CN105797771B - (R) Mn-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications - Google Patents
(R) 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 (R) 1 (1 phenethyl) thiourea modified Mn Anderson types heteropolyacid catalyst, preparation method and applications.The present invention is first by sodium molybdate and tetrabutylammonium bromide reaction generation [N (C4H9)4]4[α‑Mo8O26], then it is reacted with trihydroxy aminomethane and manganese acetate to obtain organic bilateral amido modified polyoxometallate；Then using (R) (+) 1 phenylethylamine as Material synthesis (R) 1 (1 phenethyl) isothiocyanic acid；(R) 1 (1 phenethyl) isothiocyanic acid and organic bilateral amido modified polyoxometallic acid reactant salt are finally obtained into final catalyst.Preparation method of the present invention is simple, and reaction condition is gentle, environmental-friendly；Obtained catalyst can be used for the asymmetric dihydroxylation of alkene, have the advantages that 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 (R)-
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 produced 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.Catalysis is
Most promising and most practical value research direction in polyoxometallate application.Polyoxometallate collects acid-base catalysis at the same time
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
For existing 8 polyacid catalysis industry projects are successfully 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
Explore.Chiral polyoxometallate integrates the various excellent properties of polyacid and chiral material.Its unique soluble class ore deposit
Thing metal-oxide structure, ideal is provided 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 gentle, but in most cases, high mole of catalyst amount
Fraction.Realize the application of these catalytic reactions 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 clearly
Minor structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain the synergistic effect of Chiral Amine and polyacid.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide one kind (R) -1- (1- phenethyls) thiocarbamide to repair
The Mn-Anderson types heteropolyacid catalyst of decorations, preparation method and applications, the present invention solve existing chiral organic micromolecule
Catalyst activity is relatively low, dosage is high and is not easily recycled the technical problem utilized.Preparation method of the present invention is simple, reaction condition temperature
With, it is environmental-friendly；Obtained catalyst can be used for asymmetry catalysis, have high enantioselectivity, high catalytic activity and recyclable
The advantages that utilization.
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
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, medicine and
There is potential using value in terms of functional material.In addition, polyacid has hydrophily, available green, cheap water as solvent carry 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 the thiourea modified Mn-Anderson type heteropolyacid catalysts of one kind (R) -1- (1- phenethyls)
The preparation method of (structure is shown in Fig. 1), its synthetic route is as shown in Fig. 2, comprise the following steps that：
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 (R) -1- (1- phenethyls) isothiocyanates；
4) the organic bilateral amido modified Mn- for obtaining (R) -1- (1- phenethyls) isothiocyanic acids and step 2)
Anderson types polyoxometallate is reacted 2~3 days with after DMF or DMSO dissolvings at a temperature of 45-55 DEG C, then post-treated
Obtain the thiourea modified Mn-Anderson type heteropolyacid catalysts of (R) -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, the molar ratio of manganese acetate are 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 (R) -1- in step 4)
The molar ratio of (1- phenethyls) isothiocyanic acid is 1:5~1:8.
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 (R) -1- (1- phenethyls)
Anderson type heteropolyacid catalysts.
The present invention further provides a kind of thiourea modified Mn-Anderson type heteropoly acids of above-mentioned (R) -1- (1- phenethyls)
Application of the catalyst in the asymmetric dihydroxylation field of alkene.
Above application method is specific as follows：By alkene and Mn-Anderson types thiourea modified (R) -1- (1- phenethyls)
Heteropolyacid catalyst is added to the in the mixed solvent of water and acetonitrile composition, is reacted at a temperature of 30 DEG C~50 DEG C, obtains vicinal diamines
Compound；Wherein：(R) amount of Mn-Anderson type heteropolyacid catalysts thiourea modified -1- (1- phenethyls) is alkene
0.5mol%~5mol%；The molar ratio of water and acetonitrile is 1:1~3:1, hydrogen peroxide is oxygen source, its usage amount is 1~3 equivalent
(using alkene as reference).
Mn-Anderson types heteropolyacid catalyst thiourea modified (R) -1- (1- phenethyls) is closed applied to catalyzed alkene
Into vicinal diamines after reaction, organic solvent (ethanol, methanol etc.) is added into system, polyacid separates out, and filtering, vacuum is done
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 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, so that producing synergistic effect obtains more novel properties.This hair
Bright preparation method is simple, and reaction condition is gentle, environmental-friendly；Obtained catalyst has high enantioselectivity, high catalytic activity
And the advantages that recoverable.
Brief description of the drawings
Fig. 1 is the structural diagrams of the thiourea modified Mn-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls).
Fig. 2 is the synthetic route chart of the present invention.
Fig. 3 is the nuclear magnetic spectrogram of (R) -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 (R) -1- (1- phenethyls).
Embodiment
Below using embodiment come the embodiment that the present invention will be described in detail, whereby to the present invention how application technology means
To solve technical problem, and that reaches technique effect realizes that process 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, 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
Compound stirs after ten minutes, and 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 when vacuum drying 12 is small.The transparency of crystal can lose in drying
Lose.Yield 3.58g (1.66mmol), yield 64%.
Embodiment 2
(R) 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 (R) -1- (1- phenethyls) isothiocyanates can be obtained.Yield 97%.
(R) nuclear magnetic spectrogram of -1- (1- phenethyls) isothiocyanates is shown in Fig. 3, and specific data are as follows：
1H NMR(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.2 it is small when after, 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
(R) 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, (R) -1- (1- phenethyls) isothiocyanates 0.3265g (2mmol) is added, is maintained
Under 50 DEG C of stirring conditions, in 2~3 days reaction time, bright pink clarified solution is placed in ether atmosphere crystallize after reaction, Ruo Gantian
After can obtain red crystals, that is, obtain the thiourea modified Mn-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls).
(R) 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：
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) Asymmetrical dihydroxylation of Mn-Anderson type polyacid catalyzed alkenes thiourea modified -1- (1- phenethyls) is anti-
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 (R) -1- (1- phenethyls) thiocarbamide, are eventually adding
The more acid catalysts of Mn-Anderson types of modification, react 24h, take 5ml ethanol to add reaction system, and centrifugation makes catalyst sedimentation,
3ml ethanol 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
Catalytic reaction progress, and there is preferable stereoselectivity.Using different alkene and catalyst reaction, equation is such as
Under, 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 resulting
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
This new product of implementation and/or new method of all above-mentioned content of the invention, 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 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 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 method of Mn-Anderson type heteropolyacid catalysts thiourea modified one kind (R) -1- (1- phenethyls), it is special
Sign is, comprises the following steps that：
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 (R) -1- (1- phenethyls) isothiocyanates；
4) the organic bilateral amido modified Mn-Anderson for obtaining (R) -1- (1- phenethyls) isothiocyanates and step 2)
Type polyoxometallate with DMF or DMSO dissolving after, reacted 2~3 days at a temperature of 45-55 DEG C, then it is post-treated obtain (R)-
Mn-Anderson type heteropolyacid catalysts thiourea modified 1- (1- phenethyls).
2. preparation method as claimed in claim 1, it is characterised in that in step 1), sodium molybdate and tetrabutylammonium bromide are rubbed
You are than being 1：1~2:1.
3. preparation method as claimed in claim 1, it is characterised in that in step 1), the molar ratio of sodium molybdate and concentrated hydrochloric acid is
1:1~1:2.
4. preparation method as claimed in claim 1, it is characterised 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 claimed in claim 1, it is characterised in that organic bilateral amido modified in step 4)
The molar ratio of Mn-Anderson types polyoxometallate and (R) -1- (1- phenethyls) isothiocyanates is 1:5~1:8.
6. preparation method as claimed in claim 1, it is characterised in that in step 4), post processing mode is recrystallization.
7. preparation method as claimed in claim 6, it is characterised in that solvent during recrystallization is ether.
8. Mn- thiourea modified a kind of (R) -1- (1- phenethyls) that preparation method as described in one of claim 1-7 obtains
Anderson type heteropolyacid catalysts.
A kind of 9. Mn-Anderson type heteropoly acid catalysis thiourea modified (R) -1- (1- phenethyls) as claimed in claim 8
Application of the agent in the asymmetric dihydroxylation field of alkene.
10. application as claimed in claim 9, it is characterised in that application process is specific as follows：By alkene and (R) -1- (1- benzene
Ethyl) thiourea modified Mn-Anderson type heteropolyacid catalysts be added to water and acetonitrile composition in the mixed solvent, 30 DEG C~
Reacted at a temperature of 50 DEG C, obtain vicinal diol compound；Wherein：(R) Mn-Anderson types thiourea modified -1- (1- phenethyls)
The amount of heteropolyacid catalyst is 0.5mol%~5mol% of alkene.
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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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2016
- 2016-04-06 CN CN201610211356.9A patent/CN105797771B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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