CN105772088B - (S) Mn-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications - Google Patents
(S) Mn-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications Download PDFInfo
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Abstract
The invention discloses a kind of (S) 1 (1 phenethyl) thiourea modified Mn Anderson types heteropolyacid catalyst, preparation method and applications.Sodium molybdate is first reacted generation [N (C by the present invention with tetrabutylammonium bromide4H9)4]4[α‑Mo8O26], then organic bilateral amido modified polyoxometallate is obtained by the reaction in itself and trihydroxy aminomethane and manganese acetate；Then using (R) (+) 1 phenylethylamine as Material synthesis (S) 1 (1 phenethyl) isothiocyanic acid；Final catalyst finally is obtained by the reaction in (S) 1 (1 phenethyl) isothiocyanic acid and organic bilateral amido modified polyoxometallate.Preparation method of the present invention is simple, and reaction condition is mild, environmental-friendly；Obtained catalyst is used for the asymmetric dihydroxylation of alkene, has many advantages, such as high enantioselectivity, high catalytic activity and 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 (S)-
Thiourea modified 1- (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 environmental-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 is generated without waste ".Chiral catalysis synthesis is made
One of important channel to realize " 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 passes through interaction, such as oxygen key, Van der Waals force or ion pair priming reaction substrate.Catalysis is
Most promising and most practical value research direction in polyoxometallate application.Polyoxometallate collects acid-base catalysis simultaneously
The good characteristic of agent, oxidation reduction catalyst, metal oxide nanocatalyst etc. is, it is considered to be one kind is widely used
Green multifunction catalyst.Early in early 20th century, people begin to study the catalytic performance of polyacid.To current
To have 8 polyacid catalysis industry projects and successfully being developed.It is catalyzed into for an eternal research class in Chemistry of Polyacids
Topic.After chiral polyoxometallate is successfully synthesized, people have just started chiral polyacid in asymmetric catalysis field
It explores.Chiral polyoxometallate integrates the various excellent properties of polyacid and chiral material.Its unique soluble class ore deposit
Object metal-oxide structure provides ideal for the chiral exploration transmitted in chiral non-origin of life theory and inoganic solids
Model；Its high elecrtonegativity, adjustable acid-base property, redox active and nano-scale, more multi-functional nonlinear optics,
Design, the synthesis of the new materials such as nano material, stereoselectivity catalysis and medicine bring new hope.It is although homogeneous chiral
Catalysis has the characteristics that efficient, high enantioselectivity and reaction condition are mild, but in most cases, high mole of catalyst amount
Score.Realize these applications of catalysis reaction industrially, it is necessary to which the recycling for solving expensive catalyst is a serious
Problem.The Luo Sanzhong of chemistry institute of the Chinese Academy of Sciences is taught et al. using organic amine small molecules catalyst as counter cation, more
Acid is made that outstanding work (Organic letters, 2007,9 (18) as the field of catalyst-supporting carriers:3675-
3678.).They have synthesized a series of secondary amine-tertiary amine-type proline derivative, using the polyanionic [PW of highly acid12O40
]3-The mineral acid in traditional Acid-Base concerted catalysis is substituted, has synthesized a series of chiral organic amine-polyacid hybrid materials.These materials
Expect the direct asymmetric Aldol reaction to aldehyde ketone, asymmetric Michael addition reaction etc. all shows very high catalytic activity and chiral choosing
Selecting property.Organic amine small molecules are assembled as counter cation with polyacid by electrostatic interaction, but these materials do not divide explicitly
Minor structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain the synergistic effect of Chiral Amine and polyacid.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide one kind (S) -1- (1- phenethyls) thiocarbamides to repair
The Mn-Anderson types heteropolyacid catalyst of decorations, preparation method and applications.The present invention solves existing chiral organic micromolecule
Catalyst activity is relatively low, dosage is high and the technical issues of being not easily recycled utilization.Preparation method of the present invention is simple, reaction condition temperature
With it is environmental-friendly；Obtained catalyst can be used for asymmetry catalysis to synthesize field, have high enantioselectivity, high catalytic activity
And the advantages that recoverable.
The present invention from the mentality of designing of organic micromolecule catalyst innovatively proposes that " Acid-Base " collaboration is utilized to urge
Change strategy, using the chiral organic micromolecule with potential catalytic activity as precursor, the methods of passing through organic decoration, dexterously
Organic molecule and the vacant polyanionic of high Bronsted acidity are combined, constructs chiral polyacid material.It is organic in the present invention
The polyacid of modification not only remains the original structure of polyacid, and has expanded the research field of polyacid, make its catalysis, drug and
There is potential using value in terms of functional material.In addition, polyacid has hydrophily, available green, cheap water as solvent carry out
Catalysis reaction, reaction terminate after organic solvent (ethyl alcohol, methanol etc.) can be added in into system, and polyacid is easily precipitated, and can be returned
It receives and utilizes.Technical solution of the present invention is specifically described as follows.
The present invention provides the thiourea modified Mn-Anderson type heteropolyacid catalysts of one kind (S) -1- (1- phenethyls)
The preparation method of (structure is shown in Fig. 1), synthetic route is as shown in Fig. 2, be as follows：
1) sodium molybdate is reacted with tetrabutylammonium bromide under concentrated hydrochloric acid effect, generation Mn-Anderson types heteropoly acid is female
Body [N (C4H9)4]4[α-Mo8O26]；
2) by Mn-Anderson types heteropoly acid parent [N (C obtained above4H9)4]4[α-Mo8O26] and trihydroxy amino
Methane, manganese acetate flow back in organic solvent, obtain organic bilateral amido modified Mn-Anderson type polyoxometallates；
3) using (R)-(+) -1- phenylethylamines as Material synthesis (S) -1- (1- phenethyls) isothiocyanates；
4) the organic bilateral amido modified Mn- for obtaining (S) -1- (1- phenethyls) isothiocyanic acids and step 2)
After Anderson types polyoxometallate is dissolved with DMF, DMSO or NMP, reacted 2~3 days at a temperature of 45-55 DEG C, then pass through
Post processing obtains the thiourea modified Mn-Anderson type heteropolyacid catalysts of (S) -1- (1- phenethyls).
In the present invention, in step 1), the molar ratio of sodium molybdate and tetrabutylammonium bromide is 1：1~2:1.
In the present invention, in step 1), the molar ratio of sodium molybdate and concentrated hydrochloric acid is 1:1~1:2.
In the present invention, in step 2), Mn-Anderson type heteropoly acid parents [N (C4H9)4]4[α-Mo8O26] and trihydroxy
Aminomethane, manganese acetate molar ratio be 1:(3~4):(1~2), organic solvent are selected from acetonitrile, tetrahydrofuran or 1,2- dichloro
Any one in ethane.
In the present invention, organic bilateral amido modified Mn-Anderson types polyoxometallate and (S) -1- in step 4)
The molar ratio of (1- phenethyls) isothiocyanic acid is 1:5~1:8.
In the present invention, in step 4), organic bilateral amino that (S) -1- (1- phenethyls) isothiocyanic acids and step 2) obtain
The Mn-Anderson type polyoxometallic acids reactant salt of modification is after 2~3 days, if reaction solution is not clarified, at syringe filters
Reason.
In the present invention, in step 4), post processing mode is recrystallization.Preferably, solvent during recrystallization is ether.
Mn- thiourea modified a kind of obtain the present invention also provides above-mentioned preparation method (S) -1- (1- phenethyls)
Anderson type heteropolyacid catalysts.
The present invention further provides the thiourea modified Mn-Anderson type heteropoly acid catalysis of above-mentioned (S) -1- (1- phenethyls)
Agent is in the application in the asymmetric dihydroxylation field of alkene.Application process is as follows：By alkene and (S) -1- (1- phenethyls)
Thiourea modified Mn-Anderson type heteropolyacid catalysts are added to the in the mixed solvent of water and acetonitrile composition, 30 DEG C~50
It is reacted at a temperature of DEG C, obtains vicinal diol compound；Wherein：(S) Mn-Anderson types thiourea modified -1- (1- phenethyls) are miscellaneous
The amount of polyacid catalyst is 0.5mol%~5mol% of alkene.
Preferably, the molar ratio of water and acetonitrile is 1:1~3:1, hydrogen peroxide is oxygen source, and usage amount is 1~3 equivalent
(using alkene as reference).
After reaction, after adding in organic solvent (ethyl alcohol, methanol etc.) into system, polyacid is precipitated, filtering, vacuum for catalysis
It is dry, the reusable asymmetric dihydroxylation in alkene of polyacid of recycling.
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 catalysis is reacted, and
Also the functional characteristics such as the asymmetry catalysis of organic chiral small molecule or biological medicine activity can be introduced polyacid, and make organic moiety
It is organically integrated into a whole with inorganic polyanionic, more novel properties is obtained so as to generate synergistic effect.This hair
Bright preparation method is simple, and reaction condition is mild, environmental-friendly；Obtained catalyst has high enantioselectivity, high catalytic activity
And the advantages that recoverable.
Description of the drawings
Fig. 1 is the structural diagrams of the thiourea modified Mn-Anderson type heteropolyacid catalysts of (S) -1- (1- phenethyls).
Fig. 2 is the synthetic route chart of the present invention.
Fig. 3 is the nuclear magnetic spectrogram of (S) -1- (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 magnetic spectrogram of the thiourea modified Mn-Anderson type heteropolyacid catalysts of (S) -1- (1- phenethyls).
Specific embodiment
The present invention will be described in detail below with reference to the drawings of preferred embodiments, whereby to the present invention how applied technology method
To solve technical problem, and the realization 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 the flask of 50mL, by Na2MoO4·2H2O 5.00g (20.7mmol) are dissolved in the deionized water of 12mL, and
The hydrochloric acid solution of 5.17mL 6.0N is added in, 1~2min is vigorously stirred in room temperature.Then by tetrabutylammonium bromide 3.34g
The dissolving of (10.4mmol) in 10ml deionized waters adds in flask form white precipitate immediately with vigorous stirring.This is mixed
It closes object stirring after ten minutes, precipitation is collected and is aspirated in medium porosity wave filter and respectively with 20mL water, 20mL ethyl alcohol, 20mL
Acetone and the washing of 20mL ether.This crude product (4.78g) is dissolved in 35mL acetonitriles, and under the conditions of -10 DEG C it is static for 24 hours.It 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 in drying
It loses.Yield 3.58g (1.66mmol), yield 64%.
Embodiment 2
(S) preparation of -1- (1- phenethyls) isothiocyanates
(R)-(+) -1- phenylethylamines (0.606g, 5mmol) are added in dry reaction vessel, with 20mL ethyl acetate
Dissolving is then respectively added slowly to add CS2(0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), is stirred at room temperature
After reacting 1h, di-tert-butyl dicarbonate (Boc is then added under the conditions of 0 DEG C2O) (1.091mg, 5mmol) and 4- dimethylaminos
Pyridine (DMAP) (18mg, 0.15mmol) (has gas generation, it should be noted that put after reaction 2h is stirred at room temperature in the process of stirring
Gas depressurizes), 0.79g (S) -1- (1- phenethyls) isothiocyanates can be obtained.Yield 97%.
(S) nuclear magnetic spectrogram of -1- (1- phenethyls) isothiocyanates is shown in Fig. 3, and specific data are as follows：
1HNMR(501MHz,CDCl3) δ 7.3-7.5 (dt, J=12.3,7.7Hz, 5H), 4.90-4.95 (q, J=6.7Hz,
1H), 1.65-1.70 (d, J=6.8Hz, 3H)
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 the acetonitrile solution reflux 16h of 150mL.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.
The infrared spectrum of bilateral amido modified Mn-Anderson type polyoxometallates is as shown in Figure 4.
The nuclear magnetic spectrogram of bilateral amido modified Mn-Anderson type polyoxometallates is as shown in Figure 5.
Embodiment 4
(S) preparation of Mn-Anderson type heteropolyacid catalysts thiourea modified -1- (1- phenethyls)
By organic bilateral amido modified [N (C4H9)4]3[MnMo6O18{(OCH2)3CNH2}2] 0.5g (0.2683mmol) use
After the DMF of 5mL dissolves under the conditions of 50 DEG C, (S) -1- (1- phenethyls) isothiocyanates 0.3265g (2mmol) is added in, is maintained
Under 50 DEG C of stirring conditions, bright pink clarified solution is placed in ether atmosphere crystallize after reaction by 2~3 days reaction time, Ruo Gantian
After can obtain red crystals, that is, obtain the thiourea modified Mn-Anderson type heteropolyacid catalysts of (S) -1- (1- phenethyls).
(S) nuclear magnetic spectrogram such as Fig. 6 institutes of Mn-Anderson type heteropolyacid catalysts thiourea modified -1- (1- phenethyls)
Show, specific data are as follows：
1HNMR (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
(S) Asymmetrical dihydroxylation of Mn-Anderson type polyacid catalyzed alkenes thiourea modified -1- (1- phenethyls) is anti-
It should
1.0415g (0.01mol) styrene is added in clean reaction bulb, adds 10ml mixed solvents (water and second
The molar ratio of nitrile is 1:1~3:1) 30% hydrogen peroxide of 1.7g and 0.0099g (S) -1- (1- phenethyls) thiocarbamide, are eventually adding
The Mn-Anderson type polyacid catalyst of modification, reaction for 24 hours, take 5ml ethyl alcohol to add in reaction system, and centrifugation makes catalyst sedimentation,
3ml ethyl alcohol separating catalyst again is added, filters, obtains catalyst, is dried in vacuo.Reaction system is extracted with ethyl acetate
3 times, solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains vicinal diol compound, obtains product 1.36g, and yield is
99%.The enantiomeric excess of product is measured by chiral high performance liquid chromatography, and ee values are up to 99%.The catalyst can be different degrees of
Catalysis reaction progress, and with preferable stereoselectivity.Using different alkene and catalyst reaction, equation is such as
Shown in lower, obtained experimental result is shown in Table 1.
The catalyst that above-mentioned recycling obtains is directly used in next reaction (dihydroxylation of styrene), it is acquired
The enantiomeric excess value of product measures (chiral AS-H columns, isopropanol by HPLC：N-hexane=3:7,254nm,20℃,0.5mL/
min).Catalyst recycling is obtained to the results are shown in Table 2.
The asymmetric dihydroxylation experimental result of 1 polyacid catalyzed alkene of table
The experimental result that 2 catalyst of table recycles
All above-mentioned invention contents, there is no this new products of implementation and/or new method of setting limitation other forms.
Those skilled in the art will utilize this important information, the above modification, to realize similar executive condition.It is but all
Modification or transformation belong to the right of reservation based on new product of the present invention.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, 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, 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 method of Mn-Anderson type heteropolyacid catalysts thiourea modified one kind (S) -1- (1- phenethyls), special
Sign is, is as follows：
1) sodium molybdate is reacted with tetrabutylammonium bromide under concentrated hydrochloric acid effect, generation Mn-Anderson type heteropoly acid parents [N
(C4H9)4]4[α-Mo8O26]；
2) by Mn-Anderson types heteropoly acid parent [N (C obtained above4H9)4]4[α-Mo8O26] and trihydroxy aminomethane,
Manganese acetate flows back in organic solvent, obtains organic bilateral amido modified Mn-Anderson type polyoxometallates；
3) using (R)-(+) -1- phenylethylamines as Material synthesis (S) -1- (1- phenethyls) isothiocyanates；
4) the organic bilateral amido modified Mn-Anderson for obtaining (S) -1- (1- phenethyls) isothiocyanates and step 2)
After type polyoxometallate is dissolved with DMF, DMSO or NMP, reacted 2~3 days at a temperature of 45-55 DEG C, then post-treated
The Mn-Anderson type heteropolyacid catalyst thiourea modified to (S) -1- (1- phenethyls).
2. preparation method as described in claim 1, which is characterized in that in step 1), sodium molybdate and tetrabutylammonium bromide are rubbed
You are than being 1：1~2:1.
3. preparation method as described in claim 1, which is characterized in that in step 1), the molar ratio of sodium molybdate and concentrated hydrochloric acid is
1:1~1:2.
4. preparation method as described in claim 1, which is characterized in that in step 2), Mn-Anderson type heteropoly acid parents [N
(C4H9)4]4[α-Mo8O26] with trihydroxy aminomethane, manganese acetate molar ratio be 1:(3~4):(1~2), organic solvent choosing
From in acetonitrile, tetrahydrofuran or 1,2- dichloroethanes any one.
5. preparation method as described in claim 1, which is characterized in that organic bilateral amido modified in step 4)
The molar ratio of Mn-Anderson types polyoxometallate and (S) -1- (1- phenethyls) isothiocyanates is 1:5~1:8.
6. preparation method as described in claim 1, which is characterized in that in step 4), post processing mode is recrystallization.
7. preparation method as claimed in claim 6, which is characterized in that solvent during recrystallization is ether.
8. Mn- thiourea modified a kind of (S) -1- (1- phenethyls) that preparation method as described in one of claim 1-7 obtains
Anderson type heteropolyacid catalysts.
9. a kind of Mn-Anderson type heteropoly acid catalysis thiourea modified (S) -1- (1- phenethyls) as claimed in claim 8
Agent is in the application in the asymmetric dihydroxylation field of alkene.
10. application as claimed in claim 9, which is characterized in that application process is as follows：By alkene and (S) -1- (1- phenethyls)
Thiourea modified Mn-Anderson type heteropolyacid catalysts are added to the in the mixed solvent of water and acetonitrile composition, 30 DEG C~50
It is reacted at a temperature of DEG C, obtains vicinal diol compound；Wherein：(S) Mn-Anderson types thiourea modified -1- (1- phenethyls) are miscellaneous
The amount of polyacid catalyst is 0.5mol%~5mol% of alkene.
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| CN106475139A (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 phenethyl) thiourea, preparation method and applications |
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| EP1672074A1 (en) * | 2000-05-25 | 2006-06-21 | Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO | Lactobacillus reuteri glucosyltransferase |
| CN102071012A (en) * | 2010-11-16 | 2011-05-25 | 北京化工大学 | Photosensitive material with Anderson type polyacid and preparation method thereof |
| CN104151262A (en) * | 2014-07-07 | 2014-11-19 | 浙江大学 | 4, 5-disubstituted-2-aminothiazole compound and preparation method thereof |
| CN104857988A (en) * | 2015-05-07 | 2015-08-26 | 盐城工学院 | Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof |
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