CN106008365A - Synthetic method for styrene functional monomer molecular containing supramolecular quadruple hydrogen bonding structure - Google Patents
Synthetic method for styrene functional monomer molecular containing supramolecular quadruple hydrogen bonding structure Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
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Abstract
The invention relates to a synthetic method for a styrene functional monomer molecular containing a supramolecular quadruple hydrogen bonding structure. The synthetic method adopts a reaction between 2-amino-4-hydroxyl-6-methylpyridine and 3-isopropyl-dmethyl benzyl isocyanate to obtain the styrene functional monomer molecular containing the supramolecular quadruple hydrogen bonding structure. The synthesized styrene functional monomer molecular containing the supramolecular quadruple hydrogen bonding structure structurally contains a terminal double bond containing styrene, so that the functional monomer molecular is high in activity and easy for polymerization, and can be polymerized with a divinyl benzene crosslinking agent to prepare a novel molecularly imprinted polymer. Meanwhile, the styrene functional monomer molecular structurally contains a supramolecular quadruple hydrogen bonding unit adopting a self-complementary structure, and generation of non-specific recognition sites can be reduced. As the styrene functional monomer molecular structurally contains the ureido-pyrimidinone supramolecular quadruple hydrogen bonding unit and can form a multi-hydrogen-bond structure with high multi-site binding constant together with template molecules, the template molecule recognition efficiency and the molecular imprinting effect can be remarkably improved. The synthetic method is simple to operate, short in reaction time and simple in aftertreatment.
Description
Technical field
The present invention relates to the synthetic method of a kind of phenylethylene function monomer molecule containing supermolecule Quadrupolar hydrogen bond structure.
Background technology
Rodebush and Latimer proposes the related notion of hydrogen bond first in the twenties in 20th century, and Pauling is subsequently at " The
Nature of the Chemical Bond " hydrogen bond was also done definition by book, within 2011, IUPAC gives and redefines: hydrogen
Key is exactly the attraction being bonded between hydrogen atom and another one atom or the atomic group on a molecule or molecular fragment X-H be formed
Power, have intermolecular hydrogen bonding and intramolecular hydrogen bond point, the electronegativity of its X is stronger than hydrogen atom.It is represented by X-H ... Y-Z, "
... " it is hydrogen bond.X is hydrogen bond donor (Hydrogen bond donor is called for short D), and Y is hydrogen bond receptor (Hydrogen bond
Acceptor, is called for short A).
The interaction of hydrogen bond is widely present in identification and the DNA double helical structure of protein-based enzyme, and hydrogen bond is according to multiplicity
Difference, be divided into substance hydrogen bond, two deuterium bonds, three deuterium bonds, Quadrupolar hydrogen bond and multiple hydrogen bonding.The intensity phase of single hydrogen bond
To relatively low, bond energy is the highest, and is affected greatly by solvent polarity, thus bad by single hydrogen bonded system stability.But it is triple
Hydrogen bond and Quadrupolar hydrogen bond have stronger adhesion, selectivity and directivity, and the hydrogen bond type supermolecule polymer formed generally has
There are dibit point or many sites construction unit, are the most promising construction unit constructing and designing supramolecular materials.
Supramolecular chemistry (supramolecular chemistry) refers to pass through non-co-with small molecule monomer or low polymer
Valence link effect (such as hydrogen bond, Van der Waals force, hydrophilic/hydrophobic, dipole/dipolar interaction, metallic ion coordination etc.) self assembly and
The high molecular polymer formed.Wherein hydrogen bond, especially multiple hydrogen bonding be prepare the optimal non-covalent bond of supermolecule polymer it
One, it has higher binding constants, good bonding reversibility, it is even more important that its bonding mode has the side of height
Tropism, this also makes the supermolecule polymer constructed with multiple hydrogen bonding have more preferable controllability and response, can be used to design
Intellectual material and self-repair material.
In the research process to supramolecular polymer material, scientist Meijer seminar of Holland in exploitation in 1997 based on
The supermolecule polymer of 2-urea-4 [1H]-pyrimidone (UPy) Quadrupolar hydrogen bond effect has landmark meaning.UPy system is certainly
Cumulative power is strong, and the dimerization of self-complementary has the highest binding constant (Kdim>107M-1In chloroform), its synthetic route letter
Single, raw material is easy to get, and these advantages ensure that the supermolecule polymer of formation not only has various functional characteristic, has preferably simultaneously
Mechanical strength, creep-resistant property and the high degree of polymerization, possess potential using value.Meijer teaches seminar and utilizes UPy
The synergism of Quadrupolar hydrogen bond and other noncovalent force has constructed the supermolecule polymer of series multifunctional,
[Science1997,278,1601-1604；Angew.Chem,Int,Ed.2006,45,2072-2076；Chem.Soc.2008,13
0,13755-13764], Meijer seminar utilizes UPy that polyethylene butadiene two ends carry out sense dough to obtain two teeth and gather
Monomer adduct, this monomer is at room temperature viscous liquid, but the dimerization reaction of UPy can make polymer monomer carry out being polymerized shape
Becoming the supermolecule polymer elastomer of high molecular, the supramolecular polymer material being newly formed combines the mechanicalness of traditional polymer
Matter and low viscous character, at high temperature, UPy dimer can be dissociated, and this elastomeric material becomes polymer monomer simultaneously
Working fluid state [Mater.Today 2004,7,34-39].
Hummelen etc. report [Angew.Chem.Int.Ed.2002,41,838-840] double uride pyrimidone UPy function
There is the micromolecular compound of a fullerene unit centre changed, and the fowler that be can be obtained by hydrogen bond connection by method of spin coating is dilute
Evenly distributed thin film.Vancso etc. report [Langmuir 2003,19,8618-8621] by gold surface Quadrupolar hydrogen bond uride
Pyrimidone UPy unit is modified, by the self-identifying effect of Quadrupolar hydrogen bond by non-covalent for the UPy derivant containing different function units
It is bonded to gold surface, utilizes the polymerization constant of the hydrogen bond dimerization of UPy that temperature and solvent are had response, by changing system
Temperature or solvent species, realize the adsorbate of reversible change gold surface outside guest molecule quantity and bonding merit
The stability of energy unit, and then gold surface character is modified.
Zhibin Guan etc. reports the UPy multiple hydrogen bonding system that utilizes, and processing machinery performance has the bionical oversubscription of adaptive ability
Sub-polymer；Every pair of UPy molecule is covalently bound by short alkyl chain, forms the ring of Guan Bi.When by external force, first stress make
The Quadrupolar hydrogen bond of UPy is opened, and in Guan Bi Molecular Ring, the alkyl chain of curling stretches therewith.After strain reaches to a certain degree, alkyl
Chain is fully deployed, and the stress site of whole material system is changed into covalent cross-linking site by hydrogen bond crosslinks site, thus is that material exists
Extra mechanical strength is provided under Large strain state.The mechanical behavior of this material and titin (titin) in skeletal muscle
Mechanical behavior is similar.[J.Am.Chem.Soc.,2007,129:14110-14111.J.Am.Chem.Soc.,2009,
131:8766-8768.Angew.Chem.Int.Ed.,2011,50:9026-9057]。
Along with the development of supramolecular chemistry, the understanding of noncovalent intermolecular interactions power is gradually deepened by people, and about non-
The research of the molecularly imprinted polymer of covalent bond effect also penetrates into the every field of chemical research, setting from molecularly imprinted polymer
The angle of meter is set out, and has higher selectivity and separating power by the molecularly imprinted polymer prepared by non-covalent bond effect, because of
Simple for this mode, it is easy to remove template molecule, obtain the very big concern of people.
Ivanov etc. report [Anal.Chem., 2003,75:5306-5316] by styrene and the thermal induction of divinylbenzene
In-situ copolymerization closes reaction and is prepared for the nanotube capillaries integral post of 200 μm (i.d), in liquid chromatograph one electron spray ion trap one matter
Trypsin digestion solution is analyzed under spectrum (LC mono-ESI mono-MS) pattern, under polyreaction and flowing phase optimal condition, isolated polypeptide
The post effect of mixture reaches 100,000p.m-1.Zhang etc. [Advanced Materials, 2007,19 (17): 2370-
2374] by surface aggregate method with trinitrotoluene as template molecule, nucleocapsid structure is prepared on the surface of polystyrene nanoparticle
After, obtain hollow molecules trace microsphere after removing polystyrene core with dichloromethane, and it is permissible to report prepared hollow structure
Improve the rate of adsorption of molecular engram material.
In the preparation process of molecularly imprinted polymer (Molecularly Imprinted Polymers, MIP), template is divided
The polymerizing conditions such as the consumption of son, function monomer, cross-linking agent and solvent (porogen) produce weight to prepared high recognition performance MIPs
Affect.Therefore appropriate reaction reagent and suitable reaction condition, current function monomer and friendship must be selected preparing MIPs
The range of choice of connection agent etc. also has certain limitation, and the especially kind of function monomer is relatively fewer, it is impossible to meet some specific
The demand of stay in place form molecule, the technology of preparing of novel functional monomer and cross-linking agent etc. awaits researching and developing further, to improve
The identification ability of molecularly imprinted polymer, increase binding capacity and reduce non-specific identification.Commonly used prepares non-covalent type print
The function monomer of mark polymer includes: 4-vinylpridine (4-VP) and 2-vinylpyridine (2-VP), methacrylic acid (MAA)
, acrylamide (AM), these function monomer molecules the molecularly imprinted polymer prepared, it is possible to achieve identify, the function such as separation
But, report and can not meet the template molecule of increasing configurations with commonly used function monomer kind, and current
Apply the representational function monomer reported before the function monomer of molecularly imprinted polymer design and preparation is mostly.
Chinese patent (patent No.: 201511002002) is with methacrylic acid as function monomer, and orthene is template molecule
Aggregate into molecularly imprinted polymer, can be used for enrichment/separation that the organophosphorus pesticide orthene in water environment remains.
Chinese patent (patent No.: 201511014966) is with α-methacrylic acid as function monomer, and promazine Sulfometuron Methyl is that template is divided
Son aggregates into the molecular engram solid phase extraction material that promazine Sulfometuron Methyl is special.
Chinese patent (patent No.: 201610053190) is with 4-vinylpridine as function monomer, and 18 β-enoxolone is mould
Plate molecule, cobalt acetate is that the molecularly imprinted polymer solid-phase extraction column of metal bridging agent polymerization is for separating and be enriched with 18 β-Radix Glycyrrhizae
The application of subacid.
Inquiry in State Intellectual Property Office of the People's Republic of China (SIPO): the patent containing " molecular engram " key word has 1689
Data, the patent containing " molecularly imprinted polymer " key word has 1025 data, containing " vinylpyridine, molecular engram "
The patent of key word has 257 data, and the patent containing " acrylamide, molecular engram " key word has 533, containing " methyl-prop
Olefin(e) acid, molecular engram " patent of key word has 1041 data, sums up by carrying out these patents sorting out: vinyl
The function monomer that pyridine, acrylamide, methacrylic acid these three are commonly used almost covers most application of molecular engram.
In recent years, oneself has been constructed number of types of supermolecule polymer to utilize Quadrupolar hydrogen bond uride pyrimidone UPy unit, but by UPy
This supermolecule Quadrupolar hydrogen bond construction unit, by the method for organic synthesis, is embedded in function of molecular engram monomer molecule and obtains
The relatively strong hydrogen bonding effect of many sites can either be formed with template molecule, there is again the styrene molecules with double bond and be prone to polymerization, formed
The novel structure of cross linked polymer, there is not been reported.
The feature that the function monomer molecule of Synthesis of Molecular Imprinting Polymers is most basic with requirement is exactly: should be containing polymerisable double
Key, has the functional group that can be used for identifying again, and the active force between function monomer and template molecule wants suitable.The most non-covalent
Substance Hyarogen-bonding is passed through in molecular engram polymerization prepared by key active force between template molecule and function monomer little, gathering of formation
Compound is unstable, and between template molecule and function monomer, nonspecific action is many.Research find: the dimerization of function monomer molecule and
Self aggregation effect can effectively reduce the non-specific recognition site during molecular engram, and uride pyrimidone UPy group self
The dimerization that Quadrupolar hydrogen bond interacts can be formed, therefore can effectively reduce the non-specific identification during molecular engram
The quantity in site, meanwhile, and bonding force is very strong, and meanwhile, this supermolecule Quadrupolar hydrogen bond structure of UPy contains multiple hydrogen bonded position
Point, higher with the active force of template molecule, it is to prepare the construction unit that novel molecular engram polymer is ideal.
Summary of the invention
Present invention aim at, in order to solve molecularly imprinted polymer can the limitednumber of function monomer molecule, molecular engram
During produce substantial amounts of nonspecific recognition site, the problem that identification selection is the highest, it is provided that containing supermolecule Quadrupolar hydrogen bond tie
The synthetic method of the phenylethylene function monomer molecule of structure, the method uses 2-amino-4-hydroxy-6-picoline and 3-isopropyl
Base-dimethyl benzyl isocyanate reaction, by obtaining containing supermolecule four heavy hydrogen the optimization of reaction dissolvent and response time
The phenylethylene function monomer of bond structure.The phenylethylene function monomer containing supermolecule Quadrupolar hydrogen bond structure synthesized by the present invention divides
Son, containing styrene end double bond in its structure so that function monomer molecular activity is high, it is easy to polymerization, can be with divinylbenzene
Novel molecular engram polymer is prepared in the cross-linking agent polymerization of class, contains the oversubscription that can be formed from complementary structure in molecular structure simultaneously
Sub-Quadrupolar hydrogen bond unit, it is possible to reduce the generation of non-specific recognition site.Containing urea groups pyrimidone UPy oversubscription in molecular structure
Sub-Quadrupolar hydrogen bond construction unit, can form many sites binding constant much higher deuterium bond structure with template molecule, can significantly improve
Recognition efficiency and the effect of molecular engram to template molecule, uses the function monomer molecule of the method for the invention to prepare novel
Molecularly imprinted polymer, has good using value in separation field and new function material.The method of the invention operation letter
Single, the response time is short, and post processing is simple.
The synthetic method of a kind of phenylethylene function monomer molecule containing supermolecule Quadrupolar hydrogen bond structure of the present invention, the method
Follow these steps to carry out:
A, under nitrogen protection, 2-amino-4-hydroxy-6-picoline in molar ratio: 3-isopropyl-dimethyl benzyl Carbimide.
Ester=1:1-3 weighs respectively, joins in three neck round bottom flask, reacts temperature 100 DEG C, and the time is 16-22h；
Or under nitrogen protection, 2-amino-4-hydroxy-6-picoline in molar ratio: 3-isopropyl-dimethyl benzyl isocyanate
=1:1-3 weighs respectively, is dissolved in dimethyl sulphoxide solution by 2-amino-4-hydroxy-6-picoline, then heats to
160-170 DEG C, then 3-isopropyl-dimethyl benzyl isocyanate is joined in reactant liquor, carry out temperature 160 DEG C-170 DEG C
Reaction, the time is 5min-1h；
B, step a obtained reaction system carry out isolated and purified: when reactionless solvent, reactant liquor is naturally cooled to room temperature,
With i.e. obtaining white solid, by the chloroform of white solid 1:2 by volume: acetone recrystallization, vacuum drying, i.e. obtain white solid
The phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of body；
When the dimethyl sulfoxide being maybe dried when use is reaction dissolvent, reactant liquor is naturally cooled to room temperature, pours in frozen water, have
White solid separates out, sucking filtration, collects filter cake and obtains white solid, is washed by white solid dichloromethane, vacuum drying, i.e.
Obtain the phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of white solid.
The synthetic method of a kind of phenylethylene function monomer molecule containing supermolecule Quadrupolar hydrogen bond structure of the present invention, the method
Reaction equation is:
The synthetic method of a kind of phenylethylene function monomer molecule containing supermolecule Quadrupolar hydrogen bond structure of the present invention, the method
Compared with prior art it has the beneficial effect that the method for the present invention is simple to operate, and the response time is short, and post processing is simple, the present invention
The advantage of the synthesized phenylethylene function monomer molecule containing supermolecule Quadrupolar hydrogen bond structure is: 1, containing benzene second in molecular structure
The terminal double bond of alkene so that function monomer molecular activity is high, it is easy to polymerization, can be polymerized preparation with the cross-linking agent of divinylbenzene class
Novel molecular engram polymer.2, molecular structure contains the supermolecule Quadrupolar hydrogen bond unit that can be formed from complementary structure simultaneously,
The generation of non-specific recognition site can be reduced.3, containing UPy supermolecule Quadrupolar hydrogen bond construction unit in molecular structure, can
To form many sites binding constant much higher deuterium bond structure with template molecule, can significantly improve the recognition efficiency to template molecule and
The effect of molecular engram, the phenylethylene function monomer containing supermolecule Quadrupolar hydrogen bond structure using the method for the invention to obtain divides
Prepare novel molecular engram polymer, isolation technics and new function material have good using value.
Accompanying drawing explanation
Fig. 1 is the present invention's1H NMR (nucleus magnetic hydrogen spectrum) figure；
Fig. 2 is the present invention13C NMR (nuclear-magnetism carbon spectrum) figure；
Fig. 3 is MS of the present invention (mass spectrum) figure.
Detailed description of the invention
Below in conjunction with executing example, the present invention is described in detail:
Embodiment 1
A, under nitrogen protection, by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg) and 3-isopropyl-diformazan
Base benzyl isocyanate ester (1mmol, 201mg) joins in three neck round bottom flask, reacts temperature 100 DEG C, and the time is
16h；
B, step a obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, i.e. obtains white solid,
Chloroform by white solid 1:2 by volume: acetone recrystallization, vacuum drying, i.e. obtain the supermolecule Quadrupolar hydrogen bond of white solid
The phenylethylene function monomer molecule of structure.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Embodiment 2
A, under nitrogen protection, by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg) and 3-isopropyl-diformazan
Base benzyl isocyanate ester (2mmol, 402mg) joins in three neck round bottom flask, reacts temperature 100 DEG C, the time
For 16h；
B, step a obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, i.e. obtains white solid,
Chloroform by white solid 1:2 by volume: acetone recrystallization, vacuum drying, i.e. obtain the supermolecule Quadrupolar hydrogen bond of white solid
The phenylethylene function monomer molecule of structure.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Embodiment 3
A, under nitrogen protection, by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg) and 3-isopropyl-diformazan
Base benzyl isocyanate ester (3mmol, 603mg) joins in three neck round bottom flask, reacts temperature 100 DEG C, and the time is
16h；
B, step a obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, i.e. obtains white solid,
Chloroform by white solid 1:2 by volume: acetone recrystallization, vacuum drying, i.e. obtain the supermolecule Quadrupolar hydrogen bond of white solid
The phenylethylene function monomer molecule of structure.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Embodiment 4
A, under nitrogen protection, by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg) and 3-isopropyl-diformazan
Base benzyl isocyanate ester (3mmol, 603mg) joins in three neck round bottom flask, reacts temperature 100 DEG C, and the time is
22h；
B, step a obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, i.e. obtains white solid,
Chloroform by white solid 1:2 by volume: acetone recrystallization, vacuum drying, i.e. obtain the supermolecule Quadrupolar hydrogen bond of white solid
The phenylethylene function monomer molecule of structure.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Embodiment 5
A, under nitrogen protection, is dissolved in the diformazan of 6mL by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg)
In base sulfoxide solution, then heat to 160 DEG C, 3-isopropyl-dimethyl benzyl isocyanate (1mmol, 201mg) is added
Entering in reactant liquor, react temperature 160 DEG C, the time is 1h；
B, step a is obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, pours in the frozen water of 10mL
, there is white solid to separate out, sucking filtration, collect filter cake and obtain white solid, white solid dichloromethane is washed, vacuum drying
, i.e. obtain the phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of white solid.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Embodiment 6
A, under nitrogen protection, is dissolved in the diformazan of 6mL by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg)
In base sulfoxide solution, then heat to 165 DEG C, 3-isopropyl-dimethyl benzyl isocyanate (1mmol, 201mg) is added
Entering in reactant liquor, react temperature 165 DEG C, the time is 30min；
B, step a is obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, pours in the frozen water of 10mL
, there is white solid to separate out, sucking filtration, collect filter cake and obtain white solid, white solid dichloromethane is washed, vacuum drying
, i.e. obtain the phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of white solid.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Embodiment 7
A, under nitrogen protection, is dissolved in the diformazan of 6mL by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg)
In base sulfoxide solution, then heat to 170 DEG C, by 3-isopropyl-dimethyl benzyl isocyanate (1.1mmol, 221mg)
Joining in reactant liquor, react temperature 170 DEG C, the time is 10min；
B, step a is obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, pours in the frozen water of 10mL
, there is white solid to separate out, sucking filtration, collect filter cake and obtain white solid, white solid dichloromethane is washed, vacuum drying
, i.e. obtain the phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of white solid.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Embodiment 8
A, under nitrogen protection, is dissolved in the diformazan of 6mL by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg)
In base sulfoxide solution, then heat to 170 DEG C, by 3-isopropyl-dimethyl benzyl isocyanate (1.2mmol, 241mg)
Joining in reactant liquor, react temperature 170 DEG C, the time is 5min；
B, step a is obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, pours in the frozen water of 10mL
, there is white solid to separate out, sucking filtration, collect filter cake and obtain white solid, white solid dichloromethane is washed, vacuum drying
, i.e. obtain the phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of white solid.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Embodiment 9
A, under nitrogen protection, is dissolved in the diformazan of 6mL by 2-amino-4-hydroxy-6-picoline (1mmol, 125mg)
In base sulfoxide solution, then heat to 170 DEG C, by 3-isopropyl-dimethyl benzyl isocyanate (1.3mmol, 261mg)
Joining in reactant liquor, react temperature 170 DEG C, the time is 5min；
B, step a is obtained reaction system carry out isolated and purified: reactant liquor is naturally cooled to room temperature, pours in the frozen water of 10mL
, there is white solid to separate out, sucking filtration, collect filter cake and obtain white solid, white solid dichloromethane is washed, vacuum drying
, i.e. obtain the phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of white solid.
1H NMR(400MHz,CDCl3)δ12.87(s,1H),11.97(s,1H),10.31(s,1H),7.53(s,
1H), 7.38 7.26 (m, 3H), 5.81 (s, 1H), 5.36 (s, 1H), 5.07 (s, 1H), 2.14 (d, J=
9.8Hz,6H),1.75(s,6H).13C NMR(400MHz,CDCl3)δ172.79(s),155.49(s),154.83
(s), 148.11 (s), 147.67 (s), 143.54 (s), 141.13 (s), 128.11 (s), 123.73 (d, J=18.4
Hz),121.83(s),112.37(s),106.84(s),55.76(s),29.73(s),22.09–21.80(m),
18.96(s).MS(ESI):C18H22N4O4M=326.
Claims (1)
1. the phenylethylene function monomer molecule synthesis method containing supermolecule Quadrupolar hydrogen bond structure, it is characterised in that follow these steps to carry out:
A, under nitrogen protection, 2-amino-4-hydroxy-6-picoline in molar ratio: 3-isopropyl-dimethyl benzyl isocyanate=1:1-3 weighs respectively, joins in three neck round bottom flask, reacts temperature 100 DEG C, and the time is 16-22h；
Or under nitrogen protection; 2-amino-4-hydroxy-6-picoline in molar ratio: 3-isopropyl-dimethyl benzyl isocyanate=1:1-3 weighs respectively; 2-amino-4-hydroxy-6-picoline is dissolved in dimethyl sulphoxide solution; then heat to 160-170 DEG C; again 3-isopropyl-dimethyl benzyl isocyanate is joined in reactant liquor; reacting temperature 160 DEG C-170 DEG C, the time is 5min-1h；
B, step a is obtained reaction system carry out isolated and purified: when reactionless solvent, reactant liquor is naturally cooled to room temperature, with i.e. obtaining white solid, chloroform by white solid 1:2 by volume: acetone recrystallization, vacuum drying, i.e. obtains the phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of white solid；
When the dimethyl sulfoxide being maybe dried when use is reaction dissolvent, reactant liquor is naturally cooled to room temperature, pour in frozen water, white solid is had to separate out, sucking filtration, collects filter cake and obtains white solid, washed by white solid dichloromethane, vacuum drying, i.e. obtains the phenylethylene function monomer molecule of the supermolecule Quadrupolar hydrogen bond structure of white solid.
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