CN106622371A - (R)-1-(1-phenethyl)thiourea modified Al-Anderson type heteropolyacid catalyst and preparation method and application thereof - Google Patents
(R)-1-(1-phenethyl)thiourea modified Al-Anderson type heteropolyacid catalyst and preparation method and application thereof Download PDFInfo
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses a (R)-1-(1-phenethyl)thiourea modified Al-Anderson type heteropolyacid catalyst and a preparation method and application thereof. The method includes: subjecting sodium molybdate dehydrate to reaction with aluminum chloride hexahydrate to generate a Al-Anderson type heteropolyacid parent; subjecting the Al-Anderson type heteropolyacid parent to hydrothermal reaction with tris(hydroxymethyl)aminomethane to obtain organic single-side amino modified Al-Anderson type polyoxometallate; taking (R)-1-(1-phenethyl) as a raw material for synthesizing (R)-1-(1-phenethyl)isothiocyanate; finally subjecting the organic single-side amino modified Al-Anderson type polyoxometallate to reaction with (R)-1-(1-phenethyl)isothiocyanate to obtain a target catalyst. Low cost, mild reaction conditions and environment friendliness are realized, and the catalyst is used for aldehyde catalytic oxidation for carboxylic acid preparation and is efficient, high in enantioselectivity and recyclable.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, more particularly to asymmetric selective catalysis field, it particularly relates to one
Plant (R) -1- (1- phenethyls) thiourea modified Al-Anderson type heteropolyacid catalysts, preparation method and applications.
Background technology
Calendar year 2001, Nobel laureate professor Noyori pointed out：" following synthesis chemistry must be economic, safety
, the chemistry of eco-friendly and save resources and the energy, chemist needs the effort for realization ' perfect reactive chemistry ',
The product that needs are only generated with 100% selectivity and 100% yield is produced without waste ".Chiral catalysis synthesis is made
One of important channel for realization " perfection synthesis chemistry ", wherein, chiral catalyst is the most crucial section in chiral catalysis research
Knowledge is inscribed.From in reaction principle, chiral organic micromolecule catalysis is by reversible with unstable covalent bond with reaction substrate
If the Viability intermediate of landform or by interacting, such as oxygen key, Van der Waals force or ion equity priming reaction substrate.Although
The features such as phase chiral catalysis have efficient, high enantioselectivity and gentle reaction condition, but in most cases, catalyst amount
High molar fraction.Realize the application industrially of these catalytic reactions, it is necessary to which the recycling for solving expensive catalyst is individual
Serious problem.
Catalysis is most promising and most practical value research direction in polyoxometallate application.Polyoxometallate
Integrate the good characteristic of acid base catalysator, oxidation reduction catalyst, metal oxide nanocatalyst etc. simultaneously, be considered as
It is a kind of multifunction catalyst of widely used green.Early in 20 beginnings of the century, people begin to enter the catalytic performance of polyacid
Research is gone.It is up till now that existing 8 polyacid catalysis industry projects are successfully developed.It is catalyzed into in Chemistry of Polyacids one
The eternal research topic of item.After chiral polyoxometallate is successfully synthesized, people have just started chiral polyacid not
The exploration in asymmetric catalytic field.Chiral polyoxometallate integrates the various excellent properties of polyacid and chiral material.Its is only
Special soluble class mineral metal-oxide structure, is chiral transmission in chiral non-origin of life theory and inoganic solids
Explore and provide preferable model；Its high elecrtonegativity, adjustable Acidity of Aikalinity, redox active and nano-scale are more more
The design of the new materials such as function nonlinear optics, nano material, stereoselectivity catalysis and medicine, synthesis bring new wishing
Hope.
At present, chiral organic micromolecule catalyst is difficult to realize for industrialized production, mainly due to catalyst activity compared with
Low, consumption is high and is not easily recycled utilization.Realize the application industrially of these catalytic reactions, it is necessary to solve expensive catalyst
Recycling is a serious problem.
Since Zubieta in 1993 et al. exists《Nature》Upper report is successfully prepared similar DNA using hydrothermal technique
Chiral double-stranded compound (Me2NH2)K4[V10O10(H2O)4(OH)4(PO4)7]·H2After O, people have just started chirality
Exploration of the polyacid in asymmetric catalysis field.The Chinese Academy of Sciences chemistry institute professor Luo Sanzhong grade more urged with organic amine small molecules
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, adopt
Polyanionic [the PW of highly acid12O40]3-The mineral acid in traditional Acid-Base concerted catalysis is substituted, has synthesized a series of chiralitys organic
Amine-polyacid hybrid material.Direct asymmetric Aldol reaction of these materials to aldehyde ketone, asymmetric Michael addition reaction etc. all show
Very high catalysis activity and chiral selectivity, but these materials do not have clear and definite molecular structure, it is impossible to further probe into catalytic machine
Reason, it is impossible to explain the synergy of Chiral Amine and polyacid.Dalian materialization institute Duan Chun meets seminar and utilizes polyoxometallate
(POMs) the adjustable denaturation of composition, the diversity of structure and electric charge, a series of porous with catalysis of design and assembly
The POMOFs of property, realizes their application (Journal of the American Chemical in heterogeneous catalysis
Society,2013,135(28):10186-10189.), but these materials are also without clear and definite molecular structure, it is impossible to enter one
Step probes into catalytic mechanism, it is impossible to explain the synergy of MOFs and POMs.
In sum, chiral organic micromolecule catalyst is difficult to realize for industrialized production, organic mainly due to chirality
Micromolecule catalyst activity is relatively low, consumption is high and is not easily recycled utilization.The application industrially of these catalytic reactions is realized, must
The recycling that expensive catalyst must be solved the problems, such as is individual serious.It is new that existing chiral organic micromolecule is combined with POMs
Material, without clear and definite molecular structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain chiral organic micromolecule with polyacid
Synergy.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides one kind (R) -1- (1- phenethyls) is thiourea modified
Al-Anderson type heteropolyacid catalysts, 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 for utilizing.
The present invention innovatively proposes to utilize " Acid-Base " collaboration to urge from the mentality of designing of organic micromolecule catalyst
Change strategy, using the chiral organic micromolecule with potential catalysis activity as precursor, by methods such as organic decorations, dexterously
The vacant polyanionic for making organic molecule acid with high Bronsted is combined, and constructs the thinking of chiral polyacid material, and in reality
While existing this thinking, the polyacid of organic decoration not only remains the original structure of polyacid, and has expanded the research of polyacid
Field so as to which there is potential using value in terms of catalysis, medicine and functional material.To expect to realize high catalysis activity and height
Enantioselectivity while be catalyzed, the recycling for solving the problems, such as expensive catalyst is individual serious.
Technical scheme is specifically described as follows.
The present invention provides the system of the thiourea modified Al-Anderson type heteropolyacid catalysts of one kind (R) -1- (1- phenethyls)
Preparation Method, comprises the following steps that：
1) two molybdic acid hydrate sodium and six trichloride hydrate aluminium are reacted into acid condition generation Al-Anderson types miscellaneous many
Sour Na3[Al(OH)6Mo6O18]·10H2O；
2) by Al-Anderson types heteropoly acid parent Na obtained above3[Al(OH)6Mo6O18]·10H2O and trihydroxy
Aminomethane is carried out after hydro-thermal reaction, then under room temperature and TBAB TBAB reactions to obtain organic one side amido modified
Al-Anderson type polyoxometallates [TBA]3{[NH2C(CH2O)3]AlMo6O18(OH)3}；
3) (R) -1- (1- phenethyls) isothiocyanates with (R)-(+) -1- phenylethylamines as Material synthesis；
4) by many metals of Al-Anderson types that (R) -1- (1- phenethyls) isothiocyanates is amido modified with organic one side
The reaction of oxygen hydrochlorate obtains the thiourea modified Al-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls).
In the present invention, step 1) in, the mol ratio of two molybdic acid hydrate sodium and six trichloride hydrate aluminium is 1:1～1:2, pH value
Between 1.5～2.Preferably, the mixture of pH hydrochloric acid or hydrochloric acid and acetic acid is adjusted.
In the present invention, step 2) in, the temperature of hydro-thermal reaction is 135～145 DEG C, and the reaction time is 20～30h；Al-
Anderson type heteropoly acid parent Na3[Al(OH)6Mo6O18] with the mol ratio of trihydroxy aminomethane it is 1:2～1:5；Al-
Anderson type heteropoly acid parent Na3[Al(OH)6Mo6O18] and TBAB TBAB mol ratio be 1:3～1:5.
In the present invention, step 4) in, the amido modified Al-Anderson types polyoxometallate in organic one side and (R) -1-
The mol ratio of (1- phenethyls) isothiocyanates is 1:3～1：5；Reaction temperature is 45～55 DEG C, and the reaction time is 2～3 days, instead
Solvent is answered to be polar non-solute.
The present invention also provides a kind of thiourea modified Al- of (R) -1- (1- phenethyls) that above-mentioned preparation method obtains
Anderson type heteropolyacid catalysts.
The present invention further provides a kind of thiourea modified Al-Anderson type heteropoly acids of above-mentioned (R) -1- (1- phenethyls)
Catalyst prepares the application in aromatic carboxylic acids reaction technology field in aromatic aldehyde catalysis oxidation.Application process is specific as follows：
Take appropriate aromatic aldehyde, temperature at 50～70 DEG C, with water as solvent under conditions of, add (R) -1- (1- phenethyls)
Thiourea modified Al-Anderson type heteropolyacid catalysts, under oxidant effect, stirring reaction obtains aromatic carboxylic acids.
In the present invention, (R) usage amount of -1- (1- phenethyls) thiourea modified Al-Anderson type heteropolyacid catalysts
For the 0.5mol%～2mol% of aromatic aldehyde.Oxidant is hydrogen peroxide.
Catalyst in the present invention is used for after catalytic reaction, and reaction terminates to add organic solvent (ether, second in phase system
Alcohol, methyl alcohol etc.) after, polyacid is separated out, and utilization is may be recovered after process, and the catalyst of recovery is re-used for into the catalysis of aromatic aldehyde
Oxidation reaction.
Compared to the prior art, the beneficial effects of the present invention is：The present invention not only can utilize chiral organic micromolecule
Covalent modification break the high symmetry of polyacid, introduce chiral, improve its stereoselectivity in catalytic reaction, and
Also the functional characteristic such as the asymmetry catalysis of organic chiral small molecule or biological medicine activity can be introduced polyacid, and makes organic moiety
Organically it is integrated into a whole with inorganic polyanionic, so as to produce synergy more novel properties is obtained.This is urged
Agent has the advantages that gentle reaction condition, environmental friendliness, efficient, high corresponding selection and recoverable, is applicable to work
Industry metaplasia is produced.Meanwhile, the atom centered on common base metal so that this catalyst has more low production cost, more
With market popularization value.
Description of the drawings
Fig. 1 is the synthetic route chart of the present invention.
Fig. 2 is parent Na3[Al(OH)6Mo6O18] infrared spectrum.
Fig. 3 is the nuclear magnetic spectrogram of (R) -1- (1- phenethyls) isothiocyanates.
Fig. 4 is the infrared spectrum of unilateral amido modified Al-Anderson type polyoxometallates.
Fig. 5 is the nuclear magnetic spectrogram of the thiourea modified Al-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls).
Specific embodiment
Embodiments of the present invention are described in detail using embodiment below, whereby to the present invention how application technology means
To solve technical problem, and reach technique effect realize that process can fully understand and implement according to this.
Fig. 1 is the synthetic route chart of the present invention.
Embodiment 1
Al-Anderson type heteropoly acid parent Na3[Al(OH)6Mo6O18] preparation
Take 14g (59.6mmol) sodium molybdate to be added in 500mL deionized waters, be sufficiently stirred for obtaining clarified solution, under room temperature
Strong stirring is maintained, starts to be slowly added to 6g (37.2mmol) aluminum chloride solids, be slowly added to 200mL glacial acetic acid.It is added dropwise afterwards
36% concentrated hydrochloric acid, by the pH of system 1.5～2.0 are transferred to.Stop stirring, liquid pouring is entered in beaker and is stood, treat white needles
Crystal grows.Suction filtration, obtains 11.48g white crystalline solid raw materials, yield 82%.
Parent Na3[Al(OH)6Mo6O18] infrared spectrum it is as shown in Figure 2.
Embodiment 2
(R) preparation of -1- (1- phenethyls) isothiocyanates
(R)-(+) -1- phenylethylamines (0.606g, 5mmol) is added in dry reaction vessel, is dissolved with 20mL alcohol,
Subsequently it is respectively added slowly to plus CS2(0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), is stirred at room temperature reaction 1h
Afterwards, subsequently under the conditions of 0 DEG C add di-tert-butyl dicarbonate (Boc2O) (1.091mg, 5mmol) and DMAP
(DMAP) (18mg, 0.15mmol), be stirred at room temperature after reaction 2h (has gas to produce, it should be noted that deflation subtracts in the process of stirring
Pressure), 0.7451g (R) -1- (1- phenethyls) isothiocyanates can be obtained.
(R) the nuclear magnetic spectrogram data of -1- (1- phenethyls) isothiocyanates are as shown in Figure 3.
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 Al-Anderson type polyoxometallates
By Anderson parents Na obtained above3[Al(OH)6Mo6O18] 1.071g (1mmol) is with 10mL deionized waters
Dissolving, after obtaining shallow water white transparency clear liquid, is slowly added to trihydroxy aminomethane 0.402g (3mmol).Afterwards by above-mentioned system
Water heating kettle is added, 140 DEG C are heated in water heating kettle, reaction is carried out after 24h, by 4.83g tetrabutyl phosphonium bromides under the conditions of 85 DEG C
Ammonium adds in the solution for dissolving as described above, and it is crude product to produce a large amount of white precipitates, and suction filtration is obtained colourless transparent liquid, is placed
Crystallized, amido modified Al-Anderson type polyacid [TBA] in as organic one side3{[CH2NH2C(CH2O)3]AlMo6O18
(OH)3}。
The infrared spectrum of unilateral amido modified Al-Anderson type polyoxometallates is as shown in Figure 4.
Embodiment 4
(R) preparation of -1- (1- phenethyls) thiourea modified Al-Anderson type heteropolyacid catalysts
By organic one side amido modified [TBA]3{[CH2NH2C(CH2O)3]AlMo6O18(OH)30.5g (0.279mmol) use
After the DMF of 5mL dissolves under the conditions of 50 DEG C, (R) -1- (1- phenethyls) isothiocyanates 0.224g (1.375mmol), dimension are added
Under holding 50 DEG C of stirring conditions, colorless and clear liquid is placed in ether atmosphere and crystallized by 2～3 days reaction time, reaction after terminating, some
Colourless transparent crystal is obtained after it, that is, is obtained the thiourea modified Al-Anderson type heteropoly acids of (R) -1- (1- phenethyls) and is urged
Agent.
(R) the nuclear magnetic spectrogram data of -1- (1- phenethyls) thiourea modified Al-Anderson type heteropolyacid catalysts are as schemed
Shown in 5.
1H NMR (501MHz, DMSO) δ 7.90 (s, 2H), 7.22 (d, J=52.0Hz, 5H), 2.99 (d, J=
136.8Hz, 23H), 1.52 (s, 24H), 1.23 (d, J=43.5Hz, 24H), 0.89 (s, 36H).
Application Example
(R) prepared by -1- (1- phenethyls) thiourea modified Al-Anderson type heteropolyacid catalyst catalysis oxidations aromatic aldehyde
The reaction of aromatic carboxylic acids
The aromatic aldehyde of addition 1mmol and (R) -1- (1- phenethyls) of 0.1mol% are thiourea modified in reaction tube
Al-Anderson type heteropolyacid catalysts, add 5ml H2O adds the H of 4mmol as solvent2O2As oxidant, 50～
24h is reacted at 70 DEG C.Extent of reaction and yield can be tested by GC-Ms.The product and yield of catalysis the results are shown in Table 1.Urge
2 are the results are shown in Table obtained by agent (benzaldehyde catalytic oxidation system) recycling.
The reaction result of table 1.Al-Anderson type heteropolyacid catalyst catalysis oxidation aromatic aldehydes
The experimental result that the catalyst of table 2 is recycled
All above-mentioned this intellectual properties of primarily enforcement, setting limits this new product of enforcement of other forms
And/or new method.Those skilled in the art will be using this important information, the above modification, to realize similar execution feelings
Condition.But, all modifications or transformation are based on the right that new product of the present invention belongs to reservation.
The above, is only presently preferred embodiments of the present invention, is not the restriction for making other forms to the present invention, is appointed
What those skilled in the art changed possibly also with the technology contents of the disclosure above or be modified as equivalent variations etc.
Effect embodiment.But it is every without departing from technical solution of the present invention content, according to the technical spirit of the present invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. the preparation method of the thiourea modified Al-Anderson type heteropolyacid catalysts of one kind (R) -1- (1- phenethyls), it is special
Levy and be, comprise the following steps that：
1) two molybdic acid hydrate sodium and six trichloride hydrate aluminium are reacted into acid condition generation Al-Anderson type heteropoly acid Na3
[Al(OH)6Mo6O18]·10H2O；
2) by Al-Anderson types heteropoly acid parent Na obtained above3[Al(OH)6Mo6O18]·10H2O and trihydroxy amino
Methane is carried out after hydro-thermal reaction, then is reacted and obtained the amido modified Al- in organic one side with TBAB TBAB under room temperature
Anderson type polyoxometallates [TBA]3{[NH2C(CH2O)3]AlMo6O18(OH)3}；
3) (R) -1- (1- phenethyls) isothiocyanates with (R)-(+) -1- phenylethylamines as Material synthesis；
4) by Al-Anderson type polyoxometallic acids that (R) -1- (1- phenethyls) isothiocyanates is amido modified with organic one side
Reactant salt obtains the thiourea modified Al-Anderson type heteropolyacid catalysts of (R) -1- (1- phenethyls).
2. preparation method as claimed in claim 1, it is characterised in that step 1) in, two molybdic acid hydrate sodium and six hydration trichlorines
The mol ratio for changing aluminium is 1:1～1:2；The pH value of system is between 1.5～2.
3. preparation method as claimed in claim 2, it is characterised in that the mixing of the pH hydrochloric acid of system or hydrochloric acid and acetic acid
Thing is adjusted.
4. preparation method as claimed in claim 1, it is characterised in that step 2) in, the temperature of hydro-thermal reaction is 135～145
DEG C, the reaction time is 20～30h；Al-Anderson type heteropoly acid parent Na3[Al(OH)6Mo6O18] and trihydroxy aminomethane
Mol ratio be 1:2～1:5；Al-Anderson type heteropoly acid parent Na3[Al(OH)6Mo6O18] and TBAB TBAB
Mol ratio be 1:3～1:5.
5. preparation method as claimed in claim 1, it is characterised in that step 4) in, the amido modified Al- in organic one side
Anderson types polyoxometallate is 1 with the mol ratio of (R) -1- (1- phenethyls) isothiocyanates:3～1:5；Reaction temperature
For 45～55 DEG C, the reaction time is 2～3 days.
6. a kind of preparation method as described in one of claim 1-5 is obtained (R) -1- (1- phenethyls) thiourea modified Al-
Anderson type heteropolyacid catalysts.
7. a kind of as claimed in claim 6 (R) -1- (1- phenethyls) thiourea modified Al-Anderson type heteropoly acid catalysis
Agent prepares the application in aromatic carboxylic acids reaction in aromatic aldehyde catalysis oxidation.
8. application as claimed in claim 7, it is characterised in that application process is as follows：Aromatic aldehyde is taken, in 50～70 DEG C of temperature
Degree, with water as solvent under conditions of, add (R) -1- (1- phenethyls) thiourea modified Al-Anderson type heteropoly acid catalysis
Agent, under oxidant effect, stirring reaction obtains aromatic carboxylic acids.
9. application as claimed in claim 8, it is characterised in that (R) -1- (1- phenethyls) thiourea modified Al-Anderson
The usage amount of type heteropolyacid catalyst is the 0.5mol%～2mol% of aromatic aldehyde.
10. application as claimed in claim 8, it is characterised in that oxidant is hydrogen peroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109847775A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of method of Aqueous phase preparation protonation Type B Anderson type heteropoly acid |
| 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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