CN105833909B - (S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (2- hydroxyl -1- phenethyls), preparation method and applications - Google Patents
(S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (2- hydroxyl -1- phenethyls), preparation method and applications Download PDFInfo
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Abstract
The invention discloses a kind of (S) 1 (2 hydroxyl, 1 phenethyl) thiourea modified Cr Anderson types heteropolyacid catalyst, preparation method and applications.The present invention is first by ammonium molybdate and chromic nitrate reaction generation Cr Anderson type heteropoly acids (NH4)3[Cr(OH)6Mo6O18], then it is subjected to hydro-thermal reaction with trihydroxy aminomethane and obtains the amido modified polyoxometallate in organic one side；Then final catalyst is obtained by Material synthesis (S) 1 (2 hydroxyl, 1 phenethyl) isothiocyanic acid, then the polyoxometallic acid reactant salt amido modified with organic one side of L benzene glycinol.Preparation method of the present invention is simple, and reaction condition is gentle, environmental-friendly.The heteropolyacid catalyst that the present invention obtains is used for the asymmetric dihydroxylation of alkene, has high catalytic activity, high corresponding selection, recoverable, 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- (2-
Hydroxyl -1- phenethyls) 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 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.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. at the same time, be considered
It is a kind of widely used green multifunction catalyst.Early in early 20th century, people begin to the catalytic performance of polyacid into
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.
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 the application of these catalytic reactions 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
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 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 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 the composition of polyoxometallate (POMs), 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 the synergistic effect of POMs.
The content of the invention
For deficiency of the prior art, it is an object of the invention to provide one kind (S) -1- (2- hydroxyl -1- phenethyls)
Thiourea modified Cr-Anderson types heteropolyacid catalyst, preparation method and applications.It is organic that the present invention solves existing chirality
Micromolecule catalyst activity is relatively low, dosage is high and is not easily recycled the technical problem utilized, the double hydroxyls of the asymmetry available for alkene
Change reaction.
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, of the invention is organic
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.
The present invention provides one kind (S) -1- (2- hydroxyl -1- phenethyls) thiourea modified Cr-Anderson type heteropoly acids and urges
The preparation method of agent (structure is shown in Fig. 1), comprises the following steps that：
1) using ammonium molybdate and chromic nitrate as raw material, it is 4~5 in pH value, under conditions of temperature is 80 DEG C~100 DEG C, prepares
Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18]；
2) by Cr-Anderson types heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18] and trihydroxy amino
Methane carries out hydro-thermal reaction in water heating kettle and obtains the amido modified Cr-Anderson type polyoxometallates in organic one side；
3) using L- benzene glycinol as Material synthesis (S) -1- (2- hydroxyl -1- phenethyls) isothiocyanates；
4) it is amido modified that (S) -1- (2- hydroxyl -1- phenethyls) isothiocyanic acid is reacted to the organic one side obtained with step 2)
Cr-Anderson types polyoxometallate reacted at a temperature of 45~55 DEG C and obtain (S) -1- (2- hydroxyl -1- phenethyls) sulphur
The Cr-Anderson type heteropolyacid catalysts of urea modification.
Above-mentioned steps 1) in, the molar ratio of ammonium molybdate and chromic nitrate is 1:1~1：2.
Above-mentioned steps 1) in, by between the pH value of concentrated nitric acid tune system to 4~5.
Above-mentioned steps 2) in, Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18] and trihydroxy amino first
The molar ratio 1 of alkane:2~1：5.
Above-mentioned steps 2) in, hydrothermal temperature is 135-145 DEG C, and the hydro-thermal reaction time is 20h~30h.
Above-mentioned steps 3) in, using L- benzene glycinol as Material synthesis (S) -1- (2- hydroxyl -1- phenethyls) isothiocyanates
Comprise the following steps that：
By L- benzene glycinol, CS2With triethylamine with molar ratio 1:(2~4):1 ratio mixing, is stirred at room temperature reaction 1h
After~2h, di-tert-butyl dicarbonate and 4-dimethylaminopyridine are added, 3h~5h is reacted under condition of ice bath, obtains (S) -1- (2-
Hydroxyl -1- phenethyls) isothiocyanates, wherein：Mole of L- benzene glycinol, di-tert-butyl dicarbonate and 4-dimethylaminopyridine
Than for 1:1:(0.02~0.05).
Above-mentioned steps 4) in, the amido modified Cr-Anderson types polyoxometallate in organic one side and (S) -1- (2- hydroxyls
Base -1- phenethyls) isothiocyanates molar ratio be 1:3~1：5, reaction dissolvent uses any one in DMF, DMSO or NMP
It is or several.Clarified solution is placed in ether atmosphere after reaction and is crystallized, crystal is can obtain behind some days, that is, obtains (S) -1-
(2- hydroxyl -1- phenethyls) thiourea modified Cr-Anderson type heteropolyacid catalysts.Specifically, system is after reaction, if
Reaction solution is not clarified, and is handled using syringe filters, is obtained placing after clarified solution and is crystallized in ether atmosphere.
Above-mentioned steps 5) in, suitable alkene, 30 DEG C~50 DEG C, using water and acetonitrile as mixed solvent under conditions of, add
Enter hydrogen peroxide and Cr-Anderson type heteropolyacid catalysts thiourea modified (S) -1- (2- hydroxyl -1- phenethyls), react
24h, obtains vicinal diol compound.
(the S) -1- (2- hydroxyl -1- phenethyls) being prepared the present invention also provides a kind of above-mentioned preparation method is thiourea modified
Cr-Anderson type heteropolyacid catalysts.
The present invention further provides the thiourea modified Cr-Anderson types of above-mentioned (S) -1- (2- hydroxyl -1- phenethyls) are miscellaneous
Application of more acid catalysts in the asymmetric dihydroxylation field of alkene.
Above application method is as follows：By alkene and Cr-Anderson thiourea modified (S) -1- (2- hydroxyl -1- phenethyls)
Type heteropolyacid catalyst is mixed in the in the mixed solvent that water and acetonitrile form, and is reacted at a temperature of 30 DEG C~50 DEG C, is obtained vicinal diamines
Compound；Wherein：(S) amount of Cr-Anderson type heteropolyacid catalysts thiourea modified -1- (2- hydroxyl -1- phenethyls) is
0.5mol%~5mol% of alkene.Preferably, the molar ratio of water and acetonitrile is 1:1~3:1, hydrogen peroxide is oxygen source, it makes
Dosage is 1-3 equivalents (using alkene as reference).
After above application method, after adding organic solvent (ethanol, methanol etc.) into phase system, polyacid separates out, mistake
Filter, vacuum drying, recycling obtain polyacid, the reusable asymmetric dihydroxylation in alkene.
The beneficial effects of the present invention are：Can not only the covalent modification of chiral organic micromolecule be utilized to break polyacid
High symmetry, introduce chiral, improve its stereoselectivity in catalytic reaction, and can be by organic chiral small molecule
The functional characteristic such as asymmetry catalysis or biological medicine activity introduces polyacid, and makes organic moiety and inorganic polyanionic organically
It is integrated into a whole, so that producing synergistic effect obtains more novel properties.Preparation method reaction condition of the present invention is gentle,
It is environmental-friendly；Obtained catalyst activity height, enantioselectivity is high, recoverable, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the structural diagrams of the final catalyst of the present invention.
Fig. 2 is the synthetic route diagram of the present invention.
Fig. 3 is the parent (NH of embodiment 14)3[Cr(OH)6Mo6O18] infrared spectrum.
Fig. 4 is the nuclear magnetic spectrogram of (S) -1- (2- hydroxyl -1- phenethyls) isothiocyanates.
Fig. 5 is the infrared spectrum of unilateral amido modified Cr-Anderson type polyoxometallates.
Fig. 6 is the nuclear-magnetism of the thiourea modified Cr-Anderson type heteropolyacid catalysts of (S) -1- (2- hydroxyl -1- phenethyls)
Spectrogram.
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.
The synthetic route of the present invention is as shown in Figure 2.
Embodiment 1
Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18] preparation
Take 7.41g (6mmol) ammonium molybdate to be added in 20mL deionized waters, be sufficiently stirred to obtain clarified solution, be added dropwise afterwards
Concentrated nitric acid, is transferred to 4~5. by the pH of system and is heated to seethe with excitement, and maintains strong stirring, starts 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 produce.Filter, obtain 5.26g powder
Red crystalline solid raw material, yield 82%.
Parent (NH4)3[Cr(OH)6Mo6O18] infrared spectrum see Fig. 1.
Embodiment 2
(S) preparation of -1- (2- hydroxyl -1- phenethyls) isothiocyanates
L- 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 4-dimethylaminopyridine (DMAP)
(18mg, 0.15mmol), (has gas generation, it should be noted that decompression of deflating) after reaction 2h is stirred at room temperature in the process of stirring, can
Obtain 0.7547g (S) -1- (2- hydroxyl -1- phenethyls) isothiocyanates.
(S) nuclear magnetic spectrogram of -1- (2- hydroxyl -1- phenethyls) isothiocyanates is as shown in figure 4, specific data are as follows：
1H NMR(501MHz,CDCl3):δ 7.45-7.29 (m, 5H), 5.06 (dt, J=52.6,9.1Hz, 2H), 4.49
(dd, J=8.8,7.0Hz, 1H), 1.38-1.15 (m, 1H)
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
Dissolved in water, after obtaining light red clear liquid, be slowly added to trihydroxy aminomethane 0.402g (3mmol).Afterwards by above-mentioned system
Water heating kettle is added, 140 DEG C are heated in water heating kettle, after reaction carries out 24h, by 4.83g tetrabutyl phosphonium bromides under the conditions of 85 DEG C
Ammonium adds in the solution such as above-mentioned dissolving, produces a large amount of pink precipitates i.e. crude product, filters and can obtain red liquid, is positioned to
It is the Cr-Anderson types polyacid [TBA] that organic unilateral amino decorations are repaiied to crystallization3{[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) Cr-Anderson type heteropolyacid catalysts thiourea modified -1- (2- hydroxyl -1- phenethyls)
Organic one 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- (2- hydroxyl -1- phenethyls) isothiocyanates 0.179g is added
(1mmol), maintains under 50 DEG C of stirring conditions, 2~3 days reaction time, and bright pink clarified solution is placed ether atmosphere after reaction
Middle crystallization, red crystals are can obtain behind some days, that is, it is miscellaneous to obtain the thiourea modified Cr-Anderson types of (S) -1- (1- phenethyls)
More acid catalysts.
(S) nuclear magnetic spectrogram of Cr-Anderson type heteropolyacid catalysts thiourea modified -1- (2- hydroxyl -1- phenethyls)
As shown in fig. 6, 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) asymmetry of Cr-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 molar ratio of nitrile is 1:1~3:1) 30% hydrogen peroxide of 1.7g and 0.0216g (S) -1- (2- hydroxyl -1- benzene second, are eventually adding
Base) thiourea modified more acid catalysts of Cr-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 solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains vicinal diol compound, obtains product
1.358g, yield 99%.The enantiomeric excess of product is measured by chiral high performance liquid chromatography, and ee values are up to 99%.The catalyst
The progress of catalytic reaction that can be different degrees of, and there is preferable stereoselectivity.Urged using different alkene
The reaction equation of change is as follows, and obtained experimental result is shown in Table 1.
The asymmetric dihydroxylation experimental result of 1 polyacid catalyzed alkene of table
The catalyst that above-mentioned recycling obtains is directly used in the dihydroxylation of styrene, the enantiomer mistake of resulting product
Value measures (chiral AS-H columns, isopropanol by HPLC：N-hexane=3:7,254nm,20℃,0.5mL/min).Catalyst recycles
2 are the results are shown in Table using obtained.
The experimental result that 2 catalyst of table recycles
All above-mentioned primary embodiments, do not implement this new product and/or new method setting limits other shapes
Formula.Those skilled in the art will utilize this important information, the above modification, to realize similar implementation status.But institute
There are the modification based on the present invention or transformation to 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 Cr-Anderson type heteropolyacid catalysts thiourea modified one kind (S) -1- (2- hydroxyl -1- phenethyls)
Method, it is characterised in that comprise the following steps that：
1) using ammonium molybdate and chromic nitrate as raw material, it is 4~5 in pH value, under conditions of temperature is 80 DEG C~100 DEG C, prepares Cr-
Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18]；
2) by Cr-Anderson types heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18] and trihydroxy aminomethane
Hydro-thermal reaction is carried out in water heating kettle, obtains the amido modified Cr-Anderson type polyoxometallates in organic one side；
3) using L- benzene glycinol as Material synthesis (S) -1- (2- hydroxyl -1- phenethyls) isothiocyanates；
4) the amido modified Cr- in organic one side for obtaining (S) -1- (2- hydroxyl -1- phenethyls) isothiocyanates and step 2)
Anderson types polyoxometallate reacts at a temperature of 45~55 DEG C, obtains (S) -1- (2- hydroxyl -1- phenethyls) thiocarbamide and repaiies
The Cr-Anderson type heteropolyacid catalysts of decorations.
2. preparation method as claimed in claim 1, it is characterised in that in step 1), the molar ratio of ammonium molybdate and chromic nitrate is
1:1~1：2.
3. preparation method as claimed in claim 1, it is characterised in that in step 1), pass through the pH value of concentrated nitric acid tune system to 4
Between~5.
4. preparation method as claimed in claim 1, it is characterised in that in step 2), Cr-Anderson type heteropoly acid parents
(NH4)3[Cr(OH)6Mo6O18] with the molar ratio 1 of trihydroxy aminomethane:2~1：5.
5. preparation method as claimed in claim 1, it is characterised in that in step 2), hydrothermal temperature is 135-145 DEG C,
The hydro-thermal reaction time is 20h~30h.
6. preparation method as claimed in claim 1, it is characterised in that in step 3), using L- benzene glycinol as Material synthesis
(S) -1- (2- hydroxyl -1- phenethyls) isothiocyanates comprises the following steps that：
By L- benzene glycinol, CS2With triethylamine with molar ratio 1:(2~4):1 ratio mixing, is stirred at room temperature reaction 1h~2h
Afterwards, di-tert-butyl dicarbonate and 4-dimethylaminopyridine are added, reacts 3h~5h under condition of ice bath, obtain (S) -1- (2- hydroxyls -
1- phenethyls) isothiocyanates, wherein：The molar ratio of L- benzene glycinol, di-tert-butyl dicarbonate and 4-dimethylaminopyridine is
1:1:(0.02~0.05).
7. preparation method as claimed in claim 1, it is characterised in that in step 4), the amido modified Cr- in organic one side
The molar ratio of Anderson types polyoxometallate and (S) -1- (2- hydroxyl -1- phenethyls) isothiocyanates is 1:3~1：5,
Reaction dissolvent uses any one or a few in DMF, DMSO or NMP.
8. (S) -1- (2- hydroxyl -1- phenethyls) thiocarbamide that a kind of preparation method as described in one of claim 1-7 obtains is repaiied
The Cr-Anderson type heteropolyacid catalysts of decorations.
9. a kind of Cr-Anderson types thiourea modified (S) -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 (S) -1- (2- hydroxyls -1-
Phenethyl) the in the mixed solvent mixing that is formed in water and acetonitrile of thiourea modified Cr-Anderson types heteropolyacid catalyst, 30 DEG C
Reacted at a temperature of~50 DEG C, obtain vicinal diol compound；Wherein：(S) Cr- thiourea modified -1- (2- hydroxyl -1- phenethyls)
The amount of Anderson type heteropolyacid catalysts is 0.5mol%~5mol% of alkene.
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| CN201610211338.0A CN105833909B (en) | 2016-04-06 | 2016-04-06 | (S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (2- hydroxyl -1- phenethyls), preparation method and applications |
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| CN201610211338.0A CN105833909B (en) | 2016-04-06 | 2016-04-06 | (S) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (2- hydroxyl -1- phenethyls), preparation method and applications |
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| CN106513042A (en) * | 2016-10-12 | 2017-03-22 | 上海应用技术大学 | (R)-1-(2-hydroxyl-1-phenethyl)thiourea modified Al-Anderson heteropolyacid catalyst as well as preparation method and application thereof |
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| CN106513039A (en) * | 2016-10-12 | 2017-03-22 | 上海应用技术大学 | (S)-1-(2-hydroxyl-1-phenethyl)thiourea modified Al-Anderson heteropolyacid catalyst as well as preparation method and application thereof |
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