CN103214396B - Production method of 3-cyanobenzoic acid - Google Patents
Production method of 3-cyanobenzoic acid Download PDFInfo
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- CN103214396B CN103214396B CN201310122252.7A CN201310122252A CN103214396B CN 103214396 B CN103214396 B CN 103214396B CN 201310122252 A CN201310122252 A CN 201310122252A CN 103214396 B CN103214396 B CN 103214396B
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Abstract
The invention relates to a production method of 3-cyanobenzoic acid. The production method comprises the following steps of step 1, reacting 3-cyano toluene as an initial raw material with chlorine gas in a reversed tower-type reactor to generate 3-chloromethyl cyanophenyl; and step 2, carrying out heating oxidation reaction on 3-chloromethyl cyanophenyl through hydrogen peroxide under the effects of vanadyl sulfate and sodium tungstate catalysts and benzyl chloride triethylammonium phase transfer catalyst to generate 3-cyanobenzoic acid, continuing heating and distilling to remove ethanol, cooling to room temperature, filtering, washing the filter cake through water twice, recrystallizing by ethanol and drying to obtain 3-cyanobenzoic acid white powder. The total yield of the product in two steps can reach 80 percent, the content can reach 98 percent, the cost is low, and the production method is applicable to industrialized production. The yield and purity of the product are high, the environmental pollution is small, and the cost is low.
Description
Technical field
The present invention relates to a kind of production method of 3-cyanobenzoic acid.
Background technology
3-cyanobenzoic acid is a kind of important organic synthesis intermediate.Being widely used in preparing cardiovascular drugs, microbiotic, anodyne and neural system and regulating class medicine etc., is also the important source material of synthesis liquid crystal material.The synthetic method of existing 3-cyanobenzoic acid mainly contains following several:
East China Normal University Yang Fan etc. (CN01105687.8) are with 3-cyano group toluene for raw material, and divalent cobalt is catalyzer, and Sodium Bromide is promotor, and the oxygen in air is oxygenant, preparation 3-cyanobenzoic acid, yield 80-99%.The shortcoming of this method needs to react in sealed tube, and temperature of reaction is high, and pressure is large.The method is particularly suitable for being used for short run at chemical laboratory and prepares 3-cyanobenzoic acid.
With 3-cyano group toluene be raw material, acetic acid is solvent, chromium trioxide for oxygenant, sulfuric acid is promotor, is oxidized, obtains product (J.Org.Chem., 1959,24,115) through a series of last handling process at temperature 0-5 DEG C.This technique is simple, and production cost is low.But excessive chromium trioxide process danger close, hold fire hazardous and blast, a large amount of trivalent chromium wastewater treatments is also a large problem, is thus only suitable for short run and prepares 3-cyanobenzoic acid.
In the RELATED APPLICATIONS (US6433211) of the preparation of 3-cyanobenzoic acid, with 1,3-benzene dinitrile for starting raw material, through the selective hydrolysis of methanol/water/alkali, obtain 3-cyanobenzoic acid, yield is about 75%.The single hydrolysis of wayward two CN of this reaction, thus the content of the finished product is not high, and three wastes spy is many, is unsuitable for preparing 3-cyanobenzoic acid in enormous quantities.
People's plumbic acetates such as Donald A.Watson and perfluoroalkyl polyether make catalyzer, and in the dimethyl sulphoxide solution of 3-6-chlorophenyl nitrile, normal pressure passes into carbon monoxide, and 100 DEG C of reactions obtained 3-cyanobenzoic acid after 15 hours.The yield synthesized in this way is very high, can reach 97%.But the material that this method participates in reaction is more, and reaction process is comparatively complicated, inconvenient operation.
The people such as Arvela Riina K. are in N-Methyl pyrrolidone solvent, and select NaCN and 3-chloro-benzoic acid microwave reaction within 10 minutes, can obtain 3-cyanobenzoic acid, yield can reach 99%.This synthetic method is at the microwave reaction using Recent study many, and respond well, yield is very high.But the further amplification for microwave reaction need research.
Take gavaculine as initiator, through diazotization reaction and Sandmeyer reaction, make diazo cyanalation with cuprous cyanide double salt.This reaction relates to the inorganic cyanide of severe toxicity, allly all should carry out in airtight good environment, and has worn required protective articles, and reaction terminates rear all aqueous phases and should concentrate placement, uses NaOH/H
2o
2process.Though the method is industrialization, but still there are some problems.Reacted wastewater treatment also bothers very much.And there is the greatest problem that certain hidden danger is the reaction of this class aborning in the metal cyanides of severe toxicity.
Summary of the invention
The object of the invention is for above-mentioned present situation, aiming to provide one can meet industrialization production requirements, and yield and the purity of product are high, the production method of the 3-cyanobenzoic acid that environmental pollution is little, cost is low.
The implementation of the object of the invention is, the production method of 3-cyanobenzoic acid, and reaction is carried out in two steps:
The first step, the 3-methyl cyanophenyl of 800 liters is added in 1000 liters of enamel reaction stills, be heated to 25-160 DEG C, with pump, feed liquid is squeezed into packing tower top continuously, spray downwards with 5-40 liter/min of flow velocity, upwards pass into 310 kilograms of chlorine from packing tower bottom equably with 5-40 liter/min of flow velocity, formation 3-methyl cyanophenyl and chlorine inverse motion carry out chlorination reaction simultaneously; Gas phase cools through chip enamel condenser, gas-liquid separator separates, and liquid return is in enamel reaction still; Hydrogenchloride, chlorine gas enter tail gas absorption tank emptying after water, Alkali absorption; After having reacted, feed liquid is proceeded to enamel crystallization kettle, be cooled to 5 DEG C, suction filtration, filter cake is 3-chloromethyl cyanophenyl;
Second step, adds in 2000 liters of enamel reaction stills by 200 kilograms of 3-chloromethyl cyanophenyls, 100-800 kg ethanol, 1-3 kg catalyst and 0.2-1 kilogram of benzyl triethylammonium chloride phase transfer catalyst, stirs and heats up; Keep temperature of reaction 30-50 DEG C, in reactor, slowly drip 150-450 kilogram of 30% hydrogen peroxide.Dropwise, be incubated 6 hours, oxidizing reaction generates 3-cyanobenzoic acid, continues to be heated to 100 DEG C, distills out ethanol.Be cooled to room temperature, filter, filter cake washing twice, after ethyl alcohol recrystallization, dry and obtain 3-cyanobenzoic acid white powder;
Described catalyzer is vanadylic sulfate and sodium wolframate, and mass ratio is 1:10-10:1; The consumption of catalyzer is the 0.5-1.5% of 3-chloromethyl cyanophenyl quality;
The mol ratio of described 3-chloromethyl cyanophenyl and hydrogen peroxide is 1:1-3, and the consumption of benzyl triethylammonium chloride phase transfer catalyst is the 0.1-0.5% of 3-chloromethyl cyanophenyl quality, and the mass ratio of oxidizing reaction 3-chloromethyl cyanophenyl and ethanol is 1:0.5-4;
Concrete reaction formula is as follows:
The present invention is in two steps: the first step, using 3-cyano group toluene as starting raw material, first reacts through reverse tower reactor with chlorine, generates 3-chloromethyl cyanophenyl.Second step, 3-chloromethyl cyanophenyl, at vanadylic sulfate and sodium tungstate catalyst, under the effect of benzyl triethylammonium chloride phase transfer catalyst, generates 3-cyanobenzoic acid through hydrogen peroxide oxidation reaction.Produce product two step total recovery with the present invention and can reach 80%, content can reach 98%, and cost is low, is suitable for suitability for industrialized production.
Yield and the purity of product of the present invention are high, and environmental pollution is little, cost is low.
Accompanying drawing explanation
Fig. 1 is the tower chlorination production technology schematic flow sheet of methyl cyanophenyl.
Embodiment
Reaction of the present invention is carried out in two steps:
The first step, adds the 3-methyl cyanophenyl of 800 liters, is heated to 25-160 DEG C, best 150-160 DEG C in 1000 liters of enamel reaction stills.With pump, feed liquid is squeezed into filler tower top continuously, spray downwards with 5-40 liter/min of flow velocity, the best sprays downwards with 15-20 liter/min of flow velocity; Upwards pass into 310 kilograms of chlorine from packing tower bottom equably with 5-40 liter/min of flow velocity simultaneously, form 3-methyl cyanophenyl and chlorine inverse motion, carry out chlorination reaction.Gas phase is through the cooling of chip enamel condenser, and gas-liquid separator separates, liquid return is in enamel reaction still.Hydrogenchloride, chlorine gas enter tail gas absorption tank emptying after water, Alkali absorption.
Keep temperature of reaction, in reaction, use 3-methyl cyanophenyl and 3-chloromethyl cyanophenyl content in gas chromatographic detection feed liquid at set intervals.After having reacted, stop logical chlorine, negative pressure extracts hydrogenchloride out.Feed liquid is proceeded to enamel crystallization kettle, be cooled to 5 DEG C, suction filtration, filtrate recovery, filter cake is 3-chloromethyl cyanophenyl.Be greater than 96% with the content of gas Chromatographic Determination 3-chloromethyl cyanophenyl, per pass conversion can reach 60%, applies mechanically yield 90%.
For improving 3-methyl cyanophenyl transformation efficiency, 3-chloromethyl cyanophenyl yield, the first step reaction capable of circulation 3-5 time.
Second step, urges add in enamel reaction still by 3-chloromethyl cyanophenyl, ethanol, vanadylic sulfate and sodium wolframate, benzyl triethylammonium chloride salt, stirs and heats up.Keep temperature of reaction 30-50 DEG C, best 45 DEG C, in reactor, slowly drip 30% hydrogen peroxide, dropwise, be incubated 6 hours, oxidizing reaction generates 3-cyanobenzoic acid, uses the content of 3-chloromethyl cyanophenyl in liquid chromatographic detection reactor in reaction at set intervals.When the content that front and back sample 3-chloromethyl cyanophenyl in detection reaction still for twice remains unchanged, namely react complete.
Oxidizing reaction generates 3-cyanobenzoic acid, continues to be heated to 100 DEG C, distills out ethanol.Be cooled to room temperature, filter, filter cake washing twice, after ethyl alcohol recrystallization, dry and obtain 3-cyanobenzoic acid white powder;
Continue to be heated to 100 DEG C, distill out ethanol, recovery.Be cooled to room temperature, filter, filter cake twice washing, after ethyl alcohol recrystallization, dry and obtain 3-cyanobenzoic acid white powder, be greater than 98% with liquid-phase chromatographic analysis content, yield 90%.
The consumption of catalyzer is the 0.5-1.5% of 3-chloromethyl cyanophenyl quality, best 1.2-1.5%.Catalyzer is vanadylic sulfate and sodium wolframate, and mass ratio is 1:10-10:1, best 1:5.
The mol ratio of described 3-chloromethyl cyanophenyl and hydrogen peroxide is 1:1-3, best 1:2.The consumption of benzyl triethylammonium chloride phase transfer catalyst is the 0.1-0.5% of 3-chloromethyl cyanophenyl quality, best 0.3-0.5%.The mass ratio of oxidizing reaction 3-chloromethyl cyanophenyl and ethanol is 1:0.5-4, best 1:3-4.
With reference to the accompanying drawings, with specific embodiment in detail the present invention is described in detail:
Embodiment 1:
The first step, adds the 3-methyl cyanophenyl of 800 liters, is heated to 150-160 DEG C in liter enamel reaction still of 1000 shown in Fig. 11.With pump, feed liquid is squeezed into continuously the top of enamel packing tower 2, spray downwards with 15 liters/min of flow velocitys.Upwards pass into 310 kilograms of chlorine from packing tower bottom equably with 15 liters/min of flow velocitys simultaneously, form 3-methyl cyanophenyl and chlorine inverse motion.Gas phase cools through chip enamel condenser 3, and gas-liquid separator 4 is separated, and liquid return is in enamel reaction still.Hydrogenchloride, chlorine gas enter tail gas absorption tank 5 emptying after water, Alkali absorption.
Insulation reaction, uses the content of 3-chloromethyl cyanophenyl in gas chromatographic detection reactor at set intervals in reaction process, when the content that front and back sample 3-chloromethyl cyanophenyl in detection reaction still for twice remains unchanged, and stopped reaction.After having reacted, stop logical chlorine, negative pressure extracts hydrogen chloride gas out.Feed liquid is proceeded to enamel crystallization kettle, be cooled to 5 DEG C, suction filtration, filtrate recovery, filter cake is 3-chloromethyl cyanophenyl, weighs 600 kilograms, and be greater than 96% with the content of gas Chromatographic Determination 3-chloromethyl cyanophenyl, per pass conversion can reach 60%, applies mechanically yield 90%.The fusing point of 3-chloromethyl cyanophenyl is 65.2-66.8 DEG C.
200 kilograms of 3-chloromethyl cyanophenyls, 600 kg ethanol, catalyzer 0.4 kilogram of vanadylic sulfate and 2.0 kilograms of sodium wolframates, 1 kilogram of benzyl triethylammonium chloride phase transfer catalyst are added in 2000L enamel reaction still by second step, stir and heat up.Keep temperature of reaction 45 DEG C, in reactor, slowly drip 300 kilogram of 30% hydrogen peroxide, dropwise, insulation for some time.The content of 3-chloromethyl cyanophenyl in liquid chromatographic detection reactor is used at set intervals in reaction process, when the content that front and back sample 3-chloromethyl cyanophenyl in detection reaction still for twice remains unchanged, stopped reaction.Continue to be heated to 100 DEG C, distill out ethanol, recovery.After distillation, add and be water-cooled to room temperature.Feed liquid is filtered, filter cake washing twice.After filter cake ethyl alcohol recrystallization, dry and obtain white powder solid, weigh 175 kilograms, liquid-phase chromatographic analysis 3-cyanobenzoic acid content is greater than 98%, yield 90%.3-cyanobenzoic acid fusing point 221.8-223.5 DEG C.
Embodiment 2-6: with embodiment 1, unlike passing into reactor Cl
2flow different.
In chlorination process, keep the 3-methyl cyanophenyl of 800 liters, the charging capacity of 310 kilograms of chlorine, temperature of reaction is constant, by changing Cl
2flow, investigates Cl
2flow is on the impact of 3-methyl cyanophenyl chlorination reaction.According to the content of the 3-chloromethyl cyanophenyl of gas chromatographic detection, calculate the yield of 3-chloromethyl cyanophenyl in table 1.
Table 1 Cl
2flow is on the impact of 3-methyl cyanophenyl chlorination reaction
As seen from Table 1, Cl
2flow sprays downwards as the best with 15-20 liter/min of flow velocity.
Embodiment 7-11: with embodiment 1 is different unlike chlorination reaction temperature.
In chlorination process, keeping the 3-methyl cyanophenyl of 800 liters, the charging capacity of 310 kilograms of chlorine, keep chlorine flowrate 15 liters/min constant, by changing temperature of reaction, investigating temperature to the impact of 3-methyl cyanophenyl chlorination reaction.According to the 3-chloromethyl cyanophenyl content of gas chromatographic detection, calculate the yield of 3-chloromethyl cyanophenyl in table 2.
Table 2 temperature of reaction is on the impact of 3-methyl cyanophenyl chlorination reaction
As seen from Table 2,3-methyl cyanophenyl chlorination reaction temperature is best with 150-160 DEG C.
Embodiment 12-16: with embodiment 1 is different unlike circulating reaction number of times.
In chlorination process, keep the 3-methyl cyanophenyl of 800 liters, the charging capacity of 310 kilograms of chlorine, keep constant, the temperature of reaction 150-160 of chlorine flowrate 15 liters/min DEG C constant, by changing circulating reaction number of times, investigate the reaction times to the impact of 3-methyl cyanophenyl chlorination reaction.According to the 3-chloromethyl cyanophenyl content of gas chromatographic detection, calculate the yield of 3-chloromethyl cyanophenyl in table 3.
Table 3 circulating reaction number of times is on the impact of 3-methyl cyanophenyl chlorination reaction
As seen from Table 3,3-methyl cyanophenyl chlorination reaction is to circulate 4,5 times for best.
Embodiment 17-21: with embodiment 1, the consumption unlike hydrogen peroxide is different.
In oxidising process, keep 200 kilograms of 3-chloromethyl cyanophenyls, 600 kg ethanol, catalyzer 0.4 kilogram of vanadylic sulfate and 2.0 kilograms of sodium wolframates, 1 kilogram of benzyl triethylammonium chloride phase transfer catalyst constant, under the same reaction conditions, by changing the proportioning of 3-chloromethyl cyanophenyl and hydrogen peroxide, investigate hydrogen peroxide consumption to the impact of oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, calculate the yield of 3-cyanobenzoic acid in table 4.
Table 4 hydrogen peroxide consumption is on the impact of 3-cyanobenzoic acid yield
As seen from Table 4,3-chloromethyl cyanophenyl and hydrogen peroxide consumption with 1:2 mol ratio for the best.
Embodiment 22-26: with embodiment 1 is different unlike ethanol consumption.
In oxidising process, keep 200 kilograms of 3-chloromethyl cyanophenyls, 300 kilogram of 30% hydrogen peroxide, catalyzer 0.4 kilogram of vanadylic sulfate and 2.0 kilograms of sodium wolframate, 1 kilogram of benzyl triethylammonium chloride phase transfer catalyst constant, under the same reaction conditions, by changing the proportioning of 3-chloromethyl cyanophenyl and ethanol, investigate ethanol consumption to the impact of oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, calculate the yield of 3-cyanobenzoic acid in table 5.
Table 5 solvent load is on the impact of 3-cyanobenzoic acid yield
As seen from Table 5, the mass ratio of 3-chloromethyl cyanophenyl and ethanol take 1:3-4 as the best.
Embodiment 27-31: with embodiment 1 is different unlike catalyst levels.
In oxidising process, keep 200 kilograms of 3-chloromethyl cyanophenyls, 600 kg ethanol, 300 kilogram of 30% hydrogen peroxide and 1 kilogram of benzyl triethylammonium chloride phase transfer catalyst constant, under identical reaction conditions, change the consumption (massfraction of catalyst sulfuric acid vanadyl and sodium wolframate, in 3-chloromethyl cyanophenyl), investigate catalyst levels to the impact of oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, calculate the yield of 3-cyanobenzoic acid in table 6.
Table 6 catalyst levels is on the impact of 3-cyanobenzoic acid yield
As seen from Table 6, mass ratio the best of catalyst sulfuric acid vanadyl and sodium wolframate is the 1.2-1.5% of 3-chloromethyl cyanophenyl.
Embodiment 32-36: with embodiment 1, the consumption unlike phase-transfer catalyst is different.
In oxidising process, keep 200 kilograms of 3-chloromethyl cyanophenyls, 600 kg ethanol, 300 kilogram of 30% hydrogen peroxide, catalyzer 0.4 kilogram of vanadylic sulfate and 2.0 kilograms of sodium wolframates, under the same reaction conditions, change the consumption (massfraction of benzyl triethylammonium chloride salt, in 3-chloromethyl cyanophenyl), investigate phase-transfer catalyst consumption to the impact of oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, calculate the yield of 3-cyanobenzoic acid in table 7.
Table 7 phase-transfer catalyst consumption is on the impact of 3-cyanobenzoic acid yield
As seen from Table 7, consumption the best of benzyl triethylammonium chloride phase transfer catalyst is the 0.3-0.5% of 3-chloromethyl cyanophenyl quality.
Embodiment 37-41: with embodiment 1 is different unlike temperature of reaction.
In oxidising process, keep 200 kilograms of 3-chloromethyl cyanophenyls, 600 kg ethanol, 300 kilogram of 30% hydrogen peroxide, catalyzer 0.4 kilogram of vanadylic sulfate and 2.0 kilograms of sodium wolframate, 1 kilogram of benzyl triethylammonium chloride phase transfer catalyst constant, under the same reaction conditions, change temperature of reaction, investigate temperature to the impact of oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, calculate the yield of 3-cyanobenzoic acid in table 8.
Table 8 temperature of reaction is on the impact of 3-cyanobenzoic acid yield
As seen from Table 8, second step optimal reaction temperature is 45 DEG C.
Embodiment 42-46: with embodiment 1, the massfraction ratio unlike catalyst sulfuric acid vanadyl, sodium wolframate is different.
In oxidising process, keep 200 kilograms of 3-chloromethyl cyanophenyls, 600 kg ethanol, 300 kilogram of 30% hydrogen peroxide, catalyzer (vanadylic sulfate, sodium wolframate) total amount 2.4 kilograms and 1 kilogram benzyl triethylammonium chloride phase transfer catalyst, temperature of reaction 45 DEG C is constant, under identical reaction conditions, change the massfraction ratio of the vanadylic sulfate in catalyzer, sodium wolframate, and investigate the impact of massfraction comparison oxidizing reaction of catalyst sulfuric acid vanadyl, sodium wolframate.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, calculate the yield of 3-cyanobenzoic acid in table 9.
The impact of the massfraction comparison 3-cyanobenzoic acid yield of table 9 catalyst sulfuric acid vanadyl, sodium wolframate
As seen from Table 9, the massfraction of catalyst sulfuric acid vanadyl, sodium wolframate is 1:5 than the best.
Claims (7)
- The production method of 1.3-cyanobenzoic acid, is characterized in that reaction in two steps:The first step, the 3-methyl cyanophenyl of 800 liters is added in 1000 liters of enamel reaction stills, be heated to 25-160 DEG C, with pump, feed liquid is squeezed into packing tower top continuously, spray downwards with 5-40 liter/min of flow velocity, upwards pass into 310 kilograms of chlorine from packing tower bottom equably with 5-40 liter/min of flow velocity, formation 3-methyl cyanophenyl and chlorine inverse motion carry out chlorination reaction simultaneously; Gas phase cools through chip enamel condenser, gas-liquid separator separates, and liquid return is in enamel reaction still; Hydrogenchloride, chlorine gas enter tail gas absorption tank emptying after water, Alkali absorption; After having reacted, feed liquid is proceeded to enamel crystallization kettle, be cooled to 5 DEG C, suction filtration, filter cake is 3-chloromethyl cyanophenyl;Second step, adds in 2000 liters of enamel reaction stills by 200 kilograms of 3-chloromethyl cyanophenyls, 100-800 kg ethanol, 1-3 kg catalyst and 0.2-1 kilogram of benzyl triethylammonium chloride phase transfer catalyst, stirs and heats up; Keep temperature of reaction 30-50 DEG C, in reactor, slowly drip 150-450 kilogram of 30% hydrogen peroxide; Dropwise, be incubated 6 hours, oxidizing reaction generates 3-cyanobenzoic acid, continues to be heated to 100 DEG C, distills out ethanol; Be cooled to room temperature, filter, filter cake washing twice, after ethyl alcohol recrystallization, dry and obtain 3-cyanobenzoic acid white powder;Described catalyzer is vanadylic sulfate and sodium wolframate, and mass ratio is 1:10-10:1; The consumption of catalyzer is the 0.5-1.5% of 3-chloromethyl cyanophenyl quality;The mol ratio of described 3-chloromethyl cyanophenyl and hydrogen peroxide is 1:1-3, and the consumption of benzyl triethylammonium chloride phase transfer catalyst is the 0.1-0.5% of 3-chloromethyl cyanophenyl quality, and the mass ratio of oxidizing reaction 3-chloromethyl cyanophenyl and ethanol is 1:0.5-4;Concrete reaction formula is as follows:
- 2. the production method of 3-cyanobenzoic acid according to claim 1, is characterized in that the first step circulating reaction 4,5 times.
- 3. the production method of 3-cyanobenzoic acid according to claim 1, is characterized in that feed liquid is squeezed into packing tower top by the first step pump continuously, sprays downwards with 15-20 liter/min of flow velocity.
- 4. the production method of 3-cyanobenzoic acid according to claim 1, is characterized in that the 3-methyl cyanophenyl adding 800 liters in 1000 liters of enamel reaction stills, is heated to 150-160 DEG C.
- 5. the production method of 3-cyanobenzoic acid according to claim 1, is characterized in that keeping temperature of reaction 45 DEG C, in reactor, slowly drips hydrogen peroxide.
- 6. the production method of 3-cyanobenzoic acid according to claim 1, is characterized in that the consumption of second step catalyzer is the 1.2-1.5% of 3-chloromethyl cyanophenyl quality; The mol ratio of 3-chloromethyl cyanophenyl and hydrogen peroxide is 1:2, and the consumption of benzyl triethylammonium chloride phase transfer catalyst is the 0.3-0.5% of 3-chloromethyl cyanophenyl quality, and the mass ratio of oxidizing reaction 3-chloromethyl cyanophenyl and ethanol is 1:3-4.
- 7. the production method of 3-cyanobenzoic acid according to claim 1, is characterized in that the mass ratio of second step catalyst sulfuric acid vanadyl and sodium wolframate is 1:5.
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| CN1126991A (en) * | 1993-07-06 | 1996-07-17 | 阿斯特拉公司 | Novel (1-phenyl-1-heterocyclyl) methanol and (1-phenyl-1-heterocyclyl) methylamine derivatives |
| CN1108287C (en) * | 2000-11-24 | 2003-05-14 | 中国科学院上海有机化学研究所 | Environmentally friendly process for preparing benzoic acid and its derivatives |
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| CN102059141A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing aromatic carboxylic acid and application thereof |
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| CN1126991A (en) * | 1993-07-06 | 1996-07-17 | 阿斯特拉公司 | Novel (1-phenyl-1-heterocyclyl) methanol and (1-phenyl-1-heterocyclyl) methylamine derivatives |
| CN1108287C (en) * | 2000-11-24 | 2003-05-14 | 中国科学院上海有机化学研究所 | Environmentally friendly process for preparing benzoic acid and its derivatives |
| EP1593654A1 (en) * | 2004-04-10 | 2005-11-09 | Bayer MaterialScience AG | Process for treating waste waters containing aromatic nitro compounds |
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