CN105854941B - (S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications - Google Patents
(S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications Download PDFInfo
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention discloses a kind of (S) 1 (1 phenethyl) thiourea modified Cr Anderson types heteropolyacid catalyst, preparation method and applications.The present invention reacts generation Cr Anderson type heteropoly acids (NH first by ammonium molybdate with chromic nitrate4)3[Cr(OH)6Mo6O18]；It is subjected to hydro-thermal in water heating kettle with trihydroxy aminomethane again and obtains the amido modified polyoxometallate in organic unilateral side；Then using (S) (+) 1 phenylethylamine as Material synthesis (R) 1 (1 phenethyl) isothiocyanic acid, finally by isothiocyanic acid with the amido modified polyoxometallate in organic unilateral side is obtained by the reaction target heteropolyacid catalyst.Preparation method of the present invention is simple, and obtained heteropolyacid catalyst is used for the asymmetric dihydroxylation of alkene, and environmental-friendly, recoverable has high enantioselectivity and high catalytic activity, suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of catalytic chemistry more particularly to asymmetric selective catalysis, specifically (S) -1- (1-
Phenethyl) thiourea modified Cr-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.Although
Phase chiral catalysis has the characteristics that efficient, high enantioselectivity and reaction condition are mild, but in most cases, catalyst amount
High molar fraction.Realize these applications of catalysis reaction industrially, it is necessary to which the recycling for solving expensive catalyst is
The problem of serious.
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
It is a kind of multifunction catalyst of widely used green.Early in early 20th century, people begin to the catalytic performance of polyacid into
Research is gone.To being at present, have 8 polyacid catalysis industry projects and successfully developed.It is catalyzed into 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.It is solely
Special soluble class mineral metal-oxide structure, for chiral transmission in chiral non-origin of life theory and inoganic solids
Exploration provides ideal 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
It hopes.
At present, chiral organic micromolecule catalyst is difficult to realize for industrialized production, mainly due to catalyst activity compared with
It is low, dosage is high and is not easily recycled utilization.Realize these applications of catalysis reaction industrially, it is necessary to solve expensive catalyst
The problem of recycling is a serious.
Since Zubieta in 1993 et al. exists《Nature》Upper report is successfully prepared class 9 like DNA's using hydrothermal technique
Chiral double-stranded compound (Me2NH2)K4[V10O10(H2O)4(OH)4(PO4)7]·H2After O, people have just started chirality
Polyacid is in the exploration of 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 all show the direct asymmetric Aldol reaction of aldehyde ketone, asymmetric Michael addition reaction etc.
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 specific 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 the composition of polyoxometallate (POMs), the diversity of structure and
A series of adjustable denaturation of 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 specific molecular structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain MOFs
With the synergistic effect of POMs.
In conclusion chiral organic micromolecule catalyst is difficult to realize for industrialized production, mainly due to chiral organic
Micromolecule catalyst activity is relatively low, dosage is high and is not easily recycled utilization.Realize these applications of catalysis reaction industrially, it must
The recycling that must solve the problems, such as expensive catalyst is a serious.Existing chiral organic micromolecule is combined novel with POMs
Material, without specific molecular structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain chiral organic micromolecule and polyacid
Synergistic effect.
Invention content
For above-mentioned technical problem of the prior art, the present invention provides (S) -1- (1- phenethyls) is thiourea modified
Cr-Anderson types heteropolyacid catalyst, preparation method and applications.The present invention solves existing chiral organic micromolecule catalysis
Agent activity is relatively low, dosage is high and the technical issues of being not easily recycled utilization, catalyst of the invention is synthesized available for asymmetry catalysis
Field.
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.What the present invention constructed
The polyacid of organic decoration not only remains the original structure of polyacid, and has expanded the research field of polyacid, makes it in catalysis, medicine
There is potential using value in terms of object and functional material.In addition, polyacid has hydrophily, available green, cheap water as solvent
Carry out catalysis reaction, reaction terminates after organic solvent (ethyl alcohol, methanol etc.) can be added in into system, and polyacid is easily precipitated, can be into
Row recycles.
The present invention provides one kind (S) -1- (1- phenethyls) systems of thiourea modified Cr-Anderson type heteropolyacid catalysts
Preparation Method is as follows：
1) using ammonium molybdate and chromic nitrate as raw material, the pH value of system is adjusted with acid between 4~5, in 80 DEG C~100 DEG C temperature
Degree is lower to prepare Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18]；
2) according to molar ratio 1:2~1：5 by Cr-Anderson types heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18] with trihydroxy aminomethane by hydro-thermal reaction is carried out at a temperature of 135-145 DEG C, it is amido modified to obtain organic unilateral side
Cr-Anderson type polyoxometallates；
3) using (S)-(+) -1- phenylethylamines as Material synthesis (S) -1- (1- phenethyls) isothiocyanates；
4) by (S) -1- (1- phenethyls) isothiocyanic acids and the amido modified Cr-Anderson type multi-metal oxygens in organic unilateral side
The thiourea modified Cr-Anderson type heteropolyacid catalysts of (S) -1- (1- phenethyls) are obtained by the reaction in hydrochlorate in organic solvent.
In the present invention, in step 1), the molar ratio of ammonium molybdate and chromic nitrate is 1:1~1：2.
In the present invention, in step 1), acid is nitric acid.
In the present invention, the hydro-thermal reaction time is 20h~30h.
In the present invention, in step 2), the amido modified Cr-Anderson type polyoxometallates in organic unilateral side are
[TBA]3{[NH2C(CH2O)3]CrMo6O18(OH)3, by the way that product after hydro-thermal reaction is mixed with tetrabutylammonium bromide, 80
DEG C~90 DEG C at a temperature of be prepared, Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18] and tetrabutyl phosphonium bromide
The molar ratio of ammonium is 1:3~1:5.
In the present invention, in step 4), (S) -1- (1- phenethyls) isothiocyanic acids and the amido modified Cr- in organic unilateral side
The molar ratio of Anderson type polyoxometallates is 3：1~5:1.
In the present invention, in step 4), reaction temperature is 45~55 DEG C, and organic solvent is in DMF, DMSO or NMP
Any one or more.System after reaction, if reaction solution is not clarified, is handled, after obtaining clarified solution using syringe filters
It places and is crystallized in ether atmosphere, can both obtain the final catalyst of the present invention.
The present invention also provides the thiourea modified Cr- of (the S) -1- (1- phenethyls) obtained with above-mentioned preparation method
Anderson type heteropolyacid catalysts.
The present invention further provides the thiourea modified Cr-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 specific as follows：By alkene and (S) -1- (1- benzene second
Base) thiourea modified Cr-Anderson type heteropolyacid catalysts be added to water and acetonitrile composition in the mixed solvent, 30 DEG C~50
It is reacted at a temperature of DEG C, obtains vicinal diol compound；Wherein：(S) Cr-Anderson types thiourea modified -1- (1- phenethyls) are miscellaneous
The inventory 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 the molar ratio of alkene is 1：1~3:1.
Above-mentioned catalysis after reaction, organic solvent (ethyl alcohol, methanol etc.) is added in into system, and polyacid is precipitated, filtering, very
Sky 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：
1) the high symmetry for not breaking polyacid merely with the covalent modification of chiral organic micromolecule of the invention introduces
Chirality improves its stereoselectivity in catalysis is reacted, and by the asymmetry catalysis or biology of organic chiral small molecule
The functional characteristics such as medicinal activity introduce polyacid, and organic moiety is made organically to be integrated into a whole with inorganic polyanionic,
More novel properties are obtained so as to generate synergistic effect；
2) preparation method reaction condition of the invention is mild, environmental-friendly；
3) obtained catalyst activity of the invention is high, enantioselectivity is high, recoverable, suitable for industrialization
Production.
Description of the drawings
Fig. 1 is the structural diagrams of final catalyst of the present invention.
Fig. 2 is the synthetic route chart of the present invention.
Fig. 3 is parent (NH4)3[Cr(OH)6Mo6O18] infrared spectrum.
Fig. 4 is the nuclear magnetic spectrogram of (S) -1- (1- phenethyls) isothiocyanates.
Fig. 5 is the infrared spectrum of unilateral amido modified Cr-Anderson type polyoxometallates.
Fig. 6 is the nuclear magnetic spectrogram of the thiourea modified Cr-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
Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18] preparation
7.41g (6mmol) ammonium molybdate is taken to be added in 20mL deionized waters, is sufficiently stirred to obtain clarified solution, be added dropwise later
The pH of system is transferred to 4~5. and is heated to boil by concentrated nitric acid, is maintained strong stirring, is started to be slowly added to 1.66g (7mmol) nitre
Sour chromium solid, stirring stop stirring, stand 15~30 minutes to there is a large amount of pink solids to generate.It filters, obtains 5.26g powder
Red crystalline solid raw material, yield 82%.
Parent (NH4)3[Cr(OH)6Mo6O18] infrared spectrum see Fig. 3.
Embodiment 2
(S) preparation of -1- (1- phenethyls) isothiocyanates
(S)-(+) -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%.
(S) nuclear magnetic spectrogram of -1- (1- phenethyls) isothiocyanates is shown in Fig. 4.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 unilateral amido modified Cr-Anderson type polyoxometallates
By Anderson parents (NH obtained above4)3[Cr(OH)6Mo6O18] 1.071g (1mmol) 10mL deionizations
It is dissolved in water, after obtaining light red clear liquid, is slowly added to trihydroxy aminomethane 0.402g (3mmol).Later by above-mentioned system
Water heating kettle is added in, 140 DEG C are heated in water heating kettle, after reaction carries out for 24 hours, by 4.83g tetrabutyl phosphonium bromides under the conditions of 85 DEG C
Ammonium adds in the solution such as above-mentioned dissolving, generates a large amount of pink precipitates i.e. crude product, filters and can obtain red liquid, is positioned to
The Cr-Anderson types polyacid [TBA] repaiied to crystallization, as organic unilateral amino decorations3{[CH2NH2C(CH2O)3]CrMo6O18
(OH)3}。
The infrared spectrum of unilateral amido modified Cr-Anderson type polyoxometallates is as shown in Figure 5.
Embodiment 4
(S) preparation of Cr-Anderson type heteropolyacid catalysts thiourea modified -1- (1- phenethyls)
Organic unilateral side is amido modified [TBA]3{[CH2NH2C(CH2O)3]CrMo6O18(OH)30.5g (0.275mmol) use
After the DMF of 5mL dissolves under the conditions of 50 DEG C, (S) -1- (1- phenethyls) isothiocyanates 0.224g (1.375mmol), dimension are added in
It holds under 50 DEG C of stirring conditions, 2~3 days reaction time, bright pink clarified solution is placed in ether atmosphere crystallize after reaction, it is several
It can obtain red crystals after it, that is, obtain the thiourea modified Cr-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls).
(S) nuclear magnetic spectrogram such as Fig. 6 institutes of Cr-Anderson type heteropolyacid catalysts thiourea modified -1- (1- phenethyls)
Show.Specific data are as follows：
1H NMR(501MHz,DMSO)δ7.64–6.93(m,5H),3.17(s,24H),1.98(s,2H),1.57(s,
24H),1.32(s,24H),1.24(s,3H),0.94(s,36H).
Embodiment 5
(S) Asymmetrical dihydroxylation of Cr-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 0.0213g (S) -1- (1- phenethyls) thiocarbamide, are eventually adding
The Cr-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 1.3552g, yield
It 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 different journeys
The progress of the catalysis reaction of degree, and with preferable stereoselectivity.Use different alkene and catalyst reaction, equation
As follows, 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 primary embodiments are not this new product of implementation and/or new method to other forms
It limits.Those skilled in the art will utilize this important information, the above modification, to realize similar executive condition.But
All modifications or transformation based on new product of 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 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 Cr-Anderson type heteropolyacid catalysts thiourea modified one kind (S) -1- (1- phenethyls), special
Sign is, is as follows：
1) using ammonium molybdate and chromic nitrate as raw material, the pH value of system is adjusted with acid between 4~5, at a temperature of 80 DEG C~100 DEG C
Prepare Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18]；
2) according to molar ratio 1:2~1：5, by Cr-Anderson types heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18] with trihydroxy aminomethane hydro-thermal reaction is carried out at a temperature of 135-145 DEG C, it is amido modified to obtain organic unilateral side
Cr-Anderson type polyoxometallates；
3) using (S)-(+) -1- phenylethylamines as Material synthesis (S) -1- (1- phenethyls) isothiocyanates；
4) by (S) -1- (1- phenethyls) isothiocyanates and the amido modified Cr-Anderson type polyoxometallic acids in organic unilateral side
The thiourea modified Cr-Anderson type heteropolyacid catalysts of (S) -1- (1- phenethyls) are obtained by the reaction in salt in organic solvent.
2. preparation method as described in claim 1, which is characterized in that in step 1), the molar ratio of ammonium molybdate and chromic nitrate is
1:1~1：2.
3. preparation method as described in claim 1, which is characterized in that in step 1), acid is nitric acid, and in step 2), hydro-thermal is anti-
It is 20h~30h between seasonable.
4. preparation method as described in claim 1, which is characterized in that in step 2), the amido modified Cr- in organic unilateral side
Anderson types polyoxometallate is [TBA]3{[NH2C(CH2O)3]CrMo6O18(OH)3, by will be produced after hydro-thermal reaction
Object is mixed with tetrabutylammonium bromide, is prepared at a temperature of 80 DEG C~90 DEG C, Cr-Anderson type heteropoly acid parents (NH4)3
[Cr(OH)6Mo6O18] and tetrabutylammonium bromide molar ratio be 1:3~1:5.
5. preparation method as described in claim 1, which is characterized in that in step 4), (S) -1- (1- phenethyls) isothiocyanic acid
The molar ratio of ester and the amido modified Cr-Anderson type polyoxometallates in organic unilateral side is 3：1~5:1.
6. preparation method as described in claim 1, which is characterized in that in step 4), reaction temperature is 45~55 DEG C, You Jirong
Any one or more of agent in DMF, DMSO or NMP.
7. (S) -1- (1- phenethyls) that a kind of preparation method as described in one of claim 1~6 obtains is thiourea modified
Cr-Anderson type heteropolyacid catalysts.
8. a kind of Cr-Anderson type heteropoly acid catalysis thiourea modified (S) -1- (1- phenethyls) as claimed in claim 7
Agent is in the application in the asymmetric dihydroxylation field of alkene.
9. application as claimed in claim 8, which is characterized in that application process is specific as follows：By alkene and (S) -1- (1- benzene second
Base) thiourea modified Cr-Anderson type heteropolyacid catalysts be added to water and acetonitrile composition in the mixed solvent, 30 DEG C~50
It is reacted at a temperature of DEG C, obtains vicinal diol compound；Wherein：(S) Cr-Anderson types thiourea modified -1- (1- phenethyls) are miscellaneous
The inventory of polyacid catalyst is 0.5mol%~5mol% of alkene.
10. application as claimed in claim 9, which is characterized in that the molar ratio of water and acetonitrile is 1:1~3:1, hydrogen peroxide is
Oxygen source, and the molar ratio of alkene is 1：1~3:1.
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| CN106475138A (en) * | 2016-10-12 | 2017-03-08 | 上海应用技术大学 | (S)‑1‑（1 phenethyl）Thiourea modified Al Anderson type heteropolyacid catalyst, preparation method and applications |
| 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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