CN105772088A - Mn-Anderson type heteropolyacid catalyst modified by (S)-1-(1-phenethyl) thiourea, and preparation method and application thereof - Google Patents
Mn-Anderson type heteropolyacid catalyst modified by (S)-1-(1-phenethyl) thiourea, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Mn-Anderson type heteropolyacid catalyst modified by (S)-1-(1-phenethyl) thiourea, and a preparation method and application thereof. The preparation method comprises the following steps: firstly, reacting sodium molybdate and tetrabutylammonium bromide to generate [N(C4H9)4]4[alpha-Mo8O26], and then reacting [N(C4H9)4]4[alpha-Mo8O26] with tris(hydroxymethyl) aminomethane and manganese acetate to obtain organic bilateral amino-modified polyoxometallate; then with (R)-(+)-1-phenylethylamine as a raw material, synthesizing (S)-1-(1-phenethyl) isothiocyanate; and finally, reacting (S)-1-(1-phenethyl) isothiocyanate and organic bilateral amino-modified polyoxometallate to obtain the target catalyst. The preparation method is simple, and the reaction condition is mild and environmentally friendly; and the obtained catalyst is used for asymmetric dihydroxylation of olefin, has the advantages of high enantioselectivity, high catalytic activity, recoverability and the like and is applicable to industrial production.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, particularly relate to asymmetric selective catalysis, specifically a kind of (S)-1-(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.
Catalysis is the most promising and most practical value research direction in polyoxometallate application.Polyoxometallate collects acid simultaneously
The good characteristic of base catalyst, oxidation reduction catalyst, metal oxide nanocatalyst etc. is it is considered to be a kind of
The multifunction catalyst of widely used green.As far back as 20 beginnings of the century, people begin to the catalytic performance to polyacid and carry out
Research.It is that the existing project of acid catalysis industrialization more than 8 is successfully developed up till now.It is catalyzed into in Chemistry of Polyacids one
Eternal research topic.After chirality polyoxometallate is successfully synthesized, people have just started chirality polyacid the most right
Claim the exploration of catalytic field.Chirality polyoxometallate integrates the various excellent properties of polyacid and chiral material.It is unique
Solubility class mineral metal-oxide structure, for the exploration of chirality transmission in the non-origin of life theory of chirality and inoganic solids
Provide preferable model；Its high elecrtonegativity, adjustable Acidity of Aikalinity, redox active and nano-scale, the most merits
The design of new material, the synthesis such as energy nonlinear optics, nano material, stereo selectivity catalysis and medicine bring new wishing
Hope.Although homogeneous chiral catalysis has enantioselectivity efficient, high and a feature such as reaction condition is gentle, but in most cases,
Catalyst amount high molar fraction.Realize the application industrially of these catalytic reactions, it is necessary to solve returning of expensive catalyst
Receiving utilization is a serious problem.Chinese Academy of Sciences's chemistry professor Luo Sanzhong et al. making with organic amine small molecules catalyst
For 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 polyanionic
[PW12O40]3-Substitute the mineral acid in tradition Acid-Base concerted catalysis, synthesize a series of chirality organic amine-polyacid hydridization material
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
There is no 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.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide one (S)-1-(1-phenethyl) thiourea modified
Mn-Anderson type heteropolyacid catalyst, preparation method and applications.The present invention solves existing chiral organic micromolecule and urges
Agent activity is relatively low, consumption is high and is not easily recycled the technical problem of utilization.Preparation method of the present invention is simple, reaction condition gentleness,
Environmental friendliness；The catalyst obtained can be used for asymmetry catalysis synthesis field, have high enantioselectivity, high catalytic activity and
The advantages such as recoverable.
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.In the present invention organic
The polyacid modified not only remains the original structure of polyacid, and has expanded the research field of polyacid so that it is at catalysis, medicine
With functional material aspect, there is potential using value.Additionally, polyacid has hydrophilic, available green, cheap water as solvent
Carrying out catalytic reaction, after reaction terminates to add organic solvent (ethanol, methanol etc.) in system, polyacid easily separates out, can
Recycle.Technical solution of the present invention is specifically described as follows.
(structure is shown in the invention provides Mn-Anderson type heteropolyacid catalyst thiourea modified for one (S)-1-(1-phenethyl)
Preparation method Fig. 1), its synthetic route is as in figure 2 it is shown, specifically comprise the following steps that
1) sodium molybdate and tetrabutyl ammonium bromide are reacted under concentrated hydrochloric acid effect, generate Mn-Anderson type heteropoly acid parent
[N(C4H9)4]4[α-Mo8O26]；
2) by Mn-Anderson type heteropoly acid parent [N (C obtained above4H9)4]4[α-Mo8O26] and trihydroxy aminomethane, second
Acid manganese refluxes in organic solvent, obtains organic bilateral amido modified Mn-Anderson type polyoxometallate；
3) with (R)-(+)-1-phenylethylamine as Material synthesis (S)-1-(1-phenethyl) isothiocyanate；
4) by (S)-1-(1-phenethyl) isothiocyanic acid and step 2) how golden the organic bilateral amido modified Mn-Anderson type that obtains is
After belonging to DMF, DMSO or NMP dissolving of oxygen hydrochlorate, react 2～3 days at a temperature of 45-55 DEG C, more post-treated
Obtain the thiourea modified Mn-Anderson type heteropolyacid catalyst of (S)-1-(1-phenethyl).
In the present invention, step 1) in, the mol ratio of sodium molybdate and tetrabutyl ammonium bromide is 1:1～2:1.
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, Mn-Anderson type heteropoly acid parent [N (C4H9)4]4[α-Mo8O26] and trihydroxy ammonia
Methylmethane, the mol ratio of manganese acetate are 1:(3～4): (1～2), organic solvent is selected from acetonitrile, oxolane or 1,2-
In dichloroethanes any one.
In the present invention, step 4) in organic bilateral amido modified Mn-Anderson type polyoxometallate and (S)-1-(1-
Phenethyl) mol ratio of isothiocyanic acid is 1:5～1:8.
In the present invention, step 4) in, (S)-1-(1-phenethyl) isothiocyanic acid and step 2) the organic bilateral amino that obtains repaiies
Decorations Mn-Anderson type polyoxometallic acid reactant salt 2～after 3 days, if reactant liquor is not clarified, application syringe filters at
Reason.
In the present invention, step 4) in, post processing mode is recrystallization.Preferably, solvent during recrystallization is ether.
Thiourea modified for (S)-1-(1-phenethyl) the Mn-Anderson type that the present invention also provides for that a kind of above-mentioned preparation method obtains is miscellaneous
Many acid catalysts.
The present invention further provides Mn-Anderson type heteropolyacid catalyst thiourea modified for above-mentioned (S)-1-(1-phenethyl) to exist
The application in the asymmetric dihydroxylation field of alkene.Application process is as follows: by alkene and (S)-1-(1-phenethyl) sulfur
The Mn-Anderson type heteropolyacid catalyst that urea is modified joins in the mixed solvent of water and acetonitrile composition, at 30 DEG C～50 DEG C
At a temperature of react, obtain vicinal diol compound；Wherein: Mn-Anderson type thiourea modified for (S)-1-(1-phenethyl) is miscellaneous many
The amount of acid catalyst is 0.5mol%～5mol% of alkene.
Preferably, the mol ratio of water and acetonitrile is 1:1～3:1, and hydrogen peroxide is oxygen source, and its usage amount is that 1～3 equivalents are (with alkene
Hydrocarbon is reference).
After catalytic reaction 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 is simple, and reaction condition is gentle, environmental friendliness；The catalyst obtained has high enantioselectivity, high catalytic activity
With advantages such as recoverables.
Accompanying drawing explanation
Fig. 1 is the structural diagrams of Mn-Anderson type heteropolyacid catalyst thiourea modified for (S)-1-(1-phenethyl).
Fig. 2 is the synthetic route chart of the present invention.
Fig. 3 is the nuclear magnetic spectrogram of (S)-1-(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-(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
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-(1-phenethyl) isothiocyanate
Addition (R) in dry reaction vessel-(+)-1-phenylethylamine (0.606g, 5mmol), molten by 20mL ethyl acetate
Solve, be respectively added slowly to subsequently add CS2(0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), be stirred at room temperature
After reaction 1h, under the conditions of 0 DEG C, add Bis(tert-butoxycarbonyl)oxide (Boc subsequently2O) (1.091mg, 5mmol) and 4-diformazan
Aminopyridine (DMAP) (18mg, 0.15mmol), after reaction 2h is stirred at room temperature (process in stirring has gas to produce,
It should be noted that venting decompression), 0.79g (S)-1-(1-phenethyl) isothiocyanate can be obtained.Yield 97%.
(S) nuclear magnetic spectrogram of-1-(1-phenethyl) isothiocyanate is shown in Fig. 3, and concrete data are as follows:
1HNMR(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 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-(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-(1-phenethyl) isothiocyanate 0.3265g (2mmol), dimension
Holding 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 Mn-Anderson type heteropoly acid catalysis of (S)-1-(1-phenethyl)
Agent.
(S) nuclear magnetic spectrogram of Mn-Anderson type heteropolyacid catalyst thiourea modified for-1-(1-phenethyl) is as shown in Figure 6, tool
Volume data is as follows:
1HNMR (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) asymmetric dihydroxylation of thiourea modified for-1-(1-phenethyl) Mn-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 0.0099g (S)-1-(1-phenethyl) is thiourea modified
The many acid catalysts of Mn-Anderson type, react 24h, take 5ml ethanol and add reaction system, are centrifuged and 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,
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 summary of the invention, do not set this new product of enforcement and/or the new method limiting other forms.Ability
Field technique personnel will utilize this important information, and foregoing is revised, to realize similar implementation status.But, all repair
Change or transform the right belonging to reservation based on new product of the present invention.
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-(1-phenethyl), its feature exists
In, specifically comprise the following steps that
1) sodium molybdate and tetrabutyl ammonium bromide are reacted under concentrated hydrochloric acid effect, generate Mn-Anderson type heteropoly acid parent
[N(C4H9)4]4[α-Mo8O26]；
2) by Mn-Anderson type heteropoly acid parent [N (C obtained above4H9)4]4[α-Mo8O26] and trihydroxy aminomethane, second
Acid manganese refluxes in organic solvent, obtains organic bilateral amido modified Mn-Anderson type polyoxometallate；
3) with (R)-(+)-1-phenylethylamine as Material synthesis (S)-1-(1-phenethyl) isothiocyanate；
4) by (S)-1-(1-phenethyl) isothiocyanic acid and step 2) the organic bilateral amido modified Mn-Anderson type that obtains is many
Oxometallate with DMF, DMSO or NMP dissolve after, at a temperature of 45-55 DEG C react 2～3 days, then through after place
Reason obtains the thiourea modified Mn-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, sodium molybdate and tetrabutyl ammonium bromide
Mol ratio is 1:1～2:1.
3. 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.
4. preparation method as claimed in claim 1, it is characterised in that step 2) in, Mn-Anderson type heteropoly acid parent
[N(C4H9)4]4[α-Mo8O26] be 1:(3～4 with trihydroxy aminomethane, the mol ratio of manganese acetate): (1～2), organic
Solvent be selected from acetonitrile, oxolane or 1, in 2-dichloroethanes any one.
5. preparation method as claimed in claim 1, it is characterised in that step 4) in, organic bilateral amido modified
Mn-Anderson type polyoxometallate is 1:5～1:8 with the mol ratio of (S)-1-(1-phenethyl) isothiocyanic acid.
6. preparation method as claimed in claim 1, it is characterised in that step 4) in, post processing mode is recrystallization.
7. preparation method as claimed in claim 6, it is characterised in that solvent during recrystallization is ether.
8. (S)-1-(1-phenethyl) that the preparation method as described in one of claim 1-7 obtains is thiourea modified
Mn-Anderson type heteropolyacid catalyst.
9. the Mn-Anderson type heteropolyacid catalyst that (S)-1-(1-phenethyl) as claimed in claim 8 is thiourea modified exists
The application in the asymmetric dihydroxylation field of alkene.
Apply the most as claimed in claim 9, it is characterised in that application process is as follows: by alkene and (S)-1-(1-phenethyl) sulfur
The Mn-Anderson type heteropolyacid catalyst that urea is modified joins in the mixed solvent of water and acetonitrile composition, at 30 DEG C～50 DEG C
At a temperature of react, obtain vicinal diol compound；Wherein: Mn-Anderson type thiourea modified for (S)-1-(1-phenethyl) is miscellaneous many
The amount of acid catalyst is 0.5mol%～5mol% of alkene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106475138A (en) * | 2016-10-12 | 2017-03-08 | 上海应用技术大学 | (S)‑1‑（1 phenethyl）Thiourea modified Al Anderson type heteropolyacid catalyst, preparation method and applications |
| CN106475139A (en) * | 2016-10-12 | 2017-03-08 | 上海应用技术大学 | (S) the unilateral Fe Anderson type heteropolyacid catalyst modified of 1 (1 phenethyl) thiourea, preparation method and applications |
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| CN102071012A (en) * | 2010-11-16 | 2011-05-25 | 北京化工大学 | Photosensitive material with Anderson type polyacid and preparation method thereof |
| CN104151262A (en) * | 2014-07-07 | 2014-11-19 | 浙江大学 | 4, 5-disubstituted-2-aminothiazole compound and preparation method thereof |
| CN104857988A (en) * | 2015-05-07 | 2015-08-26 | 盐城工学院 | Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof |
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| CN106475138A (en) * | 2016-10-12 | 2017-03-08 | 上海应用技术大学 | (S)‑1‑（1 phenethyl）Thiourea modified Al Anderson type heteropolyacid catalyst, preparation method and applications |
| CN106475139A (en) * | 2016-10-12 | 2017-03-08 | 上海应用技术大学 | (S) the unilateral Fe Anderson type heteropolyacid catalyst modified of 1 (1 phenethyl) thiourea, preparation method and applications |
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