CN107556214A - A kind of preparation method of paracyanobenzoic acid - Google Patents
A kind of preparation method of paracyanobenzoic acid Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of paracyanobenzoic acid.This method is using 4 chloromethyl cyanophenyls as raw material, prepares the cyano group phenmethylol of intermediate product 4 by hydrolysis in the basic conditions, adds phase transfer catalyst, activator, oxidant and catalyst, the 15h of oxidation reaction 4 is carried out at 50 100 DEG C, obtains finished product.The present invention uses specific phase transfer catalyst and catalyst in the oxidation reaction, and to add salt as the activator of phase transfer catalyst, the oxidation time of the cyano group phenmethylol of intermediate product 4 is foreshortened to 6 10 hours, the yield of the chloromethyl cyanophenyl of finished product 4 reaches more than 86.4%, and purity reaches more than 98.6%.This method is safe and pollution-free, easy to operate, and purity is high, suitable for the new method of Green Chemistry application.
Description
Technical field
The present invention relates to a kind of preparation method of paracyanobenzoic acid, belong to chemical production technology field.
Background technology
Paracyanobenzoic acid is a kind of lobate crystallization of white, molecular formula C8H5NO2, molecular weight 147.13, fusing point is
It is 217-222 DEG C, miscible with water section, it is dissolved in alcohol, ether, hot water and glacial acetic acid.Terephthalic acid (TPA) can be generated with thermokalite.To cyano group benzene
Intermediate of the formic acid as para-amiunomethylbenzoic acid, for organic synthesis, liquid crystal polymer synthesis, medicine intermediate etc..
At present, the production method of paracyanobenzoic acid mainly has following several：
Firstth, using 4- chloromethyls cyanophenyl as raw material, concentrated nitric acid is oxidant, synthesizes paracyanobenzoic acid, the synthetic route
Although simple, accessory substance is excessive, seriously polluted, and the three wastes are not disposable, is not suitable for industrial applications.
Secondth, as raw material, to synthesize paracyanobenzoic acid, but in this synthetic method, make to methanol yl benzoic acid
With formic acid, formic acid corrosivity is strong, is unsuitable for operation.
3rd, employ ammonia oxidation and prepare synthesis paracyanobenzoic acid, but there is the problem of maximum for this method
It is that very high pressure and temperature is needed in course of reaction, industrial equipment requirement can be increased, is not suitable for industrialized production.
In summary, it is excessive to there is course of reaction accessory substance in traditional synthetic method, strong and high using reagent corrosivity
The restrictive conditions such as warm high pressure, it is seen that existing method can not meet the needs of modern production paracyanobenzoic acid.
The content of the invention
In view of above-mentioned prior art is in the problem present in paracyanobenzoic acid for preparing, the present invention provides a kind of new to cyanogen
The preparation method of yl benzoic acid, this method energy consumption is relatively low, side reaction is few, reactions steps are simple, the three wastes caused by reaction are easily located
Reason, it is mutually more green than existing methods.
Technical scheme is as follows：
A kind of preparation method of paracyanobenzoic acid, comprises the following steps：
(1) 4- chloromethyl cyanophenyls are added into the aqueous solution of inorganic base, reaction is hydrolyzed at 50-100 DEG C；
(2) hydrolysis liquid is extracted with organic solvent, collects extract, is removed organic solvent, is obtained intermediate product I；
(3) phase transfer catalyst, activator, oxidant and catalyst are added in the intermediate product I that step (2) obtains,
4-15h is reacted at 50-100 DEG C, is filtered；
Wherein, in step (3), described phase transfer catalyst is methyl tricapryl ammonium chloride, methyl trioctylphosphine sulfuric acid
One or more in hydrogen ammonium, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate；Described activator is that the activator is chlorination
One kind in sodium, sodium sulphate, sodium dihydrogen phosphate, potassium chloride, sodium sulphate；Described catalyst is according to mass ratio 1-3:1 tungsten
The mixture of sour sodium dihydrate and vanadic sulfate.
In the above-mentioned technical solutions, the intermediate product I described in step (2) is 4- cyano group phenmethylols.
In above-mentioned all technical schemes, in step (1), described inorganic base is potassium carbonate, saleratus, hydroxide
One kind in potassium, sodium carbonate, sodium hydroxide, sodium acid carbonate, calcium hydroxide, ammonium carbonate, ammoniacal liquor.In step (1), 4- chloromethyls
In the presence of an inorganic base, 4 chlorine obtain intermediate product 4- cyano group phenmethylols by hydroxyl nucleophilic displacement of fluorine to cyanophenyl.The hydrolysis of step (1)
Reaction temperature is preferably 80-86 DEG C.
In above-mentioned all technical schemes, in step (1), the matter of inorganic base and water in the aqueous solution of described inorganic base
Amount is than being 1:10-30, preferential 1:15-17, the too low raw material of mass ratio is largely remaining, and the too high cyan-hydrolysis of mass ratio is benzoic acid.
In above-mentioned all technical schemes, in step (1), the mass ratio of described 4- chloromethyls cyanophenyl and inorganic base is
5:1-5:4。
In above-mentioned all technical schemes, in step (2), described organic solvent is petroleum ether, ethyl acetate, positive fourth
One kind in alcohol, hexamethylene, dichloromethane, chloroform, preferably dichloromethane.
In above-mentioned all technical schemes, in step (3), described intermediate product I, phase transfer catalyst, activator,
The mol ratio of oxidant and catalyst is 88-96:1-2:0.018-0.026:305-316:3.0-3.8.
In above-mentioned all technical schemes, in step (3), the reaction dissolvent of the reaction is water, the tert-butyl alcohol, ethanol,
One kind in toluene, glacial acetic acid, acetonitrile, preferably water.
In above-mentioned all technical schemes, in step (3), described oxidant is 10%-70% hydrogen peroxide, the tert-butyl group
One kind in hydrogen peroxide, sodium hypochlorite, preferably 10%-70% hydrogen peroxide, more preferably 30% hydrogen peroxide.
In above-mentioned all technical schemes, in step (3), after reacting liquid filtering, paracyanobenzoic acid crude product is obtained, uses stone
One kind in oily ether, ethyl acetate, n-butanol, hexamethylene, dichloromethane or chloroform recrystallizes to obtain paracyanobenzoic acid finished product.
The wherein described preferred dichloromethane of solvent for being used to recrystallize.
Reaction equation when preparing 4- cyanobenzoic acids using the method for the present invention is as follows, and wherein first step hydrolysis is to adopt
Exemplified by by the use of sodium acid carbonate as inorganic base, exemplified by second step oxidation reaction is using use hydrogen peroxide as oxidant, oxidation reaction exists
Carried out in the presence of phase transfer catalyst of the present invention, activator and catalyst：
Beneficial effects of the present invention：
(1) specific phase transfer catalyst and catalyst are used in the oxidation reaction, and to add salt as phase
The activator of transfer catalyst, it can effectively shorten the time required for reaction, improve product purity and yield.Using this
The method of invention, the oxidation time of intermediate product 4- cyano group phenmethylols foreshorten to 6-10 hours, and energy consumption of reaction is relatively low, eventually production
The yield of product 4- chloromethyl cyanophenyls reaches more than 86.4%, and purity reaches more than 98.6%.
(2) reactions steps are simple, are not related to the not easy-operating reaction condition such as high pressure-temperature.
(3) three wastes caused by reaction are easily processed, and it is more green to compare other method.
Embodiment
The invention will now be further described with reference to specific embodiments, advantages of the present invention and feature will be with description and
It is apparent.But embodiment is only exemplary, does not form any restrictions to the scope of the present invention.Those skilled in the art should
It should be appreciated that the details and form of technical solution of the present invention can be repaiied without departing from the spirit and scope of the invention
Change or replace, but these modifications and replacement are each fallen within protection scope of the present invention.In following embodiments, unless otherwise specified,
Used experimental method is that conventional method, material therefor, reagent etc. can be bought from biological or chemical company.
Embodiment 1
Potassium carbonate 138g, 4- chloromethyl cyanophenyl 151.5g and water 2300g are put into 3000mL four-hole bottles.It is heated to 80
DEG C, react 10 hours, HPLC detections are done in sampling, are confirmed that the hydrolysis of 4- chloromethyl cyanophenyls is complete, are added in hydrolysis liquid
Enter dichloromethane point extraction (each 800mL, extracting 3 times at normal temperatures), extract obtains 4- cyanogen through extractant is distilled off
Base phenmethylol 128g, purity reach 96-98%, yield：96.2%.
By 4- cyano group phenmethylol 128g, methyl trioctylphosphine ammonium hydrogen sulfate 6.2g, sodium tungstate dihydrate 4.6g, vanadic sulfate
4g, sodium chloride 4g, water 500g, it is put into four-hole bottle, oil bath heating, temperature is risen to 90 DEG C, 30% dioxygen is added dropwise into kettle
Water 400g.HPLC detections are carried out by sampling, when 4- cyano group phenmethylol disappears, reaction terminates, and the reaction time is 6h altogether, while hot mistake
Filter, obtains crude product 138g, purity 85%.Recrystallize with dichloromethane is added, obtains product 127g, product purity 98.6%,
Total recovery：86.4%.
Embodiment 2
Saleratus 10g, 4- chloromethyl cyanophenyl 15.1g and water 150g are added in 250mL four-hole bottles, is sufficiently stirred lower liter
High-temperature is reacted 10 hours, detected through HPLC to 80 DEG C, confirms that raw material hydrolysis is complete, and chloroform point extraction is added in reaction solution
Take and (each 100mL, extract 3 times at normal temperatures), extract obtains intermediate 4- cyano group phenmethylols and be total to through extractant is distilled off
12.6g is counted, purity reaches 93%-95%, yield 94.7%.
Input 4- cyano group phenmethylol 12.6g, methyl tricapryl ammonium chloride 0.62g, the water of sodium tungstate two in 500mL four-hole bottles
Compound 0.46g, sodium sulphate 0.4g, vanadic sulfate 0.4g, tert-butyl alcohol 50g, rise kettle temperature are slow with micro addition funnel to 80 DEG C
TBHP 200g is added dropwise, HPLC detections are carried out by sampling, when 4- cyano group phenmethylol disappears, reaction terminates, and amounts to
15h, crude product 13.3g is obtained, is recrystallized with n-butanol, obtain product 11.8g, purity 85.2%, yield 80.3%.
Embodiment 3
The water that potassium hydroxide 10g, 4- chloromethyl cyanophenyl 15.1g and water 120g carry out raw material is added in 250mL four-hole bottles
Solution reaction.Under mechanical stirring, it is heated to flowing back (82 DEG C), is detected by HPLC, it is known that raw material is complete when reacting 10h
Full response finishes.Petroleum ether point extraction (each 80mL, extracting 3 times at normal temperatures) is now added, extract extracts through being distilled off
Solvent is taken, obtains intermediate 4- cyano group phenmethylols, altogether 11.4g, purity reaches 88-92%, yield 85.7%.
In 250mL four-hole bottles, 4- cyano group phenmethylol 11.4g, tetrabutylammonium chloride 0.62g, sodium tungstate 0.46g are added,
Sodium sulphate 0.4g, vanadic sulfate 0.4g, sodium hypochlorite 60g, ethanol 50g, reaction temperature are increased to 78 DEG C, are carried out by sampling
HPLC is detected, and when 4- cyano group phenmethylol disappears, reaction terminates, altogether 10h, obtains crude product 13.1g, reduces temperature to room temperature, second
Acetoacetic ester recrystallizes, and stirring at normal temperature, filtering can obtain product 11.7g, purity 86.3%, yield 79.6%.
Comparative example 1
Calcium hydroxide 50g, 4- chloromethyl cyanophenyl 15.1g and water 200g are put into 250mL four-hole bottles.It is heated to 80-90
DEG C, react 10 hours, HPLC detections are done in sampling, are confirmed that the hydrolysis of 4- chloromethyl cyanophenyls is complete, are added in hydrolysis liquid
Enter hexamethylene extraction, (each 150mL, at normal temperatures extract 3 times) obtains 4- cyano group phenmethylol 9.8g, and purity is up to 78%, yield：
73.7%.
Input 4- cyano group phenmethylol 9.8g, methyl tricapryl ammonium chloride 0.62g, vanadic sulfate in 250mL four-hole bottles
0.4g, acetonitrile 50g, it is heated to flowing back (82 DEG C), dropwise addition 70% pair is now slowly added dropwise into four-hole bottle with micro addition funnel
Oxygen water 50g, drop finish, and HPLC detections are done in insulation reaction 17h, sampling, and when 4- cyano group phenmethylol disappears, reaction terminates, hexamethylene weight
Crystallization can obtain 5.2g products, purity 45.6%, yield：35.4%.
Comparative example 2
Saleratus 20g, 4- chloromethyl cyanophenyl 30.2g and water 300g are added in 500mL four-hole bottles, is sufficiently stirred lower liter
High-temperature is reacted 10 hours, detected through HPLC to 80 DEG C, confirms that raw material hydrolysis is complete, and chloroform point extraction is added in reaction solution
Take and (each 100mL, extract 3 times at normal temperatures), extract obtains intermediate 4- cyano group phenmethylols and be total to through extractant is distilled off
24.8g is counted, purity is up to 93%, yield 93.40%.
Input 4- cyano group phenmethylol 24.8g, methyl tricapryl ammonium chloride 1.24g, the water of sodium tungstate two in 500mL four-hole bottles
The tert-butyl group is slowly added dropwise with micro addition funnel to 80 DEG C in compound 0.92g, vanadic sulfate 0.8g, tert-butyl alcohol 100g, rise kettle temperature
Hydrogen peroxide 400g, HPLC detections are carried out by sampling, when 4- cyano group phenmethylol disappears, reaction terminates, and 15h, obtains and slightly produce altogether
Product 26.6g, is recrystallized with n-butanol, obtains product 15.8g, purity 45.2%, yield 53.82%.
Comparative example 3
Calcium hydroxide 50g, 4- chloromethyl cyanophenyl 15.1g and water 200g are put into 250mL four-hole bottles.It is heated to 80-90
DEG C, react 10 hours, HPLC detections are done in sampling, are confirmed that the hydrolysis of 4- chloromethyl cyanophenyls is complete, are added in hydrolysis liquid
Enter hexamethylene extraction, (each 150mL, at normal temperatures extract 3 times) obtains 4- cyano group phenmethylol 9.8g, and purity is up to 78%, yield：
73.7%.
Input 4- cyano group phenmethylol 9.8g, methyl tricapryl ammonium chloride 0.62g, vanadic sulfate in 250mL four-hole bottles
0.4g, sodium sulphate 0.4g, acetonitrile 50g, it is heated to flowing back (82 DEG C), is now slowly added dropwise with micro addition funnel into four-hole bottle
70% hydrogen peroxide 50g is added dropwise, drop finishes, and HPLC detections are done in insulation reaction 17h, sampling, when the disappearance of 4- cyano group phenmethylol, reaction knot
Beam, hexamethylene recrystallization can obtain 7.2g products, purity 45.6%, yield：49.15%.
Claims (9)
1. a kind of preparation method of paracyanobenzoic acid, comprises the following steps：
(1) 4- chloromethyl cyanophenyls are added into inorganic base aqueous solution, reaction is hydrolyzed at 50-100 DEG C；
(2) hydrolysis liquid is extracted with organic solvent, collects extract, is removed organic solvent, is obtained intermediate product I；
(3) phase transfer catalyst, activator, oxidant and catalyst are added in the intermediate product I that step (2) obtains, in 50-
4-15h is reacted at 100 DEG C, is filtered；
Wherein, in step (3), described phase transfer catalyst be methyl tricapryl ammonium chloride, methyl trioctylphosphine ammonium hydrogen sulfate,
One or more in tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate；Described activator is sodium chloride, sodium sulphate, di(2-ethylhexyl)phosphate
One kind in hydrogen sodium, potassium chloride, sodium sulphate；Described catalyst is according to mass ratio 1-3:1 sodium tungstate dihydrate and sulphur
The mixture of sour vanadyl.
2. preparation method according to claim 1, it is characterised in that in step (1), described inorganic base is carbonic acid
One kind in potassium, saleratus, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium acid carbonate, calcium hydroxide, ammonium carbonate, ammoniacal liquor.
3. preparation method according to claim 1, it is characterised in that in the aqueous solution of described inorganic base inorganic base with
The mass ratio of water is 1:10-30.
4. preparation method according to claim 1, it is characterised in that in step (1), described 4- chloromethyls cyanophenyl with
The mass ratio of inorganic base is 5:1-5:4.
5. preparation method according to claim 1, it is characterised in that in step (2), described organic solvent is oil
One kind in ether, ethyl acetate, n-butanol, hexamethylene, dichloromethane, chloroform.
6. preparation method according to claim 1, it is characterised in that in step (3), described intermediate product I, phase turn
Shifting catalyst, activator, the mol ratio of oxidant and catalyst are 88-96:1-2:0.018-0.026:305-316:3.0-
3.8。
7. preparation method according to claim 1, it is characterised in that in step (3), the reaction dissolvent of the reaction is
One kind in water, the tert-butyl alcohol, ethanol, toluene, glacial acetic acid, acetonitrile.
8. the preparation method described in as requested 1, it is characterised in that in step (3), described oxidant is 10%-70%
One kind in hydrogen peroxide, TBHP, sodium hypochlorite.
9. preparation method according to claim 1, it is characterised in that in step (3), after reacting liquid filtering, obtain to cyanogen
Yl benzoic acid crude product, recrystallize right with one kind in petroleum ether, ethyl acetate, n-butanol, hexamethylene, dichloromethane or chloroform
Cyanobenzoic acid finished product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574403A (en) * | 2020-06-11 | 2020-08-25 | 成家钢 | Preparation method of p-cyanobenzoic acid |
| CN112608227A (en) * | 2020-12-02 | 2021-04-06 | 广东石油化工学院 | Method for preparing isononanoic acid from isononanol through green oxidation |
| CN112679384A (en) * | 2021-01-13 | 2021-04-20 | 国药集团化学试剂有限公司 | Preparation method of p-cyanobenzoic acid |
| CN113307740A (en) * | 2021-05-27 | 2021-08-27 | 中瀚(齐河县)生物医药科技有限公司 | Preparation method of 2-amino-4-fluorobenzoic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214396A (en) * | 2013-04-10 | 2013-07-24 | 湖北工业大学 | Production method of 3-cyanobenzoic acid |
| CN105237317A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid |
-
2017
- 2017-09-15 CN CN201710834032.5A patent/CN107556214B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214396A (en) * | 2013-04-10 | 2013-07-24 | 湖北工业大学 | Production method of 3-cyanobenzoic acid |
| CN105237317A (en) * | 2015-10-28 | 2016-01-13 | 衢州群颖化学科技有限公司 | Combined production method for substituted benzaldehyde, substituted benzyl alcohol and substituted benzoic acid |
Non-Patent Citations (3)
| Title |
|---|
| CHARLOTTE WILES等: ""Clean and selective oxidation of aromatic alcohols using silica-supported Jones’ reagent in a pressure-driven flow reactor"", 《TETRAHEDRON LETTERS》 * |
| KAZUHIKO SATO等: ""Organic Solvent- and Halide-Free Oxidation of Alcohols with Aqueous Hydrogen Peroxide"", 《J. AM. CHEM. SOC.》 * |
| 严红燕等: ""过氧化氢催化氧化苯甲醇制苯甲酸"", 《化工科技》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574403A (en) * | 2020-06-11 | 2020-08-25 | 成家钢 | Preparation method of p-cyanobenzoic acid |
| CN112608227A (en) * | 2020-12-02 | 2021-04-06 | 广东石油化工学院 | Method for preparing isononanoic acid from isononanol through green oxidation |
| CN112679384A (en) * | 2021-01-13 | 2021-04-20 | 国药集团化学试剂有限公司 | Preparation method of p-cyanobenzoic acid |
| CN112679384B (en) * | 2021-01-13 | 2023-04-07 | 国药集团化学试剂有限公司 | Preparation method of p-cyanobenzoic acid |
| CN113307740A (en) * | 2021-05-27 | 2021-08-27 | 中瀚(齐河县)生物医药科技有限公司 | Preparation method of 2-amino-4-fluorobenzoic acid |
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