CN116396215A - Preparation method for hydrolyzing cyano compound into carboxyl compound - Google Patents
Preparation method for hydrolyzing cyano compound into carboxyl compound Download PDFInfo
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- CN116396215A CN116396215A CN202310310714.1A CN202310310714A CN116396215A CN 116396215 A CN116396215 A CN 116396215A CN 202310310714 A CN202310310714 A CN 202310310714A CN 116396215 A CN116396215 A CN 116396215A
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- -1 cyano compound Chemical class 0.000 title claims abstract description 116
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000007864 aqueous solution Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 60
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 238000010791 quenching Methods 0.000 claims abstract description 16
- 230000000171 quenching effect Effects 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000010413 mother solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 28
- 239000012452 mother liquor Substances 0.000 claims description 14
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 20
- 150000003839 salts Chemical class 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 17
- 238000000967 suction filtration Methods 0.000 description 13
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 12
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 7
- DLOOKZXVYJHDIY-UHFFFAOYSA-N 2,3,4,5-tetrachloropyridine Chemical compound ClC1=CN=C(Cl)C(Cl)=C1Cl DLOOKZXVYJHDIY-UHFFFAOYSA-N 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- CQXZSEXZQVKCHW-UHFFFAOYSA-N 3,5-difluorobenzonitrile Chemical compound FC1=CC(F)=CC(C#N)=C1 CQXZSEXZQVKCHW-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IONYGGJUUJFXJK-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzoic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IONYGGJUUJFXJK-UHFFFAOYSA-N 0.000 description 3
- PUMKBBIQQGIUJU-UHFFFAOYSA-N 2,6-dichloro-3-phenylbenzoic acid Chemical compound OC(=O)C1=C(Cl)C=CC(C=2C=CC=CC=2)=C1Cl PUMKBBIQQGIUJU-UHFFFAOYSA-N 0.000 description 3
- GONAVIHGXFBTOZ-UHFFFAOYSA-N 3,5-difluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=CC(F)=C1 GONAVIHGXFBTOZ-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- INICGXSKJYKEIV-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzonitrile Chemical compound ClC1=C(Cl)C(Cl)=C(C#N)C(Cl)=C1Cl INICGXSKJYKEIV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention relates to the technical field of C07C229/00, in particular to a method for hydrolyzing a cyano compound into a carboxyl compound. A process for the preparation of a cyano compound by hydrolysis to a carboxyl compound comprising the steps of: s1, mixing a cyano compound with a mixed acid, and then carrying out a heating reaction to obtain a reaction solution; s2, performing reaction quenching by using water and a reaction solution, cooling, suction filtering and drying to obtain a carboxyl compound, and obtaining a filtering mother solution for later use; the mixed acid comprises aqueous solution of methylsulfonic acid and aqueous solution of concentrated sulfuric acid. By adopting the method for hydrolyzing the cyano compound into the carboxyl compound, the method avoids generating a large amount of waste water, waste acid and waste salt, and brings environmental protection pressure.
Description
Technical Field
The invention relates to the technical field of C07C229/00, in particular to a method for hydrolyzing a cyano compound into a carboxyl compound.
Background
The hydrolysis of cyano compounds to carboxy compounds is generally carried out by: hydrolysis of cyano groups to carboxyl groups under acidic conditions or basic conditions gives free carboxylic acids and ammonium salts, and carboxylic acid salts and ammonia under basic conditions. Because the consumption of acid or alkali is large, a large amount of waste water, waste acid and waste salt can be generated, and environmental protection pressure is brought. Therefore, how to reduce waste water and waste salts in the synthesis process is a problem that has been studied by those skilled in the art.
The Chinese patent with the patent application number of CN201711463244.3 discloses a method for carrying out cyano hydrolysis reaction by adopting a micro-channel reactor, wherein a compound containing cyano groups (-C.ident.N) in molecules is added into a solvent, alkaline substances are added, the micro-channel reactor system is used for carrying out hydrolysis reaction under the conditions of 0-150 ℃ and 0.1-10MPa, and the technical problem of excessive acid and alkali regulation after the reaction is finished is avoided by adopting the internal structure of the micro-channel reactor.
Therefore, the preparation method for hydrolyzing the cyano compound into the carboxyl compound without generating waste water, waste acid and waste salt is a main technical problem to be solved at present.
Disclosure of Invention
The invention aims to provide a method for hydrolyzing a cyano compound into a carboxyl compound, which has the advantages of simple process, no waste water, waste acid and waste salt, and low environmental protection pressure.
In order to solve the above problems, the present invention provides a method for preparing a carboxyl compound by hydrolyzing a cyano compound, comprising the steps of:
s1, mixing a cyano compound with a mixed acid, and then carrying out a heating reaction to obtain a reaction solution;
s2, performing reaction quenching by using water and a reaction solution, cooling, suction filtering and drying to obtain a carboxyl compound, and obtaining a filtering mother solution for later use;
the mixed acid comprises aqueous solution of methylsulfonic acid and aqueous solution of concentrated sulfuric acid.
The reaction principle is as follows:
wherein: r is phenyl or a derivative thereof, heterocyclic group or a derivative thereof, alkyl or a derivative thereof.
To solve the above problems, the cyano compounds employed in the present invention include, but are not limited to, one or more of 3,4,5, 6-tetrachloro-pyridine cyanide, 3, 5-difluorobenzonitrile, 2, 4-dichloro- [1, 1-biphenyl ] -3-carbonitrile, benzonitrile, 2,3,4,5, 6-pentachlorobenzonitrile.
Preferably, in the step S1, an aqueous solution of methanesulfonic acid and an aqueous solution of concentrated sulfuric acid are sequentially added dropwise to water, and the mixture is sufficiently stirred to prepare a mixed acid aqueous solution with a mass concentration of 65-95%.
Further, the preparation temperature of the mixed acid in the step S1 is 25-30 ℃, and the mass content of the mixed acid is 88-92%.
Preferably, the mass concentration of the aqueous solution of the methylsulfonic acid and the aqueous solution of the concentrated sulfuric acid is 95-99%, and the mass ratio of the aqueous solution of the methylsulfonic acid to the aqueous solution of the concentrated sulfuric acid is (1-20): 1-20.
Preferably, the mass concentration of the aqueous solution of the methylsulfonic acid and the concentrated aqueous solution of the sulfuric acid is 98%.
Preferably, the mass ratio of the aqueous solution of methanesulfonic acid to the aqueous solution of concentrated sulfuric acid is (3-6): 1.
Preferably, in the step S1, a cyano compound is added into a mixed acid at the temperature of 0-100 ℃, after the addition is finished, the temperature is slowly raised to 60-120 ℃ for reaction for 1-20 hours, the content of intermediate amide is less than or equal to 0.5% and is qualified, and the molar ratio of the cyano compound to the mixed acid is (1-50): 1-10.
Further, the cyano compound is added into the mixed acid, after the addition is finished, the temperature is slowly raised to 95-105 ℃ for reaction for 10-12 hours, and the molar ratio of the cyano compound to the mixed acid is 1 (1-1.03).
Preferably, in the step S2, water at 25-100 ℃ is added into the reaction liquid at 60-120 ℃ to obtain a feed liquid after the completion of the dripping, the feed liquid is cooled to 0-25 ℃ and subjected to suction filtration to obtain a wet material, and the wet material is dried for 1-8 hours under the conditions that the vacuum degree is minus 0.01-0.3 MPa and the temperature is 100-120 ℃ to obtain the carboxyl compound.
Preferably, in the step S2, the reaction liquid at 60-120 ℃ is dripped into water at 25-100 ℃ to obtain feed liquid after dripping, the feed liquid is cooled to 0-25 ℃ and subjected to suction filtration to obtain wet material, and the wet material is dried for 1-8 hours under the conditions that the vacuum degree is minus 0.01-minus 0.3MPa and the temperature is 100-120 ℃ to obtain the carboxyl compound.
Preferably, in the step S2, 95-100 ℃ water is dripped into 95-105 ℃ reaction liquid or 95-105 ℃ reaction liquid is dripped into 95-100 ℃ water, the material liquid is obtained after dripping, the material liquid is cooled to 0-5 ℃ and is subjected to suction filtration to obtain wet material, and the wet material is dried for 5-6 hours under the conditions that the vacuum degree is minus 0.05-minus 0.1MPa and the temperature is 115-120 ℃ to obtain the carboxyl compound.
In order to improve the purity of the obtained carboxyl compound, the inventor creatively finds out in experiments that the purity of the obtained carboxyl compound can be improved by adopting water drops at 95-100 ℃ to 95-105 ℃ to reaction liquid or adopting water drops at 95-105 ℃ to 95-100 ℃ to obtain feed liquid after the completion of the dropwise addition, cooling the feed liquid to 0-5 ℃ to carry out suction filtration to obtain wet material, and drying the wet material for 5-6 hours under the conditions of vacuum degree of minus 0.05-minus 0.1MPa and temperature of 115-120 ℃.
Preferably, the filtration mother liquor obtained in the step S2 is subjected to negative pressure distillation, dehydration and deacidification under the conditions that the distillation vacuum degree is 0-2000 Pa and the distillation temperature is 125-145 ℃ to obtain the recovered water and the recovered methylsulfonic acid.
Further, the filtration mother liquor obtained in the step S2 is subjected to negative pressure distillation, dehydration and deacidification under the conditions that the distillation vacuum degree is 200-300 Pa and the distillation temperature is 125-130 ℃ to obtain the recovered water and the recovered methylsulfonic acid.
Preferably, the obtained filtration mother liquor is used for recovering the methanesulfonic acid and the water in a negative pressure distillation mode, the methanesulfonic acid and the water are used for the next batch reaction, and the residue obtained by distillation is a byproduct of the ammonium bisulfate.
In order to reduce the generation of a large amount of wastewater, waste acid and waste salt, the inventor creatively discovers in experiments that the obtained recovered water and recovered methanesulfonic acid can be recycled by adopting the method of carrying out negative pressure distillation dehydration deacidification on the obtained filtration mother liquor under the conditions of 0-2000 Pa of distillation vacuum degree and 125-145 ℃ of distillation temperature, and the mass content of the obtained dry product of the ammonium bisulfate is more than or equal to 98%.
And recovering the methylsulfonic acid and the water from the obtained filtration mother liquor in a negative pressure distillation mode, wherein the recovered water jacket is used for quenching the next batch of reaction, the recovered methylsulfonic acid jacket is used for the next batch of reaction, and the residue of the distillation kettle is a dry product of the ammonium bisulfate, wherein the content of the ammonium bisulfate is more than or equal to 98 percent.
Advantageous effects
1. In the method for hydrolyzing the cyano compound into the carboxyl compound, the method has the advantages of no waste water, waste acid and waste salt, and low environmental protection pressure.
2. In the method for hydrolyzing the cyano compound into the carboxyl compound, the produced reclaimed water and the reclaimed methylsulfonic acid sleeve can be used for the next batch reaction, and the residue of the distillation still is the dry product of the ammonium bisulfate, and the content is more than or equal to 98 percent.
3. By adopting the method for hydrolyzing the cyano compound into the carboxyl compound, the method avoids generating a large amount of waste water, waste acid and waste salt, and brings environmental protection pressure.
4. By adopting the method for hydrolyzing the cyano compound into the carboxyl compound, the methylsulfonic acid can be recycled, and the use amount of sulfuric acid can be reduced.
5. The method for hydrolyzing the cyano compound into the carboxyl compound has the characteristics of simple process and operation.
Detailed Description
Example 1
The present example provides a process for the preparation of a cyano compound by hydrolysis to a carboxyl compound comprising the steps of:
s1, mixing a cyano compound with a mixed acid, and then carrying out a heating reaction to obtain a reaction solution;
s2, performing reaction quenching by using water and a reaction solution, cooling, suction filtering and drying to obtain a carboxyl compound, and obtaining a filtering mother solution for later use;
the mixed acid comprises aqueous solution of methylsulfonic acid and aqueous solution of concentrated sulfuric acid.
The cyano compound is 3,4,5, 6-tetrachloro-pyridine cyanogen.
The carboxyl compound is 3,4,5, 6-tetrachloropyridine acid.
In the step S1, a methylsulfonic acid aqueous solution with the mass concentration of 98% and a sulfuric acid aqueous solution with the mass concentration of 98% are sequentially dripped into water, and are fully stirred to prepare a mixed acid aqueous solution with the mass concentration of 90%.
The mass ratio of the aqueous solution of the methylsulfonic acid to the aqueous solution of the concentrated sulfuric acid is 3:1.
In the step S1, 3,4,5, 6-tetrachloropyridine cyanogen is added into prepared mixed acid at the temperature of 25-30 ℃, after the addition is finished, the temperature is slowly raised to 100 ℃, the reaction is carried out for 10 hours, the content of intermediate amide is less than or equal to 0.5 percent and is qualified, and the molar ratio of the 3,4,5, 6-tetrachloropyridine cyanogen to the mixed acid is 1:1.
In the step S2, a reaction liquid at 100 ℃ is dripped into 98 ℃ water, wherein the mass ratio of the reaction liquid to the water is 2:1, the dripping time is 2 hours, the feed liquid is obtained after the dripping is finished, the internal temperature of the feed liquid is 130 ℃, the feed liquid is cooled to 5 ℃ at the moment, the suction filtration is carried out to obtain wet material, and the wet material is dried for 6 hours under the conditions that the vacuum degree is minus 0.1MPa and the temperature is 120 ℃ to obtain the 3,4,5, 6-tetrachloropyridine acid.
And (2) carrying out negative pressure distillation, dehydration and deacidification on the filtering mother liquor obtained in the step (S2) under the conditions of the distillation vacuum degree of 300Pa and the distillation temperature of 128 ℃ to obtain recovered water and recovered methylsulfonic acid.
Wherein the recovered water jacket is used for quenching the next batch of reaction, the recovered methylsulfonic acid jacket is used for the next batch of reaction, the residue of the distillation kettle is the dry product of the ammonium bisulfate, and the content is more than or equal to 98 percent.
The yield and purity of the 3,4,5, 6-tetrachloropyridine acid prepared in this example were measured to obtain 98.2% and 98.5% respectively.
The purity was determined by liquid chromatography.
Example 2
The present example provides a process for the preparation of a cyano compound by hydrolysis to a carboxyl compound comprising the steps of:
s1, mixing a cyano compound with a mixed acid, and then carrying out a heating reaction to obtain a reaction solution;
s2, performing reaction quenching by using water and a reaction solution, cooling, suction filtering and drying to obtain a carboxyl compound, and obtaining a filtering mother solution for later use;
the mixed acid comprises aqueous solution of methylsulfonic acid and aqueous solution of concentrated sulfuric acid.
The cyano compound is 3, 5-difluorobenzonitrile.
The carboxyl compound is 3, 5-difluorobenzoic acid.
In the step S1, a methylsulfonic acid aqueous solution with the mass concentration of 98% and a sulfuric acid aqueous solution with the mass concentration of 98% are adopted to be sequentially dripped into water, and the mixture is fully stirred to prepare a mixed acid aqueous solution with the mass concentration of 85%.
The mass ratio of the aqueous solution of the methylsulfonic acid to the aqueous solution of the concentrated sulfuric acid is 5:1.
In the step S1, 3, 5-difluorobenzonitrile is added into the prepared mixed acid at the temperature of 25-30 ℃, after the addition is finished, the temperature is slowly raised to 90 ℃, the reaction is carried out for 4 hours, the content of intermediate amide is less than or equal to 0.5 percent and is qualified, and the molar ratio of the 3, 5-difluorobenzonitrile to the mixed acid is 1:1.01.
And in the step S2, the reaction liquid at 100 ℃ is dripped into water at 60 ℃, wherein the mass ratio of the reaction liquid to the water is 3:2, the dripping time is 3h, the feed liquid is obtained after the dripping, the internal temperature of the feed liquid is 105 ℃, the temperature of the feed liquid is reduced to 25 ℃ at the moment, the wet material is obtained by suction filtration, and the wet material is dried for 5h under the conditions that the vacuum degree is-0.1 MPa and the temperature is 110 ℃, so as to obtain the 3, 5-difluorobenzoic acid.
And (2) carrying out negative pressure distillation, dehydration and deacidification on the filtering mother liquor obtained in the step (S2) under the conditions of the distillation vacuum degree of 600Pa and the distillation temperature of 132 ℃ to obtain recovered water and recovered methylsulfonic acid.
Wherein the recovered water jacket is used for quenching the next batch of reaction, the recovered methylsulfonic acid jacket is used for the next batch of reaction, the residue of the distillation kettle is the dry product of the ammonium bisulfate, and the content is more than or equal to 98 percent.
The yield and purity of the 3, 5-difluorobenzoic acid prepared in this example were determined to be 98.5% and 98.8%, respectively.
The purity was determined by liquid chromatography.
Example 3
The present example provides a process for the preparation of a cyano compound by hydrolysis to a carboxyl compound comprising the steps of:
s1, mixing a cyano compound with a mixed acid, and then carrying out a heating reaction to obtain a reaction solution;
s2, performing reaction quenching by using water and a reaction solution, cooling, suction filtering and drying to obtain a carboxyl compound, and obtaining a filtering mother solution for later use;
the mixed acid comprises aqueous solution of methylsulfonic acid and aqueous solution of concentrated sulfuric acid.
The cyano compound is 2, 4-dichloro- [1, 1-biphenyl ] -3-carbonitrile.
The carboxyl compound is 2, 4-dichloro- [1, 1-biphenyl ] -3-formic acid.
In the step S1, a methylsulfonic acid aqueous solution with the mass concentration of 98% and a sulfuric acid aqueous solution with the mass concentration of 98% are adopted to be sequentially dripped into water, and the mixture is fully stirred to prepare a mixed acid aqueous solution with the mass concentration of 80%.
The mass ratio of the aqueous solution of the methylsulfonic acid to the aqueous solution of the concentrated sulfuric acid is 5:1.
In the step S1, 2, 4-dichloro- [1, 1-biphenyl ] -3-carbonitrile is added into the prepared mixed acid at the temperature of 25-30 ℃, after the addition is finished, the temperature is slowly raised to 90 ℃, the reaction is carried out for 4 hours, the content of intermediate amide is less than or equal to 0.5 percent and is qualified, and the molar ratio of the 2, 4-dichloro- [1, 1-biphenyl ] -3-carbonitrile to the mixed acid is 1:1.01.
In the step S2, a reaction liquid at 100 ℃ is dripped into water at 60 ℃, wherein the mass ratio of the reaction liquid to the water is 3:1, the dripping time is 2 hours, the feed liquid is obtained after the dripping, the internal temperature of the feed liquid is 105 ℃, the temperature of the feed liquid is reduced to 25 ℃ at the moment, the wet material is obtained through suction filtration, and the wet material is dried for 5 hours under the conditions that the vacuum degree is minus 0.1MPa and the temperature is 110 ℃, so as to obtain the 2, 4-dichloro- [1, 1-biphenyl ] -3-formic acid.
And (2) carrying out negative pressure distillation, dehydration and deacidification on the filtering mother liquor obtained in the step (S2) under the conditions of the distillation vacuum degree of 600Pa and the distillation temperature of 132 ℃ to obtain recovered water and recovered methylsulfonic acid.
Wherein the recovered water jacket is used for quenching the next batch of reaction, the recovered methylsulfonic acid jacket is used for the next batch of reaction, the residue of the distillation kettle is the dry product of the ammonium bisulfate, and the content is more than or equal to 98 percent.
The yield and purity of 2, 4-dichloro- [1, 1-biphenyl ] -3-carboxylic acid prepared in this example were measured to obtain 98.6 and 99.2% respectively.
The purity was determined by liquid chromatography.
Example 4
The present example provides a process for the preparation of a cyano compound by hydrolysis to a carboxyl compound comprising the steps of:
s1, mixing a cyano compound with a mixed acid, and then carrying out a heating reaction to obtain a reaction solution;
s2, performing reaction quenching by using water and a reaction solution, cooling, suction filtering and drying to obtain a carboxyl compound, and obtaining a filtering mother solution for later use;
the mixed acid comprises aqueous solution of methylsulfonic acid and aqueous solution of concentrated sulfuric acid.
The cyano compound is benzonitrile.
The carboxyl compound is benzoic acid.
In the step S1, a methylsulfonic acid aqueous solution with the mass concentration of 98% and a sulfuric acid aqueous solution with the mass concentration of 98% are adopted to be sequentially dripped into water, and the mixture is fully stirred to prepare a mixed acid aqueous solution with the mass concentration of 75%.
The mass ratio of the aqueous solution of the methylsulfonic acid to the aqueous solution of the concentrated sulfuric acid is 4:1.
In the step S1, benzonitrile is added into the prepared mixed acid at the temperature of 25-30 ℃, after the addition is finished, the temperature is slowly raised to 95 ℃, the reaction is carried out for 5 hours, the content of intermediate amide is less than or equal to 0.5 percent, and the molar ratio of the benzonitrile to the mixed acid is 1:1.02.
In the step S2, a reaction liquid at 100 ℃ is dripped into water at 80 ℃, wherein the mass ratio of the reaction liquid to the water is 4:1, the dripping time is 4 hours, the feed liquid is obtained after the dripping, the internal temperature of the feed liquid is 115 ℃, the feed liquid is cooled to 25 ℃ at the moment, the wet material is obtained through suction filtration, and the wet material is dried for 4 hours under the conditions that the vacuum degree is-0.1 MPa and the temperature is 115 ℃, so that the benzoic acid is obtained.
And (2) carrying out negative pressure distillation, dehydration and deacidification on the filtering mother liquor obtained in the step (S2) under the conditions that the distillation vacuum degree is 800Pa and the distillation temperature is 136 ℃ to obtain recovered water and recovered methylsulfonic acid.
Wherein the recovered water jacket is used for quenching the next batch of reaction, the recovered methylsulfonic acid jacket is used for the next batch of reaction, the residue of the distillation kettle is the dry product of the ammonium bisulfate, and the content is more than or equal to 98 percent.
By measuring the yield and purity of benzoic acid obtained in this example, yields and purities of 98.5% and 99.4%, respectively, were obtained
The purity was determined by liquid chromatography.
Example 5
The present example provides a process for the preparation of a cyano compound by hydrolysis to a carboxyl compound comprising the steps of:
s1, mixing a cyano compound with a mixed acid, and then carrying out a heating reaction to obtain a reaction solution;
s2, performing reaction quenching by using water and a reaction solution, cooling, suction filtering and drying to obtain a carboxyl compound, and obtaining a filtering mother solution for later use;
the mixed acid comprises aqueous solution of methylsulfonic acid and aqueous solution of concentrated sulfuric acid.
The cyano compound is 2,3,4,5, 6-pentachloronitrile.
The carboxyl compound is 2,3,4,5, 6-pentachlorobenzoic acid.
In the step S1, a methylsulfonic acid aqueous solution with the mass concentration of 98% and a sulfuric acid aqueous solution with the mass concentration of 98% are adopted to be sequentially dripped into water, and the mixture is fully stirred to prepare a mixed acid aqueous solution with the mass concentration of 85%.
The mass ratio of the aqueous solution of the methylsulfonic acid to the aqueous solution of the concentrated sulfuric acid is 6:1.
In the step S1, 2,3,4,5, 6-pentachloronitrile is added into the prepared mixed acid at the temperature of 25-30 ℃, after the addition is finished, the temperature is slowly raised to 95 ℃, the reaction is carried out for 5 hours, the content of intermediate amide is less than or equal to 0.5 percent, and the molar ratio of the 2,3,4,5, 6-pentachloronitrile to the mixed acid is 1:1.
In the step S2, a reaction liquid at 100 ℃ is dripped into water at 100 ℃, wherein the mass ratio of the reaction liquid to the water is 3:1, the dripping time is 2 hours, the feed liquid is obtained after the dripping, the internal temperature of the feed liquid is 130 ℃, the feed liquid is cooled to 25 ℃ at the moment, the wet material is obtained through suction filtration, and the wet material is dried for 5 hours under the conditions that the vacuum degree is minus 0.1MPa and the temperature is 120 ℃, so that the 2,3,4,5, 6-pentachlorobenzoic acid is obtained.
And (2) carrying out negative pressure distillation, dehydration and deacidification on the filtering mother liquor obtained in the step (S2) under the conditions that the distillation vacuum degree is 800Pa and the distillation temperature is 136 ℃ to obtain recovered water and recovered methylsulfonic acid.
Wherein the recovered water jacket is used for quenching the next batch of reaction, the recovered methylsulfonic acid jacket is used for the next batch of reaction, the residue of the distillation kettle is the dry product of the ammonium bisulfate, and the content is more than or equal to 98 percent.
The yield and purity of 2,3,4,5, 6-pentachlorobenzoic acid obtained in this example were measured to obtain 98.6% and 99.8%, respectively.
The purity was determined by liquid chromatography.
Comparative example 1
The present example provides a process for the preparation of a cyano compound by hydrolysis to a carboxyl compound comprising the steps of:
s1, mixing a cyano compound with 90% sulfuric acid, and then carrying out a heating reaction to obtain a reaction solution;
s2, performing reaction quenching by using water and a reaction solution, and performing cooling, suction filtration, washing, suction filtration and drying to obtain a carboxyl compound, wherein the obtained quenching filtration mother solution and the washing filtration mother solution are subjected to waste acid treatment;
the cyano compound is 3,4,5, 6-tetrachloro-pyridine cyanogen.
The carboxyl compound is 3,4,5, 6-tetrachloropyridine acid.
In the step S1, a sulfuric acid aqueous solution with the mass concentration of 98% is dropwise added into water, and the mixture is fully stirred to prepare a sulfuric acid aqueous solution with the mass concentration of 90%.
In the step S1, 3,4,5, 6-tetrachloropyridine cyanogen is added into prepared 90% sulfuric acid at the temperature of 25-30 ℃, after the addition is finished, the temperature is slowly raised to 105 ℃ for reaction for 12 hours, the content of intermediate amide is less than or equal to 0.5%, and the molar ratio of the 3,4,5, 6-tetrachloropyridine cyanogen to the sulfuric acid is 1:8.
In the step S2, a reaction liquid at 100 ℃ is dripped into 98 ℃ water, wherein the mass ratio of the reaction liquid to the water is 2:1, the dripping time is 2 hours, the feed liquid is obtained after the dripping, the internal temperature of the feed liquid is 128 ℃, the feed liquid is cooled to 5 ℃ at the moment, the wet material is obtained through suction filtration, the wet material is washed twice by water, and the dosage of single washing water is 50% of that of 90% sulfuric acid. And (3) carrying out suction filtration to obtain wet material, and drying the wet material for 8 hours under the condition that the vacuum degree is-0.1 MPa and the temperature is 120 ℃ to obtain the 3,4,5, 6-tetrachloropyridine acid.
And (2) performing waste acid treatment on the filtering mother liquor obtained in the step (S2), wherein the amount of generated waste acid is 4 times of the product yield.
And (2) performing waste acid treatment on the washing and filtering mother liquor obtained in the step (S2), wherein the amount of generated waste acid is 4 times of the product yield.
The yield and purity of 3,4,5, 6-tetrachloropyridine acid prepared in this example were measured to obtain 93.5% and 96.4% respectively.
The purity was determined by liquid chromatography.
Claims (10)
1. A process for the preparation of a cyano compound by hydrolysis to a carboxy compound, comprising the steps of:
s1, mixing a cyano compound with a mixed acid, and then carrying out a heating reaction to obtain a reaction solution;
s2, performing reaction quenching by using water and a reaction solution, cooling, suction filtering and drying to obtain a carboxyl compound, and obtaining a filtering mother solution for later use;
the mixed acid comprises aqueous solution of methylsulfonic acid and aqueous solution of concentrated sulfuric acid.
2. The method for preparing a carboxyl compound by hydrolyzing a cyano compound according to claim 1, wherein the step S1 is prepared by adding aqueous solution of methanesulfonic acid and aqueous solution of concentrated sulfuric acid to water dropwise in this order, and stirring the mixture sufficiently to prepare a mixed acid aqueous solution having a mass concentration of 65 to 95%.
3. The method for producing a carboxyl compound by hydrolyzing a cyano compound according to claim 2, wherein the mass concentration of the aqueous solution of methylsulfonic acid and the aqueous solution of concentrated sulfuric acid is 95 to 99%, and the mass ratio of the aqueous solution of methylsulfonic acid to the aqueous solution of concentrated sulfuric acid is (1 to 20): 1 to 20.
4. The method for producing a carboxyl compound by hydrolysis of a cyano compound according to claim 3, wherein the mass ratio of the aqueous solution of methylsulfonic acid to the aqueous solution of concentrated sulfuric acid is (3-6): 1.
5. The process for producing a carboxyl compound by hydrolyzing a cyano compound according to any one of claims 1 to 4, wherein the cyano compound is added to a mixed acid at 0 to 100℃in S1, and after the addition, the reaction is carried out by slowly heating to 60 to 120℃for 1 to 20 hours, wherein the molar ratio of the cyano compound to the mixed acid is (1 to 50): 1 to 10.
6. The process for producing a carboxyl compound by hydrolysis of a cyano compound as claimed in claim 5, wherein the cyano compound is added to a mixed acid, and after the addition, the reaction is carried out by slowly heating to 95 to 105℃for 10 to 12 hours, wherein the molar ratio of the cyano compound to the mixed acid is 1 (1 to 1.03).
7. The method for preparing the carboxyl compound by hydrolyzing the cyano compound according to claim 1, wherein in the step S2, water at 25-100 ℃ is added into a reaction solution at 60-120 ℃ or water at 60-120 ℃ is added into water at 25-100 ℃ in a dropwise manner, a feed liquid is obtained after the completion of the dropwise addition, the feed liquid is cooled to 0-25 ℃ and filtered to obtain a wet material, and the wet material is dried for 1-8 hours under the conditions that the vacuum degree is minus 0.01-minus 0.3MPa and the temperature is 100-120 ℃ to obtain the carboxyl compound.
8. The method for preparing a carboxyl compound by hydrolyzing a cyano compound according to claim 7, wherein in the step S2, 95-100 ℃ water is dripped into 95-105 ℃ reaction solution or 95-105 ℃ reaction solution is dripped into 95-100 ℃ water, a feed liquid is obtained after the dripping is finished, the feed liquid is cooled to 0-5 ℃ and filtered to obtain a wet material, and the wet material is dried for 5-6 hours under the conditions that the vacuum degree is minus 0.05-minus 0.1MPa and the temperature is 115-120 ℃ to obtain the carboxyl compound.
9. The process for producing a carboxyl compound by hydrolysis of a cyano compound as claimed in claim 1, wherein the filtration mother liquor obtained in S2 is subjected to negative pressure distillation at a distillation vacuum degree of 0 to 2000Pa and a distillation temperature of 125 to 145 ℃ to obtain recovered water and recovered methanesulfonic acid.
10. The process for producing a carboxyl compound by hydrolysis of a cyano compound as claimed in claim 9, wherein the filtration mother liquor obtained in S2 is subjected to negative pressure distillation at a distillation vacuum degree of 200 to 300Pa and a distillation temperature of 125 to 130 ℃ to obtain recovered water and recovered methanesulfonic acid.
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