CN105854952A - (S)-1-(2-hydroxyl-1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as a preparation method and application thereof - Google Patents

(S)-1-(2-hydroxyl-1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as a preparation method and application thereof Download PDF

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CN105854952A
CN105854952A CN201610211213.8A CN201610211213A CN105854952A CN 105854952 A CN105854952 A CN 105854952A CN 201610211213 A CN201610211213 A CN 201610211213A CN 105854952 A CN105854952 A CN 105854952A
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phenethyl
hydroxyl
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CN105854952B (en
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余焓
戴国勇
何慧红
李亮
韩生
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Shanghai Yuanxin Material Technology Co.,Ltd.
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Abstract

The invention discloses a (S)-1-(2-hydroxyl-1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as a preparation method and application thereof. The preparation method comprises the following steps: firstly, enabling sodium molybdate andtetrabutylammonium bromide to react so as to generate [N(C4H9)4]4[alpha-Mo8O26]; secondly, enabling [N(C4H9)4]4[alpha-Mo8O26], tris(hydroxymethyl) aminomethane and manganous acetate to react so as to obtain organic double-sided amino modified polyoxometallate; thirdly, by taking L-phenylglycinol as a raw material, synthesizing (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanic acid; and enabling (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanic acid and the organic double-sided amino modified polyoxometallate to react, thereby obtaining the target, namely, the heteropolyacid catalyst. The preparation method disclosed by the invention is gentle in reaction condition and environment-friendly, and the obtained catalyst can be adopted for asymmetric dihydroxylation reaction of olefin, is high in enantioselectivity and catalytic activity, can be recycled, and is applicable to industrial production.

Description

(S) thiourea modified for-1-(2-hydroxyl-1-phenethyl) Mn-Anderson type heteropolyacid catalyst, preparation method and applications
Technical field
The invention belongs to technical field of catalytic chemistry, particularly relate to asymmetric selective catalysis, specifically (S)-1-(2-hydroxyl -1-phenethyl) thiourea modified Mn-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. Homogeneous chiral catalysis has the feature such as enantioselectivity efficient, high and reaction condition gentleness.
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, at " Nature " upper report, the hands that hydrothermal technique is successfully prepared similar DNA Double-stranded compound (the Me of property2NH2)K4[V10O10(H2O)4(OH)4(PO4)7]·H2After O, people have just started chirality Polyacid is in the exploration of asymmetric catalysis field.Chinese Academy of Sciences's chemistry professor Luo Sanzhong et al. urging with organic amine small molecules Agent as counter cation, polyacid as the field of catalyst-supporting carriers be made that outstanding work (Organic letters, 2007,9(18):3675-3678.).They have synthesized a series of secondary amine-tertiary amine-type proline derivative, use highly acid how cloudy [the PW of ion12O40]3-Substitute the mineral acid in tradition Acid-Base concerted catalysis, synthesize a series of chirality organic amine-polyacid hydridization Material.These materials direct asymmetric Aldol reaction to aldehyde ketone, asymmetric Michael addition reaction etc. all shows the highest urging Changing activity and chiral selectivity, organic amine small molecules is assembled by electrostatic interaction with polyacid as counter cation, but these materials Material does not has clear and definite molecular structure, it is impossible to probe into catalytic mechanism further, it is impossible to explain the synergism of Chiral Amine and polyacid. Dalian materialization institute Duan Chun meet seminar meet utilize the composition of polyoxometallate (POMs), the multiformity of structure and electric charge can Modulation, a series of porous POMOFs with catalysis of design and assembly, it is achieved that they are in heterogeneous catalysis Application (Journal of the American Chemical Society, 2013,135 (28): 10186-10189.), but these materials are same Sample does not has clear and definite molecular structure, it is impossible to probe into catalytic mechanism further, it is impossible to explain the synergism of MOFs Yu POMs.
Summary of the invention
For deficiency of the prior art, it is an object of the invention to provide one (S)-1-(2-hydroxyl-1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst, preparation method and applications.The present invention solves existing chiral organic micromolecule Catalyst activity is relatively low, consumption is high and is not easily recycled the technical problem of utilization.The catalyst that the present invention obtains can be used for alkene Asymmetric 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 has machine maintenance The polyacid of decorations 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 has potential using value.Additionally, polyacid has hydrophilic, available green, cheap water as solvent enter Row catalytic reaction, after reaction terminates to add organic solvent (ethanol, methanol etc.) in system, polyacid easily separates out, and can enter Row recycles.
The present invention provides the Mn-Anderson type heteropolyacid catalyst (knot that a kind of (S)-1-(2-hydroxyl-1-phenethyl) is thiourea modified Structure is shown in Fig. 1) preparation method, specifically comprise the following steps that
1) by sodium molybdate, tetrabutyl ammonium bromide according to the ratio mixing that mol ratio is 1:1～2:1, under concentrated hydrochloric acid effect, room temperature Reaction, obtains parent [N (C4H9)4]4[α-Mo8O26]；
2) by parent obtained above [N (C4H9)4]4[α-Mo8O26] reflux in organic solvent with trihydroxy aminomethane, manganese acetate Obtain organic bilateral amido modified Mn-Anderson type polyoxometallate；
3) (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate with L-benzene glycinol as Material synthesis；
4) by (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanic acid and organic bilateral amido modified Mn-Anderson type polyoxometallic acid Salt is dissolved in reaction dissolvent, reacts 2-3 days at a temperature of 45-55 DEG C, and post processing obtains (S)-1-(2-hydroxyl-1-phenethyl) thiourea The Mn-Anderson type heteropolyacid catalyst modified.
In the present invention, step 1) in, the mol ratio of sodium molybdate and concentrated hydrochloric acid is 1:1～1:2.
In the present invention, step 2) in, parent [N (C4H9)4]4[α-Mo8O26] with trihydroxy aminomethane, manganese acetate mole Ratio is 1:(3～4): (1～2).
In the present invention, step 2) in, organic solvent is polar non-solute.Preferably, organic solvent be acetonitrile or 1,2-dichloroethanes.
In the present invention, step 3) in, (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate with L-benzene glycinol as Material synthesis Specifically comprise the following steps that L-benzene glycinol, CS2With triethylamine with mol ratio 1:(2～4): the ratio mixing of 1, in room After temperature stirring reaction 1h～2h, add Bis(tert-butoxycarbonyl)oxide and DMAP under condition of ice bath, after adding, continue Stirring reaction 3h～5h under condition of ice bath is held in continuation of insurance, obtains (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate；Wherein, L- The mol ratio of benzene glycinol, Bis(tert-butoxycarbonyl)oxide and DMAP is 1:1:(0.02～0.05).
In the present invention, step 4) in, (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanic acid is with organic bilateral amido modified The mol ratio of Mn-Anderson type polyoxometallate is 5:1～8:1；Reaction dissolvent is DMF or DMSO.Reaction knot After bundle, clear liquor is placed in ether atmosphere and crystallize, available red crystals behind some skies, i.e. obtain (S)-1-(2-hydroxyl-1-benzene Ethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst.Concrete, after system reaction terminates, if reactant liquor is the most clear Clearly, application syringe filters processes, and places in ether atmosphere and crystallize after obtaining clear liquor.
It is thiourea modified that the present invention also provides for (S)-1-(2-hydroxyl-1-phenethyl) that a kind of above-mentioned preparation method prepares Mn-Anderson type heteropolyacid catalyst.
The present invention further provides the thiourea modified Mn-Anderson type heteropoly acid catalysis of one (S)-1-(2-hydroxyl-1-phenethyl) Agent is in the application in the asymmetric dihydroxylation field of alkene.Concrete application process is as follows: take appropriate alkene, 30 DEG C～50 DEG C, with water and acetonitrile as mixed solvent under conditions of, add hydrogen peroxide and (S)-1-(2-hydroxyl-1-phenethyl) thiourea The Mn-Anderson type heteropolyacid catalyst modified, reacts 24h, obtains vicinal diol compound.
Preferably, the mol ratio of water and acetonitrile is 1:1～3:1, and the usage amount of hydrogen peroxide is 1～3 equivalents (with alkene as reference), (S) the amount alkene of Mn-Anderson type heteropolyacid catalyst thiourea modified for-1-(2-hydroxyl-1-phenethyl) 0.5mol%～ 5mol%.
After application response terminates, after adding organic solvent (ethanol, methanol etc.) in system, polyacid separates out, and filters, vacuum Being dried, 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: the present invention is possible not only to utilize being total to of chiral organic micromolecule The high symmetry of polyacid is broken in valency modification, introduces chirality, improves its stereo selectivity in catalytic reaction, and Can by the asymmetry catalysis of little for organic chiral molecule or biological medicine activity etc. functional characteristic introduce polyacid, and make organic moiety with Inorganic polyanionic is organically integrated into a whole, thus produces synergism and obtain the character of more novelties.The present invention Preparation method reaction condition is gentle, environmental friendliness；The catalyst obtained has enantioselectivity efficient, high and recoverable Etc. advantage, it is adaptable to industrialized production.
Accompanying drawing explanation
Fig. 1 is the structural representation of the final catalyst of the present invention.
Fig. 2 is the synthetic route diagram of the present invention.
Fig. 3 is the nuclear magnetic spectrogram of (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate.
Fig. 4 is the infrared spectrum of bilateral amido modified Mn-Anderson type polyoxometallate.
Fig. 5 is the nuclear magnetic spectrogram of bilateral amido modified Mn-Anderson type polyoxometallate.
Fig. 6 is the nuclear magnetic spectrogram of Mn-Anderson type heteropolyacid catalyst thiourea modified for (S)-1-(2-hydroxyl-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.
The synthetic route of the present invention is shown in Fig. 2.
Embodiment 1
Polyacid parent [N (C4H9)4]4[α-Mo8O26] preparation
In the flask of 50mL, by Na2MoO4·2H2O 5.00g (20.7mmol) is dissolved in the deionized water of 12mL, And add the hydrochloric acid solution of 5.17mL 6.0N, it is stirred vigorously 1～2min in room temperature.Then by tetrabutyl ammonium bromide 3.34g (10.4mmol) dissolving in 10ml deionized water, adds in flask with vigorous stirring and forms white precipitate immediately.Should After mixture stirs 10 minutes, precipitation is collected in the suction of medium porosity wave filter and uses 20mL water, 20mL respectively Ethanol, 20mL acetone and the washing of 20mL ether.This crude product (4.78g) is dissolved in 35mL acetonitrile, and at-10 DEG C Under the conditions of static 24h.To clarify, colourless, the crystal of block structure is by collected by suction and vacuum drying 12 hours. The transparency of crystal can be lost when dry.Yield 3.58g (1.66mmol), productivity 64%.
Embodiment 2
(S) preparation of-1-(2-hydroxyl-1-phenethyl) isothiocyanate
In dry reaction vessel, add L-benzene glycinol (0.6859g, 5mmol), dissolve with 20mL ethanol, divide subsequently It is not slowly added to add CS2(0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), after reaction 1h is stirred at room temperature, Bis(tert-butoxycarbonyl)oxide (Boc is added subsequently under the conditions of 0 DEG C2O) (1.091mg, 5mmol) and DMAP (DMAP) (18mg, 0.15mmol), (has gas to produce in the process stirred, it should be noted that to put after reaction 2h is stirred at room temperature Gas reduces pressure), 0.7194g (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate can be obtained.
(S) nuclear magnetic spectrogram of-1-(2-hydroxyl-1-phenethyl) isothiocyanate is as it is shown on figure 3, concrete data are as follows:
1H NMR(501MHz,CDCl3) δ 7.39 7.22 (m, 5H), 4.99 (dt, J=52.6,9.1Hz, 2H), 4.43 (dd, J=8.8,7.0Hz, 1H), 1.25 (dd, J=51.2,35.5Hz, 1H).
Embodiment 3
The preparation of bilateral amido modified Mn-Anderson type polyoxometallate
Take [N (C4H9)4]4[α-Mo8O26](8.00g,3.7mmol),Mn(CH3COO)3·2H2O (1.49g, 5.6mmol) with And (HOCH2)3CNH2(1.56g, 12.8mmol), at the acetonitrile solution backflow 16h of 150mL.This orange solution is cooled down To room temperature, and it is filtered to remove imperceptible black solid.Filtrate is exposed to ether fume.After 2 hours, white depositions leaches. Orange filtrate is again exposed to ether fume several days.Obtain a large amount of orange crystal.They are isolated by filtration, with acetonitrile washing and The amount of ether is little, and is dried under vacuum.
The infrared spectrum of bilateral amido modified Mn-Anderson type polyoxometallate is as shown in Figure 4.
The nuclear magnetic spectrogram of bilateral amido modified Mn-Anderson type polyoxometallate is as shown in Figure 5.
Embodiment 4
(S) preparation of Mn-Anderson type heteropolyacid catalyst thiourea modified for-1-(2-hydroxyl-1-phenethyl)
By organic bilateral amido modified [N (C4H9)4]3[MnMo6O18{(OCH2)3CNH2}2] 0.5g (0.2683mmol) is with 5 After the DMF of mL dissolves under the conditions of 50 DEG C, add (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate 0.3583g (2 Mmol), maintaining under 50 DEG C of stirring conditions, response time 2～3 days, bright pink clear liquor is placed ether atmosphere after terminating by reaction Middle crystallization, available red crystals behind some skies, i.e. obtain the thiourea modified Mn-Anderson of (S)-1-(2-hydroxyl-1-phenethyl) Type heteropolyacid catalyst.
(S) nuclear magnetic spectrogram of Mn-Anderson type heteropolyacid catalyst thiourea modified for-1-(2-hydroxyl-1-phenethyl) is shown in Fig. 6, Concrete data are as follows:
1H NMR (501MHz, DMSO) δ 66.06 (s, 12H), δ 7.28 (s, 10H), 3.12 (s, 24H), 1.53 (s, 24H), 1.27(s,24H),0.89(s,36H)。
Embodiment 5
(S) Asymmetrical dihydroxylation of Mn-Anderson type polyacid catalyzed alkene thiourea modified for-1-(2-hydroxyl-1-phenethyl) is anti- Should.
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 0.0099g (S)-1-(2-hydroxyl-1-phenethyl) is thiourea modified The many acid catalysts of Mn-Anderson type, react 24h, take 5ml ethanol and add reaction system, centrifugal make catalyst sedimentation, Add 3ml ethanol separating catalyst again, filter, obtain catalyst, vacuum drying.By ethyl acetate by reaction system Extracting 3 times, obtained product removal of solvent under reduced pressure, column chromatography for separation obtains vicinal diol compound, obtains product 1.36g, 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, 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, do not set this new product of enforcement and/or the new method limiting other forms. 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 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 (10)

1. a preparation method for Mn-Anderson type heteropolyacid catalyst thiourea modified for (S)-1-(2-hydroxyl-1-phenethyl), its It is characterised by, specifically comprises the following steps that
1) by sodium molybdate, tetrabutyl ammonium bromide according to the ratio mixing that mol ratio is 1:1～2:1, under concentrated hydrochloric acid effect, room Temperature reaction, obtains parent [N (C4H9)4]4[α-Mo8O26]；
2) by parent obtained above [N (C4H9)4]4[α-Mo8O26] reflux in organic solvent with trihydroxy aminomethane, manganese acetate Obtain organic bilateral amido modified Mn-Anderson type polyoxometallate；
3) (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate with L-benzene glycinol as Material synthesis；
4) by (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanic acid and organic bilateral amido modified Mn-Anderson type polyoxometallic acid Salt is dissolved in reaction dissolvent, reacts 2-3 days at a temperature of 45-55 DEG C, and post processing obtains (S)-1-(2-hydroxyl-1-phenethyl) thiourea The Mn-Anderson type heteropolyacid catalyst modified.
2. preparation method as claimed in claim 1, it is characterised in that step 1) in, sodium molybdate and the mol ratio of concentrated hydrochloric acid For 1:1～1:2.
3. preparation method as claimed in claim 1, it is characterised in that step 2) in, parent [N (C4H9)4]4[α-Mo8O26] It is 1:(3～4 with the mol ratio of trihydroxy aminomethane, manganese acetate): (1～2).
4. preparation method as claimed in claim 1, it is characterised in that step 2) in, organic solvent is that aprotic, polar is molten Agent.
5. preparation method as claimed in claim 1, it is characterised in that step 2) in, organic solvent is acetonitrile or 1,2- Dichloroethanes.
6. preparation method as claimed in claim 1, it is characterised in that step 3) in, close with L-benzene glycinol for raw material Become specifically comprising the following steps that L-benzene glycinol, CS of (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate2With triethylamine to rub You are than 1:(2～4): the ratio mixing of 1, after reaction 1h～2h is stirred at room temperature, under condition of ice bath, add two dimethyl dicarbonates Butyl ester and DMAP, after adding, continue to keep stirring reaction 3h～5h under condition of ice bath, obtain (S)-1-(2-hydroxyl Base-1-phenethyl) isothiocyanate；Wherein, L-benzene glycinol, Bis(tert-butoxycarbonyl)oxide and DMAP mole Ratio is 1:1:(0.02～0.05).
7. preparation method as claimed in claim 1, it is characterised in that: step 4) in, (S)-1-(2-hydroxyl-1-phenethyl) different sulfur Cyanic acid is 5:1～8:1 with the mol ratio of organic bilateral amido modified Mn-Anderson type polyoxometallate.
8. preparation method as claimed in claim 1, it is characterised in that: step 4) in, reaction dissolvent is DMF or DMSO.
9. (S)-1-(2-hydroxyl-1-phenethyl) that the preparation method as described in one of claim 1-8 prepares is thiourea modified Mn-Anderson type heteropolyacid catalyst.
10. a Mn-Anderson type thiourea modified for (S)-1-(2-hydroxyl-1-phenethyl) as claimed in claim 9 described is miscellaneous Many acid catalysts are in the application in the asymmetric dihydroxylation field of alkene.
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