CN105854941A - (S)-1-(1-phenethyl) thiourea-modified Cr-Anderson heteropolyacid catalyst, and preparation method and application thereof - Google Patents
(S)-1-(1-phenethyl) thiourea-modified Cr-Anderson heteropolyacid catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an (S)-1-(1-phenethyl) thiourea-modified Cr-Anderson heteropolyacid catalyst, and a preparation method and an application thereof. The method comprises the following steps: firstly, reacting ammonium molybdate and chromic nitrate to generate Cr-Anderson heteropolyacid (NH4)3[Cr(OH)6Mo6O18]; carrying out hydrothermal reaction on the Cr-Anderson heteropolyacid and tris(hydroxymethyl)aminomethane in a hydrothermal kettle to obtain an organic unilateral amino-modified polyoxometallate; and with (S)-(+)-1-phenylethylamine as a raw material, synthesizing (R)-1-(1-phenethyl) isothiocyanic acid; and finally reacting (R)-1-(1-phenethyl) isothiocyanic acid and the organic unilateral amino-modified polyoxometallate to obtain the target heteropolyacid catalyst. The preparation method is simple; and the obtained heteropolyacid catalyst is applied to asymmetric dihydroxylation of olefin, is friendly to environment, can be recycled, has high enantioselectivity and high catalytic activity and is suitable for industrial production.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, particularly relate to asymmetric selective catalysis, specifically (S)-1-(1-benzene second
Base) thiourea modified Cr-Anderson type heteropolyacid catalyst, preparation method and applications.
Background technology
Calendar year 2001, Nobel laureate professor Noyori pointed out: " following synthesis chemistry must be economical, safe,
Eco-friendly and save resource and the chemistry of the energy, chemist needs the effort for realization ' perfect reactive chemistry ',
I.e. only generate the product of needs with the selectivity of 100% and the yield of 100% and do not have refuse to produce ".Chiral catalysis synthesizes
As one of important channel realizing " perfect synthesis chemistry ", wherein, chiral catalyst is the core in chiral catalysis research
Heart problem in science.From reaction principle, chiral organic micromolecule catalysis be by with reaction substrate with unstable covalent bond
If reversibly forming reactive intermediate or by interacting, such as oxygen key, Van der Waals force or ion equity priming reaction substrate.
Although homogeneous chiral catalysis has the feature such as enantioselectivity efficient, high and reaction condition gentleness, but in most cases, urges
Agent consumption high molar fraction.Realize the application industrially of these catalytic reactions, it is necessary to solve the recovery of expensive catalyst
Utilization is a serious problem.
Catalysis is the most promising and most practical value research direction in polyoxometallate application.Polyoxometallate is simultaneously
Integrate the good characteristic of acid base catalysator, oxidation reduction catalyst, metal oxide nanocatalyst etc. it is considered to be
A kind of multifunction catalyst of widely used green.As far back as 20 beginnings of the century, people begin to enter the catalytic performance of polyacid
Go research.It is that the existing project of acid catalysis industrialization more than 8 is successfully developed up till now.It is catalyzed in order in Chemistry of Polyacids
One eternal research topic.After chirality polyoxometallate is successfully synthesized, people have just started chirality polyacid and have existed
The exploration of asymmetric catalysis field.Chirality polyoxometallate integrates the various excellent properties of polyacid and chiral material.Its
Unique solubility class mineral metal-oxide structure, for chirality transmission in the non-origin of life theory of chirality and inoganic solids
Exploration provides preferable model；Its high elecrtonegativity, adjustable Acidity of Aikalinity, redox active and nano-scale, more
The design of new material, the synthesis such as the catalysis of multi-functional nonlinear optics, nano material, stereo selectivity and medicine bring new
Hope.
At present, chiral organic micromolecule catalyst is difficulty with for industrialized production, relatively low mainly due to catalyst activity,
Consumption is high and is not easily recycled utilization.Realize the application industrially of these catalytic reactions, it is necessary to solve returning of expensive catalyst
Receiving utilization is a serious problem.
Since Zubieta in 1993 et al. uses hydrothermal technique to be successfully prepared class 9 like DNA at " Nature " upper report
Chirality double-stranded compound (Me2NH2)K4[V10O10(H2O)4(OH)4(PO4)7]·H2After O, people just start
Chirality polyacid is in the exploration of asymmetric catalysis field.Chinese Academy of Sciences's chemistry professor Luo Sanzhong et al. with little point of organic amine
Muonic catalysis agent is made that outstanding work (Organic as counter cation, polyacid as the field of catalyst-supporting carriers
letters,2007,9(18):3675-3678.).They have synthesized a series of secondary amine-tertiary amine-type proline derivative, use strong acid
Polyanionic [the PW of property12O40]3-Substitute tradition Acid-Base concerted catalysis in mineral acid, synthesized a series of chirality organic amine-
Polyacid hybrid material.These materials direct asymmetric Aldol reaction to aldehyde ketone, asymmetric Michael addition reaction etc. all shows
The highest catalysis activity and chiral selectivity.Organic amine small molecules is assembled by electrostatic interaction with polyacid as counter cation,
But these materials do not have clear and definite molecular structure, it is impossible to probe into catalytic mechanism further, it is impossible to explain the association of Chiral Amine and polyacid
Same-action.Dalian materialization institute Duan Chun meet seminar meet utilize the composition of polyoxometallate (POMs), the multiformity of structure and
The adjustable degeneration of electric charge, a series of porous POMOFs with catalysis of design and assembly, it is achieved that they are heterogeneous
Application (Journal of the American Chemical Society, 2013,135 (28): 10186-10189.) in catalysis, but this
A little materials are also without clear and definite molecular structure, it is impossible to probe into catalytic mechanism further, it is impossible to explain MOFs's Yu POMs
Synergism.
In sum, chiral organic micromolecule catalyst is difficulty with for industrialized production, mainly due to organic little point of chirality
Muonic catalysis agent activity is relatively low, consumption is high and is not easily recycled utilization.Realize the application industrially of these catalytic reactions, it is necessary to
The recycling solving expensive catalyst is a serious problem.It is novel that existing chiral organic micromolecule is combined with POMs
Material, does not has clear and definite molecular structure, it is impossible to probe into catalytic mechanism further, it is impossible to explain chiral organic micromolecule and polyacid
Synergism.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides (S)-1-(1-phenethyl) thiourea modified
Cr-Anderson type heteropolyacid catalyst, preparation method and applications.The present invention solves the catalysis of existing chiral organic micromolecule
Agent activity is relatively low, consumption is high and is not easily recycled the technical problem of utilization, and the catalyst of the present invention can be used for asymmetry catalysis synthesis
Field.
The present invention, from the mentality of designing of organic micromolecule catalyst, proposes to utilize " Acid-Base " concerted catalysis innovatively
Strategy, to have the chiral organic micromolecule of potential catalysis activity as precursor, by methods such as organic decorations, dexterously
The vacant polyanionic making organic molecule acid with high Bronsted is combined, and constructs chirality polyacid material.The present invention constructs
The polyacid of organic decoration not only remains the original structure of polyacid, and has expanded the research field of polyacid so that it is catalysis,
Medicine and functional material aspect have potential using value.Additionally, polyacid has hydrophilic, available green, cheap water are made
Solvent carries out catalytic reaction, and after reaction terminates to add organic solvent (ethanol, methanol etc.) in system, polyacid easily separates out,
May be recovered utilization.
The present invention provides the preparation method of the Cr-Anderson type heteropolyacid catalyst that a kind of (S)-1-(1-phenethyl) is thiourea modified,
Specifically comprise the following steps that
1) with ammonium molybdate and chromic nitrate as raw material, with the pH value of acid regulation system between 4～5, at a temperature of 80 DEG C～100 DEG C
Preparation Cr-Anderson type heteropoly acid parent (NH4)3[Cr(OH)6Mo6O18]；
2) according to mol ratio 1:2～1:5 by Cr-Anderson type heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18]
With trihydroxy aminomethane by carrying out hydro-thermal reaction at a temperature of 135-145 DEG C, obtain organic one side amido modified
Cr-Anderson type polyoxometallate；
3) with (S)-(+)-1-phenylethylamine as Material synthesis (S)-1-(1-phenethyl) isothiocyanate；
4) by Cr-Anderson type polyoxometallate amido modified with organic one side for (S)-1-(1-phenethyl) isothiocyanic acid organic
In solvent, reaction obtains the thiourea modified Cr-Anderson type heteropolyacid catalyst of (S)-1-(1-phenethyl).
In the present invention, step 1) in, the mol ratio of ammonium molybdate and chromic nitrate is 1:1～1:2.
In the present invention, step 1) in, acid is nitric acid.
In the present invention, the hydro-thermal reaction time is 20h～30h.
In the present invention, step 2) in, the amido modified Cr-Anderson type polyoxometallate in described organic one side is
[TBA]3{[NH2C(CH2O)3]CrMo6O18(OH)3, it is by mixing hydro-thermal reaction afterproduct with tetrabutyl ammonium bromide,
Prepare at a temperature of 80 DEG C～90 DEG C, Cr-Anderson type heteropoly acid parent (NH4)3[Cr(OH)6Mo6O18] and four fourths
The mol ratio of base ammonium bromide is 1:3～1:5.
In the present invention, step 4) in, the Cr-Anderson that (S)-1-(1-phenethyl) isothiocyanic acid is amido modified with organic one side
The mol ratio of type polyoxometallate is 3:1～5:1.
In the present invention, step 4) in, reaction temperature is 45～55 DEG C, and organic solvent is selected from DMF, DMSO or NMP
In any one or more.After system reaction terminates, if reactant liquor is not clarified, application syringe filters processes, and obtains clear
Place in ether atmosphere after clear liquid and crystallize, both can obtain the final catalyst of the present invention.
The present invention also provides for the Cr-Anderson thiourea modified for (S)-1-(1-phenethyl) obtained with above-mentioned preparation method
Type heteropolyacid catalyst.
The present invention further provides Cr-Anderson type heteropolyacid catalyst thiourea modified for above-mentioned (S)-1-(1-phenethyl) at alkene
The application in asymmetric dihydroxylation field.Application process is specific as follows: by alkene and (S)-1-(1-phenethyl)
Thiourea modified Cr-Anderson type heteropolyacid catalyst joins in the mixed solvent of water and acetonitrile composition, 30 DEG C～50 DEG C
At a temperature of react, obtain vicinal diol compound；Wherein: Cr-Anderson type thiourea modified for (S)-1-(1-phenethyl) is miscellaneous many
The inventory of acid catalyst is 0.5mol%～5mol% of alkene.Preferably, the mol ratio of water and acetonitrile is 1:1～3:1,
Hydrogen peroxide is oxygen source, and it is 1:1～3:1 with the mol ratio of alkene.
After above-mentioned catalytic reaction terminates, adding organic solvent (ethanol, methanol etc.) in system, polyacid separates out, and filters, very
Empty dry, the polyacid of recovery can be used further to the asymmetric dihydroxylation of alkene.
Compared to the prior art, the beneficial effects of the present invention is:
1) the not covalent modification merely with chiral organic micromolecule of the present invention breaks the high symmetry of polyacid, introduces chirality,
Improve its stereo selectivity in catalytic reaction, and asymmetry catalysis or the biological medicine of little for organic chiral molecule are lived
Property etc. functional characteristic introduce polyacid, and make organic moiety and inorganic polyanionic organically be integrated into a whole, thus produce
Raw synergism obtains the character of more novelties；
2) the preparation method reaction condition of the present invention is gentle, environmental friendliness；
3) catalyst activity obtained of the present invention is high, enantioselectivity is high, recoverable, it is adaptable to industrialized production.
Accompanying drawing explanation
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-phenethyl) isothiocyanate.
Fig. 5 is the infrared spectrum of unilateral amido modified Cr-Anderson type polyoxometallate.
Fig. 6 is the nuclear magnetic spectrogram of Cr-Anderson type heteropolyacid catalyst thiourea modified for (S)-1-(1-phenethyl).
Detailed description of the invention
Hereinafter using embodiment to describe embodiments of the present invention in detail, to the present invention, how application technology means solve whereby
Certainly technical problem, and the process that realizes reaching technique effect can fully understand and implement according to this.
Embodiment 1
Cr-Anderson type heteropoly acid parent (NH4)3[Cr(OH)6Mo6O18] preparation
Take 7.41g (6mmol) ammonium molybdate to join in 20mL deionized water, be sufficiently stirred for obtaining clear liquor, drip dense afterwards
Nitric acid, is transferred to the pH of system 4～5. and is heated to boiling, maintain strong stirring, start to be slowly added to 1.66g (7mmol)
Chromic nitrate solid, stirring, to there being a large amount of pink solid to produce, stops stirring, stands 15～30 minutes.Sucking filtration, obtains
5.26g pink crystalline solid raw material, yield 82%.
Parent (NH4)3[Cr(OH)6Mo6O18] infrared spectrum see Fig. 3.
Embodiment 2
(S) preparation of-1-(1-phenethyl) isothiocyanate
Addition (S) in dry reaction vessel-(+)-1-phenylethylamine (0.606g, 5mmol), use 20mL acetic acid ethyl dissolution,
It is respectively added slowly to subsequently add CS2(0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), be stirred at room temperature reaction
After 1h, under the conditions of 0 DEG C, add Bis(tert-butoxycarbonyl)oxide (Boc subsequently2O) (1.091mg, 5mmol) and 4-dimethylamino
Pyridine (DMAP) (18mg, 0.15mmol), (has gas to produce in the process stirred, should note after reaction 2h is stirred at room temperature
Meaning venting decompression), 0.79g (R)-1-(1-phenethyl) isothiocyanate can be obtained.Yield 97%.
(S) nuclear magnetic spectrogram of-1-(1-phenethyl) isothiocyanate is shown in Fig. 4.Concrete 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 polyoxometallate
By Anderson parent (NH obtained above4)3[Cr(OH)6Mo6O18] 1.071g (1mmol) uses 10mL deionized water
Middle dissolving, after obtaining light red clear liquid, is slowly added to trihydroxy aminomethane 0.402g (3mmol).Afterwards by above-mentioned system
Add water heating kettle, water heating kettle is heated to 140 DEG C, after reaction carries out 24h, by the 4.83g tetrabutyl under the conditions of 85 DEG C
Ammonium bromide adds as, in the solution of above-mentioned dissolving, produced a large amount of pink precipitate i.e. crude product, and sucking filtration i.e. can get red liquid,
Placement is crystallized, and is organic unilateral amino and adorns the Cr-Anderson type polyacid repaiied
[TBA]3{[CH2NH2C(CH2O)3]CrMo6O18(OH)3}。
The infrared spectrum of unilateral amido modified Cr-Anderson type polyoxometallate is as shown in Figure 5.
Embodiment 4
(S) preparation of Cr-Anderson type heteropolyacid catalyst thiourea modified for-1-(1-phenethyl)
By amido modified for organic one side [TBA]3{[CH2NH2C(CH2O)3]CrMo6O18(OH)30.5g (0.275mmol) is with 5
After the DMF of mL dissolves under the conditions of 50 DEG C, add (S)-1-(1-phenethyl) isothiocyanate 0.224g (1.375mmol),
Maintaining under 50 DEG C of stirring conditions, response time 2～3 days, reaction will crystallize in bright pink clear liquor placement ether atmosphere after terminating,
Available red crystals behind some skies, i.e. obtains the thiourea modified Cr-Anderson type heteropoly acid catalysis of (R)-1-(1-phenethyl)
Agent.
(S) nuclear magnetic spectrogram of Cr-Anderson type heteropolyacid catalyst thiourea modified for-1-(1-phenethyl) is as shown in Figure 6.Tool
Volume 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
(S) asymmetric dihydroxylation of thiourea modified for-1-(1-phenethyl) Cr-Anderson type polyacid catalyzed alkene
In clean reaction bulb, add 1.0415g (0.01mol) styrene, add 10ml mixed solvent (rubbing of water and acetonitrile
That ratio is 1:1～3:1), it is eventually adding 1.7g 30% hydrogen peroxide and 0.0213g (S)-1-(1-phenethyl) is thiourea modified
The many acid catalysts of Cr-Anderson type, react 24h, take 5ml ethanol and add reaction system, are centrifuged and make catalyst sedimentation, then
Add 3ml ethanol separating catalyst again, filter, obtain catalyst, vacuum drying.By ethyl acetate, reaction system is extracted
Taking 3 times, obtained product removal of solvent under reduced pressure, column chromatography for separation obtains vicinal diol compound, obtains product 1.3552g,
Yield is 99%.The enantiomeric excess of product is recorded by chiral high performance liquid chromatography, and ee value reaches 99%.This catalyst can
The carrying out of catalytic reaction in various degree, and there is preferable stereo selectivity.Use different alkene and catalyst reaction,
Equation is as follows, and obtained experimental result is shown in Table 1.
The catalyst that above-mentioned recovery obtains is directly used in next reaction (cinnamic dihydroxylation), obtained product
Enantiomeric excess value by HPLC measure (chirality AS-H post, isopropanol: normal hexane=3:7,254nm, 20 DEG C,
0.5mL/min).Catalyst recycle obtained by the results are shown in Table 2.
The asymmetric dihydroxylation experimental result of table 1 polyacid catalyzed alkene
The experimental result that table 2 catalyst recycles
All above-mentioned primary embodiments, are not the restriction that other forms are implemented this new product and/or new method.
Those skilled in the art will utilize this important information, and foregoing is revised, to realize similar implementation status.But, base
All modifications or transformation in new product of the present invention belong to the right that the present invention retains.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, any
Those skilled in the art are changed possibly also with the technology contents of the disclosure above or are modified as the equivalence of equivalent variations
Embodiment.But every without departing from technical solution of the present invention content, according to the technical spirit of the present invention, above example is made
Any simple modification, equivalent variations and remodeling, still fall within the protection domain of technical solution of the present invention.
Claims (11)
1. the preparation method of the Cr-Anderson type heteropolyacid catalyst that (S)-1-(1-phenethyl) is thiourea modified, it is characterised in that specifically comprise the following steps that
1) with ammonium molybdate and chromic nitrate as raw material, with the pH value of acid regulation system between 4～5, at a temperature of 80 DEG C～100 DEG C, Cr-Anderson type heteropoly acid parent (NH is prepared4)3[Cr(OH)6Mo6O18]；
2) according to mol ratio 1:2～1:5, by Cr-Anderson type heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18] at a temperature of 135-145 DEG C, carry out hydro-thermal reaction with trihydroxy aminomethane, obtain the Cr-Anderson type polyoxometallate that organic one side is amido modified；
3) with (S)-(+)-1-phenylethylamine as Material synthesis (S)-1-(1-phenethyl) isothiocyanate；
4) Cr-Anderson type polyoxometallate amido modified with organic one side for (S)-1-(1-phenethyl) isothiocyanic acid is reacted in organic solvent obtain the thiourea modified Cr-Anderson type heteropolyacid catalyst of (S)-1-(1-phenethyl).
2. preparation method as claimed in claim 1, it is characterised in that step 1) in, the mol 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 step 1) in, acid is nitric acid.
4. preparation method as claimed in claim 1, it is characterised in that step 2) in, the hydro-thermal reaction time is 20h～30h.
5. preparation method as claimed in claim 1, it is characterised in that step 2) in, the amido modified Cr-Anderson type polyoxometallate in described organic one side is [TBA]3{[NH2C(CH2O)3]CrMo6O18(OH)3, it prepares at a temperature of 80 DEG C～90 DEG C by being mixed with tetrabutyl ammonium bromide by hydro-thermal reaction afterproduct, Cr-Anderson type heteropoly acid parent (NH4)3[Cr(OH)6Mo6O18] and the mol ratio of tetrabutyl ammonium bromide be 1:3～1:5.
6. preparation method as claimed in claim 1, it is characterised in that step 4) in, the mol ratio of the Cr-Anderson type polyoxometallate that (S)-1-(1-phenethyl) isothiocyanic acid is amido modified with organic one side is 3:1～5:1.
7. preparation method as claimed in claim 1, it is characterised in that step 4) in, reaction temperature is 45～55 DEG C, organic solvent any one or more in DMF, DMSO or NMP.
8. the Cr-Anderson type heteropolyacid catalyst thiourea modified for (S)-1-(1-phenethyl) that the preparation method as described in one of claim 1～6 obtains.
9. the Cr-Anderson type heteropolyacid catalyst that (S)-1-(1-phenethyl) as claimed in claim 1 the is thiourea modified application in the asymmetric dihydroxylation field of alkene.
Apply the most as claimed in claim 8, it is characterized in that, application process is specific as follows: joined by Cr-Anderson type heteropolyacid catalyst thiourea modified to alkene and (S)-1-(1-phenethyl) in the mixed solvent of water and acetonitrile composition, react at a temperature of 30 DEG C～50 DEG C, obtain vicinal diol compound；Wherein: 0.5mol%～5mol% that inventory is alkene of the Cr-Anderson type heteropolyacid catalyst that (S)-1-(1-phenethyl) is thiourea modified.
11. apply as claimed in claim 9, it is characterised in that the mol ratio of water and acetonitrile is 1:1～3:1, and hydrogen peroxide is oxygen source, and it is 1:1～3:1 with the mol ratio of alkene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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| 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN108503568A (en) * | 2017-02-27 | 2018-09-07 | 无锡杰西医药股份有限公司 | A kind of high-purity isosulfocyanate compound preparation method suitable for industrialized production |
| CN110446697A (en) * | 2017-02-27 | 2019-11-12 | 无锡杰西医药股份有限公司 | A kind of high-purity isosulfocyanate compound preparation method suitable for industrialized production |
| 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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