CN102719844A - Method for preparing benzaldehyde through phenylcarbinol oxidation - Google Patents
Method for preparing benzaldehyde through phenylcarbinol oxidation Download PDFInfo
- Publication number
- CN102719844A CN102719844A CN2012102255152A CN201210225515A CN102719844A CN 102719844 A CN102719844 A CN 102719844A CN 2012102255152 A CN2012102255152 A CN 2012102255152A CN 201210225515 A CN201210225515 A CN 201210225515A CN 102719844 A CN102719844 A CN 102719844A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- phenylcarbinol
- reaction
- supercritical
- acetonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides a method for preparing benzaldehyde through phenylcarbinol oxidation. According to the method, ionic liquid serves as a supporting electrolyte, acetonitrile serves as a cosolvent, a high-pressure reactor provided with electrodes is used for performing electrochemical electrolysis in a supercritical CO2 environment with a reaction temperature of 25-70 DEG C (system pressure is 10-25MPa), and the phenylcarbinol is converted to the benzaldehyde through selective oxidation. According to the method, features of the supercritical CO2 such as small viscosity, zero surface tension and friendly environment are utilized, advantages of the ionic liquid such as stable physicochemical properties and high electrical conductivity are combined, a constant potential electrolysis technology is adopted to control the efficient selective oxidation of the phenylcarbinol to the benzaldehyde effectively, and the yield and the selectivity of the benzaldehyde can reach above 99.8% under an optimum condition.
Description
Technical field
The present invention relates to a kind of preparation method of benzaldehyde.Particularly, the present invention relates to a kind of phenylcarbinol electrochemistry oxygen and turn to method of benzaldehyde.
Background technology
Aromatic aldehyde is one type of important organic chemical industry's midbody, is mainly used in industries such as medicine, plastics, additive, spices, and therefore, it is very important organic reaction that aromatic alcohol is oxidized to corresponding aroma aldehyde.Yet, generating carboxylic acid because peroxidation very easily takes place aromatic aldehyde, the selectivity that causes aromatic alcohol to be oxidized to aromatic aldehyde reduces greatly, seriously restricts the output of aromatic aldehyde.In recent years, Many researchers utilizes transition-metal catalyst to improve the selectivity of benzyl alcohol oxidation for phenyl aldehyde, obtains good effect; But still receive the each side restriction; For example: catalyzer and organic solvent cost are high and be non-ambient close friend type material, and catalyzer is prone to inactivation, separation difficulty etc.
The electrochemistry organic synthesis receives publicity as a kind of clean synthesis method, does not need poisonous or dangerous redox agent, and reaction conditions is gentle, and energy consumption is low, and can reaction carried out according to the target of anticipation through the control electrolysis voltage.But in the electrochemistry organic synthesis, organism is usually as solvent or ionogen, organic high viscosity, and low spread coefficient, therefore toxicity and be difficult to all seriously restrict organic synthesis with problems such as product separate need the non-traditional medium of exploitation as ionogen.
Supercritical CO
2Because of it is nontoxic, be prone to obtain and low-viscosity, high diffusibility, characteristics such as zero surface tension, and as a kind of environmentally friendly solvent, it is used to separating and extracting, aspects such as chemical reaction and material prepn.But in electrochemical reaction, supercritical CO
2Do not have electroconductibility, himself not can be used as electrochemical mediators, needs the adding of " supporting electrolyte ", and supercritical CO
2Have to be solved with " supporting electrolyte " problem such as whether dissolve.
Ionic liquid obtains investigator's attention in recent years as a kind of eco-friendly medium.The salt that ionic liquid is formed, is in a liquid state at normal temperatures by yin, yang ion (positively charged ion is an organic cation usually) is so be called " ionic liquid at room temperature " or " room temperature melting salt " again.Compare with Traditional electrochemical medium-electrolytic solution, ionic liquid has many good qualities: the electrochemical potential window that (1) is wide, high electrochemical stability; (2) the thermal stable temperature scope of broad and better chemical stability; (3) can change ion liquid physicochemical property through the design of yin, yang ionic; (4) anti-combustion, non-volatile, easy to be recycled etc.Though ionic liquid is obtaining certain application aspect the electrochemical reaction research, ionic liquid has viscosity and the big shortcoming of surface tension equally, influences its application as electrochemical mediators.
Therefore, supercritical CO
2Though do not have electroconductibility, but work as supercritical CO
2In when being dissolved with ionic liquid, ionic liquid will be given its electroconductibility.Because ionic liquid is at supercritical CO
2Middle solubleness is very low, and present method is utilized to supercritical CO
2The middle polar co-solvent (like methyl alcohol, ethanol, acetone, acetonitrile) of adding makes ionic liquid at supercritical CO
2In solubleness increase greatly.In above-mentioned mixed system, carry out electrochemical reaction and can make full use of many advantages of electrochemistry, ionic liquid and supercutical fluid; The controllability of electrochemical reaction for example; Ion liquid wide electrochemical window; Characteristics such as the LV of supercutical fluid, high diffusibility, no surface tension realize that the phenylcarbinol efficient selective is oxidized to the process of phenyl aldehyde.
Summary of the invention
The objective of the invention is to solve phenylcarbinol and prepare the low problem of selectivity that peroxo-causes in the phenyl aldehyde process, through utilizing constant potential electrolysis, at supercritical CO
2Effectively improve the selectivity of benzyl alcohol oxidation producing benzaldehyde in the system, and reduce environmental pollution.
The objective of the invention is to adopt following technical scheme to realize.
A kind of method of benzyl alcohol selective preparing benzaldehyde by oxidizing, this method are included in and are dissolved with ion liquid supercritical CO
2Utilize the constant potential electrolysis method to make benzyl alcohol selective be oxidized to the step of phenyl aldehyde in the system.
Among the above-mentioned preparation method, electrolysis voltage is 2 ~ 3 V, is preferably 2.4 ~ 2.9 V, more preferably 2.7 ~ 2.8 V
Among the above-mentioned preparation method, temperature of reaction is 25 ~ 70 ℃, is preferably 30 ~ 60 ℃, more preferably 40 ~ 50 ℃.
Among the above-mentioned preparation method, described ionic liquid comprises glyoxaline ion liquid, ion liquid of quaternaries, season phosphonium salt class ionic liquid, pyridines ionic liquid; Preferably, said ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim] [BF
4]) or 1-butyl-3-Methylimidazole hexafluorophosphate ([Bmim] [PF
6]).
Among the above-mentioned preparation method, utilize cosolvent to strengthen ionic liquid and supercritical CO
2Dissolving, cosolvent is methyl alcohol, ethanol, acetone, acetonitrile, is preferably acetonitrile.
Among the above-mentioned preparation method, supercritical CO
2System pressure is 10 ~ 25 MPa, is preferable over 12 ~ 20 MPa, more preferably with 16 ~ 18 MPa.
Among the above-mentioned preparation method, acetonitrile and CO
2Mass ratio be 0.09 ~ 0.47, be preferably 0.19 ~ 0.37, more preferably 0.23 ~ 0.33.
Among the above-mentioned preparation method, the mass ratio of ionic liquid and acetonitrile is 0.1 ~ 0.35, is preferably 0.17 ~ 0.25.
Among the above-mentioned preparation method, phenylcarbinol and ionic liquid mol ratio are 0.1:1 ~ 0.01:1, are preferably 0.05:1.
Among the above-mentioned preparation method, have three electrodes in the reaction kettle, be respectively working electrode, counter electrode and reference electrode.Electrode materials is a metal platinum.
In a specific embodiments, the method for benzyl alcohol oxidation producing benzaldehyde of the present invention comprises the steps:
(1) in 50mL high pressure three electrode reaction stills, add phenylcarbinol 0.05 g, acetonitrile 12 g, ionic liquid 2 g charge into the CO of 31.5 g
2
(2) reaction kettle in the step (1) is put into 45 ℃ water-bath, under 200 r/min stirring velocitys, stirred, to temperature, pressure-stabilisation.
(3) reaction system stable in the step (2) is inserted in the electrochemical workstation,, feed a certain amount of electric weight with 2.7 V constant potential electrolysiss.
(4) with reacted (3) cooling cooling, collect liquid product, analyze, obtain phenyl aldehyde yield and selectivity with gc.
The method of this benzyl alcohol oxidation producing benzaldehyde, it is main that the control benzyl alcohol selective is oxidized to phenyl aldehyde, suppresses the peroxo-of phenyl aldehyde according to being to utilize constant potential electrolysis, and in electrolytic process, the phenylcarbinol dehydrogenation is oxidized, CO
2Be reduced.Wherein, ionic liquid plays the effect of conduction, gives supercritical CO
2Electroconductibility, and supercritical CO
2High diffusibility, characteristics such as zero surface tension well solve problems such as ion liquid high viscosity, low diffustivity, and utilize CO
2Pressure is regulated the selectivity and the yield of phenylcarbinol producing benzaldehyde; The cosolvent acetonitrile makes ionic liquid well be dissolved in supercritical CO simultaneously
2In, form a kind of new electrochemical reaction medium.
The method of this benzyl alcohol oxidation producing benzaldehyde, remarkable advantage are to utilize supercritical CO
2Characteristics such as high diffusibility, low-viscosity, advantages such as the physico-chemical property of coupled ion liquid is stable, wide electrochemical window under the cosolvent effect, utilize constant potential electrolysis effectively to control the electrooxidation of phenylcarbinol, realize the preparation of highly selective phenyl aldehyde.Compare with the traditional preparation process method of benzaldehyde, the phenyl aldehyde yield and the selectivity of (1) preparation are high; (2) preparation process is simple, cleaning, pollution-free; (3) need not transition-metal catalyst; (4) reaction product is easily separated.
Embodiment
Below in conjunction with embodiment the method for benzyl alcohol oxidation producing benzaldehyde provided by the invention is described in further detail, but does not therefore limit the present invention.
Embodiment 1
Present embodiment explanation phenylcarbinol is being dissolved with ionic liquid [Bmim] [PF
6] supercritical CO
2In carry out 2.7 V constant potential electrolysiss, temperature of reaction is 45 ℃, the energising amount is 99 C, the method for oxidation producing benzaldehyde.
Get phenylcarbinol 0.05 g respectively, ionic liquid [Bmim] [PF
6] 2.00 g, acetonitrile 12.00 g, the 50mL three electrode autoclaves of packing into, sealing.Use CO then
2Trier charges into CO in reaction kettle
2To pressure be 0.3 ~ 0.4 MPa, open the air outlet again gaseous tension reduced to 0.1 MPa, 3 ~ 4 times so repeatedly, drain the air in the clean reaction kettle.Continuation is logical CO in reaction kettle
2, the CO of feeding
2About 31.5 g of quality, then reaction kettle being placed temperature is 45 ℃ of water-baths, opens stirring.Through after a while, after reaction pressure is stabilized in 15.6 MPa, three electrodes of electrochemical workstation should be connected with three electrode pairs on the reaction kettle, open electrochemical workstation, preheating 20 min.After the preheating, select 2.7 V constant potential electrolysiss, stopped reaction when the energising amount is 99 C.The taking-up reaction kettle cools.
Liquid product utilizes marker method with GC-Shimadzu 2014 gas chromatographic analysiss, and the transformation efficiency of analytical calculation phenylcarbinol is 100%, phenyl aldehyde yield 99.8%, phenyl aldehyde selectivity 99.8%.
Embodiment 2
Present embodiment explanation phenylcarbinol is being dissolved with ionic liquid [Bmim] [PF
6] supercritical CO
2In carry out 2.7 V constant potential electrolysiss, temperature of reaction is 45 ℃, the energising amount is 89 C, the method for oxidation producing benzaldehyde.
Get phenylcarbinol 0.05 g respectively, ionic liquid [Bmim] [PF
6] 2.00 g, acetonitrile 12.00 g, the 50mL three electrode autoclaves of packing into, sealing.Use CO then
2Trier charges into CO in reaction kettle
2To pressure be 0.3 ~ 0.4 MPa, open the air outlet again gaseous tension reduced to 0.1 MPa, 3 ~ 4 times so repeatedly, drain the air in the clean reaction kettle.Continuation is logical CO in reaction kettle
2, the CO of feeding
2About 31.6 g of quality, then reaction kettle being placed temperature is 45 ℃ of water-baths, opens stirring.Through after a while, after reaction pressure stabilizes to 16.48MPa, three electrodes of electrochemical workstation should be connected with three electrode pairs on the reaction kettle, open electrochemical workstation, preheating 20 min.After the preheating, select 2.7 V constant potential electrolysiss, stopped reaction when the energising amount is 89 C.The taking-up reaction kettle cools.
Liquid product utilizes marker method with GC-Shimadzu 2014 gas chromatographic analysiss, and the transformation efficiency of analytical calculation phenylcarbinol is 90.92%, phenyl aldehyde yield 90.83%, and the phenyl aldehyde selectivity is greater than 99.8%.
Embodiment 3
Present embodiment explanation phenylcarbinol is being dissolved with ionic liquid [Bmim] [PF
6] supercritical CO
2In carry out 2.7 V constant potential electrolysiss, temperature of reaction is 45 ℃, the energising amount is 109 C, the process method of oxidation producing benzaldehyde.
Get phenylcarbinol 0.05 g respectively, ionic liquid [Bmim] [PF
6] 2.00 g, acetonitrile 12.00 g, the three electrode autoclaves of packing into, sealing.Use CO then
2Trier charges into CO in reaction kettle
2To pressure be 0.3 ~ 0.4 MPa, open the air outlet again gaseous tension reduced to 0.1 MPa, 3 ~ 4 times so repeatedly, drain the air in the clean reaction kettle.Continuation is logical CO in reaction kettle
2, the CO of feeding
2About 31.6 g of quality, then reaction kettle being placed temperature is 45 ℃ of water-baths, opens stirring.Through after a while, after reaction pressure stabilizes to 16.48MPa, three electrodes of electrochemical workstation should be connected with three electrode pairs on the reaction kettle, open electrochemical workstation, preheating 20 min.After the preheating, select 2.7 V constant potential electrolysiss, stopped reaction when the energising amount is 109 C.The taking-up reaction kettle cools.
Liquid product utilizes marker method with GC-Shimadzu 2014 gas chromatographic analysiss, and the transformation efficiency of analytical calculation phenylcarbinol is 100%, phenyl aldehyde yield 99.2%, phenyl aldehyde selectivity 99.2%.
Embodiment 4
Present embodiment explanation phenylcarbinol is being dissolved with ionic liquid [Bmim] [PF
6] supercritical CO
2In carry out 2.9 V constant potential electrolysiss, temperature of reaction is 45 ℃, the energising amount is 89 C, the process method of oxidation producing benzaldehyde.
Get phenylcarbinol 0.05 g respectively, ionic liquid [Bmim] [PF
6] 2.00 g, acetonitrile 12.00 g, the 50mL three electrode autoclaves of packing into, sealing.Use CO then
2Trier charges into CO in reaction kettle
2To pressure be 0.3 ~ 0.4 MPa, open the air outlet again gaseous tension reduced to 0.1 MPa, 3 ~ 4 times so repeatedly, drain the air in the clean reaction kettle.Continuation is logical CO in reaction kettle
2, the CO of feeding
2About 32.1 g of quality, then reaction kettle being placed temperature is 45 ℃ of water-baths, opens stirring.Through after a while, after reaction pressure stabilizes to 19.97 MPa, three electrodes of electrochemical workstation should be connected with three electrode pairs on the reaction kettle, open electrochemical workstation, preheating 20 min.After the preheating, select 2.9 V constant potential electrolysiss, stopped reaction when the energising amount is 89 C.The taking-up reaction kettle cools.
Liquid product is analyzed with GC-Shimadzu 2014, utilizes marker method, and the transformation efficiency of analytical calculation phenylcarbinol is 91.84%, phenyl aldehyde yield 89.54%, phenyl aldehyde selectivity 97.4%.
Embodiment 5
Present embodiment explanation phenylcarbinol is being dissolved with ionic liquid [Bmim] [PF
6] supercritical CO
2In carry out 2.7 V constant potential electrolysiss, temperature of reaction is 45 ℃, the energising amount is 89 C, the process method of oxidation producing benzaldehyde.
Get phenylcarbinol 0.05 g respectively, ionic liquid [Bmim] [PF
6] 3.00 g, acetonitrile 12.00 g, the three electrode autoclaves of packing into, sealing.Use CO then
2Trier charges into CO in reaction kettle
2To pressure be 0.3 ~ 0.4 MPa, open the air outlet again gaseous tension reduced to 0.1 MPa, 3 ~ 4 times so repeatedly, drain the air in the clean reaction kettle.Continuation is logical CO in reaction kettle
2, the CO of feeding
2About 31.3 g of quality, then reaction kettle being placed temperature is 45 ℃ of water-baths, opens stirring.Through after a while, after reaction pressure stabilizes to 12.9 MPa, three electrodes of electrochemical workstation should be connected with three electrode pairs on the reaction kettle, open electrochemical workstation, preheating 20 min.After the preheating, select 2.7 V constant potential electrolysiss, stopped reaction when the energising amount is 89 C.The taking-up reaction kettle cools.
Liquid product utilizes marker method with GC-Shimadzu 2014 gas chromatographic analysiss, and the transformation efficiency of analytical calculation phenylcarbinol is 86.45%, phenyl aldehyde yield 86.45%, phenyl aldehyde selectivity 100%.
Embodiment 6
Present embodiment explanation phenylcarbinol is being dissolved with ionic liquid [Bmim] [PF
6] supercritical CO
2In carry out 2.7 V constant potential electrolysiss, temperature of reaction is 45 ℃, the energising amount is 89 C, the method for oxidation producing benzaldehyde.
Get phenylcarbinol 0.05 g respectively, ionic liquid [Bmim] [PF
6] 2.00 g, acetonitrile 12.000, the 50mL three electrode autoclaves of packing into, sealing.Use CO then
2Trier charges into CO in reaction kettle
2To pressure be 0.3 ~ 0.4 MPa, open the air outlet again gaseous tension reduced to 0.1 MPa, 3 ~ 4 times so repeatedly, drain the air in the clean reaction kettle.Continuation is logical CO in reaction kettle
2, the CO of feeding
2About 32.0 g of quality, then reaction kettle being placed temperature is 45 ℃ of water-baths, opens and stirs.Through after a while, after reaction pressure stabilizes to 19.35 MPa, three electrodes of electrochemical workstation should be connected with three electrode pairs on the reaction kettle, open electrochemical workstation, preheating 20 min.After the preheating, select 2.7 V constant potential electrolysiss, stopped reaction when the energising amount is 89 C.The taking-up reaction kettle cools.
Liquid product utilizes marker method with GC-Shimadzu 2014 gas chromatographic analysiss, and the transformation efficiency of analytical calculation phenylcarbinol is 87.58%, phenyl aldehyde yield 87.58%, phenyl aldehyde selectivity 100%.
Embodiment 7
Present embodiment explanation phenylcarbinol is being dissolved with ionic liquid [Bmim] [PF
6] supercritical CO
2In carry out 2.7 V constant potential electrolysiss, temperature of reaction is 40 ℃, the energising amount is 99 C, the method for oxidation producing benzaldehyde.
Get phenylcarbinol 0.05 g respectively, ionic liquid [Bmim] [BF
4] 2.00 g, acetonitrile 12.00 g, the 50mL three electrode autoclaves of packing into, sealing.Use CO then
2Trier charges into CO in reaction kettle
2To pressure be 0.3 ~ 0.4 MPa, open the air outlet again gaseous tension reduced to 0.1 MPa, 3 ~ 4 times so repeatedly, drain the air in the clean reaction kettle.Continuation is logical CO in reaction kettle
2, the CO of feeding
2About 32.0 g of quality, then reaction kettle being placed temperature is 40 ℃ of water-baths, opens and stirs.Through after a while, after reaction pressure stabilizes to 15.7 MPa, three electrodes of electrochemical workstation should be connected with three electrode pairs on the reaction kettle, open electrochemical workstation, preheating 20 min.After the preheating, select 2.7 V constant potential electrolysiss, stopped reaction when the energising amount is 99 C.The taking-up reaction kettle cools.
Liquid product utilizes marker method with GC-Shimadzu 2014 gas chromatographic analysiss, and the transformation efficiency that analytical calculation draws phenylcarbinol is 99.1%, phenyl aldehyde yield 98.9%, phenyl aldehyde selectivity 99.8%.
Claims (9)
1. the method for a benzyl alcohol selective preparing benzaldehyde by oxidizing, this method is included in and is dissolved with ion liquid supercritical CO
2Utilize the constant potential electrolysis method to make benzyl alcohol selective be oxidized to the step of phenyl aldehyde in the system.
2. process method according to claim 1 is characterized in that electrolysis voltage is 2 ~ 3 V, is preferably 2.4 ~ 2.9 V, more preferably 2.7 ~ 2.8 V.
3. process method according to claim 1 is characterized in that temperature of reaction is 25 ~ 70 ℃, is preferably 30 ~ 60 ℃, more preferably 40 ~ 50 ℃.
4. process method according to claim 1 is characterized in that, described ionic liquid comprises glyoxaline ion liquid, ion liquid of quaternaries, season phosphonium salt class ionic liquid, pyridines ionic liquid; Preferably, said ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate ([Bmim] [BF
4]) or 1-butyl-3-Methylimidazole hexafluorophosphate ([Bmim] [PF
6]).
5. process method according to claim 1 is characterized in that, utilizes cosolvent to strengthen ionic liquid and supercritical CO
2Dissolving, cosolvent is methyl alcohol, ethanol, acetone, acetonitrile, is preferably acetonitrile.
6. process method according to claim 1 is characterized in that supercritical CO
2System pressure is 10 ~ 25 MPa, is preferable over 12 ~ 20 MPa, more preferably with 16 ~ 18 MPa.
7. process method according to claim 1 is characterized in that, acetonitrile and CO
2Mass ratio be 0.09 ~ 0.47, be preferably 0.19 ~ 0.37, more preferably 0.23 ~ 0.33; The mass ratio of ionic liquid and acetonitrile is 0.1 ~ 0.35, is preferably 0.17 ~ 0.25; Phenylcarbinol and ionic liquid mol ratio are 0.1:1 ~ 0.01:1, are preferably 0.05:1.
8. process method according to claim 1 is characterized in that, has three electrodes in the reaction kettle, is respectively working electrode, and counter electrode and reference electrode, the material of electrode are metal platinum.
9. according to each described method in the claim 1 to 8, it is characterized in that said method comprises the steps: (1) in the high pressure three electrode reaction stills of 50mL, add phenylcarbinol 0.05 g, acetonitrile 12 g, ionic liquid 2 g, charge into the CO of 31.5 g
2(2) reaction kettle in the step (1) is put into 45 ℃ water-bath, under 200 r/min stirring velocitys, stirred, to temperature, pressure-stabilisation; (3) reaction system stable in the step (2) is inserted electrochemical workstation, the constant voltage method is carried out the electrochemical oxidation phenyl aldehyde; (4) with reacted (3) cooling cooling, collect liquid product, analyze, obtain phenyl aldehyde yield and selectivity with gc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102255152A CN102719844A (en) | 2012-07-03 | 2012-07-03 | Method for preparing benzaldehyde through phenylcarbinol oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102255152A CN102719844A (en) | 2012-07-03 | 2012-07-03 | Method for preparing benzaldehyde through phenylcarbinol oxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102719844A true CN102719844A (en) | 2012-10-10 |
Family
ID=46945702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102255152A Pending CN102719844A (en) | 2012-07-03 | 2012-07-03 | Method for preparing benzaldehyde through phenylcarbinol oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102719844A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107059047A (en) * | 2017-01-19 | 2017-08-18 | 李得杰 | SC‑CO2The method that electrochemistry prepares the butenoic acid of 3 methyl 3 in system |
| CN110632242A (en) * | 2018-06-22 | 2019-12-31 | 科之杰新材料集团有限公司 | Method for testing formaldehyde content in concrete admixture |
| CN110724107A (en) * | 2019-10-17 | 2020-01-24 | 浙江工业大学 | Preparation method and application of diallyl ionic liquid |
| JP2020023578A (en) * | 2013-03-08 | 2020-02-13 | フィールド アップグレーディング リミテッド | Device and method of obtaining diols and other chemicals using decarboxylation |
| CN111218695A (en) * | 2020-02-18 | 2020-06-02 | 广西师范大学 | method for realizing ketone alpha site methylation reaction under electrochemical condition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925820A (en) * | 1982-08-05 | 1984-02-09 | Mitsubishi Chem Ind Ltd | Preparation of polyphenylene ether |
| US5364506A (en) * | 1993-04-28 | 1994-11-15 | The Board Of Trustees Of The Leland Stanford Junior University | Method and apparatus for partial oxidation of methane and cogeneration of electrical energy |
| DE19538872A1 (en) * | 1995-10-19 | 1997-04-24 | Karlsruhe Forschzent | Process for treating organic compound |
| CN101880903A (en) * | 2009-12-28 | 2010-11-10 | 上海大学 | Method for electrochemically preparing electroconductive polymer thin film in presence of CO2 |
-
2012
- 2012-07-03 CN CN2012102255152A patent/CN102719844A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925820A (en) * | 1982-08-05 | 1984-02-09 | Mitsubishi Chem Ind Ltd | Preparation of polyphenylene ether |
| US5364506A (en) * | 1993-04-28 | 1994-11-15 | The Board Of Trustees Of The Leland Stanford Junior University | Method and apparatus for partial oxidation of methane and cogeneration of electrical energy |
| DE19538872A1 (en) * | 1995-10-19 | 1997-04-24 | Karlsruhe Forschzent | Process for treating organic compound |
| CN101880903A (en) * | 2009-12-28 | 2010-11-10 | 上海大学 | Method for electrochemically preparing electroconductive polymer thin film in presence of CO2 |
Non-Patent Citations (4)
| Title |
|---|
| SHA LIAO，ET AL.: "High-pressure phase equilibria for the binary system carbon dioxide +benzyl alcohol", 《THE JOURNAL OF SUPERCRITICAL FLUIDS》, vol. 55, 30 November 2010 (2010-11-30), XP027437223, DOI: doi:10.1016/j.supflu.2010.08.014 * |
| 周震寰 等: "超临界CO2/离子液体体系", 《化学通报》, no. 4, 19 May 2005 (2005-05-19) * |
| 廖莎: "苯甲醇在溶有离子液体的超临界CO2中的电化学氧化", 《北京化工大学硕士论文》, 15 May 2012 (2012-05-15) * |
| 陈晓亭: "离子液体在超临界二氧化碳中导电性及相关过程相行为的研究", 《北京化工大学硕士论文》, 15 January 2010 (2010-01-15) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020023578A (en) * | 2013-03-08 | 2020-02-13 | フィールド アップグレーディング リミテッド | Device and method of obtaining diols and other chemicals using decarboxylation |
| CN107059047A (en) * | 2017-01-19 | 2017-08-18 | 李得杰 | SC‑CO2The method that electrochemistry prepares the butenoic acid of 3 methyl 3 in system |
| CN107059047B (en) * | 2017-01-19 | 2018-12-04 | 李得杰 | SC-CO2The method that electrochemistry prepares 3-methyl-3-butenoic acid in system |
| CN110632242A (en) * | 2018-06-22 | 2019-12-31 | 科之杰新材料集团有限公司 | Method for testing formaldehyde content in concrete admixture |
| CN110724107A (en) * | 2019-10-17 | 2020-01-24 | 浙江工业大学 | Preparation method and application of diallyl ionic liquid |
| CN110724107B (en) * | 2019-10-17 | 2021-07-23 | 浙江工业大学 | Preparation method and application of diallyl ionic liquid |
| CN111218695A (en) * | 2020-02-18 | 2020-06-02 | 广西师范大学 | method for realizing ketone alpha site methylation reaction under electrochemical condition |
| CN111218695B (en) * | 2020-02-18 | 2021-05-28 | 广西师范大学 | Method for realizing ketone alpha site methylation reaction under electrochemical condition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Integrating hydrogen production with aqueous selective semi‐dehydrogenation of tetrahydroisoquinolines over a Ni2P bifunctional electrode | |
| Javed et al. | An approach to classification and hi-tech applications of room-temperature ionic liquids (RTILs): A review | |
| Cardoso et al. | Organic electrosynthesis: from laboratorial practice to industrial applications | |
| CN102719844A (en) | Method for preparing benzaldehyde through phenylcarbinol oxidation | |
| Baslé et al. | Aerobic and Electrochemical Oxidative Cross‐Dehydrogenative‐Coupling (CDC) Reaction in an Imidazolium‐Based Ionic Liquid | |
| US8845877B2 (en) | Heterocycle catalyzed electrochemical process | |
| Tateno et al. | Photoelectrochemical oxidation of benzylic alcohol derivatives on BiVO4/WO3 under visible light irradiation | |
| US8506789B2 (en) | Method of producing coupled radical products | |
| US11352705B2 (en) | Hydrocarbon oxidation by water oxidation electrocatalysts in non-aqueous solvents | |
| Zhao et al. | Electro-oxidation of benzyl alcohol in a biphasic system consisting of supercritical CO2 and ionic liquids | |
| CN107858700A (en) | The electrochemical method for synthesizing of the benzothiazole of 2 substitutions | |
| Rocco et al. | Cathodic behaviour of dicationic imidazolium bromides: The role of the spacer | |
| CN101792378B (en) | Method for preparing anisaldehyde | |
| Muhammad et al. | Effect of supramolecular polymeric aggregation in room temperature ionic liquids (RTILs) on catalytic activity in the synthesis of 4H-chromene derivatives and Knoevenagel condensation | |
| Li et al. | Electrochemical synthesis of thiazoles from 2, 5-dihydrothiazolines mediated by bromide/tetrachlorohydroquinone dual redox catalysts | |
| Miao et al. | Photoelectrochemical Glycerol Oxidation Coupled with Hydrogen Production | |
| CN206381990U (en) | A kind of intermediate synthesis reaction vessel agitator of clethodim triketone | |
| Sasaki et al. | Reaction kinetics and mechanism for hydrothermal degradation and electrolysis of glucose for producing carboxylic acids | |
| Zhu et al. | Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol | |
| CN101153018A (en) | Br*nsted acidity ion liquid containing N-alkyl pyrrolidone group, producing method and use of the same | |
| CN106622364A (en) | Solid phase preparation method of ionic liquid polyoxometallate nano electrocatalyst | |
| Yuksel et al. | Electrolysis of glycerol in subcritical water | |
| CN102050712B (en) | Preparation method of anisaldehyde | |
| CN114591181A (en) | Method for preparing high-purity ionic liquid | |
| CN115652346A (en) | Method for synthesizing 3-mercaptoindolizine compound by electrocatalytic oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121010 |