CN101130489A - Method for synthesizing benzaldehyde in ionic liquid - Google Patents
Method for synthesizing benzaldehyde in ionic liquid Download PDFInfo
- Publication number
- CN101130489A CN101130489A CNA2007101332343A CN200710133234A CN101130489A CN 101130489 A CN101130489 A CN 101130489A CN A2007101332343 A CNA2007101332343 A CN A2007101332343A CN 200710133234 A CN200710133234 A CN 200710133234A CN 101130489 A CN101130489 A CN 101130489A
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- ionic liquid
- reaction
- tungsten
- benzaldehyde
- catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a making method of benzaldehyde through tungsten, molybdenum peroxy compound to catalyze and oxidize benzenemethanol in the ion liquid, which relates to two kinds of catalyst with tungsten, molybdenum peroxy heteropoly compound and tungsten, molybdenum peroxy compound, wherein two kinds of catalyst are dissolved in the ion liquid to remain in the ion liquid after reacting; the extracted product and non-reacted substrate can form after finishing the reaction; the ion liquid and catalyst can be recycled to use; the receiving rate of benzaldehyde can reach 96. 6% after reacting for 3h.
Description
Technical field
The present invention relates to a kind of benzyl alcohol oxidation and produce the reaction of phenyl aldehyde, realize in ionic liquid that specifically tungsten, molybdenum are assorted many and produce method of benzaldehyde with many peralcohol catalyzing hydrogen peroxide Oxybenzene methyl alcohol.
Background technology
Phenyl aldehyde industrial be a kind of important aromatic aldehyde, be mainly used in the raw material of important intermediate such as making dyestuff, medicine, spices, condiment product, agricultural chemicals.The domestic production phenyl aldehyde is based on the benzyl chloride oxidation style at present, and yield is not high, and corrosion contamination is serious; External industrial production phenyl aldehyde adopts the toluene liquid phase oxidation mostly, but there is the energy consumption height in this method, to the unfriendly deficiency that waits of environment.
Utilizing the benzyl alcohol selective oxidation to produce benzaldehyde is important functional group's conversion reaction in laboratory and the organic synthesis, there are at present a variety of methods can realize this conversion, as: with chromium compound with at hypochlorite catalytic oxidation benzyl chloride in the presence of the phase transfer catalyst with CrO in the presence of medium and the part arranged
3Oxybenzene methyl alcohol (Chemical engineeringjournal, 2001,82:43-56), but the existence of halide and high valence state metallic compound brings serious environmental problem; (Tetrahedron Lett 1998 39:7549-7552) abandons with an organic solvent as reaction medium the people such as Aoki, is catalyst with sodium tungstate, H
2O
2Be oxidant, under solvent-free condition, realized the benzyl alcohol oxidation benzaldehyde, but catalyst and phase transfer catalyst can not reclaim in this system.
Per-compound has been applied in the oxidation reaction of phenmethylol as a kind of effective oxidation catalyst, and Campell studies show that tungsten, molybdenum double focusing per-compound be catalysis H effectively
2O
2Oxidation alcohol (J.Chem.Soc., DaltonTrans.1989,1203-1208.).Ishii etc. use the assorted many per-compound catalysis H of phosphorus tungsten in halohydrocarbon solution
2O
2Oxidation has also realized Alcohol oxidation (J.Org.Chem.; 1988; 53 (15): 3587-3593).But all can not avoid with an organic solvent or have a catalyst recovery hard problem.
Ionic liquid, peralcohol and hydrogen peroxide are formed a new green oxidation system and are carried out benzyl alcohol oxidation and produce the reaction process of phenyl aldehyde and yet there are no report.
Summary of the invention
The object of the present invention is to provide a kind of method of in ionic liquid, producing benzaldehyde with tungsten, the oxidation of molybdenum peroxide compound as catalyst, such catalyst can both be dissolved in the ionic liquid before and after reaction, in some ionic liquid, this catalyst system and catalyzing is homogeneous reaction system, i.e. ionic liquid, H
2O
2Can dissolve each other with substrate, but after the reaction end, system becomes two-phase system, the product benzaldehyde is separately a phase.This is so that reaction finishes that the separation of afterproduct becomes is very simple, and remaining ionic liquid and catalyst can recycle through simple process.Ionic liquid replaces conventional organic solvents to solve environmental problem as a kind of green solvent, and ionic liquid and catalyst recovery recycling meets the Green Chemistry principle simultaneously.
Used solvent is that ionic liquid is avoided with an organic solvent among the present invention, and used ionic liquid is [C
nMim] BF
4[C
nMim] PF
6And [C
nMim] the TA three major types, n=4 wherein, 8.
The catalyst that the present invention uses has two big classes: (I) phosphorus tungsten, molybdenum peroxide heteropoly compound, structural formula is: Q
3{ PO
4[MO (O
2)
2]
4, metallic atom centered by the M can be the metallic atoms such as W or Mo; Q is cationic moiety, can use [R
1R
2R
3R
4N
+] expression, wherein R
1, R
2, R
3, R
4Can be H
-Or alkyl or benzyl or pyridine groups and homologue thereof.(II) tungsten, molybdenum peroxide are with the polyvoltine compound, and structural formula is: Q
2[M
2O
3(O
2)
4], metallic atom centered by the M can be the metallic atoms such as W or Mo; Q is cationic moiety, can use [R
1R
2R
3R
4N
+] expression, wherein R
1, R
2, R
3, R
4Can be H
-Or alkyl or benzyl or pyridine groups and homologue thereof.This two classes catalyzer can be good at being dissolved in the ionic liquid in heated and stirred a little, all is dissolved in the ionic liquid before and after the reaction.
Used ionic liquid consumption is 1-2mL in the process of the present invention, and catalyst levels is the 1/100-1/50 of substrate
Used oxygenant is an aqueous hydrogen peroxide solution in the process of the present invention, and the concentration of aqueous hydrogen peroxide solution is 5%-30%, and the hydrogen peroxide consumption is 1.1 times of substrate.
Oxidation reaction condition gentleness of the present invention, temperature of reaction are between 50 to 100 ℃, and temperature of reaction is between 70 to 90 ℃ preferably.
The oxidation reaction process of phenmethylol of the present invention is simple, the conversion ratio height of phenmethylol, and the selective height of aldehyde, catalyst can separate and reclaim after reaction finishes easily with ionic liquid, and can be recycled.
Embodiment
Give further instruction below by example to the present invention.
Example 1 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 1mL
4Mim] [BF
4] the inner catalyst that adds 0.08mmol: [C
16H
33NC
5H
5]
2W
2O
3(O
2)
4With 10mmol phenmethylol and 11mmol30%H
2O
2, this moment reaction system be homogeneous phase, behind 50 ℃ of electromagnetic agitation 2.5h, the conversion ratio of phenmethylol is 96.3%, benzaldehyde selectively be 78.7%.The system upper strata was benzaldehyde after reaction finished, and product and unreacted phenmethylol easily can be separated from system by extracted with diethyl ether.
Example 2 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.08mmol: [C
16H
33NC
5H
5]
2Mo
2O
3(O
2)
4With 10mmol phenmethylol and 11mmol 30%H
2O
2, this moment reaction system be homogeneous phase, behind 70 ℃ of electromagnetic agitation 2.5h, the conversion ratio of phenmethylol is 71.8%, benzaldehyde selectively be 70.9%.The system upper strata was benzaldehyde after reaction finished, and product and unreacted phenmethylol easily can be separated from system by extracted with diethyl ether.
Example 3 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 1mL
4Mim] [PF
6] the inner catalyst that adds 0.08mmol: [C
16H
33NC
5H
5]
2W
2O
3(O
2)
4With 10mmol phenmethylol and 11mmol 30%H
2O
2, this moment, reaction system was two-phase, and the upper strata is water, and lower floor is ionic liquid layer.Behind 100 ℃ of induction stirring 2.5h, the transformation efficiency of phenylcarbinol is 98.6%, and the selectivity of phenyl aldehyde is 46.6%.Reaction still is two-phase after finishing, and dissolution of benzaldehyde can easily be separated product and unreacted phenmethylol by extracted with diethyl ether in ionic liquid from system.
Example 4 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 1mL
4Mim] [TA] inner catalyst that adds 0.08mmol: [C
16H
33NC
5H
5]
2W
2O
3(O
2)
4With 10mmol phenmethylol and 11mmol 30%H
2O
2, this moment, reaction system was homogeneous phase.Behind the induction stirring 2.5h, the transformation efficiency of phenylcarbinol is 91.7% at a certain temperature, and the selectivity of phenyl aldehyde is 45.4%.Reaction still is homogeneous phase after finishing, and dissolution of benzaldehyde can easily be separated product and unreacted phenmethylol by extracted with diethyl ether in ionic liquid from system.
Example 5 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.08mmol: [C
16H
33NC
5H
5]
3{ PO
4[WO (O
2)
2]
4And 10mmol phenmethylol and 11mmol 30%H
2O
2, this moment reaction system be homogeneous phase, behind the electromagnetic agitation 3h, the conversion ratio of phenmethylol is 99.2% at a certain temperature, benzaldehyde selectively be 97.4%.The system upper strata was benzaldehyde after reaction finished, and product and unreacted phenmethylol easily can be separated from system by extracted with diethyl ether.Remaining ionic liquid is placed 24h in the vacuum drying oven, and resulting ionic liquid adds substrate phenylcarbinol and hydrogen peroxide again, the same circulating reaction, and reaction result is as shown in the table.
The ionic liquid and the catalyzer that reclaim can be used for above-mentioned reaction 5 times, and reaction result is as shown in the table:
| Run | Phenmethylol Conversion/% | Benzaldehyde Selectivity/% |
| Fresh 123 | 99.2 95.2 94.8 90.6 | 97.4 99.5 97.6 98.8 |
| 4 5 | 87.5 81.4 | 97.4 96.8 |
Example 6 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [BF
4] the inner catalyst that adds 0.08mmol: [C
16H
33N (CH
3)
3]
3{ PO
4[MoO (O
2)
2]
4And 10mmol phenmethylol and 11mmol30%H
2O
2, this moment reaction system be homogeneous phase, behind the electromagnetic agitation 3h, the conversion ratio of phenmethylol is 53.7% at a certain temperature, benzaldehyde selectively be 39.4%.The system upper strata was benzaldehyde after reaction finished, and product and unreacted phenmethylol easily can be separated from system by extracted with diethyl ether.
Example 7 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [PF
6] the inner catalyst that adds 0.08mmol: [C
16H
33NC
5H
5]
3{ PO
4[WO (O
2)
2]
4And 10mmol phenmethylol and 11mmol 30%H
2O
2, this moment, reaction system was two-phase, and the upper strata is water, and lower floor is ionic liquid layer.Behind the induction stirring 3h, the transformation efficiency of phenylcarbinol is 77.4% at a certain temperature, and the selectivity of phenyl aldehyde is 45.6%.The system upper strata was benzaldehyde after reaction finished, and product and unreacted phenmethylol easily can be separated from system by extracted with diethyl ether.
Example 8 is in having two neck reaction bulbs of magnetic agitation, to the ionic liquid [C of 2mL
4Mim] [TA] inner catalyst that adds 0.08mmol: [C
16H
33NC
5H
5]
3{ PO
4[WO (O
2)
2]
4And 10mmol phenmethylol and 11mmol 30%H
2O
2, this moment reaction system be homogeneous phase, behind the electromagnetic agitation 3h, the conversion ratio of phenmethylol is 91.4% at a certain temperature, benzaldehyde selectively be 56.1%.Reaction still is homogeneous phase after finishing, and dissolution of benzaldehyde can easily be separated product and unreacted phenmethylol by extracted with diethyl ether in ionic liquid from system.
Above-mentioned example shows, adopts the new reaction system of synthesizing benzoic alcohol provided by the present invention, according to the condition that is provided, can be effectively, highly selective and green with benzyl alcohol oxidation to phenyl aldehyde.Catalyst can be dissolved in the ionic liquid in course of reaction, is easy to reclaim together and recycle with ionic liquid.The oxidant that the present invention uses is H
2O
2, be water after the reaction, be easy to water is removed by simple process.This oxidation reaction system avoids using the poisonous halogenated hydrocarbons of tradition to be solvent, and environmentally friendly, course of reaction is simple to operation, provides a new process route for the green of benzaldehyde generates.
Claims (3)
1. the method for a synthesizing benzaldehyde in ionic liquid, it is characterized in that in different kinds of ions liquid, with the aqueous hydrogen peroxide solution is oxygenant, is catalyzer with tungsten, molybdenum peroxide heteropoly compound or tungsten, molybdenum peroxide with the polyvoltine compound, prepare phenyl aldehyde at 50-100 ℃ of following catalytic oxidation phenylcarbinol, the ionic liquid consumption is 1-2mL, and catalyst levels is the 1/100-1/50 of phenylcarbinol amount of substance, and the hydrogen peroxide consumption is 1.1 times of phenylcarbinol amount of substance; Used ionic liquid is [C
nMim] BF
4[C
nMim] PF
6And [C
nMim] CF
3The COO three major types, n=4 wherein, 8.
By claim 1 described a kind of in ionic liquid the method for synthesizing benzaldehyde, it is characterized in that used catalyst be tungsten, molybdenum with many per-compound, its molecular formula is: Q
2[M
2O
3(O
2)
4], metallic atom centered by the M is W or Mo metallic atom; Q is cationic moiety, with [R
1R
2R
3R
4N
+] expression, wherein R
1, R
2, R
3, R
4H
-Or alkyl or benzyl, or pyridine groups and homologue thereof.
By claim 1 described a kind of in ionic liquid the method for synthesizing benzaldehyde, it is characterized in that used catalyst is the assorted many per-compound of tungsten, molybdenum, its molecular formula is: Q
3{ PO
4[MO (O
2)
2]
4, metallic atom centered by the M, or W or Mo metallic atom; Q is cationic moiety, with [R
1R
2R
3R
4N
+] expression, wherein R
1, R
2, R
3, R
4H
-Or alkyl or benzyl, or pyridine groups and homologue thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101332343A CN101130489A (en) | 2007-09-26 | 2007-09-26 | Method for synthesizing benzaldehyde in ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101332343A CN101130489A (en) | 2007-09-26 | 2007-09-26 | Method for synthesizing benzaldehyde in ionic liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101130489A true CN101130489A (en) | 2008-02-27 |
Family
ID=39127920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101332343A Pending CN101130489A (en) | 2007-09-26 | 2007-09-26 | Method for synthesizing benzaldehyde in ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101130489A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508631B (en) * | 2009-03-31 | 2012-12-05 | 贵州大学 | Method for oxidizing ethanol into corresponding aldehyde in catalyst action |
| CN102898474A (en) * | 2012-10-10 | 2013-01-30 | 江苏大学 | Polyacid compound, preparation method and application in oxidized fuel oil desulfuration |
| CN105061319A (en) * | 2015-08-11 | 2015-11-18 | 泉州理工职业学院 | Imidazole peroxy-molybdate and preparation method therefor |
| CN105772099A (en) * | 2016-05-03 | 2016-07-20 | 苏州大学 | Ionic liquid and preparation method and application thereof |
| CN109999908A (en) * | 2019-04-16 | 2019-07-12 | 盐城师范学院 | A kind of method that hydroxy compounds is oxidized to carbonyls |
-
2007
- 2007-09-26 CN CNA2007101332343A patent/CN101130489A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508631B (en) * | 2009-03-31 | 2012-12-05 | 贵州大学 | Method for oxidizing ethanol into corresponding aldehyde in catalyst action |
| CN102898474A (en) * | 2012-10-10 | 2013-01-30 | 江苏大学 | Polyacid compound, preparation method and application in oxidized fuel oil desulfuration |
| CN102898474B (en) * | 2012-10-10 | 2015-09-02 | 江苏大学 | A kind of polyacid compounds and preparation method and the purposes in oxidation fuel desulfuration |
| CN105061319A (en) * | 2015-08-11 | 2015-11-18 | 泉州理工职业学院 | Imidazole peroxy-molybdate and preparation method therefor |
| CN105772099A (en) * | 2016-05-03 | 2016-07-20 | 苏州大学 | Ionic liquid and preparation method and application thereof |
| CN105772099B (en) * | 2016-05-03 | 2018-09-25 | 苏州大学 | A kind of ionic liquid and its preparation method and application |
| CN109999908A (en) * | 2019-04-16 | 2019-07-12 | 盐城师范学院 | A kind of method that hydroxy compounds is oxidized to carbonyls |
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Open date: 20080227 |