(S) thiourea modified for-1-(2-hydroxyl-1-phenethyl) Cr-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 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.
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 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.
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
Cr-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, can be used for the asymmetric dihydroxylation of alkene.
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, and the present invention's is 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.
The present invention provides the Cr-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) with ammonium molybdate and chromic nitrate as raw material, it is 4~5 at pH value, under conditions of temperature is 80 DEG C~100 DEG C, preparation
Cr-Anderson type heteropoly acid parent (NH4)3[Cr(OH)6Mo6O18];
2) by Cr-Anderson type heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18] with trihydroxy aminomethane at water
Hot still carries out hydro-thermal reaction and obtains the Cr-Anderson type polyoxometallate that organic one side is amido modified;
3) (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate with L-benzene glycinol as Material synthesis;
4) by the reaction of (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanic acid and step 2) organic one side of obtaining is amido modified
Cr-Anderson type polyoxometallate reacts at a temperature of 45~55 DEG C that to obtain (S)-1-(2-hydroxyl-1-phenethyl) thiourea modified
Cr-Anderson type heteropolyacid catalyst.
Above-mentioned steps 1) in, the mol ratio of ammonium molybdate and chromic nitrate is 1:1~1:2.
Above-mentioned steps 1) in, adjust the pH value of system between 4~5 by concentrated nitric acid.
Above-mentioned steps 2) in, Cr-Anderson type heteropoly acid parent (NH4)3[Cr(OH)6Mo6O18] and trihydroxy aminomethane
Mol ratio 1:2~1:5.
Above-mentioned steps 2) in, hydrothermal temperature is 135-145 DEG C, and the hydro-thermal reaction time is 20h~30h.
Above-mentioned steps 3) in, the concrete step of (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate with L-benzene glycinol as Material synthesis
Rapid as follows:
By L-benzene glycinol, CS2With triethylamine with mol ratio 1:(2~4): the ratio of 1 mixing, be stirred at room temperature reaction 1h~
After 2h, add Bis(tert-butoxycarbonyl)oxide and DMAP, react 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).
Above-mentioned steps 4) in, the amido modified Cr-Anderson type polyoxometallate in organic one side and (S)-1-(2-hydroxyl-1-
Phenethyl) mol ratio of isothiocyanate is 1:3~1:5, reaction dissolvent uses in DMF, DMSO or NMP any one
Plant or several.Clear liquor is placed crystallization in ether atmosphere after terminating by reaction, and behind some skies, available crystal, i.e. obtains
(S) Cr-Anderson type heteropolyacid catalyst thiourea modified for-1-(2-hydroxyl-1-phenethyl).Concrete, system reaction terminates
After, if reactant liquor is not clarified, application syringe filters processes, and places in ether atmosphere and crystallize after obtaining clear liquor.
Above-mentioned steps 5) in, appropriate alkene, at 30 DEG C~50 DEG C, with water and acetonitrile as mixed solvent under conditions of, add
Enter the Cr-Anderson type heteropolyacid catalyst that hydrogen peroxide is thiourea modified with (S)-1-(2-hydroxyl-1-phenethyl), react 24h,
Obtain vicinal diol compound.
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
Cr-Anderson type heteropolyacid catalyst.
The present invention further provides the thiourea modified Cr-Anderson type heteropoly acid catalysis of above-mentioned (S)-1-(2-hydroxyl-1-phenethyl)
Agent is in the application in the asymmetric dihydroxylation field of alkene.
Above-mentioned application process is as follows: by miscellaneous many for Cr-Anderson type thiourea modified to alkene and (S)-1-(2-hydroxyl-1-phenethyl)
Acid catalyst mixes in the mixed solvent that water and acetonitrile form, and reacts, obtain vicinal diamines chemical combination at a temperature of 30 DEG C~50 DEG C
Thing;Wherein: the amount of the Cr-Anderson type heteropolyacid catalyst that (S)-1-(2-hydroxyl-1-phenethyl) is thiourea modified is alkene
0.5mol%~5mol%.Preferably, the mol ratio of water and acetonitrile is 1:1~3:1, and hydrogen peroxide is oxygen source, and its usage amount is
1-3 equivalent (with alkene as reference).
After above-mentioned application process terminates, after adding organic solvent (ethanol, methanol etc.) in phase system, polyacid separates out, and filters,
Vacuum drying, reclaims and obtains polyacid, can be used further to the asymmetric dihydroxylation of alkene.
The beneficial effects of the present invention is: be possible not only to utilize the covalent modification of chiral organic micromolecule to break the height of polyacid
Symmetry, introduces chirality, improves its stereo selectivity in catalytic reaction, and can by little for organic chiral molecule not
The functional characteristics such as asymmetric catalytic or biological medicine activity introduce polyacid, and make organic moiety organically tie with inorganic polyanionic
It is combined into an entirety, thus produces synergism and obtain the character of more novelties.Preparation method reaction condition of the present invention gentleness,
Environmental friendliness;The catalyst activity obtained is high, enantioselectivity is high, recoverable, it is adaptable to industrialized production.
Accompanying drawing explanation
Fig. 1 is the structural diagrams of the final catalyst of the present invention.
Fig. 2 is the synthetic route diagram of the present invention.
Fig. 3 is the parent (NH of embodiment 14)3[Cr(OH)6Mo6O18] infrared spectrum.
Fig. 4 is the nuclear magnetic spectrogram of (S)-1-(2-hydroxyl-1-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-(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 as shown in Figure 2.
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. 1.
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), 0.7547g (S)-1-(2-hydroxyl-1-phenethyl) isothiocyanate can be obtained.
(S) as shown in Figure 4, concrete data are as follows for the nuclear magnetic spectrogram of-1-(2-hydroxyl-1-phenethyl) isothiocyanate:
1H NMR(501MHz,CDCl3): δ 7.45-7.29 (m, 5H), 5.06 (dt, J=52.6,9.1Hz, 2H), 4.49 (dd,
J=8.8,7.0Hz, 1H), 1.38-1.15 (m, 1H).
Embodiment 3
The preparation of unilateral amido modified Cr-Anderson type 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) Cr-Anderson type heteropolyacid catalyst thiourea modified for-1-(2-hydroxyl-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-(2-hydroxyl-1-phenethyl) isothiocyanate 0.179g (1
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 Cr-Anderson type thiourea modified for (S)-1-(1-phenethyl) miscellaneous
Many acid catalysts.
(S) nuclear magnetic spectrogram such as Fig. 6 institute of Cr-Anderson type heteropolyacid catalyst thiourea modified for-1-(2-hydroxyl-1-phenethyl)
Showing, concrete data are as follows:
1H NMR (501MHz, DMSO): δ 7.64 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) Asymmetrical dihydroxylation of Cr-Anderson type polyacid catalyzed alkene thiourea modified for-1-(2-hydroxyl-1-phenethyl)
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 0.0216g (S)-1-(2-hydroxyl-1-phenethyl) is thiourea modified
The many acid catalysts of Cr-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 1.358g,
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 that different alkene carries out being catalyzed is anti-
Answering equation as follows, obtained experimental result is shown in Table 1.
The asymmetric dihydroxylation experimental result of table 1 polyacid catalyzed alkene
The catalyst that above-mentioned recovery obtains is directly used in cinnamic dihydroxylation, the enantiomeric excess value of obtained product
(chirality AS-H post, isopropanol: normal hexane=3:7,254nm, 20 DEG C, 0.5mL/min) is measured by HPLC.Catalyst returns
Receive utilize obtained by the results are shown in Table 2.
The experimental result that table 2 catalyst recycles
All above-mentioned primary embodiments, do not implement this new product and/or new method sets and limits other forms.This
Skilled person will utilize this important information, and foregoing is revised, to realize similar implementation status.But, all
Amendment based on the present invention or transformation 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.