CN105854940B - (R) Cr-Anderson types heteropolyacid catalyst thiourea modified -1- (1- phenethyls), preparation method and applications - Google Patents
(R) Cr-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 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]；It is subjected to hydro-thermal reaction in water heating kettle with trihydroxy aminomethane again and obtains the amido modified polyoxometallate in organic one side；Then using (R) (+) 1 phenylethylamine as Material synthesis (R) 1 (1 phenethyl) isothiocyanic acid, then by it with the amido modified polyoxometallic acid reactant salt in organic one side obtained above is obtained target heteropolyacid catalyst.Preparation method of the present invention is simple, environmental-friendly, and obtained catalyst is used for the asymmetric dihydroxylation of alkene, has high enantioselectivity and high catalytic activity, 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) 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.
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.
Since Zubieta in 1993 et al. exists《Nature》Upper report is successfully prepared similar DNA using hydrothermal technique
Chiral double-stranded compound (Me2NH2)K4[V10O10(H2O)4(OH)4(PO4)7]·H2After O, people have just started chirality
Exploration of the polyacid in asymmetric catalysis field.The Chinese Academy of Sciences chemistry institute Luo Sanzhong teach et al. urged with organic amine small molecules
Agent is made that outstanding work (Organic as the field of catalyst-supporting carriers as counter cation, polyacid
letters,2007,9(18):3675-3678.).They have synthesized a series of secondary amine-tertiary amine-type proline derivative, use
Polyanionic [the PW of highly acid12O40]3-The mineral acid in traditional Acid-Base concerted catalysis is substituted, it is organic to have synthesized a series of chiralitys
Amine-polyacid hybrid material.These materials 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.
In addition, at present, chiral organic micromolecule catalyst is difficult to realize for industrialized production, live mainly due to catalyst
Property is relatively low, dosage is high and is not easily recycled utilization.Realize the application of these catalytic reactions industrially, it is necessary to solve expensive catalysis
The problem of recycling of agent is a serious.
The content of the invention
For deficiency of the prior art, it is an object of the invention to provide one kind (R) -1- (1- phenethyls) is thiourea modified
Cr-Anderson types heteropolyacid catalyst, preparation method and applications.Preparation method of the present invention is simple, obtained heteropoly acid
Catalyst is environmental-friendly, recoverable, has high enantioselectivity and high catalytic activity, suitable for industrialized production, this hair
It is bright to solve that existing chiral organic micromolecule catalyst activity is relatively low, dosage is high and be not easily recycled the technical problem utilized.
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.The chirality of the present invention
Polyacid material not only remains the original structure of polyacid, and has expanded the research field of polyacid, makes it in catalysis, medicine and work(
There can be potential using value in terms of material.In addition, polyacid has hydrophily, available green, cheap water as solvent are urged
Change reaction, reaction terminates after organic solvent (ethanol, methanol etc.) can be added into system, and polyacid easily separates out, and may be recovered
Utilize.
The present invention provides one kind (R) -1- (1- phenethyls) thiourea modified Cr-Anderson types heteropolyacid catalyst (knots
Structure such as Fig. 1) preparation method, its synthetic route is as shown in Fig. 2, comprise the following steps that：
1) using ammonium molybdate and chromic nitrate as raw material, with the pH value of sour regulation system 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) 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, obtains the amido modified Cr-Anderson type polyoxometallates in organic one side；
3) using (R)-(+) -1- phenylethylamines as Material synthesis (R) -1- (1- phenethyls) isothiocyanates；
4) by (R) -1- (1- phenethyls) isothiocyanic acids and the amido modified Cr-Anderson type multi-metal oxygens in organic one side
Hydrochlorate reacts to obtain the thiourea modified Cr-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls) in organic solvent.
Above-mentioned steps 1) in, the molar ratio of ammonium molybdate and chromic nitrate is 1:1~1：2.
Above-mentioned steps 1) in, acid is nitric acid.
Above-mentioned steps 2) in, Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18] and trihydroxy amino first
The molar ratio of alkane is 1:2~1：5；Hydrothermal temperature is 135-145 DEG C, and the hydro-thermal reaction time is 20h~30h；Preferably, You Jidan
The amido modified Cr-Anderson types polyoxometallate in side is [TBA]3{[NH2C(CH2O)3]CrMo6O18(OH)3, it passes through
By product after hydro-thermal reaction and tetrabutylammonium bromide with molar ratio 1:3~1：5 ratio mixing, makes at a temperature of 80 DEG C~90 DEG C
It is standby to obtain.
Above-mentioned steps 4) in, (R) -1- (1- phenethyls) isothiocyanic acids and the amido modified Cr-Anderson in organic one side
The molar ratio of type polyoxometallate is 3：1~5:1.
Above-mentioned steps 4) in, reaction temperature is 45~55 DEG C, and organic solvent is any one in DMF, DMSO or NMP
Kind is a variety of.Reaction time is 2~3 days, places in ether atmosphere clarified solution crystallize after reaction, crystalline substance is obtained behind some days
Body, that is, obtain the thiourea modified Cr-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls).
Cr-Anderson types thiourea modified (R) -1- (1- phenethyls) for obtaining the present invention also provides above-mentioned preparation method
Heteropolyacid catalyst.
Further, the present invention also provides the thiourea modified Cr-Anderson types of above-mentioned (R) -1- (1- phenethyls) are miscellaneous more
Application of the acid catalyst in the asymmetric dihydroxylation field of alkene.Preferably, application process is as follows：By alkene and (R)-
Cr-Anderson type heteropolyacid catalysts thiourea modified 1- (1- phenethyls) are added to the mixed solvent formed with water and acetonitrile
In, 30 DEG C~50 DEG C, at a temperature of react, obtain vicinal diol compound；Wherein：The R) -1- (1- phenethyls) is thiourea modified
The inventory of Cr-Anderson type heteropolyacid catalysts is 0.5mol%~5mol% of alkene.
The beneficial effects of the present invention are：
(1) present invention can not only utilize the covalent modification of chiral organic micromolecule to break the high symmetry of polyacid,
Chirality is introduced, improves its stereoselectivity in catalytic reaction, and can be by the asymmetry catalysis of organic chiral small molecule
Or the functional characteristic such as biological medicine activity introduces polyacid, and organic moiety is set organically to be combined into one with inorganic polyanionic
It is overall, so that producing synergistic effect obtains more novel properties.
(2) reaction condition of the present invention is gentle, environmental-friendly；Obtained catalyst recoverable, has high mapping selection
The advantages that property and catalytic activity are high, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the structural diagrams of final catalyst of the present invention.
Fig. 2 is the synthetic route diagram of the present invention.
Fig. 3 is parent (NH4)3[Cr(OH)6Mo6O18] infrared spectrum.
Fig. 4 is the nuclear magnetic spectrogram of (R) -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 (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
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 it is as shown in Figure 3.
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 (Boc2O) (1.091mg, 5mmol) and 4- dimethylaminos are then added under the conditions of 0 DEG C
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 as shown in figure 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
Dissolved in water, after obtaining light red clear liquid, be slowly added to trihydroxy aminomethane 0.402g (3mmol).Afterwards by above-mentioned system
Add in water heating kettle, be heated to 140 DEG C, after reaction carries out 24h, add 4.83g tetrabutylammonium bromide under the conditions of 85 DEG C
In the solution stated, a large amount of pink precipitates i.e. crude product is produced, filters and can obtain red liquid, placement is crystallized, and is
The Cr-Anderson types polyacid [TBA] that organic one side amino decorations are repaiied3{[NH2C(CH2O)3]CrMo6O18(OH)3}。
The infrared spectrum of unilateral amido modified Cr-Anderson type polyoxometallates is as shown in Figure 5.
Embodiment 4
(R) preparation of Cr-Anderson type heteropolyacid catalysts thiourea modified -1- (1- phenethyls)
Organic one side is amido modified [TBA]3{[NH2C(CH2O)3]CrMo6O18(OH)30.5g (0.275mmol) uses 5mL
DMF dissolve under the conditions of 50 DEG C after, add (R) -1- (1- phenethyls) isothiocyanates 0.224g (1.375mmol), maintain
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 Cr-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls).
(R) nuclear magnetic spectrogram such as Fig. 6 institutes of Cr-Anderson type heteropolyacid catalysts thiourea modified -1- (1- phenethyls)
Show, specific nuclear magnetic data is 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
(R) Asymmetrical dihydroxylation of Cr-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 0.0213g (R) -1- (1- phenethyls) thiocarbamide, are eventually adding
The more acid catalysts of Cr-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 1.3673g, yield
For 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 catalytic reaction of degree, and there is preferable stereoselectivity.The reactional equation being catalyzed using different alkene
Formula 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 recycling embodiment 5 obtains is directly recycled for the dihydroxylation of styrene, resulting product
Enantiomeric excess value measures (chiral AS-H columns, isopropanol by HPLC：N-hexane=3:7,254nm,20℃,0.5mL/min).Urge
Agent recycling is obtained to the results are shown in Table 2.
The experimental result that 2 catalyst of table recycles
All above-mentioned primary embodiments, this new product of the implementation to other forms and/or new method are not set
Definite limitation.Those skilled in the art will utilize this important information, the above modification, to realize similar implementation status.But
It is that all modifications or transformation based on embodiment 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 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 (9)
1. the preparation method of Cr-Anderson type heteropolyacid catalysts thiourea modified one kind (R) -1- (1- phenethyls), it is special
Sign is, comprises the following steps that：
1) using ammonium molybdate and chromic nitrate as raw material, with the pH value of sour regulation system 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) 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 (R)-(+) -1- phenylethylamines as Material synthesis (R) -1- (1- phenethyls) isothiocyanates；
4) by (R) -1- (1- phenethyls) isothiocyanates and the amido modified Cr-Anderson type polyoxometallic acids in organic one side
Salt is organic
Reaction obtains the thiourea modified Cr-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls) in solvent.
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), acid is nitric acid.
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 of trihydroxy aminomethane it is 1:2~1：5；Hydrothermal temperature is 135-145 DEG C, water
The thermal response time is 20h~30h.
5. preparation method as claimed in claim 1, it is characterised in that in step 4), (R) -1- (1- phenethyls) isothiocyanic acid
The molar ratio of ester and the amido modified Cr-Anderson type polyoxometallates in organic one side is 3：1~5:1.
6. preparation method as claimed in claim 1, it is characterised 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. Cr- thiourea modified a kind of (R) -1- (1- phenethyls) that preparation method as described in one of claim 1~6 obtains
Anderson type heteropolyacid catalysts.
A kind of 8. Cr-Anderson type heteropoly acid catalysis thiourea modified (R) -1- (1- phenethyls) as claimed in claim 7
Application of the agent in the asymmetric dihydroxylation field of alkene.
9. application as claimed in claim 8, it is characterised in that application process is as follows：By alkene and (R) -1- (1- phenethyls)
Thiourea modified Cr-Anderson type heteropolyacid catalysts are added to the in the mixed solvent formed with water and acetonitrile, and 30 DEG C~50
DEG C, at a temperature of react, obtain vicinal diol compound；Wherein：The thiourea modified Cr-Anderson of (the R) -1- (1- phenethyls)
The inventory of type heteropolyacid catalyst is 0.5mol%~5mol% of alkene.
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| CN106513044A (en) * | 2016-10-12 | 2017-03-22 | 上海应用技术大学 | (R)-1-(1-phenethyl)thiourea unilaterally modified Fe-Anderson heteropolyacid catalyst as well as preparation method and application thereof |
| CN106622371A (en) * | 2016-10-12 | 2017-05-10 | 上海应用技术大学 | (R)-1-(1-phenethyl)thiourea modified Al-Anderson type heteropolyacid catalyst and preparation method and application thereof |
| CN110483246A (en) * | 2018-05-15 | 2019-11-22 | 中国石油天然气股份有限公司 | A kind of β-Anderson type heteropolymolybdate organic derivative of unilateral modification |
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