CN103214396A - Production method of 3-cyanobenzoic acid - Google Patents
Production method of 3-cyanobenzoic acid Download PDFInfo
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- CN103214396A CN103214396A CN2013101222527A CN201310122252A CN103214396A CN 103214396 A CN103214396 A CN 103214396A CN 2013101222527 A CN2013101222527 A CN 2013101222527A CN 201310122252 A CN201310122252 A CN 201310122252A CN 103214396 A CN103214396 A CN 103214396A
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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
The 3-cyanobenzoic acid is a kind of important organic synthesis intermediate.Being widely used in preparing painstaking effort tubing medicine, microbiotic, anodyne and neural system and regulating class medicine etc., also is the important source material of synthetic liquid crystal material.The synthetic method of existing 3-cyanobenzoic acid mainly contains following several:
(CN01105687.8) such as the Yang Fan of East China Normal University is raw material with 3-cyano group toluene, and divalent cobalt is a catalyzer, and Sodium Bromide is a promotor, and airborne oxygen is oxygenant, preparation 3-cyanobenzoic acid, yield 80-99%.The shortcoming of this method is to react in sealed tube, the temperature of reaction height, and pressure is big.This method is particularly suitable for being used for short run at chemical laboratory and prepares the 3-cyanobenzoic acid.
With 3-cyano group toluene is that raw material, acetic acid are that solvent, chromium trioxide are oxygenant, and sulfuric acid is promotor, and temperature 0-5 ℃ of following oxidation makes product (J.Org.Chem., 1959,24,115) through a series of last handling processes.This technology is simple, and production cost is low.But excessive chromium trioxide is handled danger close, causes fire and blast easily, and a large amount of trivalent chromium wastewater treatments also is a big problem, thereby only is suitable for short run and prepares the 3-cyanobenzoic acid.
In the relevant patent (US6433211) of the preparation of 3-cyanobenzoic acid, with 1, the 3-benzene dinitrile is a starting raw material, and the selective hydrolysis through methanol/alkali obtains the 3-cyanobenzoic acid, and yield is about 75%.This reacts the single hydrolysis of wayward two CN, thereby the content of the finished product is not high, and three wastes spy is many, is unsuitable for preparing in enormous quantities the 3-cyanobenzoic acid.
Human plumbic acetate such as Donald A.Watson and perfluoroalkyl polyether are made catalyzer, and in the dimethyl sulphoxide solution of 3-6-chlorophenyl nitrile, normal pressure feeds carbon monoxide, and 100 ℃ of reactions obtained the 3-cyanobenzoic acid after 15 hours.The synthetic yield is very high in this way, can reach 97%.It is more that but this method participates in the material of reaction, and reaction process is comparatively complicated, inconvenient operation.
People such as Arvela Riina K. select for use NaCN and 3-chloro-benzoic acid microwave reaction can obtain the 3-cyanobenzoic acid in 10 minutes in the N-Methyl pyrrolidone solvent, and yield can reach 99%.This synthetic method is being used the many microwave reactions of Recent study, and respond well, yield is very high.But the further amplification for microwave reaction is still waiting research.
With the gavaculine is initiator, through diazotization reaction and Sandmeyer reaction, makes diazo cyano groupization with cuprous cyanide double salt.This reaction relates to the inorganic cyanide of severe toxicity, and all should carry out in airtight good environment, and have worn essential protective articles, and reaction finishes all waters of back should concentrate placement, uses NaOH/H
2O
2Handle.Though the industrialization of this method, but still there are some problems.Reacted wastewater treatment also bothers very much.And the metal cyanides of severe toxicity to have certain hidden danger aborning be the greatest problem of this class reaction.
Summary of the invention
The objective of the invention is at above-mentioned present situation, aim to provide and a kind ofly can satisfy the suitability for industrialized production requirement, the yield of product and purity height, 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-methylbenzene nitrile that adds 800 liters in 1000 liters of enamel reaction stills, be heated to 25-160 ℃, with pump feed liquid is squeezed into the packing tower top continuously, spray downwards with 5-40 liter/minute flow velocity, simultaneously upwards feed 310 kilograms of chlorine equably from the packing tower bottom, form 3-methylbenzene nitrile and chlorine inverse motion and carry out chlorination reaction with 5-40 liter/minute flow velocity; Gas phase is cooled off through chip enamel condenser, gas-liquid separator separates, and liquid return is in enamel reaction still; Hydrogenchloride, chlorine gas enter the emptying after water, alkali absorb of tail gas tourie; After reaction is finished, change feed liquid over to the enamel crystallization kettle, be cooled to 5 ℃, suction filtration, filter cake are 3-chloromethylbenzene nitrile;
Second step added 200 kilograms of 3-chloromethylbenzene nitriles, 100-800 kilogram ethanol, 1-3 kilogram catalyzer and 0.2-1 kilogram benzyl triethylammonium chloride salt phase-transfer catalyst in 2000 liters of enamel reaction stills, stirred and heated up; Keep 30-50 ℃ of temperature of reaction, in reactor, slowly drip 150-450 kilogram 30% hydrogen peroxide.Dropwise, be incubated 6 hours, oxidizing reaction generates the 3-cyanobenzoic acid, continues to be heated to 100 ℃, distills out ethanol.Be cooled to room temperature, filter, filter cake washing twice, behind ethyl alcohol recrystallization, oven dry obtains 3-cyanobenzoic acid white powder;
Described catalyzer is vanadylic sulfate and sodium wolframate, and mass ratio is 1:10-10:1; Catalyst consumption is the 0.5-1.5% of 3-chloromethylbenzene nitrile quality;
The mol ratio of described 3-chloromethylbenzene nitrile and hydrogen peroxide is 1:1-3, and the consumption of benzyl triethylammonium chloride salt phase-transfer catalyst is the 0.1-0.5% of 3-chloromethylbenzene nitrile quality, and oxidizing reaction 3-chloromethylbenzene nitrile and alcoholic acid mass ratio are 1:0.5-4;
Concrete reaction formula is as follows:
The present invention is in two steps: the first step, as starting raw material, react generation 3-chloromethylbenzene nitrile earlier through reverse tower reactor with chlorine with 3-cyano group toluene.In second step, 3-chloromethylbenzene nitrile under the effect of benzyl triethylammonium chloride salt phase-transfer catalyst, generates 3-cyanobenzoic acid through the hydrogen peroxide oxidation reaction at vanadylic sulfate and sodium tungstate catalyst.Produce two step of product 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.
The yield of product of the present invention and purity height, environmental pollution is little, cost is low.
Description of drawings
Fig. 1 is the tower chlorination production technology schematic flow sheet of methylbenzene nitrile.
Embodiment
Reaction of the present invention is carried out in two steps:
The first step adds 800 liters 3-methylbenzene nitrile in 1000 liters of enamel reaction stills, is heated to 25-160 ℃, best 150-160 ℃.With pump feed liquid is squeezed into the filler cat head continuously, spray downwards with 5-40 liter/minute flow velocity, the best sprays downwards with 15-20 liter/minute flow velocity; Simultaneously upwards feed 310 kilograms of chlorine equably from the packing tower bottom, form 3-methylbenzene nitrile and chlorine inverse motion, carry out chlorination reaction with 5-40 liter/minute flow velocity.Gas phase is cooled off through chip enamel condenser, gas-liquid separator separates, and liquid return is in enamel reaction still.Hydrogenchloride, chlorine gas enter the emptying after water, alkali absorb of tail gas tourie.
Keep temperature of reaction, use 3-methylbenzene nitrile and 3-chloromethylbenzene nitrile content in the gas chromatographic detection feed liquid in the reaction at set intervals.After reaction is finished, stop logical chlorine, negative pressure is extracted hydrogenchloride out.Change feed liquid over to the enamel crystallization kettle, be cooled to 5 ℃, suction filtration, filtrate recovery set usefulness, filter cake is 3-chloromethylbenzene nitrile.Greater than 96%, per pass conversion can reach 60%, applies mechanically yield 90% with the content of gas Chromatographic Determination 3-chloromethylbenzene nitrile.
For improving 3-methylbenzene nitrile transformation efficiency, 3-chloromethylbenzene nitrile yield, the first step reaction capable of circulation 3-5 time.
Second step, 3-chloromethylbenzene nitrile, ethanol, vanadylic sulfate and sodium wolframate, benzyl triethylammonium chloride salt are urged in the adding enamel reaction still, stir and heat up.Keep 30-50 ℃ of temperature of reaction, best 45 ℃, in reactor, slowly drip 30% hydrogen peroxide, dropwise, be incubated 6 hours, oxidizing reaction generates the 3-cyanobenzoic acid, uses the content of 3-chloromethylbenzene nitrile in the liquid chromatographic detection reactor in the reaction at set intervals.When the content of 3-chloromethylbenzene nitrile in twice sampling in the front and back detection reaction still remains unchanged, i.e. reaction finishes.
Oxidizing reaction generates the 3-cyanobenzoic acid, continues to be heated to 100 ℃, distills out ethanol.Be cooled to room temperature, filter, filter cake washing twice, behind ethyl alcohol recrystallization, oven dry obtains 3-cyanobenzoic acid white powder;
Continue to be heated to 100 ℃, distill out ethanol, recovery set is used.Be cooled to room temperature, filter, twice washing of filter cake, behind ethyl alcohol recrystallization, oven dry obtains 3-cyanobenzoic acid white powder, uses liquid-phase chromatographic analysis content greater than 98%, yield 90%.
Catalyst consumption is the 0.5-1.5% of 3-chloromethylbenzene nitrile 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-chloromethylbenzene nitrile and hydrogen peroxide is 1:1-3, best 1:2.The consumption of benzyl triethylammonium chloride salt phase-transfer catalyst is the 0.1-0.5% of 3-chloromethylbenzene nitrile quality, best 0.3-0.5%.Oxidizing reaction 3-chloromethylbenzene nitrile and alcoholic acid mass ratio are 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 800 liters 3-methylbenzene nitrile in 1000 liters of enamel reaction stills 1 shown in Figure 1, is heated to 150-160 ℃.With pump feed liquid is squeezed into the top of enamel packing tower 2 continuously, spray downwards with 15 liters of/minute flow velocitys.Simultaneously upwards feed 310 kilograms of chlorine equably from the packing tower bottom, form 3-methylbenzene nitrile and chlorine inverse motion with 15 liters of/minute flow velocitys.Gas phase is through 3 coolings of chip enamel condenser, and gas-liquid separator 4 separates, and liquid return is in enamel reaction still.Hydrogenchloride, chlorine gas enter tail gas tourie 5 emptying after water, alkali absorb.
Insulation reaction is used the content of 3-chloromethylbenzene nitrile in the gas chromatographic detection reactor at set intervals in the reaction process, when the content of 3-chloromethylbenzene nitrile in twice sampling in the front and back detection reaction still remains unchanged, and stopped reaction.After reaction is finished, stop logical chlorine, negative pressure is extracted hydrogen chloride gas out.Change feed liquid over to the enamel crystallization kettle, be cooled to 5 ℃, suction filtration, filtrate recovery set usefulness, filter cake is 3-chloromethylbenzene nitrile, weighs 600 kilograms, and the content of using gas Chromatographic Determination 3-chloromethylbenzene nitrile is greater than 96%, and per pass conversion can reach 60%, applies mechanically yield 90%.The fusing point of 3-chloromethylbenzene nitrile is 65.2-66.8 ℃.
Second step added 200 kilograms of 3-chloromethylbenzene nitriles, 600 kilograms of ethanol, 0.4 kilogram of vanadylic sulfate of catalyzer and 2.0 kilograms of sodium wolframates, 1 kilogram of benzyl triethylammonium chloride salt phase-transfer catalyst in the 2000L enamel reaction still, stirred and heated up.Keep 45 ℃ of temperature of reaction, in reactor, slowly drip 300 kilogram of 30% hydrogen peroxide, dropwise insulation for some time.Use the content of 3-chloromethylbenzene nitrile in the liquid chromatographic detection reactor in the reaction process at set intervals, when the content of 3-chloromethylbenzene nitrile in twice sampling in the front and back detection reaction still remains unchanged, stopped reaction.Continue to be heated to 100 ℃, distill out ethanol, recovery set is used.After distillation finishes, add and be water-cooled to room temperature.Feed liquid is filtered twice of filter cake washing.Filter cake with ethyl alcohol recrystallization after, oven dry obtains the white powder solid, weighs 175 kilograms, liquid-phase chromatographic analysis 3-cyanobenzoic acid content is greater than 98%, yield 90%.221.8-223.5 ℃ of 3-cyanobenzoic acid fusing point.
Embodiment 2-6: with embodiment 1, different is to feed reactor Cl
2The flow difference.
In chlorination process, keep 800 liters 3-methylbenzene nitrile, the charging capacity of 310 kilograms of chlorine, temperature of reaction is constant, by changing Cl
2Flow is investigated Cl
2Flow is to the influence of 3-methylbenzene nitrile chlorination reaction.According to the content of the 3-chloromethylbenzene nitrile of gas chromatographic detection, the yield that calculates 3-chloromethylbenzene nitrile sees Table 1.
Table 1 Cl
2Flow is to the influence of 3-methylbenzene nitrile chlorination reaction
As seen from Table 1, Cl
2It is the best that flow sprays downwards with 15-20 liter/minute flow velocity.
Embodiment 7-11: with embodiment 1, different is the chlorination reaction temperature difference.
In chlorination process, keep 800 liters 3-methylbenzene nitrile, the charging capacity of 310 kilograms of chlorine, keep 15 liters/minute of chlorine flowrates constant, by changing temperature of reaction, investigate the influence of temperature to 3-methylbenzene nitrile chlorination reaction.According to the 3-chloromethylbenzene nitrile content of gas chromatographic detection, the yield that calculates 3-chloromethylbenzene nitrile sees Table 2.
Table 2 temperature of reaction is to the influence of 3-methylbenzene nitrile chlorination reaction
As seen from Table 2,3-methylbenzene nitrile chlorination reaction temperature is the best with 150-160 ℃.
Embodiment 12-16: with embodiment 1, different is circulating reaction number of times difference.
In chlorination process, keep 800 liters 3-methylbenzene nitrile, the charging capacity of 310 kilograms of chlorine, keep that 15 liters/minute of chlorine flowrates are constant, temperature of reaction 150-160 is ℃ constant, by changing the circulating reaction number of times, investigates the influence of reaction times to 3-methylbenzene nitrile chlorination reaction.According to the 3-chloromethylbenzene nitrile content of gas chromatographic detection, the yield that calculates 3-chloromethylbenzene nitrile sees Table 3.
Table 3 circulating reaction number of times is to the influence of 3-methylbenzene nitrile chlorination reaction
As seen from Table 3,3-methylbenzene nitrile chlorination reaction is the best to circulate 4,5 times.
Embodiment 17-21: with embodiment 1, different is the consumption difference of hydrogen peroxide.
In oxidising process, keep 200 kilograms of 3-chloromethylbenzene nitriles, 600 kilograms of ethanol, 0.4 kilogram of vanadylic sulfates of catalyzer and 2.0 kilograms of sodium wolframates, 1 kilogram of benzyl triethylammonium chloride salt phase-transfer catalyst constant, under same reaction conditions, by changing the proportioning of 3-chloromethylbenzene nitrile and hydrogen peroxide, investigate of the influence of hydrogen peroxide consumption to oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, the yield that calculates the 3-cyanobenzoic acid sees Table 4.
Table 4 hydrogen peroxide consumption is to the influence of 3-cyanobenzoic acid yield
As seen from Table 4,3-chloromethylbenzene nitrile and hydrogen peroxide consumption are the best with the 1:2 mol ratio.
Embodiment 22-26: with embodiment 1, different is ethanol consumption difference.
In oxidising process, keep 200 kilograms of 3-chloromethylbenzene nitriles, 300 kilogram of 30% hydrogen peroxide, 0.4 kilogram of vanadylic sulfate of catalyzer and 2.0 kilograms of sodium wolframate, 1 kilogram of benzyl triethylammonium chloride salt phase-transfer catalyst constant, under same reaction conditions, by changing 3-chloromethylbenzene nitrile and alcoholic acid proportioning, investigate of the influence of ethanol consumption to oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, the yield that calculates the 3-cyanobenzoic acid sees Table 5.
Table 5 solvent load is to the influence of 3-cyanobenzoic acid yield
As seen from Table 5,3-chloromethylbenzene nitrile and alcoholic acid mass ratio are best with 1:3-4.
Embodiment 27-31: with embodiment 1, different is the catalyst levels difference.
In oxidising process, keep 200 kilograms of 3-chloromethylbenzene nitriles, 600 kilograms of ethanol, 300 kilogram of 30% hydrogen peroxide and 1 kilogram of benzyl triethylammonium chloride salt phase-transfer catalyst constant, under identical reaction conditions, change the consumption (massfraction of catalyst sulfuric acid vanadyl and sodium wolframate, in 3-chloromethylbenzene nitrile), investigate the influence of catalyst levels to oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, the yield that calculates the 3-cyanobenzoic acid sees Table 6.
Table 6 catalyst levels is to the influence of 3-cyanobenzoic acid yield
As seen from Table 6, the mass ratio of catalyst sulfuric acid vanadyl and sodium wolframate the best is the 1.2-1.5% of 3-chloromethylbenzene nitrile.
Embodiment 32-36: with embodiment 1, different is the consumption difference of phase-transfer catalyst.
In oxidising process, keep 200 kilograms of 3-chloromethylbenzene nitriles, 600 kilograms of ethanol, 300 kilogram of 30% hydrogen peroxide, 0.4 kilogram of vanadylic sulfate of catalyzer and 2.0 kilograms of sodium wolframates, under same reaction conditions, change the consumption (massfraction of benzyl triethylammonium chloride salt, in 3-chloromethylbenzene nitrile), investigate of the influence of phase-transfer catalyst consumption to oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, the yield that calculates the 3-cyanobenzoic acid sees Table 7.
Table 7 phase-transfer catalyst consumption is to the influence of 3-cyanobenzoic acid yield
As seen from Table 7, the consumption of benzyl triethylammonium chloride salt phase-transfer catalyst the best is the 0.3-0.5% of 3-chloromethylbenzene nitrile quality.
Embodiment 37-41: with embodiment 1, different is the temperature of reaction difference.
In oxidising process, keep 200 kilograms of 3-chloromethylbenzene nitriles, 600 kilograms of ethanol, 300 kilogram of 30% hydrogen peroxide, 0.4 kilogram of vanadylic sulfate of catalyzer and 2.0 kilograms of sodium wolframate, 1 kilogram of benzyl triethylammonium chloride salt phase-transfer catalyst constant, under same reaction conditions, change temperature of reaction, investigate the influence of temperature oxidizing reaction.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, the yield that calculates the 3-cyanobenzoic acid sees Table 8.
Table 8 temperature of reaction is to the influence of 3-cyanobenzoic acid yield
As seen from Table 8, the second step optimal reaction temperature is 45 ℃.
Embodiment 42-46: with embodiment 1, different is the massfraction ratio difference of catalyst sulfuric acid vanadyl, sodium wolframate.
In oxidising process, keep 200 kilograms of 3-chloromethylbenzene nitriles, 600 kilograms of ethanol, 300 kilogram of 30% hydrogen peroxide, 2.4 kilograms and 1 kilogram benzyl triethylammonium chloride salt phase-transfer catalyst of catalyzer (vanadylic sulfate, sodium wolframate) total amount, 45 ℃ of temperature of reaction are constant, under identical reaction conditions, change the vanadylic sulfate in the catalyzer, the massfraction ratio of sodium wolframate, and investigate the influence of the massfraction comparison oxidizing reaction of catalyst sulfuric acid vanadyl, sodium wolframate.According to the 3-cyanobenzoic acid content of liquid chromatographic detection, the yield that calculates the 3-cyanobenzoic acid sees Table 9.
The influence 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)
1.3-the production method of cyanobenzoic acid is characterized in that reaction in two steps:
The first step, the 3-methylbenzene nitrile that adds 800 liters in 1000 liters of enamel reaction stills, be heated to 25-160 ℃, with pump feed liquid is squeezed into the packing tower top continuously, spray downwards with 5-40 liter/minute flow velocity, simultaneously upwards feed 310 kilograms of chlorine equably from the packing tower bottom, form 3-methylbenzene nitrile and chlorine inverse motion and carry out chlorination reaction with 5-40 liter/minute flow velocity; Gas phase is cooled off through chip enamel condenser, gas-liquid separator separates, and liquid return is in enamel reaction still; Hydrogenchloride, chlorine gas enter the emptying after water, alkali absorb of tail gas tourie; After reaction is finished, change feed liquid over to the enamel crystallization kettle, be cooled to 5 ℃, suction filtration, filter cake are 3-chloromethylbenzene nitrile;
Second step added 200 kilograms of 3-chloromethylbenzene nitriles, 100-800 kilogram ethanol, 1-3 kilogram catalyzer and 0.2-1 kilogram benzyl triethylammonium chloride salt phase-transfer catalyst in 2000 liters of enamel reaction stills, stirred and heated up; Keep 30-50 ℃ of temperature of reaction, in reactor, slowly drip 150-450 kilogram 30% hydrogen peroxide.Dropwise, be incubated 6 hours, oxidizing reaction generates the 3-cyanobenzoic acid, continues to be heated to 100 ℃, distills out ethanol.Be cooled to room temperature, filter, filter cake washing twice, behind ethyl alcohol recrystallization, oven dry obtains 3-cyanobenzoic acid white powder;
Described catalyzer is vanadylic sulfate and sodium wolframate, and mass ratio is 1:10-10:1; Catalyst consumption is the 0.5-1.5% of 3-chloromethylbenzene nitrile quality;
The mol ratio of described 3-chloromethylbenzene nitrile and hydrogen peroxide is 1:1-3, and the consumption of benzyl triethylammonium chloride salt phase-transfer catalyst is the 0.1-0.5% of 3-chloromethylbenzene nitrile quality, and oxidizing reaction 3-chloromethylbenzene nitrile and alcoholic acid mass ratio are 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 the first step squeezes into the packing tower top with pump continuously with feed liquid, sprays downwards with 15-20 liter/minute flow velocity.
4. the production method of 3-cyanobenzoic acid according to claim 1 is characterized in that adding in 1000 liters of enamel reaction stills 800 liters 3-methylbenzene nitrile, is heated to 150-160 ℃.
5. the production method of 3-cyanobenzoic acid according to claim 1 is characterized in that keeping 45 ℃ of temperature of reaction, slowly drips hydrogen peroxide in reactor.
6. the production method of 3-cyanobenzoic acid according to claim 1 is characterized in that the second step catalyst consumption is the 1.2-1.5% of 3-chloromethylbenzene nitrile quality; The mol ratio of 3-chloromethylbenzene nitrile and hydrogen peroxide is 1:2, and the consumption of benzyl triethylammonium chloride salt phase-transfer catalyst is the 0.3-0.5% of 3-chloromethylbenzene nitrile quality, and oxidizing reaction 3-chloromethylbenzene nitrile and alcoholic acid mass ratio are 1:3-4.
7. the production method of 3-cyanobenzoic acid according to claim 1 is characterized in that the mass ratio of the second step catalyst sulfuric acid vanadyl and sodium wolframate is 1:5.
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| CN107556214A (en) * | 2017-09-15 | 2018-01-09 | 大连奇凯医药科技有限公司 | A kind of preparation method of paracyanobenzoic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556214A (en) * | 2017-09-15 | 2018-01-09 | 大连奇凯医药科技有限公司 | A kind of preparation method of paracyanobenzoic acid |
| CN107556214B (en) * | 2017-09-15 | 2019-08-06 | 大连奇凯医药科技有限公司 | A kind of preparation method of paracyanobenzoic acid |
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