CN100348565C - Method for preparing aromatic aldehyde ketone by utilizing air as oxidant in hydro solvent system - Google Patents
Method for preparing aromatic aldehyde ketone by utilizing air as oxidant in hydro solvent system Download PDFInfo
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- CN100348565C CN100348565C CNB2004100989369A CN200410098936A CN100348565C CN 100348565 C CN100348565 C CN 100348565C CN B2004100989369 A CNB2004100989369 A CN B2004100989369A CN 200410098936 A CN200410098936 A CN 200410098936A CN 100348565 C CN100348565 C CN 100348565C
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Abstract
The present invention relates to a method for preparing aromatic aldehyde ketone by catalyzing air as an oxidant in a hydro solvent system, which is characterized in that a catalyzing quantity of 2, 2, 6, 6-6-tetramethyl piperidine-oxyl(TEMPO), 1, 3-dibromo-5, 5-dimethylhydantoin and sodium nitrite is used as a catalyst, and water is used as a solvent. Air whose atmospheric pressure is lower than 1.2MPas is used as an oxidant, and a series of aromatic alcohols and heteroaromatic alcohols are oxidized into corresponding aromatic aldehyde and ketone with high selectivity at a temperature below 160 DEG C.
Description
Technical field
The present invention relates to a kind of method for preparing aromatic aldehyde ketone, particularly, relating to a kind of is solvent with water, is the method that oxygenant prepares aromatic aldehyde ketone with oxygen or air.
Background technology
It is one of most important functional group conversion reaction in the organic chemistry that the aromatic alcohol oxidation prepares aromatic aldehyde, and the catalytic oxidation system of seeking high-efficiency cleaning is vitochemical research focus always.
In the past few decades, chemists have developed the effective oxidation system of two big classes.A kind of be transition metal-catalyzed be the catalytic oxidation system of oxygen source with oxygen or air, the product separate easily of catalyzed reaction, and do not have too many refuse.But catalyzer costs an arm and a leg, and metal commonly used has palladium (Pd), ruthenium precious metals such as (Ru), and needs baroque part.The common meeting of the catalytic activity of this class catalyzer is inactivation because of the water of reaction generation; Heteroatoms in the reaction substrate (N, S etc.) can make poisoning of catalyst.Another kind be nitroxyl free radical (representation compound: 2,2,6,6-tetramethyl piperidine-oxyradical: TEMPO) catalytic catalytic oxidation system with stoichiometric oxygenant.Oxygenant commonly used is clorox (NaClO), halogen etc.This catalyst system efficient is very high, but produces a large amount of inorganic wastes.
Summary of the invention
The object of the present invention is to provide catalytic air oxidation in a kind of water solvent system to prepare the method for aromatic aldehyde ketone.
For achieving the above object, the present invention has adopted the catalyzer that does not contain transition metal, is oxygenant with oxygen or air, is solvent with water, and aromatic alcohol and assorted aromatic alcohol are oxidized to corresponding aroma aldehyde and ketone.
Specifically, the present invention is with 2 of catalytic amount, 2,6,6-tetramethyl piperidine-oxyradical (TEMPO), 1,3-two bromo-5,5-dimethyl hydantion and Sodium Nitrite are catalyzer, air with 0.1-1.2MPa is an oxygenant, can be oxidized to corresponding aroma aldehyde and ketone to a series of aromatic alcohol and assorted aromatic alcohol by highly selective under 40-120 ℃.
Wherein: 2,2,6,6-tetramethyl piperidine-oxyradical and derivative thereof: nitrite: bromo-derivative=1: 2-4: 4mmol;
2,2,6,6-tetramethyl piperidine-oxyradical and derivative thereof: fragrant benzylalcohol=1: 100mmol;
Reaction times 1.5-16 hour;
In the composition of catalyzer, TEMPO can modify, such as with more economical 4-benzoyl-2,2,6,6-tetramethyl piperidine-oxyradical (4-benzoyl-TEMPO) or 4-acetamido-2,2,6, and 6-tetramethyl piperidine-oxyradical (the 4-acetamido-TEMPO); 1,3-two bromo-5, the 5-dimethyl hydantion can substitute with N-bromo-succinimide or pyridinium tribromide salt; Sodium Nitrite can be other nitrite, as potassium nitrite, nitrous acid acid lithium etc.
The present invention has following effect:
1. with water as solvent, with 1mol%TEMPO/4mol%1,3-two bromo-5,5-dimethyl hydantion/4mol%NaNO
2The catalyzer of forming, the air of 0.9MPa, 80 degree in 1.5 hours, can be oxidized to phenyl aldehyde to benzylalcohol; The transformation efficiency of reaction and selectivity are all greater than 99%.
2. with water as solvent, with 1mol%TEMPO/4mol%1,3-two bromo-5,5-dimethyl hydantion/4mol%NaNO
2The catalyzer of forming, the air of 0.9MPa, 80 degree were oxidized to chlorinated benzene formaldehyde (neighbour, or contraposition) to chloro benzylalcohol (adjacent, or contraposition) in 7 hours; Xylyl alcohol (adjacent, or contraposition) is oxidized to tolyl aldehyde (adjacent, or contraposition).The transformation efficiency of reaction and selectivity are all greater than 99%, and the separation yield of reaction product is greater than 95%.
3. with water as solvent, with 1mol%TEMPO/4mol%1,3-two bromo-5,5-dimethyl hydantion/4mol%NaNO
2The catalyzer of forming, the air of 0.9MPa, 80 degree in 6 hours, can be oxidized to the 3-pyridylaldehyde to the 3-piconol, and transformation efficiency is greater than 98%, and selectivity is greater than 99%; Separation yield is greater than 90%.
4. with water as solvent, with 1mol%TEMPO/2mol% pyridinium tribromide salt/4mol%NaNO
2The catalyzer of forming, the air of 0.9MPa, 80 degree in 6 hours, can be oxidized to 2 thiophene carboxaldehyde to the 2-thiophen(e)alcohol, and the transformation efficiency of reaction is greater than 99%, and selectivity is greater than 98%.The separation yield of reaction product is greater than 90%.
5. with water as solvent, with 1mol%TEMPO/4mol%1,3-two bromo-5,5-dimethyl hydantion/4mol%NaNO
2The catalyzer of forming, the air of 0.9MPa, 80 degree were oxidized to methyl phenyl ketone to α-Jia Jibianchun in 4 hours.The reaction transformation efficiency and selectivity all greater than 99%, the separation yield 98% of reaction product.
The present invention is applicable to that the high-selectivity oxidation of fragrant benzylalcohol becomes aldehyde and ketone, is particularly useful for the selective oxidation reaction of assorted fragrant benzylalcohol (containing N, S etc.).
The present invention is applicable to fine chemicals and the aldehyde of basic chemical and the productions of ketone such as medicine intermediate, agrochemicals, spices.
Compared with prior art, advantage of the present invention and effect:
1) uses water as solvent, reaction safety;
2) product separation is simple, inorganic wastes is few
3) 1,3-two bromo-5, the security of 5-dimethyl hydantion is better
Prior art feature and effect:
One, transition-metal catalyst/oxygen (or air) catalytic oxidation system:
1) with oxygen or air oxidant;
2) product separation is simple, inorganic wastes is few;
3) the expensive and easy inactivation, low of high-level efficiency but catalyzer to containing heteroatoms (N, S etc.) substrate activity.
Two, TEMPO/ stoichiometric oxidant catalytic oxidation system:
1) highly selective, wide application range of substrates;
2 reaction conditions gentlenesses;
3) a large amount of inorganic wastes, separation trouble.
Three, TEMPO/Br
2/ NaNO
2/ O
2(air) oxidation system:
1) highly selective;
2) use bromine, inconvenience, toxic.
In sum, be not difficult to find out that novelty of the present invention and creativeness are:
Novelty: the present invention realize not containing transition metal, with oxygen or air as oxygenant in the reaction system of water as solvent with aromatic alcohol, the synthetic corresponding aldehyde of assorted aromatic alcohol (containing N, elements such as S) catalyzed oxidation and ketone.
Creative: the present invention uses Sodium Nitrite effectively to activate molecular oxygen as the Equivalent of NO, by the bromine positive ion that produces with the nitrite of catalytic amount and original position (from 1,3-two bromo-5, the hypobromous acid that 5-dimethyl hydantion and water effect produce), with water as solvent, make the TEMPO effect of catalytic amount down with active fragrant benzylalcohol with make the assorted fragrant benzylalcohol highly selective of metal catalyst inactivation be oxidized to corresponding aldehyde usually easily and ketone becomes possibility.Simultaneously, owing to use water as solvent, greatly to the safety problem that has reduced oxygen or air oxidant.Make that amplifying neoteric oxidation system bears less risk.
Embodiment
Embodiment 1
In 300mL teflon-lined autoclave pressure, add 3.24g benzylalcohol (30mmol), 46.8mg TEMPO (0.3mmol), 343mg 1,3-two bromo-5,5-dimethyl hydantion (1.2mmol), 84mg NaNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 1.5 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 99.8%, product phenyl aldehyde selectivity 100%.Separation yield is 88%.
Embodiment 2
In 300mL teflon-lined autoclave pressure, add 3.66g 4-xylyl alcohol (30mmol), 46.8mg TEMPO (0.3mmol), 343mg 1,3-two bromo-5,5-dimethyl hydantion (1.2mmol), 84mg NaNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.1MPa, and autoclave pressure is put in the oil bath that is warming up to 120 degree in advance, reacts 2 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 100%, product p-tolyl aldehyde selectivity 100%.Separation yield is 98%.
Embodiment 3
In 300mL teflon-lined autoclave pressure, add 3.66g 3-xylyl alcohol (30mmol), 46.8mg 4-benzoyl-TEMPO (0.3mmol), 343mg N-bromo-succinimide (1.2mmol), 84mg KNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 2 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 99.7%, tolyl aldehyde selectivity 100% between product.Separation yield is 98%.
Embodiment 4
In 300mL teflon-lined autoclave pressure, add 3.66g 2-xylyl alcohol (30mmol), 46.8mg 4-acetamido-TEMPO (0.3mmol), 343mg pyridinium tribromide salt (1.2mmol), 84mg LiNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 2.5 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 100%, product o-methyl-benzene formaldehyde selectivity 100%.Separation yield is 95%.
Embodiment 5
In 300mL teflon-lined autoclave pressure, add 4.28g 4-chlorobenzyl alcohol (30mmol), 46.8mg TEMPO (0.3mmol), 343mg 1,3-two bromo-5,5-dimethyl hydantion (1.2mmol), 84mg NaNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 6 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 100%, product 4-chloro-benzaldehyde selectivity 100%.Separation yield is 95%.
Embodiment 6
In 300mL teflon-lined autoclave pressure, add 4.28g 3-chlorobenzyl alcohol (30mmol), 46.8mg TEMPO (0.3mmol), 343mg 1,3-two bromo-5,5-dimethyl hydantion (1.2mmol), 84mg NaNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 6 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 100%, product m chlorobenzaldehyde selectivity 100%.Separation yield is 96%.
Embodiment 7
In 300mL teflon-lined autoclave pressure, add 4.28g 2-chlorobenzyl alcohol (30mmol), 46.8mg TEMPO (0.3mmol), 343mg 1,3-two bromo-5,5-dimethyl hydantion (1.2mmol), 84mg NaNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 7 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 99.2%, product 4-chloro-benzaldehyde selectivity 99.8%.Separation yield is 96%.
Embodiment 8
In 300mL teflon-lined autoclave pressure, add 4.28g 2-chlorobenzyl alcohol (30mmol), 46.8mg TEMPO (0.3mmol), 343mg 1,3-two bromo-5,5-dimethyl hydantion (1.2mmol), 84mg NaNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 7 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 99.2%, product 4-chloro-benzaldehyde selectivity 99.8%.Separation yield is 96%.
Embodiment 9
In 300mL teflon-lined autoclave pressure, add 3.66g α-Jia Jibianchun (30mmol), 46.8mg TEMPO (0.3mmol), 343mg 1,3-two bromo-5,5-dimethyl hydantion (1.2mmol), 84mg NaNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 4 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 99.6%, selectivity of product 100%.The separation yield of product methyl phenyl ketone is 97%.
Embodiment 10
In 300mL teflon-lined autoclave pressure, add 3.27g 3-piconol (30mmol), 46.8mg TEMPO (0.3mmol), 343mg 1,3-two bromo-5,5-dimethyl hydantion (1.2mmol), 84mg NaNO
2(1.2mmol), 10mL water and 2.0mL acetic acid, the seal-off pressure still, filling air gas to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 80 degree in advance, reacts 6 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 98.2%, selectivity of product 100%.The separation yield 92% of product 3-pyridylaldehyde.
Embodiment 11
In 300mL teflon-lined autoclave pressure, add 3.42g 2-thiophen(e)alcohol (30mmol), 46.8mg TEMPO (0.3mmol), 172mg 1,3-two bromo-5,5-dimethyl hydantion (0.6mmol), 84mg NaNO
2(1.2mmol), 10mL water, the seal-off pressure still, filling air gas to tensimeter is 1.2MPa, and autoclave pressure is put in the oil bath that is warming up to 40 degree in advance, reacts 16 hours.After cooling and the careful release, use organic solvent extraction three times, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 100%, selectivity of product 98.4%.The separation yield 93% of product 2 thiophene carboxaldehyde.
The comparative example relevant with invention:
1) United States Patent (USP): US Patent5,118,866 (TEPMO/Cu (I) catalysis O
2Oxidation alcohol generates the technology of aldehyde)
Contain 10.0 gram vitamin A (34.9mmol), 545 milligrams of TEMPO (3.49mmol), 345 milligrams of cuprous chloride (CuCl to one, 3.49mmol) and 75 milliliters of N, in the solution of dinethylformamide (DMF), at room temperature with the speed aerating oxygen of per minute 50-60 milliliter.The logical 2 hours oxygen time.Reaction solution is poured in 150 milliliters of salt solutions, and it is colourless to be extracted to organic layer with methyl tertiary butyl ether.Organic layer washes and uses anhydrous sodium sulfate drying with water, and solvent is sloughed in decompression.Resistates obtains 9.1 gram products by silicagel column fast with methylene dichloride, and yield is 91.6%.Contain in the product and be no more than 5% cis-isomeride, degree of purity of production with nucleus magnetic resonance (
1H-NMR) obtain confirming.Crude product obtains the pure product of 7.2 grams, yield 72.6% with the normal hexane recrystallization.Fusing point 60-62 degree.
2) German Patent (DE4007923A1) (TEMPO catalyzing N aClO oxidation alcohol generates the technology of aldehyde)
To one contain 16 gram 2-fluoro-3-sec.-propyl-benzylalcohols (95mmol), 0.3 gram TEMPO (1.9mmol), 0.56 Potassium Bromide (KBr, 4.8mmol), 1.5 gram sodium dihydrogen phosphate dihydrate (NaH
2PO
42H
2O, 9.5mmol), 1.7 gram phosphate dihydrate disodium hydrogen (Na
2HPO
42H
2O, 9.5mmol), the mixed solution of 90 milliliters of methylene dichloride and 90 ml waters, hierarchy of control temperature is 20 degree, the clorox of Dropwise 5 5.6 grams 14% in 30 minutes (NaClO, the 105mmol) aqueous solution, and with the pH of pH meter monitoring reaction liquid between 6.5-8.0.Reaction is told dichloromethane layer after finishing, and organic layer washs with saturated sodium bicarbonate aqueous solution, sloughs the resistates underpressure distillation of solvent, collects 38 ℃/0.2mBar cut, and yield is 79%.
3) European patent (EP775,684) (TEMPO catalysis TCIA oxidation alcohol generates the technology of aldehyde) contains 3.5 gram trichloroisocyanuric acid (TCIA with one, 15.1mmol), 3.7 the gram sodium-acetate (45.1mmol), 10 milligrams of TEMPO (0.06mmol) and 40 milliliters of methylene dichloride suspension, be cooled to-the 7-9 degree.Stir 20 milliliters of dichloromethane solutions of Dropwise 5 gram 1-octanol (38.4mmol) in 20 minutes down.Add back hierarchy of control temperature and reach 80 minutes at-7-9 degree.Like this, reaction has just been finished.White depositions is filtered, and filtrate is respectively with saturated sodium bicarbonate aqueous solution and salt washing.The crude product distillation obtains 4.5 gram n-octaldehydes, chromatogram content 98.2% (area percentage).
4) world patent (WO03/006435A1) (TEMPO catalysis I
2Oxidation alcohol generates the technology of aldehyde)
Add 3.0 kilograms of sodium bicarbonates (35.6mol) and 30 premium on currency in the toluene/tetrahydrofuran solution that contains 2.2 kilograms of 5-methoxyl groups-3-thionaphthene methyl alcohol (11.34mol), it is molten fully clear to be stirred to sodium bicarbonate.Add 6 kilograms of iodine (I under the room temperature
2, 23.7mol), aging 1 hour.Add 140 gram TEMPO (0.90mol) then.Reaction mixture at room temperature stirs 2-6 hour to the raw material completely consumed.Reaction mixture is kept room temperature, and S-WAT (Na2SO3) aqueous solution that adds 15 liter 10% is to remove excessive iodine.Organic layer is washed with 15 premium on currency after the layering, and organic layer is further used 2.2 kilogram of 10% aqueous sodium carbonate and 2 kilograms of washings respectively.
5) United States Patent (USP): US Patent5,136,102 (TEPMO catalysis HNO
3/ O
2Oxidation alcohol generates the technology of ketone)
In 100 milliliters round-bottomed flask, add 4.2 gram sec-n-octyl alcohols, 1 gram TEMPO, 25 milliliters of acetonitriles, 0.25 gram Potassium Bromide (KBr) and 1 gram water.Nitric acid (the HNO that in mixed solution, adds 1 gram 70%
3).Aerating oxygen stream bubbling.Control reaction temperature was at room temperature reacted 4 hours.Material content is less than 0.1%, and the selectivity of product methyln-hexyl ketone is greater than 99.9%.
6) United States Patent (USP): US Patent5,155,279 (TEPMO catalysis HNO
3/ O
2The technology of oxidation alcohol)
In 100 milliliters round-bottomed flask, add 6 grams, 12 carbon alcohol, 1 gram TEMPO, 25 milliliters of acetonitriles, 0.25 gram Potassium Bromide (KBr) and 1 gram water.Nitric acid (the HNO that in mixed solution, adds 1 gram 70%
3).Aerating oxygen stream bubbling.Control reaction temperature was reacted 4 hours under 35 degree.Feed stock conversion is greater than 99%, and the selectivity of aldehyde is 3%, and the dimer selectivity is 7%, and the selectivity of acid is 90%.
7) Chinese patent: 200410003791.X (TEMPO/Br
2/ NaNO
2The technology of oxidation alcohol) in 300mL teflon-lined autoclave pressure, add 1.09g 3-piconol (10mmol), 62.4mg TEMPO (0.4mmol), 55.2mg NaNO
2(0.8mmol), 10mL contains the methylene dichloride of 128mg bromine (0.8mmol), the seal-off pressure still, and filling air to tensimeter is 0.9MPa, and autoclave pressure is put in the oil bath that is warming up to 100 degree in advance, reacts five hours.After cooling and the careful release, organic phase is analyzed with gas-chromatography (GC), and transformation efficiency is 94.4%, selectivity of product 100%.The separation yield 93.5% of product 3-pyridylaldehyde.
Claims (4)
1. catalytic air oxidation prepares the method for aromatic aldehyde ketone in the water solvent system, with 2,2,6,6-tetramethyl piperidine-oxyradical and derivative thereof, nitrite and produce the bromo-derivative of hypobromous acid with water effect original position, oxygen or atmospheric oxidation fragrance benzylalcohol generate aldehyde and ketone;
Wherein: 2,2,6,6-tetramethyl piperidine-oxyradical and derivative thereof: nitrite: bromo-derivative=1: 2-4: 4mmol;
2,2,6,6-tetramethyl piperidine-oxyradical and derivative thereof: fragrant benzylalcohol=1: 100mmol;
Oxygen or air effect pressure 0.1-1.2MPa;
Reaction times 1.5-16 hour;
Temperature of reaction 40-120 ℃;
Described 2,2,6, the derivative of 6-tetramethyl piperidine-oxyradical is a 4-benzoyl-2,2,6,6-tetramethyl piperidine-oxyradical or 4-acetamido-2,2,6,6-tetramethyl piperidine-oxyradical;
Described fragrant benzylalcohol comprises assorted fragrant benzylalcohol.
2. the method for claim 1, described bromo-derivative is 1,3-two bromo-5,5-dimethyl hydantion, N-bromo-succinimide or pyridinium tribromide salt.
3. the method for claim 1, described assorted fragrant benzylalcohol include the methyl alcohol that N or S replace as heteroatomic aromatic heterocycle.
4. the method for claim 1, described nitrite is Sodium Nitrite or potassium nitrite.
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| CN101565361B (en) * | 2008-04-25 | 2012-05-23 | 中国科学院大连化学物理研究所 | Method for preparing carbonyl compound by oxygen catalysis and alcohol oxidation |
| CN101632941B (en) * | 2008-07-22 | 2011-08-24 | 郑州大学 | Catalyst for preparing aldehydes or ketones by selective oxidation of alcohols with molecular oxygen and application thereof |
| CN101768064B (en) * | 2008-12-26 | 2013-07-24 | 中国科学院大连化学物理研究所 | Method for preparing aromatic aldehyde employing oxygen to catalyze and oxidize aromatic primary alcohol |
| FR2984889B1 (en) * | 2011-12-22 | 2017-02-24 | Roquette Freres | IMPROVED METHOD OF SELECTIVE OXIDATION OF 5-HYDROMETHYL FURALDEHYDE |
| CN105772099B (en) * | 2016-05-03 | 2018-09-25 | 苏州大学 | A kind of ionic liquid and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1512962A1 (en) * | 1988-02-29 | 1989-10-07 | Рижский политехнический институт им.А.Я.Пельше | Method of producing benzaldehyde |
| DE4007923A1 (en) * | 1989-03-22 | 1990-09-27 | Basf Ag | Di:substd. benzaldehyde prepn. - by liq. phase oxidn. of corresp. benzyl alcohol using hypohalite and morpholine, pyrrolidine or piperidine deriv. |
| SU1657488A1 (en) * | 1989-09-27 | 1991-06-23 | Рижский политехнический институт им.А.Я.Пельше | Method for obtaining benzaldehyde |
| US5136102A (en) * | 1991-10-18 | 1992-08-04 | Shell Oil Company | Process for the preparation of ketones |
-
2004
- 2004-12-16 CN CNB2004100989369A patent/CN100348565C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1512962A1 (en) * | 1988-02-29 | 1989-10-07 | Рижский политехнический институт им.А.Я.Пельше | Method of producing benzaldehyde |
| DE4007923A1 (en) * | 1989-03-22 | 1990-09-27 | Basf Ag | Di:substd. benzaldehyde prepn. - by liq. phase oxidn. of corresp. benzyl alcohol using hypohalite and morpholine, pyrrolidine or piperidine deriv. |
| SU1657488A1 (en) * | 1989-09-27 | 1991-06-23 | Рижский политехнический институт им.А.Я.Пельше | Method for obtaining benzaldehyde |
| US5136102A (en) * | 1991-10-18 | 1992-08-04 | Shell Oil Company | Process for the preparation of ketones |
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