is calculated by analysis of: c,68.68; h,6.71; n,1.31. Found: c68.81; h,6.99; n1.23. 1 H NMR(CD 2 Cl 2 ,400MHz):δ7.77(t,J＝7.7Hz,1H),7.47(dd,J＝8.1,1.8Hz,2H),7.18(d,J＝8.1Hz,2H),7.16(d,J＝7.7Hz,2H),6.90-6.94(m,4H),6.49(dd,J＝7.9,3.2Hz,2H),2.97(sept,J＝6.9Hz,2H),2.60-2.67(m,2H),2.45-2.52(m,2H),2.00-2.05(m,2H),1.52-1.63(m,6H),1.33-1.42(m,4H),1.33(d,J＝6.9Hz,6H),1.30-1.34(m,2H),1.22(d,J＝6.9Hz,6H),1.11-1.24(m,6H),1.02-1.09(m,2H),0.91(s,6H),0.77(s,6H),-0.68(s,6H)。 13 C NMR(CD 2 Cl 2 ,100MHz)δ157.97,157.89,156.47(d,Jc, F ＝234Hz),149.58,140.27,140.15(d,Jc, F ＝6.1Hz),139.42(d d,Jc, F ＝1.7Hz),133.12,133.03(d,Jc, F ＝7.9Hz),132.88,129.52,129.43,128.70,128.49,125.85,125.78,114.45(d,Jc, F ＝22.3Hz),113.65(d,Jc, F ＝23.2Hz),51.75,50.95,49.61,45.53,43.87,42.50,39.57,38.24,33.76,32.22,31.58,31.56,30.92,30.37,25.85,22.39。
Zirconium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (3- ((1 r,3r,5s,7 r) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl ] -2-phenoxide) ] (complex 20)
To a suspension of 135mg (0.581 mmol) zirconium tetrachloride in 50mL of anhydrous toluene was added 800. Mu.L (2.32 mmol) of 2.9MMeMgBr in diethyl ether in one portion via syringe at-30 ℃. To the resulting suspension 500mg (0.581 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (3- ((1 r,3r,5s,7 r) -3, 5-dimethyladamantan-1-yl) -5-fluoro-4 '-isopropyl- [1,1' -biphenyl) are added in one portion immediately ]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 390mg (68%) of a white-off-white solid are produced. C (C) 61 H 71 F 2 ZrNO 2 Is calculated by analysis of: c,74.80; h,7.31; n,1.43. Found: c75.06; h,7.64; n1.19. 1 H NMR(CD 2 Cl 2 ,400MHz):δ7.76(t,J＝7.8Hz,1H),7.46(dd,J＝8.1,1.8Hz,2H),7.19(d,J＝8.0Hz,2H),7.15(d,J＝7.8Hz,2H),6.92(dd,J＝11.7,3.3Hz,2H),6.89(d,J＝1.8Hz,2H),6.51(dd,J＝8.0,3.3Hz,2H),2.97(sept,J＝6.9Hz,2H),2.65-2.73(m,2H),2.48-2.56(m,2H),2.00-2.06(m,2H),1.52-1.65(m,6H),1.33-1.43(m,6H),1.33(d,J＝6.9Hz,6H),1.22(d,J＝6.9Hz,6H),1.15-1.23(m,6H),1.06-1.14(m,2H),0.92(s,6H),0.79(s,6H),-0.42(s,6H)。 13 C NMR(CD 2 Cl 2 ,100MHz)δ158.29,157.34,156.51(d,Jc, F ＝235Hz),149.53,140.25,139.61(d,Jc, F ＝6.1Hz),139.29(d,Jc, F ＝1.7Hz),133.42(d,Jc, F ＝7.9Hz),133.26,133.03,129.53,129.35,128.72,128.37,125.79,125.39,114.57(d,Jc, F ＝22.3Hz),113.61(d,Jc, F ＝23.2Hz),51.76,49.61,45.66,43.88,42.81,42.52,39.67,38.30,33.77,32.23,31.59,31.56,30.94,30.39。
Hafnium dimethyl [2', 2' "- (pyridine-2, 6-diyl) bis (5-fluoro-3- ((3 r,5r,7 r) -3,5, 7-trimethyladamantan-1-yl) - [1,1' -biphenyl ] -2-phenoxide) ] (complex 21)
119mg (0.373 mmol) of hafnium tetrachloride were introduced via syringe at 0deg.C<0.05% zr) in 50mL of anhydrous toluene, 510 μl (1.49 mmol) of 2.9M MeMgBr in diethyl ether was added in one portion. To the resulting suspension was added 300mg (0.373 mmol) of 2', 2' "- (pyridine-2, 6-diyl) bis (5-fluoro-3- ((3 r,5r,7 r) -3,5, 7-trimethyladamant-1-yl) - [1,1' -biphenyl) immediately in one portion]-2-phenol). The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20mL of hot toluene and the combined organic extracts were filtered through a thin pad of celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5mL of n-hexane and the precipitate obtained was filtered off (G4), washed with 2 x 5mL of n-hexane and then dried in vacuo. 271mg (72%) of a white solid was produced. C (C) 57 H 63 F 2 HfNO 2 Is calculated by analysis of: c,67.74; h,6.28; n,1.39. Found: c67.98; h,6.42; n1.37. 1 H NMR(CD 2 Cl 2 ,400MHz):δ7.79(t,J＝7.7Hz,1H),7.55(td,J＝7.5,1.5Hz,2H),7.49(td,J＝7.4,1.3Hz,2H),7.22(dd,J＝7.4,0.9Hz,2H),7.18(d,J＝7.8Hz,2H),7.11(dd,J＝7.4,0.9Hz,2H),6.97(dd,J＝11.7,3.3Hz,2H),6.52(dd,J＝7.8,3.3Hz,2H),1.74-1.80(m,6H),1.58-1.64(m,6H),1.17-1.24(m,6H),1.00-1.07(m,6H),0.88(s,18H),-0.74(s,6H)。 13 C NMR(CD 2 Cl 2 ,100MHz)
δ158.06,158.04,157.51,156.37(d,Jc, F ＝234Hz),141.79(d,
Jc, F ＝1.7Hz),140.46,140.05(d,Jc, F ＝5.9Hz),139.99,132.98,
132.90,132.79(d,Jc, F ＝7.9Hz),131.28,130.17,130.08,129.52,128.71,125.79,125.52,114.23(d,Jc, F ＝23.2Hz),114.02(d,Jc, F ＝22.4Hz),50.73,46.62,40.75,32.64,31.09。
Polymerization examples
Solvent, polymeric grade toluene and/or isohexane are supplied from ExxonMobil Chemical Company and purified by passing through a series of columns: two 500cm from Labclear (Oakland, california) 3 OxyClear series column, then packed with dryTwo 500cm molecular sieves (8-12 mesh; aldrich Chemical Company) 3 Tandem column, and packed with dry +.>Two 500cm molecular sieves (8-12 mesh; aldrich Chemical Company) 3 And (5) connecting columns in series.
1-octene (98%) (Aldrich Chemical Company) was dried over Na-K alloy with stirring overnight and then filtered through Basic alumina (Aldrich Chemical Company, brockman Basic 1). Tri (n-octyl) aluminum (TNOA) was purchased from Aldrich Chemical Company or Akzo Nobel and used as received.
The polymer grade ethylene is further purified by passing it through a series of columns: 500cm from Labclear (Oakland, california) 3 Oxyclear cylinder, then filled with dry500cm of molecular sieve (8-12 meshes; aldrich Chemical Company) 3 Column, and filled with dry +.>5 of molecular sieves (8-12 mesh; aldrich Chemical Company) 00cm 3 And (5) a column.
The polymerization grade propylene is further purified by passing it through a series of columns: 2,250cm from Labclear 3 Oxyclear cylinder then filled with2,250cm of molecular sieve (8-12 meshes; aldrich Chemical Company) 3 The column is then filled with +.>Two tandem 500cm molecular sieves (8 mesh-12 mesh; aldrich Chemical Company) 3 Column, 500cm filled with Selexsorb CD (BASF) 3 Column, finally 500cm filled with Selexsorb COS (BASF) 3 And (5) a column.
Methylaluminoxane (MAO) was purchased from Albemarle Corporation as 10wt% in toluene. N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was purchased from Albemarle Corporation. All the complex and activator were added to the reactor as a dilute solution in toluene. The concentrations of the solutions of activator, scavenger and complex added to the reactor were selected such that 40 microliters-200 microliters of solution was added to the reactor to ensure accurate delivery.
Reactor description and preparation
In an inert atmosphere (N) 2 ) Polymerization was carried out in a drying oven using an autoclave equipped with external heaters for temperature control, glass inserts (for C 2 And C 2 /C 8 Test, internal volume of reactor = 23.5mL; for C 3 Experiment, 22.5 mL), septum inlet, regulated supply of nitrogen, ethylene and propylene, and equipped with a disposable polyetheretherketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110 ℃ or 115 ℃ for 5 hours, followed by purging at 25 ℃ for 5 hours.
Ethylene Polymerization (PE) or ethylene/1-octene copolymerization (EO)
The reactor was prepared as described above and then purged with ethylene. Toluene (solvent) was added via syringe at room temperature and atmospheric pressureUnless otherwise indicated), optionally 1-octene (0.1 mL in use), and optionally MAO. The reactor was then brought to the process temperature (typically 80 ℃) and ethylene was added to the process pressure (typically 75psig = 618.5kPa or 200psig = 1480.3 kPa) while stirring at 800 rpm. An optional scavenger solution (e.g., TNOA in isohexane) is then added to the reactor via an injector under process conditions. An optional solution of a non-coordinating activator (e.g., N-dimethylanilinium tetrakis (pentafluorophenyl) borate) is added to the reactor via an injector under process conditions, and then a procatalyst (i.e., complex or catalyst) solution (in toluene) is added to the reactor via an injector under process conditions. Ethylene was admitted to the autoclave (via the use of a computer controlled solenoid valve) during polymerization to maintain reactor gauge pressure (+/-2 psi). The reactor temperature is monitored and typically maintained within +/-1 ℃. By adding about 50psi O to the autoclave 2 /Ar(5mol％O 2 ) The gas mixture was stopped for about 30 seconds. The polymerization is quenched after a predetermined cumulative amount of ethylene has been added or for a polymerization time of at most 30 minutes. The reactor was cooled and vented. The polymer was isolated after removal of the solvent in vacuo. The reported yields include the total weight of polymer and residual catalyst. Catalyst activity is reported as grams of polymer/mmol transition metal compound/hour reaction time (g/mmol/hr).
Propylene polymerization
The reactor was prepared as described above, then heated to 40 ℃ and purged with propylene gas at atmospheric pressure. Toluene (solvent, unless otherwise indicated), optionally MAO, and liquid propylene (1.0 mL) were added via syringe. The reactor was then heated to the process temperature (70 ℃ C. Or 100 ℃ C.) while stirring at 800 rpm. An optional scavenger solution (e.g., TNOA in isohexane) is then added to the reactor via an injector under process conditions. An optional solution of a non-coordinating activator (e.g., N-dimethylanilinium tetrakis (pentafluorophenyl) borate) is then added to the reactor via an injector under process conditions, and a procatalyst (i.e., complex or catalyst) solution (in toluene) is then added to the reactor via an injector under process conditions. Monitoring deviceThe reactor temperature was measured and typically maintained within +/-1 ℃. By adding about 50psiO to the autoclave 2 /Ar(5mol％O 2 ) The gas mixture was stopped for about 30 seconds. The polymerization is quenched based on a predetermined pressure loss of about 8psi or a polymerization time of up to 30 minutes. The reactor was cooled and vented. The polymer was isolated after removal of the solvent in vacuo. The reported yields include the total weight of polymer and residual catalyst. Catalyst activity is typically reported as grams of polymer/mmol transition metal compound/hour reaction time (g/mmol/hr).
Polymer characterization
For analytical experiments, a polymer sample solution was prepared by dissolving the polymer in 1,2, 4-trichlorobenzene (TCB, 99+%, purity from Sigma-Aldrich) containing 2, 6-di-tert-butyl-4-methylphenol (BHT, 99%, from Aldrich) at 165 ℃ for about 3 hours in an oscillating oven. Typical concentrations of polymer in solution are 0.1 to 0.9mg/mL, with BHT concentrations of 1.25mg BHT/mL TCB. The sample was cooled to 135 ℃ for testing.
Such as those described in U.S. Pat. nos. 6,491,816;6,491,823;6,475,391;6,461,515;6,436,292;6,406,632;6,175,409;6,454,947;6,260,407 and 6,294,388 (each of which is incorporated herein by reference) are incorporated herein by reference. Molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (mwd=mw/Mn), which is sometimes also referred to as Polydispersity (PDI) of the polymer, were measured by gel permeation chromatography using Symyx Technology GPC equipped with an evaporative light scattering detector and calibrated using polystyrene standard samples (Polymer Laboratories: polystyrene calibration kit S-M-10: mp (peak Mw) between 5,000 and 3,390,000). Three series Polymer Laboratories were used: PLgel 10 μm Mixed-B300X 7.5mm column samples (250. Mu.L polymer in TCB solution was injected into the system) were tested at an eluent flow rate of 2.0 mL/min (135℃sample temperature, 165℃oven/column). Column extension correction (spreading correction) correction is not employed. Using materials available from Symyx Technologies The software or Automation Studio software available from freeboard. The molecular weight obtained was relative to a linear polystyrene standard.
Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point of the polymer. The samples were pre-annealed at 220 ℃ for 15 minutes and then allowed to cool to room temperature overnight. The sample was then heated to 220 ℃ at a rate of 100 ℃/min and then cooled at a rate of 50 ℃/min. The melting point was collected during the heating phase.
Table 1 shows the ethylene polymerization results obtained using catalyst complexes 1 to 21 and 23 to 27. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 1.1 eq, 75psig ethylene, al (N-octyl) 3 =500 nmol, temperature=80 ℃, total volume=5 mL.
TABLE 1 polymerization of ethylene
Table 1 (subsequent)
Table 2 shows the ethylene-octene copolymerization results obtained using catalysts 1 to 21 and 23 to 27. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 27.5nmol,0.1ml octene, al (N-octyl) 3 =500 nmol, temperature=80 ℃, total volume=5 mL, ethylene=75 psi.
TABLE 2 ethylene-octene copolymer
Table 2 (subsequent)
Table 3 shows the ethylene-octene copolymerization results obtained using catalysts 1 to 21 and 23 to 27. General conditions: catalyst complex = 25nmol, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 27.5nmol,0.1ml octene, al (N-octyl) 3 =500 nmol, temperature=80 ℃, total volume=5 mL, ethylene=200 psi.
TABLE 3 ethylene-octene copolymer
Table 3 (subsequent)
Table 4 shows the propylene polymerization results obtained for catalysts 1 to 28. General conditions: catalyst complex=15 nmol (with the exception of 25nmol for catalyst 26 and 20nmol for catalysts 22 and 28), N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator=1.1 molar equivalents relative to the catalyst complex, propylene=1 ml, al (N-octyl) 3 =500 nmol, total volume=5 ml.
TABLE 4 polymerization of propylene
Table 4 (subsequent)
Table 5 shows the propylene polymerization results obtained for catalysts 1 to 28. General conditions: catalyst complex=15 nmol (exception of catalyst 26 is 25nmol; exception of catalysts 22 and 28 is 20 nmol), N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator=1.1 molar equivalents relative to catalyst complex, propylene=1 ml, al (N-octyl) 3 =500 nmol, total volume=5 ml.
TABLE 5 polymerization of propylene
Table 5 (subsequent)
All documents, including any priority documents and/or test procedures described herein are incorporated by reference to the extent such documents are not inconsistent with this invention. It will be apparent from the foregoing summary and the specific embodiments that, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the present invention is not intended to be so limited. Likewise, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a composition, element, or group of elements is in front of the transitional term "comprising," it is to be understood that the transitional term "consisting essentially of," consisting of, "" selected from, "or" being the same composition or group of elements in front of the recited composition, element, or elements, and vice versa is also contemplated.

Claims (27)

1. A polymerization catalyst compound represented by formula (II):
wherein:
m is a group 3, 4, 5 or 6 transition metal or lanthanide;
e and E' are each O;
each L is independently a lewis base selected from the group consisting of ethers, thioethers, amines, nitriles, imines, pyridines, halogenated hydrocarbons, and phosphines;
each X is independently an anionic ligand;
n is 1, 2 or 3;
m is 0, 1 or 2;
n+m is not more than 4;
R 1 and R is 1' Independent and independentGround is C 4 -C 40 A tertiary hydrocarbyl group;
R 2 、R 3 、R 4 、R 2' 、R 3' and R is 4' Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 1 And R is 2 、R 2 And R is 3 、R 3 And R is 4 、R 1' And R is 2' 、R 2' And R is 3' 、R 3' And R is 4' Optionally joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and substituents on the rings optionally joined to form additional rings; any two L groups are optionally joined together to form a bidentate lewis base;
the X group optionally bonds with the L group to form a monoanionic bidentate group;
any two X groups are optionally joined together to form a dianionic ligand group;
R 5 、R 6 、R 7 、R 8 、R 5' 、R 6' 、R 7' 、R 8' 、R 10 、R 11 and R is 12 Each of which is independently hydrogen, C 1 -C 40 Hydrocarbon radicals, C 1 -C 40 Substituted hydrocarbon radicals, hetero atoms or hetero atom-containing radicals, or R 5 And R is 6 、R 6 And R is 7 、R 7 And R is 8 、R 5' And R is 6' 、R 6' And R is 7' 、R 7' And R is 8' 、R 10 And R is 11 Or R is 11 And R is 12 Optionally joined to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocycles, or unsubstituted heterocycles each having 5, 6, 7, or 8 ring atoms, and wherein substituents on the rings optionally join to form additional rings.
2. The catalyst compound of claim 1, wherein M is Hf, zr, or Ti.
3. The catalyst compound of claim 1 wherein R 1 And R is 1' Independently C 4 -C 40 Cyclic tertiary hydrocarbyl groups.
4. The catalyst compound of claim 1 wherein R 1 And R is 1' Independently C 4 -C 40 Polycyclic tertiary hydrocarbon groups.
5. The catalyst compound of any one of claims 1-4, wherein each X is independently selected from the group consisting of: substituted or unsubstituted hydrocarbyl groups containing 1 to 20 carbon atoms, hydrogen groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halogen groups, and combinations thereof, wherein two X optionally form part of a fused ring or ring system.
6. The catalyst compound of any one of claims 1-4, wherein each L is independently selected from the group consisting of: ethers, thioethers, amines, phosphines, pyridines, and combinations thereof.
7. The catalyst compound of claim 6, wherein each L is independently selected from the group consisting of: diethyl ether, tetrahydrofuran, dimethyl sulfide, triethylamine, and combinations thereof.
8. The catalyst compound of claim 6, wherein two or more L form a fused ring or part of a ring system.
9. The catalyst compound of claim 1 wherein M is Zr or Hf, E and E' are both oxygen, R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl groups.
10. The catalyst compound of claim 1 wherein M is Zr or Hf, E and E' are both oxygen, R 1 And R is 1' Are both adamantan-1-yl or substituted adamantan-1-yl.
11.The catalyst compound of claim 1 wherein M is Zr or Hf, E and E' are both oxygen, R 1 、R 1' 、R 3 And R is 3' Is adamantan-1-yl or substituted adamantan-1-yl.
12. The catalyst compound of claim 1 wherein M is Zr or Hf, E and E' are both oxygen, R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl, R 7 And R is 7' Are all C 1 -C 20 An alkyl group.
13. The catalyst compound of claim 1 wherein M is Zr or Hf, E and E' are both O, R 1 And R is 1' Are all C 4 -C 20 Cyclic tertiary alkyl, R 7 And R is 7' Are all C 1 -C 3 An alkyl group.
14. The catalyst compound of claim 1, wherein the catalyst compound is represented by one or more of the following formulas:
15. a catalyst system comprising an activator and the catalyst compound of any one of claims 1-14.
16. The catalyst system of claim 15, wherein the activator comprises an alumoxane or a non-coordinating anion.
17. The catalyst system of claim 15, wherein the activator is soluble in a non-aromatic hydrocarbon solvent.
18. The catalyst system of claim 15, wherein the catalyst system is free of aromatic solvents.
19. The catalyst system of claim 15, wherein the activator is represented by the formula:
(Z) d + (A d- )
Wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; h is hydrogen; (L-H) + Is a Bronsted acid; a is that d- Is a non-coordinating anion having a charge d-; d is an integer from 1 to 3.
20. The catalyst system of claim 15, wherein the activator is represented by the formula:
[R 1′ R 2′ R 3′ EH] d+ [Mt k+ Q n ] d- (V)
wherein:
e is nitrogen or phosphorus;
d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6; n-k=d;
R 1′ 、R 2′ and R is 3′ Independently C optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups 1 -C 50 A hydrocarbon group,
wherein R is 1′ 、R 2′ And R is 3′ Together comprising 15 or more carbon atoms;
mt is an element selected from group 13 of the periodic table; and
each Q is independently hydrogen, a bridged or unbridged dialkylamido, halo, alkoxy, aryloxy, hydrocarbyl, or substituted hydrocarbyl.
21. The catalyst system of claim 20, wherein each Q is independently a halogenated hydrocarbon group or a substituted halogenated hydrocarbon group.
22. The catalyst system of claim 15, wherein the activator is represented by the formula:
(Z) d + (A d- )
wherein A is d- Is a non-coordinating anion having a charge d-; d is an integer from 1 to 3, (Z) d + Represented by one or more of the following formulas:
23. the catalyst system of claim 15, wherein the activator is one or more of the following:
N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (pentafluorophenyl) borate,
N-methyl-4-nonadecyl-N-octadecyl-anilinium tetrakis (perfluoronaphthyl) borate,
dioctadecyl methyl ammonium tetrakis (pentafluorophenyl) borate,
dioctadecyl methyl ammonium tetra (perfluoronaphthyl) borate,
n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
Triphenylcarbon tetrakis (pentafluorophenyl) borate
Trimethyl ammonium tetrakis (perfluoronaphthyl) borate,
triethylammonium tetrakis (perfluoronaphthyl) borate,
tripropylammonium tetrakis (perfluoronaphthyl) borate,
tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate,
tri (tert-butyl) ammonium tetrakis (perfluoronaphthyl) borate,
n, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate,
n, N-diethylanilinium tetrakis (perfluoronaphthyl) borate,
n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (perfluoronaphthyl) borate),
tetra (perfluoronaphthyl) boronic acid
Triphenylcarbon tetrakis (perfluoronaphthyl) borate，
Triphenylphosphine tetrakis (perfluoronaphthyl) borate，
Triethylsilane tetra (perfluoronaphthyl) borate，
Benzene tetra (perfluoronaphthyl) borate (diazonium))，
Trimethyl ammonium tetrakis (perfluorobiphenyl) borate,
triethylammonium tetrakis (perfluorobiphenyl) borate,
tripropylammonium tetrakis (perfluorobiphenyl) borate,
tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate,
Tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate,
n, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate,
n, N-diethylanilinium tetrakis (perfluorobiphenyl) borate,
n, N-dimethyl- (2, 4, 6-trimethyl) tetrakis (perfluorobiphenyl) borateAnilinium), tetrakis (perfluorobiphenyl) borate，
Triphenylcarbon tetrakis (perfluorobiphenyl) borate，
Triphenylphosphine tetrakis (perfluorobiphenyl) borate，
Triethylsilane tetra (perfluorobiphenyl) borate，
Benzene tetra (perfluorobiphenyl) borate (diazonium)，
[ 4-tert-butyl-PhNMe 2H ] [ C6F3 (C6F 5) 2) 4B ],
the preparation method comprises the steps of carrying out trimethyl ammonium tetraphenyl borate,
triethylammonium tetraphenylborate, which is prepared from a mixture of water and a solvent,
tripropylammonium tetraphenylborate is used as a catalyst,
tri (n-butyl) ammonium tetraphenylborate,
tri (tert-butyl) ammonium tetraphenyl borate,
tetraphenylboronic acid N, N-dimethylanilinium,
tetraphenylboronic acid N, N-diethylanilinium,
tetraphenylboronic acid N, N-dimethyl- (2, 4, 6-trimethylanilinium), tetraphenylboronic acid，
Triphenylcarbon tetraphenyl borate，
Tetraphenylboronic acid triphenylphosphine，
Triethylsilane tetraphenylborate，
Tetraphenylboronic acid benzene (diazonium))，
Trimethyl ammonium tetrakis (pentafluorophenyl) borate,
triethylammonium tetrakis (pentafluorophenyl) borate,
tripropylammonium tetrakis (pentafluorophenyl) borate,
tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,
Tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate,
n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
n, N-diethylanilinium tetrakis (pentafluorophenyl) borate,
n, N-dimethyl- (2, 4, 6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate，
Triphenylcarbon tetrakis (pentafluorophenyl) borate，
Triphenylphosphine tetrakis (pentafluorophenyl) borate，
Triethylsilane tetra (pentafluorophenyl) borate，
Benzene tetra (pentafluorophenyl) borate (diazonium)，
Trimethyl ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
triethylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
tripropylammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
tri (n-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
dimethyl (tert-butyl) ammonium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
n, N-dimethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
n, N-diethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate,
n, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (2, 3,4, 6-tetrafluorophenyl) borate),
tetrakis (2, 3,4, 6-tetrafluorophenyl) borate，
Triphenylcarbon tetrakis (2, 3,4, 6-tetrafluorophenyl) borate，
Triphenylphosphine tetrakis (2, 3,4, 6-tetrafluorophenyl) borate，
Triethylsilane tetrakis (2, 3,4, 6-tetrafluorophenyl) borate，
Benzene tetrakis (2, 3,4, 6-tetrafluorophenyl) borate (diazonium)，
Trimethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
Triethylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
tripropylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
tri (n-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
Tri (tert-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
n, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
N, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate,
N, N-dimethyl- (2, 4, 6-trimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate，
Triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate，
Triphenylphosphine tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate，
Triethylsilane tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate，
Benzene tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (diazonium)，
Di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate,
dicyclohexylammonium tetrakis (pentafluorophenyl) borate,
tris (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate，
Tris (2, 6-dimethylphenyl) phosphorus tetrakis (pentafluorophenyl) borate，
Triphenylcarbon tetrakis (perfluorophenyl) borate，
1- (4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluorophenyl) pyrrolidine，
A tetrakis (pentafluorophenyl) borate salt, and a method of preparing the same,
4- (tris (pentafluorophenyl) boronic acid) -2,3,5, 6-tetrafluoropyridine, and
Triphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate。
24. A process for polymerizing olefins comprising contacting one or more olefins with the catalyst system of any of claims 15-23.
25. The process of claim 24, wherein the process is carried out at a temperature of from 0 ℃ to 300 ℃, at a pressure of from 0.35MPa to 10 MPa and for a time of up to 300 minutes.
26. The method of claim 24, further comprising obtaining a polymer.
27. The process of claim 24 wherein the olefin comprises one or more substituted or unsubstitutedC 2 -C 40 Alpha-olefins.
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