CN105797769B - (R) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (phenethyl of 2 hydroxyl 1), preparation method and applications - Google Patents
(R) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (phenethyl of 2 hydroxyl 1), preparation method and applications Download PDFInfo
- Publication number
- CN105797769B CN105797769B CN201610211236.9A CN201610211236A CN105797769B CN 105797769 B CN105797769 B CN 105797769B CN 201610211236 A CN201610211236 A CN 201610211236A CN 105797769 B CN105797769 B CN 105797769B
- Authority
- CN
- China
- Prior art keywords
- hydroxyl
- preparation
- phenethyls
- anderson
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0249—Ureas (R2N-C(=O)-NR2)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/26—Polyhydroxylic alcohols containing only six-membered aromatic rings as cyclic part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/40—Halogenated unsaturated alcohols
- C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of (R) 1 (phenethyl of 2 hydroxyl 1) thiourea modified Mn Anderson types heteropolyacid catalyst, preparation method and applications.The present invention is first by sodium molybdate and TBAB reaction generation [N (C4H9)4]4[α‑Mo8O26], then it is reacted with trihydroxy aminomethane, manganese acetate to obtain organic bilateral amido modified polyoxometallate；Then (R) 1 (phenethyl of 2 hydroxyl 1) isothiocyanic acid is synthesized, then (R) 1 (phenethyl of 2 hydroxyl 1) isothiocyanic acid and organic bilateral amido modified polyoxometallic acid reactant salt are obtained into target heteropolyacid catalyst.The preparation method reaction condition of the present invention is gentle, environment-friendly；Obtained catalyst is applied to the asymmetric dihydroxylation of alkene, and catalytic activity is high, enantioselectivity is high, recoverable, suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, more particularly to asymmetric selective catalysis, specifically a kind of (R)-
Thiourea modified 1- (2- hydroxyl -1- phenethyls) Mn-Anderson types heteropolyacid catalyst, preparation method and applications.
Background technology
Nobel laureate professor Noyori points out within 2001：" following synthesis chemistry must be economic, safety
, chemistry environment-friendly and that save resource and the energy, chemist needed to realize ' perfect reactive chemistry ' and effort,
The product that needs are only generated with 100% selectivity and 100% yield produces without waste ".Chiral catalysis synthesis is made
To realize one of the important channel of " perfection synthesis chemistry ", wherein, chiral catalyst is the most crucial section in chiral catalysis research
Knowledge is inscribed.From reaction principle, chiral organic micromolecule catalysis is by reversible with unstable covalent bond with reaction substrate
If the Viability intermediate of landform or by interaction, such as oxygen key, Van der Waals force or ion equity priming reaction substrate.Homogeneous hand
Property catalysis have the characteristics that efficient, high enantioselectivity and reaction condition are gentle.
Catalysis is most promising and most practical value research direction in polyoxometallate application.Polyoxometallate
Integrate the good characteristic of acid base catalysator, oxidation reduction catalyst, metal oxide nanocatalyst etc. simultaneously, be considered as
It is a kind of widely used green multifunction catalyst.Early in early 20th century, people begin to enter the catalytic performance of polyacid
Research is gone.To being at present, existing 8 polyacid catalysis industry projects are successfully developed.It is catalyzed into in Chemistry of Polyacids one
The eternal research topic of item.After chiral polyoxometallate is successfully synthesized, people have just started chiral polyacid not
The exploration in asymmetric catalytic field.Chiral polyoxometallate integrates the various excellent properties of polyacid and chiral material.Its is only
Special soluble class mineral metal-oxide structure, for chiral transmission in chiral non-origin of life theory and inoganic solids
Exploration provides preferable model；Its high elecrtonegativity, adjustable acid-base property, redox active and nano-scale are more more
Design, the synthesis of the new materials such as function nonlinear optics, nano material, stereoselectivity catalysis and medicine bring new wish
Hope.
Since Zubieta in 1993 et al. exists《Nature》Upper report is successfully prepared similar DNA using hydrothermal technique
Chiral double-stranded compound (Me2NH2)K4[V10O10(H2O)4(OH)4(PO4)7]·H2After O, people have just started chirality
Exploration of the polyacid in asymmetric catalysis field.The Chinese Academy of Sciences chemistry institute Luo Sanzhong teach et al. urged with organic amine small molecules
Agent is made that outstanding work (Organic as the field of catalyst-supporting carriers as counter cation, polyacid
letters,2007,9(18):3675-3678.).They have synthesized a series of secondary amine-tertiary amine-type proline derivative, use
Polyanionic [the PW of highly acid12O40]3-The mineral acid in traditional Acid-Base concerted catalysis is substituted, it is organic to have synthesized a series of chiralitys
Amine-polyacid hybrid material.These materials are all shown to the direct asymmetric Aldol reaction, asymmetric Michael addition reaction etc. of aldehyde ketone
Very high catalytic activity and chiral selectivity.Organic amine small molecules are assembled as counter cation with polyacid by electrostatic interaction,
But these materials do not have clear and definite molecular structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain the association of Chiral Amine and polyacid
Same-action.Dalian materialization institute Duan Chun meet seminar meet using polyoxometallate (POMs) composition, the diversity of structure and
A series of adjustable denaturation of electric charge, porous POMOFs with catalysis of design and assembly, realizes them and is urged in multiphase
Application (Journal of the American Chemical Society, 2013,135 (28) in change:10186-
10189.), but these materials are also without clear and definite molecular structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain MOFs
With POMs synergy.
More than, although one of the important channel of chiral catalysis synthesis as realization " perfection synthesis chemistry ", due to chirality
Organic micromolecule catalyst activity is relatively low, dosage is high and is not easily recycled utilization, and its is fresh to be used for industrialized production less.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide one kind (R) -1- (2- hydroxyl -1- phenethyls) sulphur
The Mn-Anderson types heteropolyacid catalyst of urea modification, preparation method and applications.The preparation method of the present invention is simple, obtains
Heteropolyacid catalyst catalyst activity it is high, dosage is few and is easily recycled.Catalyst is obtained to close available for asymmetry catalysis
Into field.
The present invention innovatively proposes to utilize " Acid-Base " collaboration to urge from the mentality of designing of organic micromolecule catalyst
Change strategy, using the chiral organic micromolecule with potential catalytic activity as precursor, the methods of passing through organic decoration, dexterously
The vacant polyanionic for making organic molecule acid with high Bronsted is combined, and constructs chiral polyacid material, what is obtained is chiral miscellaneous
More acid catalysts not only remain the original structure of polyacid, and have expanded the research field of polyacid, make its catalysis, medicine and
There is potential using value in terms of functional material.In addition, polyacid has hydrophily, available green, cheap water as solvent are carried out
Catalytic reaction, reaction terminate after organic solvent (ethanol, methanol etc.) can be added into system, and polyacid easily separates out, and can be returned
Receive and utilize.
Technical solution of the present invention is specifically described as follows：
The present invention provides one kind (R) -1- (2- hydroxyl -1- phenethyls) thiourea modified Mn-Anderson type heteropoly acids and urged
The preparation method of agent (structure is shown in Fig. 1), synthetic route is as shown in Fig. 2 comprise the following steps that：
1) it is 1 according to mol ratio by sodium molybdate, TBAB：1~2:1 ratio mixing, under concentrated hydrochloric acid effect
Room temperature reaction, obtains parent [N (C4H9)4]4[α-Mo8O26]；
2) by parent obtained above [N (C4H9)4]4[α-Mo8O26] with trihydroxy aminomethane, manganese acetate organic molten
Backflow obtains organic bilateral amido modified Mn-Anderson type polyoxometallates in agent；
3) using D- benzene glycinol as Material synthesis (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanates；
4) by (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanic acids and organic bilateral amido modified Mn-Anderson types
Polyoxometallate is 5 according to mol ratio:1~8:1 ratio mixed dissolution reacts in reaction dissolvent at a temperature of 45-55 DEG C
Obtain the thiourea modified Mn-Anderson type heteropolyacid catalysts of (R) -1- (2- hydroxyl -1- phenethyls).
In the present invention, in step 1), the mol ratio of sodium molybdate and concentrated hydrochloric acid is 1:1~1：2.
In the present invention, in step 2), [N (C4H9)4]4[α-Mo8O26] and trihydroxy aminomethane, the mol ratio of manganese acetate
For 1:(3~4):(1~2).
In the present invention, in step 2), organic solvent is polar non-solute.
In the present invention, in step 2), organic solvent is acetonitrile or 1,2- dichloroethanes.
In the present invention, in step 3), using D- benzene glycinol as Material synthesis (R) -1- (2- hydroxyl -1- phenethyls) different sulphur cyanogen
Acid esters comprises the following steps that：By D- benzene glycinol, CS2With triethylamine with mol ratio 1:(2~4):1 ratio mixing, in room
After warm stirring reaction 1h~2h, di-tert-butyl dicarbonate and DMAP are added under condition of ice bath, after adding, continues to protect
Stirring reaction 3h~5h under condition of ice bath is held, obtains (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanates；Wherein, D- benzene is sweet
The mol ratio of ammonia alcohol, di-tert-butyl dicarbonate and DMAP is 1:1:(0.02~0.05).
In the present invention, in step 4), one or more of the reaction dissolvent in DMF, DMSO or NMP.
In the present invention, in step 4), (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanic acid is obtained with step 2) organic
Bilateral amido modified Mn-Anderson types polyoxometallate is after solvent reaction 2~3 days, if reaction solution is not clarified, application
Syringe filters processing, is obtained placing after clarified solution and is crystallized in ether atmosphere, and crystal is can obtain behind some days, that is, obtains (R) -1-
(2- hydroxyl -1- phenethyls) thiourea modified Mn-Anderson type heteropolyacid catalysts.
The present invention also provides (R) -1- (2- hydroxyl -1- phenethyls) thiocarbamide that a kind of above-mentioned preparation method is prepared and repaiied
The Mn-Anderson type heteropolyacid catalysts of decorations.
The present invention further provides a kind of thiourea modified Mn-Anderson of above-mentioned (R) -1- (2- hydroxyl -1- phenethyls)
Application of the type heteropolyacid catalyst in the asymmetric dihydroxylation field of alkene.Application process is as follows：By alkene and (R)-
Mn-Anderson types heteropolyacid catalyst thiourea modified 1- (2- hydroxyl -1- phenethyls) is molten in the mixing that water and acetonitrile form
Mixed in agent, reacted at a temperature of 30 DEG C~50 DEG C, obtain vicinal diol compound；Wherein：(R) -1- (2- hydroxyl -1- benzene second
Base) dosages of thiourea modified Mn-Anderson type heteropolyacid catalysts is 0.5mol%~5mol% of alkene.
Preferably, the mol ratio of water and acetonitrile is 1:1~3:1, hydrogen peroxide is oxygen source, and its usage amount is 1~3 equivalent
(using alkene as reference).
After asymmetric dihydroxylation terminates, after adding organic solvent (ethanol, methanol etc.) into system, more acid outs
Go out, filter, vacuum drying, the reusable asymmetric dihydroxylation in alkene of polyacid of recovery.
Compared to the prior art, the beneficial effects of the present invention are：The present invention can not only utilize chiral organic micromolecule
Covalent modification break the high symmetry of polyacid, introduce chiral, improve its stereoselectivity in catalytic reaction, and
Also the functional characteristic such as the asymmetry catalysis of organic chiral small molecule or biological medicine activity can be introduced polyacid, and makes organic moiety
Organically it is integrated into a whole with inorganic polyanionic, more novel properties is obtained so as to produce synergy.This hair
Bright preparation method reaction condition is gentle, environment-friendly, and obtained catalyst has efficient, high enantioselectivity and recoverable
The advantages that, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the structural diagrams of final catalyst of the present invention.
Fig. 2 is the synthetic route diagram of the present invention.
Fig. 3 is the nuclear magnetic spectrogram of (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanates.
Fig. 4 is the infrared spectrum of bilateral amido modified Mn-Anderson type polyoxometallates.
Fig. 5 is the nuclear magnetic spectrogram of bilateral amido modified Mn-Anderson type polyoxometallates.
Fig. 6 is the nuclear-magnetism of the thiourea modified Mn-Anderson type heteropolyacid catalysts of (R) -1- (2- hydroxyl -1- phenethyls)
Spectrogram.
Embodiment
Embodiments of the present invention are described in detail using embodiment below, whereby to the present invention how application technology means
To solve technical problem, and the implementation process for reaching technique effect can fully understand and implement according to this.
Embodiment 1
Polyacid parent [N (C4H9)4]4[α-Mo8O26] preparation
In 50mL flask, by Na2MoO4·2H2O 5.00g (20.7mmol) are dissolved in 12mL deionized water, and
5.17mL 6.0N hydrochloric acid solution is added, 1~2min is stirred vigorously in room temperature.Then by TBAB 3.34g
The dissolving of (10.4mmol) in 10ml deionized waters, add in flask form white precipitate immediately with vigorous stirring.This is mixed
After compound stirs 10 minutes, precipitation is collected and is aspirated in medium porosity wave filter and uses 20mL water, 20mL ethanol, 20mL respectively
Acetone and the washing of 20mL ether.This crude product (4.78g) is dissolved in 35mL acetonitriles, and the static 24h under the conditions of -10 DEG C.Will be clear
Clearly, colourless, the crystal of block structure is by collected by suction and in vacuum drying 12 hours.The transparency of crystal can lose when drying
Lose.Yield 3.58g (1.66mmol), yield 64%.
Embodiment 2
(R) preparation of -1- (2- hydroxyl -1- phenethyls) isothiocyanates
D- benzene glycinol (0.6859g, 5mmol) is added in dry reaction vessel, is dissolved with 20mL ethanol, is then divided
It is not slowly added to add CS2(0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), after reaction 1h is stirred at room temperature, with
Di-tert-butyl dicarbonate (Boc is added under the conditions of 0 DEG C afterwards2O) (1.091mg, 5mmol) and DMAP (DMAP)
(18mg, 0.15mmol), (there is gas generation in the process of stirring, it should be noted that decompression of deflating) after reaction 2h is stirred at room temperature, can
Obtain 0.7194g (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanates.
(R) nuclear magnetic spectrogram of -1- (2- hydroxyl -1- phenethyls) isothiocyanates is as shown in figure 3, specific data are as follows：
1H NMR(501MHz,CDCl3) δ 7.39-7.22 (m, 5H), 4.99 (dt, J=52.6,9.1Hz, 2H), 4.43
(dd, J=8.8,7.0Hz, 1H), 1.25 (dd, J=51.2,35.5Hz, 1H)
Embodiment 3
The preparation of bilateral amido modified Mn-Anderson type polyoxometallates
Take [N (C4H9)4]4[α-Mo8O26](8.00g,3.7mmol),Mn(CH3COO)3·2H2O(1.49g,5.6mmol)
And (HOCH2)3CNH2(1.56g, 12.8mmol), in 150mL acetonitrile solution backflow 16h.The orange solution is cooled to room
Temperature, and it is filtered to remove imperceptible black solid.Filtrate is exposed to ether fume.After 2 hours, white depositions filter out.Orange filter
Liquid is again exposed to ether fume several days.Obtain a large amount of orange crystals.They are isolated by filtration, and are washed and the amount of ether with acetonitrile
It is small, and be dried under vacuum.
Infrared spectrum such as Fig. 4 of bilateral amido modified Mn-Anderson type polyoxometallates.
Nuclear magnetic spectrogram such as Fig. 5 of bilateral amido modified Mn-Anderson type polyoxometallates.
Embodiment 4
(R) preparation of Mn-Anderson type heteropolyacid catalysts thiourea modified -1- (2- hydroxyl -1- phenethyls)
By organic bilateral amido modified [N (C4H9)4]3[MnMo6O18{(OCH2)3CNH2}2] 0.5g (0.2683mmol) use
After 5mL DMF dissolves under the conditions of 50 DEG C, (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanates 0.3585g is added
(2mmol), maintain under 50 DEG C of stirring conditions, 2~3 days reaction time, react and bright pink clarified solution is placed into ether atmosphere after terminating
Middle crystallization, red crystals are can obtain behind some days, that is, obtain the thiourea modified Mn- of (R) -1- (2- hydroxyl -1- phenethyls)
Anderson type heteropolyacid catalysts.
(R) nuclear magnetic spectrogram of Mn-Anderson type heteropolyacid catalysts thiourea modified -1- (2- hydroxyl -1- phenethyls)
Such as Fig. 6.Specific data are as follows：
1H NMR (501MHz, DMSO) δ 66.06 (s, 12H), δ 7.28 (s, 10H), 3.12 (s, 24H), 1.53 (s,
24H),1.27(s,24H),0.89(s,36H)。
Embodiment 5
(R) asymmetry of Mn-Anderson type polyacid catalyzed alkenes thiourea modified -1- (2- hydroxyl -1- phenethyls) is double
Hydroxylating
1.0415g (0.01mol) styrene is added in clean reaction bulb, adds 10ml mixed solvents (water and second
The mol ratio of nitrile is 1:1~3:1) hydrogen peroxide of 1.7g 30% and 0.0099g (R) -1- (2- hydroxyl -1- benzene second, are eventually adding
Base) thiourea modified more acid catalysts of Mn-Anderson types, react 24h, take 5ml ethanol to add reaction system, centrifugation makes catalysis
Agent settles, and adds 3ml ethanol separating catalyst again, filters, obtains catalyst, is dried in vacuo.It will be reacted with ethyl acetate
System extracts 3 times, and resulting product removal of solvent under reduced pressure, column chromatography for separation obtains vicinal diol compound, obtains product
1.36g, yield 99%.The enantiomeric excess of product is measured by chiral high performance liquid chromatography, and ee values are up to 99%.The catalyst is all
The progress of catalytic reaction that can be different degrees of, and there is preferable stereoselectivity.Use different alkene and catalyst
The equation of reaction is as follows, and resulting experimental result is shown in Table 1.
The catalyst that above-mentioned recovery obtains is directly used in next reaction (dihydroxylation of styrene), it is resulting
The enantiomeric excess value of product determines (chiral AS-H posts, isopropanol by HPLC：N-hexane=3:7,254nm,20℃,0.5mL/
min).2 are the results are shown in Table obtained by catalyst recycling.
The asymmetric dihydroxylation experimental result of the polyacid catalyzed alkene of table 1
The experimental result that the catalyst of table 2 recycles
This new product of implementation and/or new method of all above-mentioned embodiments, not setting limitation other forms.
Those skilled in the art will utilize this important information, the above modification, to realize similar implementation status.It is but all
Modification or transformation based on the present invention belong to the right that the present invention retains.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. the preparation side of Mn-Anderson type heteropolyacid catalysts thiourea modified one kind (R) -1- (2- hydroxyl -1- phenethyls)
Method, it is characterised in that comprise the following steps that：
1) it is 1 according to mol ratio by sodium molybdate, TBAB：1~2:1 ratio mixing, the room temperature under concentrated hydrochloric acid effect
Reaction, is prepared parent [N (C4H9)4]4[α-Mo8O26]；
2) by parent obtained above [N (C4H9)4]4[α-Mo8O26] returned in organic solvent with trihydroxy aminomethane, manganese acetate
Stream obtains organic bilateral amido modified Mn-Anderson type polyoxometallates；
3) using D- benzene glycinol as Material synthesis (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanates；
4) the organic bilateral amido modified Mn- for obtaining (R) -1- (2- hydroxyl -1- phenethyls) isothiocyanates and step 2)
Anderson types polyoxometallate is 5 according to mol ratio:1~8:1 ratio mixed dissolution is in reaction dissolvent, 45-55 DEG C
At a temperature of react and obtain the thiourea modified Mn-Anderson type heteropolyacid catalysts of (R) -1- (2- hydroxyl -1- phenethyls).
2. preparation method as claimed in claim 1, it is characterised in that in step 1), the mol ratio of sodium molybdate and concentrated hydrochloric acid is
1:1~1：2.
3. preparation method as claimed in claim 1, it is characterised in that in step 2), parent [N (C4H9)4]4[α-Mo8O26] with
Trihydroxy aminomethane, the mol ratio of manganese acetate are 1:(3~4):(1~2).
4. preparation method as claimed in claim 1, it is characterised in that in step 2), organic solvent is polar non-solute.
5. preparation method as claimed in claim 1, it is characterised in that in step 2), organic solvent is acetonitrile or 1,2- bis-
Chloroethanes.
6. preparation method as claimed in claim 1, it is characterised in that in step 3), using D- benzene glycinol as Material synthesis
(R) -1- (2- hydroxyl -1- phenethyls) isothiocyanates comprises the following steps that：By D- benzene glycinol, CS2With triethylamine to rub
That ratio 1:(2~4):1 ratio mixing, after reaction 1h~2h is stirred at room temperature, di-tert-butyl dicarbonate is added under condition of ice bath
And DMAP, after adding, continue to keep stirring reaction 3h~5h under condition of ice bath, obtain (R) -1- (2- hydroxyls -1-
Phenethyl) isothiocyanates；Wherein, the mol ratio of D- benzene glycinol, di-tert-butyl dicarbonate and DMAP is 1:
1:(0.02~0.05).
7. preparation method as claimed in claim 1, it is characterised in that in step 4), reaction dissolvent be selected from DMF, DMSO or
Any one or a few in NMP.
A kind of 8. (R) -1- (2- hydroxyl -1- phenethyls) sulphur that preparation method as described in one of claim 1-7 is prepared
The Mn-Anderson type heteropolyacid catalysts of urea modification.
9. a kind of Mn-Anderson types thiourea modified (R) -1- (2- hydroxyl -1- phenethyls) as claimed in claim 8 are miscellaneous more
Application of the acid catalyst in the asymmetric dihydroxylation field of alkene.
10. application as claimed in claim 9, it is characterised in that application process is as follows：By alkene and (R) -1- (2- hydroxyls -1-
Phenethyl) the in the mixed solvent mixing that is formed in water and acetonitrile of thiourea modified Mn-Anderson types heteropolyacid catalyst, 30 DEG C
Reacted at a temperature of~50 DEG C, obtain vicinal diol compound；Wherein：(the R) -1- (2- hydroxyl -1- phenethyls) is thiourea modified
The dosage of Mn-Anderson type heteropolyacid catalysts is 0.5mol%~5mol% of alkene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610211236.9A CN105797769B (en) | 2016-04-06 | 2016-04-06 | (R) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (phenethyl of 2 hydroxyl 1), preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610211236.9A CN105797769B (en) | 2016-04-06 | 2016-04-06 | (R) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (phenethyl of 2 hydroxyl 1), preparation method and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105797769A CN105797769A (en) | 2016-07-27 |
| CN105797769B true CN105797769B (en) | 2018-03-30 |
Family
ID=56459691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610211236.9A Active CN105797769B (en) | 2016-04-06 | 2016-04-06 | (R) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (phenethyl of 2 hydroxyl 1), preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105797769B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106475140A (en) * | 2016-10-12 | 2017-03-08 | 上海应用技术大学 | (S) the unilateral Fe Anderson type heteropolyacid catalyst modified of 1 (1 ethoxy 1 isopropyl) thiourea, preparation method and applications |
| CN106475143A (en) * | 2016-10-12 | 2017-03-08 | 上海应用技术大学 | (R) the unilateral Fe Anderson type heteropolyacid catalyst modified of 1 (2 hydroxyl 1 phenethyl) thiourea, preparation method and applications |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284400A (en) * | 1999-08-17 | 2001-02-21 | 罗姆和哈斯公司 | Heteropoly acid/multimetal oxacid salt catalyst |
| WO2002081438A2 (en) * | 2001-04-09 | 2002-10-17 | Dow Agrosciences Lcc | Process for producing thiosemicarbazides |
| CN1390643A (en) * | 2002-06-17 | 2003-01-15 | 中国科学院大连化学物理研究所 | Application method of heteropoly acid type catalyst |
| CN103570493A (en) * | 2013-10-31 | 2014-02-12 | 江苏紫奇化工科技有限公司 | Method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation |
-
2016
- 2016-04-06 CN CN201610211236.9A patent/CN105797769B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284400A (en) * | 1999-08-17 | 2001-02-21 | 罗姆和哈斯公司 | Heteropoly acid/multimetal oxacid salt catalyst |
| WO2002081438A2 (en) * | 2001-04-09 | 2002-10-17 | Dow Agrosciences Lcc | Process for producing thiosemicarbazides |
| CN1390643A (en) * | 2002-06-17 | 2003-01-15 | 中国科学院大连化学物理研究所 | Application method of heteropoly acid type catalyst |
| CN103570493A (en) * | 2013-10-31 | 2014-02-12 | 江苏紫奇化工科技有限公司 | Method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation |
Non-Patent Citations (2)
| Title |
|---|
| Mapping the synthesis of low nuclearity polyoxometalates from octamolybdates to Mn-Anderson clusters;Mali H. Rosnes et al.;《Dalton Transactions》;20120716;10071-10079 * |
| Sorting the Assemblies of Unsymmetrically Covalently Functionalized Mn-Anderson Polyoxometalate Clusters with Mass Spectrometry;Yu-Fei Song et al.;《Inorg. Chem.》;20081231;9137-9139 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105797769A (en) | 2016-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105833909B (en) | (S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (2- hydroxyl -1- phenethyls), preparation method and applications | |
| CN105772085B (en) | (S) the thiourea modified Cr Anderson types heteropolyacid catalyst of 1 (1 ethoxy, 1 isopropyl), preparation method and applications | |
| CN105833911B (en) | The Cr Anderson types heteropolyacid catalyst of 1 Phenethylthiourea modification, preparation method and applications | |
| CN105665019B (en) | (S) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (phenylpropyl of 3 hydroxyl 1), preparation method and applications | |
| CN105854941B (en) | (S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications | |
| CN105797769B (en) | (R) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (phenethyl of 2 hydroxyl 1), preparation method and applications | |
| CN105833910B (en) | (R) the thiourea modified Cr Anderson types heteropolyacid catalyst of 1 (phenethyl of 2 hydroxyl 1), preparation method and applications | |
| CN105854952B (en) | (S) Mn-Anderson types heteropolyacid catalyst thiourea modified -1- (2- hydroxyl -1- phenethyls), preparation method and applications | |
| CN105772100B (en) | (R) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (1- (2- naphthyls) ethyl), preparation method and applications | |
| CN105854940B (en) | (R) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications | |
| CN105772088B (en) | (S) Mn-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications | |
| CN105797770B (en) | (S) the thiourea modified Cr Anderson types heteropolyacid catalyst of 1 (phenylpropyl of 3 hydroxyl 1), preparation method and applications | |
| CN105772086B (en) | (S) the thiourea modified Mn Anderson types heteropolyacid catalyst of 1 (isopropyl of 1 ethoxy 1), preparation method and applications | |
| CN105964306A (en) | Poly(ionic liquid)-based magnetic nanoparticle and its preparation method and use in three-ingredient reaction | |
| CN105772102B (en) | (R) Mn-Anderson types heteropolyacid catalyst thiourea modified -1- (1- (2- naphthyls) ethyl), preparation method and applications | |
| CN105797771B (en) | (R) Mn-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications | |
| CN105772101B (en) | The Mn Anderson types heteropolyacid catalyst of 1 Phenethylthiourea modification, preparation method and applications | |
| CN106622371A (en) | (R)-1-(1-phenethyl)thiourea modified Al-Anderson type heteropolyacid catalyst and preparation method and application thereof | |
| CN103657724B (en) | Keggin type vacancy polyacid and application thereof in catalytic synthesis of benzoxazole derivative | |
| CN103055939A (en) | Preparation method for porous biomimetic catalytic material and application thereof | |
| CN106475141A (en) | (S) the unilateral Fe Anderson type heteropolyacid catalyst modified of 1 (3 hydroxyl 1 phenylpropyl) thiourea, preparation method and applications | |
| CN106513041A (en) | (S)-1-(3-hydroxy-1-phenylpropyl)thiourea modified Al-Anderson type heteropolyacid catalyst, preparation method and application thereof | |
| CN106513042A (en) | (R)-1-(2-hydroxyl-1-phenethyl)thiourea modified Al-Anderson heteropolyacid catalyst as well as preparation method and application thereof | |
| CN107519932A (en) | A kind of phase transfer catalyst for benzyl alcohol oxidation synthesizing benzaldehyde and preparation method thereof | |
| CN106513043A (en) | (R)-1-(2-(naphthyl)ethyl)thiourea modified Al-Anderson type heteropolyacid catalyst, and preparation method and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 200235 Caobao Road, Xuhui District, Shanghai, No. 120-121 Patentee after: SHANGHAI INSTITUTE OF TECHNOLOGY Address before: No. 120-121, Caobao Road, Xuhui District, Shanghai 200235 Patentee before: Shanghai Institute of Technology |
|
| CP03 | Change of name, title or address | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210909 Address after: 201109 Building 8, No. 894, Jianchuan Road, Minhang District, Shanghai Patentee after: Shanghai Yuanxin Material Technology Co.,Ltd. Address before: 200235 Caobao Road, Xuhui District, Shanghai, No. 120-121 Patentee before: SHANGHAI INSTITUTE OF TECHNOLOGY |
|
| TR01 | Transfer of patent right |