CN1164361C - Phase-transfer catalyst for control of oxidizing reaction and oxidizing reaction procedure - Google Patents

Phase-transfer catalyst for control of oxidizing reaction and oxidizing reaction procedure Download PDF

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CN1164361C
CN1164361C CNB011236531A CN01123653A CN1164361C CN 1164361 C CN1164361 C CN 1164361C CN B011236531 A CNB011236531 A CN B011236531A CN 01123653 A CN01123653 A CN 01123653A CN 1164361 C CN1164361 C CN 1164361C
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catalyst
reaction
substrate
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ketone
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CN1401425A (en
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奚祖威
孙渝
李坤兰
周宁
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China Petroleum and Chemical Corp
Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to US10/432,874 priority patent/US6960693B2/en
Priority to AU2002221508A priority patent/AU2002221508A1/en
Priority to JP2002546480A priority patent/JP2004513972A/en
Priority to PCT/CN2001/001589 priority patent/WO2002044110A1/en
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Abstract

The present invention relates to a phase-transfer catalyst for control of an oxidizing reaction, which can be represented by a general formula: Q<m>H<n>XM<p>O<4+3> or Q<m>MO<3>(L). The catalyst in such a type can not be dissolved in a reaction medium, but active species dissolved in the reaction medium can be formed under the action of one of the reactants, and the catalyst further reacts with other reactants, so the catalyst can react selectively, and the catalyst is restored to an initial structure and is separated out from a reaction system when one of the reactants is consumed off. The catalyst can be recovered by simple separation, the recovered catalyst can be used circularly, and the circular using effect is equivalent to the reaction effect of an original catalyst. The separation of the catalyst in such a type is similar to that of a heterogeneous catalyst and completely embodies the characteristics of a uniform-phase catalyst in the reaction process, and the phase-transfer catalyst can satisfy the requirements for technical economy; furthermore, the phase-transfer catalyst is a novel and is suitable for large-scale industrial application.

Description

Be used for oxidation reaction control phase transfer catalyst and oxidation reaction process
Technical field
The present invention relates to a kind of oxidation reaction phase transfer catalyst and oxidation reaction process thereof of being used for, a kind of reaction control phase transfer catalyst and oxidation reaction process thereof that is used for the homogeneous oxidizing reaction particularly is provided.
Background technology
Catalytic process is the core of modern chemistry and commercial Application thereof.According to the form of catalyst in course of reaction, catalytic process is divided into two kinds of heterogeneous catalytic reaction and even phase catalytic reactions.At present, the chemical industry process is based on heterogeneous catalytic reaction, but the catalyst that is had owing to even phase catalytic reaction is active high, advantages such as reaction condition gentleness, and even phase catalytic reaction also is the important branch of basic research and commercial Application always.
The greatest difficulty of even phase catalytic reaction extensive use is: employed even phase catalyst is difficult to separation and reclaims [" the even progress of catalysis mutually ", Chemical Industry Press, 1990] owing to be dissolved in reaction system fully after reaction finishes.And most even phase catalyst contains transition metal, and price is more expensive, thus catalyst can separate and reclaim be the key factor that can entire reaction course economical rationality.
At present, for various even phase catalytic reactions, also from reaction system, do not separate and reclaim the systems approach of catalyst.Once carried out some good tries, as immobilized [" Catalysis by Supported Complexes ", 1981] of even phase catalyst, it is that even phase catalyst is carried on inorganic carrier (as SiO 2, diatomite, active carbon etc.) go up or be bonded on the organic polymer carrier (as polystyrene chlorine ball etc.) by chemical action, form the solid catalyst that is insoluble to reaction system, can after finishing, reaction separate and reclaim catalyst easily like this.But this method can reduce the catalytic activity of even phase catalyst significantly, and the metal on the while is immobilized also comes off easily, cause the loss of noble metal, so the example of practical application is few.
Summary of the invention
The objective of the invention is to overcome the difficult problem of separating and reclaiming of general even phase catalyst, the phase transfer catalyst that provides a kind of novel reaction to control.Such catalyst shows the characteristics of even phase catalyst, catalytic activity height fully in course of reaction; Separation at the entire reaction rear catalyst is then similar to heterogeneous catalyst, and the catalyst after reclaiming can recycle, and the effect that recycles is suitable with the reaction effect of raw catalyst.
Phase transfer catalyst and the oxidation reaction process thereof that is used for the reaction control of oxidation reaction provided by the present invention is characterised in that: itself be insoluble in the reaction medium at the employed catalyst of reaction system; But catalyst forms the active specy that is dissolved in reaction medium under the effect of one of reactant that drops into; The active specy and another reactant effect that form optionally generate target product; After one of reactant had been consumed, catalyst promptly returned to initial structure and just separates out from reaction system; Catalyst can separate and reclaim easily, and can be recycled.With the oxidation reaction is example, and overall process is shown below.
In the formula, R=or alkyl
Specifically, phase transfer catalyst involved in the present invention comprises by general formula Q mH nXM pO 4+3p(I) represented heteropllyacids compound, wherein, M is a central metal atom, can be metallic atoms such as Mo, W or V; Q is a cationic moiety, can use [R 1R 2R 3R 4N +] expression, wherein R 1, R 2, R 3, R 4Can be H-, C 1-C 20The alkyl of straight or branched, cycloalkyl, benzyl, or R 1R 2R 3N is pyridine and homologue thereof; X is a hetero atom, can be P or As; 2≤m≤7, n=0 or 1; P=2,3,4.
In addition, this phase transfer catalyst can also be by general formula Q mMO 3(L) (II) represented complex compound, M is a central metal atom in the formula, can be metallic atoms such as Mo, W; Q is a cationic moiety, can be [R 1R 2R 3R 4N +], R wherein 1, R 2, R 3, R 4Can be H-, C 1-C 20The alkyl of straight or branched, cycloalkyl, benzyl, or R 1R 2R 3N is pyridine and homologue thereof; L is the bidentate ligand that contains N or O.When L is N, N bidentate ligand, comprise R 1, R 2-2,2 '-bipyridyl (R 1, R 2Can be H-, the C on 2～9 1-C 20Substituting groups such as the alkyl of straight or branched, cycloalkyl, aryl), R 1, R 2, R 3-o-phenanthroline (R 1, R 2, R 3Can be H-, the C on 2～9 1-C 20Substituting groups such as the alkyl of straight or branched, cycloalkyl, aryl), m=0; When L is N, O bidentate ligand, comprise the western Buddhist alkali of oxine, 2-carboxyl pyridine, salicylide and primary amine formation etc., m=1; When L is O, O bidentate ligand, comprise β-carbonyl ketone or ester, m=1.Above-mentioned this class catalyst itself is insoluble in the reaction medium; But under the effect of oxygen source, form the oxidation activity species that are dissolved in the reaction medium; These oxidation activity species and another reactant effect make its optionally oxidation, obtain the target oxidation product; Be consumed and work as oxygen source, catalyst promptly returns to initial structure and just separates out from reaction system.At this moment separate by simple, as centrifugal or filtration, these catalyst can be reclaimed easily; Catalyst after the recovery can recycle, and the effect that recycles is suitable with the reaction effect of raw catalyst.
In addition, the invention provides a kind of oxidation reaction process that reacts control, it is characterized in that: course of reaction comprises following steps:
(a) utilize above-mentioned general formula (I) or (II) represented phase transfer catalyst;
(b) in homogeneous phase or water/oily two phase reaction medium, oxygen source and substrate react under the catalysis of reaction control phase transfer catalyst, generate product;
(c) after reaction was finished, by centrifugal or filter to isolate reaction control phase transfer catalyst, catalyst was reusable.
Above-mentioned oxidation reaction is carried out under-20 ℃-110 ℃,
The ratio of above-mentioned substrate and hydrogen peroxide or alkyl peroxide is the scope at 1: 100 to 100: 1.
In above-mentioned reaction, employed reaction medium comprises: alcohols solvent can be methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, the tert-butyl alcohol, or other alcohol; Alkane solvents is C 5-C 18Linear paraffin, branched paraffin, or cycloalkane; Aromatic hydrocarbon solvent is benzene, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene, or other single replacement or polysubstituted alkylbenzene; Esters solvent can be fatty acid ester, aromatic esters, or trialkylphosphate such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, trioctyl phosphate; Ether solvent is alkyl ether, aromatic radical ethers or aryl alkyl ethers; Ketones solvent is dialkyl group ketone, aryl alkyl ketone; Nitrile solvents is acetonitrile, benzonitrile; And halogenated hydrocarbon solvent, be halogenated alkane, or halogenated aryl hydrocarbon; Employed reaction medium can be a single solvent, also can be the mixed solvent of above-mentioned several solvent compositions.
In above-mentioned reaction, employed oxygen source is hydrogen peroxide (H 2O 2) or alkyl peroxide (ROOH).
In above-mentioned reaction, employed hydrogen peroxide is the aqueous hydrogen peroxide solution of 5%-90%; Employed alkyl peroxide is TBHP, ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide or cyclohexyl hydroperoxide; Employed oxygen source is the aqueous hydrogen peroxide solution of directly input or the solution of alkyl peroxide.
In above-mentioned reaction, use by the oxidation reaction original position produce when replacing the generated in-situ hydrogen peroxide of quinhydrones, after reaction is finished, isolate catalyst, product and unreacted raw material, replace quinone under the effect of transition metal hydrogenation catalyst with hydrogen reaction, regenerate initial replacement quinhydrones.
Above-mentioned employed replacement quinhydrones has the general structure shown in the following structural formula:
Figure C0112365300081
R wherein 5, R 6Be H or C 1-C 10Alkyl substituent, also can use the mixture of above-mentioned replacement quinhydrones more than 2 kinds or 2 kinds to be used for in-situ hydrogen peroxide.
Above-mentioned employed transition metal hydrogenation catalyst is to contain palladium, platinum, chromium, rhodium, nickel or ruthenium catalyst.
In above-mentioned reaction, related substrate is alkene, alkane, aromatic hydrocarbons, ketone, alcohol, thioether, or sulfoxide, oxidation reaction takes place is that alkene epoxidation, alkene section are split and be oxidized to that aldehyde, ketone or carboxylic acid, alkane hydroxylating, aromatic hydrocarbons hydroxylating, alcohol are oxidized to ketone, oxidation of ketones becomes ester, sulfide oxidation to become sulfoxide, or sulfoxide is oxidized to sulfone.
The olefin substrate that described epoxidation reaction of olefines relates to comprises the organic compound that contains a carbon-carbon double bond at least, be the alkene of armaticity, alkene, aryl alkyl alkene, cycloolefin, linear alkene and the branched-chain alkene of fatty, for example propylene, 1-butylene, 2-butylene, isobutene, cyclopentene, cyclohexene, styrene etc.; Or diene, triolefin and contain the unsaturated compound of more carbon-carbon double bonds, or unsaturated polymer; Perhaps derivatives such as the ester of unrighted acid and formation thereof or glyceride; Except that alkyl substituent, olefin substrate also can contain other substituting group, as halogen, carboxylic acid group, ester group, alkoxyl, hydroxyl, sulfydryl, nitro, itrile group, acyl group or amino, as chloropropene, allyl alcohol, phenyl allyl ether; The substrate of epoxidation reaction is a kind of compound, or the mixture of several compounds.
Described alkene section is split the substrate that is oxidized to aldehyde, ketone or carboxylic acid reaction has identical scope with the substrate of above-mentioned epoxidation reaction of olefines.
The substrate that described alkane hydroxylating relates to comprises C 5-C 30Linear paraffin, branched paraffin, cycloalkane and substituted ring alkane, substituting group also comprises halogen, carboxylic acid group, ester group, alkoxyl, hydroxyl, sulfydryl, nitro, itrile group, acyl group or amino.
The substrate that described aromatic hydrocarbons hydroxylating relates to comprises C 6-C 30Aromatic hydrocarbons and substituted arene, except that the hydro carbons substituting group, substituting group also comprises halogen, carboxylic acid group, ester group, alkoxyl, hydroxyl, sulfydryl, nitro, itrile group, acyl group or amino.
The reaction substrate that described alcohol is oxidized to aldehydes or ketones comprises aromatic alcohol, fatty alcohol, aryl alkyl alcohol, cyclic alkanol, straight chain alcohol or branched-chain alcoho, and glycol also can be oxidized to corresponding aldehydes or ketones.
Described oxidation of ketones is that the substrate of ester comprises aromatic ketone, aliphatic ketone, aryl alkyl ketone, cyclic ketones, straight chain ketone or side chain ketone.
Described sulfide oxidation is that the substrate of sulfoxide comprises fragrant thioether, fatty thioether, aryl alkyl thioether, epithio ether, straight chain thioether or side chain thioether.
The reaction substrate that described sulfoxide is oxidized to sulfone comprises fragrant sulfoxide, fatty sulfoxide, aryl alkyl sulfoxide, ring sulfoxide, straight chain sulfoxide or side chain sulfoxide.
The reaction condition gentleness of the present invention in each kinds of oxidation reaction, reaction temperature are between-20 ℃ to 110 ℃, and reaction temperature is between 30 to 100 ℃ preferably.In addition, the ratio of substrate and hydrogen peroxide or alkyl peroxide can be in 1: 100 to 100: 1 scope, and scope is 1: 10 to 10: 1 preferably.
The phase transfer catalyst of novel reaction control provided by the invention can change into corresponding oxidation product with substrate selective ground Catalytic Oxygen widely.Catalyst dissolution embodies the characteristics and the effect of even phase catalyst fully in reaction system in course of reaction, thereby the reaction condition gentleness; And after entire reaction, owing to lack oxygen source, catalyst is separated out from reaction system.The separation of catalyst is similar with heterogeneous catalyst like this, and this has solved the difficult problem of separating and reclaiming of above-mentioned even phase catalyst, can satisfy the requirement of Technological Economy, is the new catalyst that is fit to large-scale industrial application.
The specific embodiment
Give further instruction below by example to the present invention.
The epoxidation of example 1 cyclohexene
The 40mmol cyclohexene is dissolved in 40mL and mixes in the trimethylbenzene, adds 15% aqueous hydrogen peroxide solution (w/w) of 20mmol, the catalyst [(C of 0.2mmol 2H 5) 3NCH 2Ph] 2HAsMo 2O 10Under 65 ℃, react after 1 hour, the conversion ratio of cyclohexene is 49.0%, and the selectivity of 7-oxa-bicyclo[4.1.0 is 95.2%.This moment, catalyst was separated out from reaction system, and catalyst, vacuum drying are reclaimed in centrifugal back.Distill out unreacted raw material cyclohexene and product 7-oxa-bicyclo[4.1.0 in the organic layer.Liquid adds epoxidation catalyst, cyclohexene and the hydrogen peroxide of recovery again at the bottom of the resulting distillation, the same circular response, and reaction result is as shown in the table.
The catalyst that reclaims is capable of circulation to be used for above-mentioned reaction five times, and reaction result is as shown in the table.
Catalyst circulation time cyclohexene conversion ratio 7-oxa-bicyclo[4.1.0 selectivity
Number % %
Fresh catalyst 49.0 95.2
I 48.6 96.0
II 48.2 96.5
III 48.7 95.7
IV 48.5 95.8
V 48.6 95.7
Change dissolvant of reaction system, oxygen source, catalyst, all the other conditions are identical with example 1, and the result of epoxidation reaction is as shown in the table.
Cyclohexene epoxy hexamethylene
Temperature
Solvent oxygen source catalyst conversion ratio alkane selectivity
(℃) ％ ％
The tert-butyl alcohol 35% peroxidating [(C 6H 12) (C 2H 5) 2NH] 3[PMo 4O 16] 50 45.6 93.7
Hydrogen solution
Cyclohexane t-butyl peroxy [(2-C 3H 7) 4N] 2HAsW 2O 1045 35.8 95.2
Change hydrogen solution
Tricresyl phosphate isopropylbenzene peroxide [(CH 3) 3NCH 2Ph] 2HPMo 2O 1055 46.7 93.1
Ethyl ester hydrogen/different third
Benzole soln
Methyl phenyl ethers anisole 65% peroxidating [_-C 5H 5NC 4H 9] 7PV 4O 1630 47.9 88.7
Hydrogen solution
Acetophenone ethylbenzene peroxidating [(2-C 4H 9)-(_-35 38.9 82.7
Hydrogen solution C 5H 4N) (C 6H 13)] 3[PMo 4O 16]
Benzonitrile 50% peroxidating [(t-C 4H 9) 2N (C 2H 5) 2] 3AsW 2O 1035 48.6 94.6
Hydrogen solution
Chloroform cyclohexane peroxide [_-C 5H 5NC 12H 25] 2HPMo 2O 1045 49.0 96.8
Change hydrogen solution
The epoxidation of example 2 cyclohexene
2 methyl naphthoquinone 20mmol is dissolved in the mixed solvent of 15mL repefral and 15mL diisobutyl carbinol (DIBC), adds 2% 5%Pd/C (W/W) catalyst, 6atm hydrogen, and 45 ℃ were reacted 6 hours, and made the 2 methyl naphthoquinone hydrogenation reach 50%.Stop hydrogenation, cross and filter out the Pd/C catalyst.In filtrate, add cyclohexene 30mmol then, catalyst [_-C 5H 5NC 4H 9] 7PV 4O 160.09mmol, at 1atm O 2Down, 65 ℃ were reacted 2 hours, and this moment, catalyst was separated out from reaction system, and the conversion ratio of cyclohexene is 33.0%, and the selectivity of 7-oxa-bicyclo[4.1.0 is 98.3%.Suction filtration reclaims catalyst, the catalyst that obtains air dry in the air at normal temperatures.Distill out unreacted raw material cyclohexene and product 7-oxa-bicyclo[4.1.0.Liquid adds 2%Pd/C (W/W) catalyst at the bottom of the resulting distillation, adds epoxidation catalyst and the cyclohexene that reclaims behind the same catalytic hydrogenation again, the same circular response, and reaction result is as shown in the table.
Catalyst circulation number of times cyclohexene conversion ratio 7-oxa-bicyclo[4.1.0 selectivity
％ ％
Fresh catalyst 33.0 98.3
I 33.1 97.5
II 32.8 97.9
III 32.7 97.2
IV 32.8 97.3
V 32.7 97.0
Change dissolvant of reaction system, reducing agent, hydrogenation catalyst, all the other conditions are identical with example 2, and the result of epoxidation reaction is as shown in the table.
Solvent reducing agent hydrogenation catalyst cyclohexene epoxy cyclohexane
The conversion ratio selectivity
％ ％
Beta-methylnaphthalene and tricresyl phosphate 1, the inferior hydrazine Raney of 2-diphenyl Ni 32.8 98.2
Monooctyl ester
Mesitylene and hydrogenation 2-EAQ Pd/Al 2O 333.3 96.4
The terpene pine camphor
Methyl phenyl ethers anisole and adjacent benzene two hydroquinones Pt/Al 2O 329.5 98.7
The formic acid diethylester
C9 aromatic hydrocarbons and acetic acid first 2,5-diethyl hydrogenation Ru/C 24.3 96.8
Base cyclohexyl pyrazine
The epoxidation of example 3 propylene
20mmol 2-tert-butyl group anthraquinone is dissolved in 15ml and mixes in the mixed solvent of trimethylbenzene and 15ml tributyl phosphate composition, under 0.125g 5%Pd/C catalysis, and 45 ℃, 6atm H 2Under carry out hydrogenation reaction, after 10mmol 2-tert-butyl anthracene quinhydrones generates, cessation reaction.Remove by filter Pd/C, mother liquor leads to O 2Complete oxidation generates hydrogen peroxide and 2-tert-butyl group anthraquinone.Oxidation liquid is transferred in the autoclave of band glass lining, adds 0.09mmol[_-C 5H 5NC 12H 25] 3[PW 4O 16] and charge into the 60mmol propylene, 50 ℃ were reacted 4 hours down.Propylene is 90% with respect to the conversion ratio of 2-tert-butyl anthracene quinhydrones, and the selectivity that generates expoxy propane is 95%.The catalyst of separating out after the reaction reclaims by centrifugation, is used for secondary response down.Isolate unreacted propylene, expoxy propane and water in the reaction mother liquor, 2-tert-butyl group anthraquinone can be under 5%Pd/C catalysis hydrogenation, regenerate 2-tert-butyl anthracene quinhydrones.Catalyst circulation is used 3 times the following table that the results are shown in.
The catalyst circulation propylene transforms the expoxy propane choosing
Inferior selecting property of digit rate
(to quinhydrones, (to propylene,
％) ％)
Fresh catalyst 90 95
I 89 93
II 89 94
III 88 91
But some other reaction control phase transfer catalyst is catalytic epoxidation of propone also.The results are shown in following table.
The choosing of propylene conversion expoxy propane
Temperature
The solvent catalyst reducing agent is (to selecting property of reduction
(℃) agent, %) (to propylene, %)
Toluene and tricresyl phosphate [(C 6H 12) 4N] 32-ethyl anthracene 75 40 96
Monooctyl ester [PMo 4O 16] quinhydrones
Phthalic acid two [_-C 5H 5NC 16H 33] 32-butyl anthracene 55 90 95
Methyl esters and tricresyl phosphate [PW 3O 13] quinhydrones
Second fat
The tert-butyl alcohol [(C 2H 5) 3NCH 2Ph] 21,2-diphenyl 55 83 91
[HAsW 2O 10] inferior hydrazine
C 9Aromatic hydrocarbons and acetic acid [(C 4H 9) 3NCH 2Ph] 32,5-diethyl 60 88 88
Methyl cyclohexane ester [PW 4O 16] the hydrogenation pyrazine
Dimethylbenzene and hydrogenation [_-C 5H 5NC 14H 29] 32,3-diethyl 35 90 82
Terpene pine camphor [AsW 4O 16] the naphthalene quinhydrones
Catalyst is all separated out from reaction system with the form of precipitation after reaction finishes, and reclaims through simple filtering or centrifugation, can be recycled.Employed reducing agent is oxidized in reaction in the reaction, can make its recovery through catalytic hydrogenation after the reaction, reuses again.
Example 4 2-butanols oxidation system 2-butanone
40mmol 2-butanols is dissolved in the 50mL dichloroethanes, in the aqueous solution of 35% hydrogen peroxide of adding 20mmol (w/w), and the catalyst [(C of 0.2mmol 2H 5) 3NCH 2Ph] 2HAsMo 2O 10Under 65 ℃, react after 1 hour, the conversion ratio of 2-butanols is 31.0%, and the selectivity of 2-butanone is 88.2%.This moment, catalyst was separated out from reaction system, and catalyst, vacuum drying are reclaimed in centrifugal back.The catalyst that reclaims is capable of circulation to be used for above-mentioned reaction three times, and reaction result is as shown in the table.
Catalyst circulation number of times 2-butanols Conv.% 2-butanone Selectivity%
Fresh catalyst 31.0 88.2
I 30.6 89.0
II 31.2 88.0
III 31.7 88.1
The epoxidation of example 5 1-heptene
20mmol is dissolved in 15mL C with the 2-EAQ 9In the mixed solvent of aromatic hydrocarbons and 15mL acetic acid methyl cyclohexane ester, add 2% 5%Pd-C (W/W) catalyst, 6atm hydrogen, 45 ℃ were reacted 6 hours, and made 2-EAQ hydrogenation reach 50%.Stop hydrogenation, cross and filter out the Pd-C catalyst.In filtrate, add 1-heptene 30mmol, catalyst [(n-C then 8H 17) 4N] 2HAsW 2O 100.09mmol, at 1atm O 2Down, 65 ℃ were reacted 6 hours, and this moment, catalyst was separated out from reaction system, and the conversion ratio of 1-heptene is 31.0%, 1, and the selectivity of 2-epoxy heptane is 93.7%.Suction filtration reclaims catalyst, the catalyst that obtains air dry in the air at normal temperatures, and recirculation is used for above-mentioned reaction three times, and reaction result is as shown in the table.
Catalyst circulation number of times 1-heptene Conv.% 1,2-epoxy heptane Selectivity%
Fresh catalyst 31.0 93.7
I 31.1 92.5
II 30.8 93.9
III 30.7 93.2
Example 6 isoeugenols (1) and trans-ferulaic acid (2) oxidation system vanillic aldehyde (3)
30.5mmol 1 or 2 are dissolved in the 40mL tert-butyl alcohol, add 85% aqueous hydrogen peroxide solution (W/W) of 91.5mmol.The anhydrous MgSO of reaction solution 4After the drying, add the [(t-C of 0.3mmol (1mol%) 4H 9) 4N] 3PMo 4O 16Catalyst.60 ℃ reaction is after 2 hours down, and 1 or 2 conversion ratio all reaches 100%, 3 productive rate＞60%.NaHSO with 10% 3The aqueous solution decomposes unreacted H 2O 2After, catalyst is separated out from reaction system.Centrifugal recovery catalyst, the catalyst that obtains capable of circulationly are used for above-mentioned reaction after＜50 ℃ of following vacuum drying.
Figure C0112365300161
Example 7 aminomethyl phenyl sulfide oxidation system methyl phenyl sulfoxide
40mmol aminomethyl phenyl thioether is dissolved in the 20mL chloroform, adds 1mol/L isopropyl benzene hydroperoxide/cumene solution of 10mmol, adds (I) catalyst of 0.1mmol again.0 ℃ reaction is after 2 hours down, and catalyst is separated out from reaction system, and the conversion ratio of aminomethyl phenyl thioether reaches 24.3%, and the productive rate of methyl phenyl sulfoxide is 23.1%.The catalyst of separating out filters the back and reclaims, and after the vacuum drying, capable of circulationly is used for above-mentioned reaction.
Figure C0112365300162
The positive enanthic acid of example 8 1-methylcyclohexene oxidation systems-6-ketone
1-methylcyclohexene 10mmol is dissolved in the 20mL tert-butyl alcohol, adds 15% aqueous hydrogen peroxide solution (W/W) of 40mmol, adds the [(n-C of 0.05mmol again 6H 13) 4N] 2HPMo 2O 10Catalyst.80 ℃ reaction is after 24 hours down, and the productive rate of positive enanthic acid-2-ketone is 90%.Use 10% NaHSO then 3The aqueous solution decomposes unreacted H 2O 2, this moment, catalyst was separated out from reaction system.Catalyst is reclaimed in centrifugal back, after the vacuum drying, capable of circulationly is used for above-mentioned reaction.
Example 9 cyclohexanone oxidation system caprolactones
Cyclohexanone 40mmol is dissolved in the 40mL acetonitrile, adds 50% aqueous hydrogen peroxide solution (w/w) of 10mmol, adds the [(CH of 0.2mmol again 3) 3NCH 2Ph] 7PV 4O 1625 ℃ of reactions are after 28 hours, and catalyst is separated out from system.The conversion ratio of cyclohexanone is 18%, and the selectivity of caprolactone is 92%.The catalyst filtered and recycled of separating out after the vacuum drying, capable of circulationly is used for above-mentioned reaction.
Example 10 cyclohexane oxidation system cyclohexanol and cyclohexanone
In the 43ml cyclohexane, add 40mmol 35% aqueous hydrogen peroxide solution (w/w), add 1mmol[N (C again 6H 13) 4] 5[PV 2O 10].Under 65 ℃, react after 12 hours, catalyst is separated out from system.Cyclohexane conversion is 55% (to hydrogen peroxide), and the selectivity of cyclohexanol is 31%, and the selectivity of cyclohexanone is 57%.The catalyst filtered and recycled of separating out after the vacuum drying, capable of circulationly is used for above-mentioned reaction.
Show that by above-mentioned example the phase transfer catalyst that adopts novel reaction provided by the present invention to control in suitable reaction medium, according to the condition that invention is provided, can optionally be made different products with substrate catalysis widely.Catalyst dissolution embodies the characteristics and the effect of even phase catalyst fully in reaction system in course of reaction, thereby the reaction condition gentleness; And after entire reaction, owing to lack a certain reactant, catalyst is insoluble to reaction system, is easy to separate reclaim and recycle.The separation of catalyst is similar with heterogeneous catalyst like this, can satisfy the requirement of Technological Economy, is the new catalyst that is fit to large-scale industrial application.

Claims (11)

1. a reaction control phase transfer catalyst that is used for oxidation reaction is characterized in that: the heteropllyacids compound Q of described catalyst for representing with structural formula mH nXM pO 4+3p, in the formula, M is a central metal atom, is Mo, W or V metallic atom; Q is a cationic moiety, with [R 1R 2R 3R 4N +] expression, wherein R 1, R 2, R 3, R 4Be H-, C 1-C 20Alkyl, cycloalkyl or the benzyl of straight or branched; X is a hetero atom, is P or As; 2≤m≤7, n=0 or 1; P=2,3,4.
2. a reaction control phase transfer catalyst that is used for oxidation reaction is characterized in that the complex compound Q of described these catalyst for representing with structural formula mMO 3(L), wherein, M is a central metal atom, is Mo or W metallic atom; Q is a cationic moiety, is [R 1R 2R 3R 4N +], R wherein 1, R 2, R 3, R 4Be H-, C 1-C 20Alkyl, cycloalkyl or the benzyl of straight or branched; L is the following bidentate ligand that contains N or O: when L is N, N bidentate ligand, be R 1, R 2-2,2 '-bipyridyl or R 1, R 2, R 3-o-phenanthroline, wherein R 1, R 2, R 3Be H-, the C on 2～9 1-C 20Alkyl, cycloalkyl or the aryl of straight or branched, m=0; When L is N, O bidentate ligand, be the western Buddhist alkali of oxine, 2-carboxyl pyridine, salicylide or substituted salicylic aldehydes and primary amine formation, m=1; When L is O, O bidentate ligand, be β-carbonyl ketone or ester, m=1.
3. oxidation reaction method that reacts control, it is characterized in that: reaction method comprises following steps:
(a) utilize claim 1 or 2 described phase transfer catalysts;
(b) in homogeneous phase or water/oily two phase reaction medium, oxygen source and substrate react under the catalysis of reaction control phase transfer catalyst, the ratio of substrate and hydrogen peroxide or alkyl peroxide is the scope at 1: 100 to 100: 1, and oxidation reaction is carried out under-20 ℃-110 ℃, generates product;
(c) after reaction was finished, by centrifugal or filter to isolate reaction control phase transfer catalyst, catalyst was reusable.
4. according to the described oxidation reaction method of claim 3, it is characterized in that: employed reaction medium comprises: alcohols solvent is methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol or the tert-butyl alcohol; Alkane solvents is C 5-C 18Linear paraffin, branched paraffin, or cycloalkane; Aromatic hydrocarbon solvent is benzene, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene, or other single replacement or polysubstituted alkylbenzene; Esters solvent is fatty acid ester, aromatic esters, trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate or trioctyl phosphate; Ether solvent is alkyl ether, aromatic radical ethers or aryl alkyl ethers; Ketones solvent is dialkyl group ketone, aryl alkyl ketone; Nitrile solvents is acetonitrile or benzonitrile; Perhaps halogenated hydrocarbon solvent is a halogenated alkane, or halogenated aryl hydrocarbon; But employed reaction medium single solvent, or the mixed solvent of above-mentioned several solvent compositions.
5. according to the described oxidation reaction method of claim 3, it is characterized in that: employed oxygen source is hydrogen peroxide or alkyl peroxide.
6. according to the described oxidation reaction method of claim 5, it is characterized in that: employed hydrogen peroxide is the aqueous hydrogen peroxide solution of 5%-90%; Employed alkyl peroxide is the solution of TBHP, ethylbenzene hydroperoxide, isopropyl benzene hydroperoxide or cyclohexyl hydroperoxide.
7. according to the described oxidation reaction method of claim 3, it is characterized in that: when the oxygen source that uses is served as reasons the generated in-situ hydrogen peroxide of replacement quinhydrones, after reaction is finished, isolate catalyst, product and unreacted raw material, replace quinone under the effect of transition metal hydrogenation catalyst with hydrogen reaction, regenerate initial replacement quinhydrones.
8. according to the described oxidation reaction method of claim 7, employed replacement quinhydrones has the general structure shown in following:
Figure C011236530003C1
Or
R wherein 5, R 6Be H or C 1-C 10Alkyl substituent, also can use the mixture of above-mentioned replacement quinhydrones more than 2 kinds or 2 kinds to be used for in-situ hydrogen peroxide.
9. according to the described oxidation reaction method of claim 8, employed transition metal hydrogenation catalyst is to contain palladium, platinum, chromium, rhodium, nickel or ruthenium catalyst.
10. according to the described oxidation reaction method of claim 3, it is characterized in that: related oxidation reaction is that alkene epoxidation, alkene section are split and be oxidized to that aldehyde, ketone or carboxylic acid, alkane hydroxylating, aromatic hydrocarbons hydroxylating, alcohol are oxidized to ketone, oxidation of ketones becomes ester, sulfide oxidation to become sulfoxide, or sulfoxide is oxidized to sulfone.
11. according to the described oxidation reaction method of claim 10, it is characterized in that: the olefin substrate that described epoxidation reaction of olefines relates to comprises armaticity alkene, fatty alkene, aryl alkyl alkene, cycloolefin, linear alkene and the branched-chain alkene that contains a carbon-carbon double bond at least; Or diene, triolefin and contain the unsaturated compound of more carbon-carbon double bonds, or unsaturated polymer; The perhaps ester of unrighted acid and formation thereof or glyceride ester derivatives; Except that alkyl substituent, olefin substrate also can contain other substituting group, as halogen, carboxylic acid group, ester group, alkoxyl, hydroxyl, sulfydryl, nitro, itrile group, acyl group or amino; The substrate of epoxidation reaction is a kind of compound, or the mixture of several compounds; Described alkene section is split the substrate that is oxidized to aldehyde, ketone or carboxylic acid reaction has identical scope with the substrate of above-mentioned epoxidation reaction of olefines;
The substrate that described alkane hydroxylating relates to comprises C 5-C 30Linear paraffin, branched paraffin, cycloalkane and substituted ring alkane, substituting group also comprises halogen, carboxylic acid group, ester group, alkoxyl, hydroxyl, sulfydryl, nitro, itrile group, acyl group or amino;
The substrate that described aromatic hydrocarbons hydroxylating relates to comprises C 6-C 30Aromatic hydrocarbons and substituted arene, except that the hydro carbons substituting group, substituting group also comprises halogen, carboxylic acid group, ester group, alkoxyl, hydroxyl, sulfydryl, nitro, itrile group, acyl group or amino;
The reaction substrate that described alcohol is oxidized to aldehydes or ketones comprises aromatic alcohol, fatty alcohol, aryl alkyl alcohol, cyclic alkanol, straight chain alcohol or branched-chain alcoho, and glycol also can be oxidized to corresponding aldehydes or ketones;
Described oxidation of ketones is that the substrate of ester comprises aromatic ketone, aliphatic ketone, aryl alkyl ketone, cyclic ketones, straight chain ketone or side chain ketone;
Described sulfide oxidation is that the substrate of sulfoxide comprises fragrant thioether, fatty thioether, aryl alkyl thioether, epithio ether, straight chain thioether or side chain thioether;
The reaction substrate that described sulfoxide is oxidized to sulfone comprises fragrant sulfoxide, fatty sulfoxide, aryl alkyl sulfoxide, ring sulfoxide, straight chain sulfoxide or side chain sulfoxide.
CNB011236531A 2000-11-29 2001-08-27 Phase-transfer catalyst for control of oxidizing reaction and oxidizing reaction procedure Expired - Fee Related CN1164361C (en)

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US10/432,874 US6960693B2 (en) 2000-11-29 2001-11-29 Oxidation reaction process catalyzed by phase-transfer catalyst controlling reaction
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CN1880310B (en) * 2005-06-17 2011-06-15 中国科学院大连化学物理研究所 Method for preparing epoxy cyclohexane and cyclohexane
CN1923777B (en) * 2005-08-31 2011-07-20 中国科学院大连化学物理研究所 Preparation method of 1,2-aliphatic glycol
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CN110386859B (en) * 2018-04-23 2021-11-16 中国科学院大连化学物理研究所 Method for treating aqueous phase after olefin epoxidation reaction
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