CN105906502A - Preparation method of 3,5-dichlorobenzoyl chloride - Google Patents
Preparation method of 3,5-dichlorobenzoyl chloride Download PDFInfo
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- CN105906502A CN105906502A CN201610282999.2A CN201610282999A CN105906502A CN 105906502 A CN105906502 A CN 105906502A CN 201610282999 A CN201610282999 A CN 201610282999A CN 105906502 A CN105906502 A CN 105906502A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
- C07C227/20—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters by hydrolysis of N-acylated amino-acids or derivatives thereof, e.g. hydrolysis of carbamates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
Abstract
The invention relates to a preparation method of 3,5-dichlorobenzoyl chloride, and belongs to the field of compound synthesis technology. The preparation method of 3,5-dichlorobenzoyl chloride comprises the following steps: (1) the first reaction: reacting anthranilic acid with acetic anhydride to prepare 2-acetamidobenzoic acid; (2) the second reaction: reacting 2-acetamidobenzoic acid with chlorine to prepare 3,5-dichloro-2-acetamidobenzoic acid; (3) the third reaction: reacting 3,5-dichloro-2-acetamidobenzoic acid with hydrochloric acid to prepare 3,5-dichloro-2-aminobenzoic acid; (4) the fourth reaction: reacting 3,5-dichloro-2-aminobenzoic acid with sodium nitrite, hydrochloric acid and isopropanol to prepare 3,5-dichloro-benzoic acid; (5) the fifth reaction: reacting 3,5-dichloro-benzoic acid with thionyl chloride to obtain the 3,5-dichlorobenzoyl chloride. The preparation method of 3,5-dichlorobenzoyl chloride has protected amino groups prior to chlorination, thereby effectively preventing oxidization of amino groups; and the yield of chlorination is over 95%.
Description
Technical field
The present invention relates to compou nd synthesis technical field, particularly relate to a kind of 3, the preparation method of 5-dichlorobenzoyl chloride.
Background technology
3,5-dichlorobenzoyl chlorides are a kind of important pesticide intermediates, and its molecular structure is as follows:
.3,5-dichlorobenzoyl chlorides are of many uses, and it can prepare different material by differential responses, are mainly used in pesticide producing, and medicine produces, DYE PRODUCTION etc..In pesticide producing, 3,5-dichlorobenzoyl chlorides can carry out benzoylation reaction with methionine and ether thereof under sodium hydroxide solution environment, it is thus achieved that derivant can promote plant growing, improve plant situation, or make insecticide.As medicine intermediate, the different derivants of 3,5-dichlorobenzoyl chlorides can treat various disease, it and tropine and the mixture reaction of hydrogen chloride, can prepare the class medicine for the headache treating people, and effect is the best, and pharmaceutical properties is stable, and has no side effect；3,5-dichlorobenzoyl chloride can also be used to prepare tri-benzoyl nitrine as balance vassopressin medicine；Form product with selenium reaction and be used for doing the photosensitizer of photo；Also can be used to prepare acetonyl benzamide；In recent years, it is also used to prepare purine derivative and is widely used in medical treatment, and the derivant that especially it and aminoacid reaction generate has bigger application development prospect.
Synthesis 3, the method for 5-dichlorobenzoyl chloride has multiple, such as hypochlorite partial oxidation 3,5-dichloro ethylbenzene, generates 3,5-dichlorobenzoic acid, then generation 3,5-dichlorobenzoyl chloride after chloride；And for example 5 one chlorine isophthalic diformazan phthalein chlorine (n) are at a temperature of 250 DEG C one 276 DEG C, under conditions of Pd1C2 or (pd/BaSQ, or Pd/lA:=0) make catalyst react 4 hours obtain 3,5-dichlorobenzoyl chloride.These two kinds of method severe reaction conditions, yield are relatively low, early have dropped out the synthetic method of main flow.At present both at home and abroad industrialized route with ortho-aminobenzoic acid be raw material direct chlorination, diazotising, chloride route relatively conventional.But ortho-aminobenzoic acid chlorination all uses direct chlorinated with chlorine method, because amino is oxidized to quinone in chlorination process, no matter institute selects which kind of solvent such as acetic acid, hydrochloric acid, dichloroethanes or DMF in this way, yield is the highest.
Summary of the invention
It is an object of the invention to, overcome existing preparation 3, the problem that yield existing for 5-dichlorobenzoyl chloride method is low, it is provided that a kind of 3, the novel processing step of 5-dichlorobenzoyl chloride；The method that the present invention provides, in preparation 3, effectively prevent the oxidation of amino during 5-dichlorobenzoyl chloride, total recovery is high.
Technical scheme
A kind of 3, the preparation method of 5-dichlorobenzoyl chloride, comprise the following steps:
(1) first reaction: ortho-aminobenzoic acid and acetic anhydride prepare 2-acetaminobenzoic acid；
(2) second reactions: 2-acetaminobenzoic acid and chlorine reaction prepare 3,5-bis-chloro-2-acetaminobenzoic acid；
(3) the 3rd reactions: 3,5-bis-chloro-2-acetaminobenzoic acid and hydrochloric acid reaction prepare 3,5-bis-chloro-2-amino benzoic Acid；
(4) the 4th reactions: 3,5-bis-chloro-2-amino benzoic Acid and sodium nitrite, hydrochloric acid, isopropanol reaction prepare 3,5-Dichloro-benzoic acid；
(5) the 5th reactions: 3,5-Dichloro-benzoic acid and thionyl chloride reaction, obtain 3,5-dichlorobenzoyl chloride.
Its course of reaction is as follows:
First reaction
Second reaction
3rd reaction
4th reaction
5th reaction
。
Above-mentioned preparation method,
Second reaction, with glacial acetic acid as solvent, the selectivity of this solvent is preferable, and reaction can be made to produce less by-product；Do not find the solvent that can substitute at present.It is preferred, therefore, that with glacial acetic acid as solvent.
4th reaction, the reaction not adding copper sulfate is relatively slow, and by-product is many；After employing copper sulfate, yield is high；It is preferred, therefore, that employing copper sulfate as catalyst.
Above-mentioned preparation method, follows the tracks of extent of reaction by liquid chromatographic detection；
First reaction: liquid chromatograph impurity peaks reaches less than 0.3%, stopped reaction；
Second reaction: liquid chromatograph 2-acetaminobenzoic acid does not turns peak and reaches less than 0.1%, stopped reaction；Within about 12 hours, react；
3rd reaction: liquid chromatograph 3,5-bis-chloro-2-acetaminobenzoic acid does not turns peak and reaches less than 0.1%, stopped reaction；Within about 3 hours, react；
4th reaction: liquid chromatograph 3,5-bis-chloro-2-amino benzoic Acid does not turns peak and reaches less than 0.1%, stopped reaction；Within about 3 hours, react；
5th reaction: liquid chromatograph 3,5-Dichloro-benzoic acid does not turns peak and reaches less than 0.1%, stopped reaction；Within about 3-5 hour, react.
Above-mentioned preparation method:
The reaction temperature of the first reaction, temperature is non-fusible less than 100 DEG C of reactants, causes raw material coking higher than 150 DEG C, is and causes yield to reduce；It is preferred, therefore, that be 100-150 DEG C；More preferably 120 DEG C, now yield is higher.
The reaction temperature of the second reaction, less than 40 DEG C, then reaction rate is relatively slow, and the utilization rate causing chlorine is low, and the response time is longer；The selectivity then causing chlorination higher than 50 DEG C reduces, and impurity increases, and yield is low；It is preferred, therefore, that be 40-50 DEG C；More preferably 40 DEG C, now yield is higher.
The reaction temperature of the 3rd reaction, less than 110 DEG C, material does not seethes with excitement；Due to boiling point, temperature can not be raised to more than 130 DEG C；It is advantageous to be 110-130 DEG C；More preferably 120 DEG C, now yield is higher.
The reaction temperature of the 4th reaction, less than 80 DEG C, material does not seethes with excitement；Due to boiling point, temperature can not be raised to more than 100 DEG C；It is preferred, therefore, that be 80-100 DEG C, more preferably 80 DEG C, now yield is higher.
The reaction temperature of the 5th reaction, less than 80 DEG C, material does not seethes with excitement；Due to boiling point, temperature can not be raised to more than 100 DEG C；It is preferred, therefore, that be 80-100 DEG C, more preferably 80 DEG C, now yield is higher.
Above-mentioned preparation method,
3rd reaction: hydrogen chloride and 3 in hydrochloric acid, 5-bis-chloro-2-acetaminobenzoic acid mol ratio is then reacted incomplete less than 2:1, is then wasted hydrochloric acid more than 3:1, increases cost；It is preferred, therefore, that be 2-3:1；Preferred about 2.5:1；
4th reaction: hydrogen chloride in hydrochloric acid, sodium nitrite, 3, the mol ratio of 5-bis-chloro-2-amino benzoic Acid is 5:1.2:1, if sodium nitrite consumption reduces, reaction not exclusively, wastes raw material at most.
In the step 3 of above-mentioned preparation method, use the hydrochloric acid of any concentration all can prepare 3,5-bis-chloro-2-amino benzoic Acid, and the goal of the invention that yield is high can be realized；Preferably, the mass concentration of hydrochloric acid is 36.5%.
In the step 4 of above-mentioned preparation method, use the hydrochloric acid of any concentration, sodium nitrite solution all can prepare 3,5-dichlorobenzoyl chloride and the goal of the invention that yield is high can be realized；Preferably, the mass concentration of hydrochloric acid is 36.5%, and the mass concentration of sodium nitrite solution is 30%.
Beneficial effect
The purity of the 3,5-dichlorobenzoyl chloride that this method that the present invention provides prepares is higher；The present invention provide this method prepare 3,5-dichlorobenzoyl chloride the first reaction yield the more than 99%, the 3rd reaction receive more than 99%, the 4th reaction yield reaches more than 95%, the 5th reaction yield more than 98%；Owing to being protected amino before chlorination, the method that the present invention provides, in preparation 3, effectively prevent the oxidation of amino during 5-dichlorobenzoyl chloride, chlorination yield is more than 95%.Total recovery more than 84.5%, relatively additive method is high.
Detailed description of the invention
Embodiment
1
Adding 137g ortho-aminobenzoic acid and 110g acetic anhydride in the four-hole bottle of 1000mL, carry out the first reaction at 100 DEG C, liquid chromatograph impurity peaks reaches stopped reaction when less than 3% (lower same), obtains 2-acetaminobenzoic acid (the required response time is about 12h).First reaction terminates, and adds 500g glacial acetic acid, be slowly introducing 150g chlorine and carry out the second reaction after stirring at 40 DEG C in above-mentioned four-hole bottle, and liquid chromatograph 2-acetaminobenzoic acid does not turns peak and reaches stopped reaction when less than 0.1% (lower same)；The required response time is about 12 hours.After second reaction terminates, the product in four-hole bottle is taken out, carries out sucking filtration, washing, obtain 3,5-bis-chloro-2-acetaminobenzoic acid solid.Then by 3,5-bis-chloro-2-acetaminobenzoic acid solid adds the 36.5%(mass concentration to 400g, hydrochloric acid the most together) carries out the 3rd reaction, reaction temperature is 120 DEG C, liquid chromatograph 3,5-bis-chloro-2-acetaminobenzoic acid does not turns peak and reaches stopped reaction when less than 0.1% (lower same), and the required response time is about 3 hours；Course of reaction constantly distills out the acetic acid of generation, obtains 3, chloro-2 amino benzoic Acid of 5-bis-(solid).Then the product that the 3rd reacts is joined the 36.5%(mass concentration of the isopropanol of 120g, 400g, lower with) hydrochloric acid and 0.5g copper sulfate mixed system in, 276g30%(mass concentration is dropwise dripped under the conditions of 80 DEG C, the most together) sodium nitrite solution carries out the 4th reaction, liquid chromatograph 3,5-bis-chloro-2-amino benzoic Acid does not turns peak and reaches stopped reaction when less than 0.1% (lower same), and the required response time is 3 hours.4th reacts complete sucking filtration obtains 3,5-dichlorobenzoic acid solid.Then by 3,5-dichlorobenzoic acid solid joins in the thionyl chloride of 350g and carries out the 5th reaction at 80 DEG C, liquid chromatograph 3,5-Dichloro-benzoic acid does not turns peak and reaches stopped reaction when less than 0.1% (lower same), the required response time is about 3 hours, reacting complete first air-distillation and go out thionyl chloride, then the distillation that carries out reducing pressure obtains 3, (distill is liquid to 5-dichlorobenzoyl chloride.Fusing point is 28 DEG C, and winter, solvent crystallization was solid) 181.1g, content 98.5%, total recovery 86.5%.
Embodiment
2
In the four-hole bottle of 1000mL, add 137g ortho-aminobenzoic acid and 110g acetic anhydride, at 120 DEG C, carry out the first reaction, obtain 2-acetaminobenzoic acid.First reaction terminates, and adds 500g glacial acetic acid, be slowly introducing 150g chlorine and carry out the second reaction after stirring at 40 DEG C in above-mentioned four-hole bottle.Second reaction terminate after, by four-hole bottle product take out, carry out sucking filtration, wash 3,5-bis-chloro-2-acetaminobenzoic acid solid.Then by 3, the addition of 5-bis-chloro-2-acetaminobenzoic acid solid carries out the 3rd reaction to 36.5% hydrochloric acid of 400g, and reaction temperature is 120 DEG C, and course of reaction constantly distills out the acetic acid of generation, obtains 3, chloro-2 amino benzoic Acid of 5-bis-.Then the product that 3rd reacts joins 36.5% hydrochloric acid of the isopropanol of 120g, 400g, and in the copper sulfate mixed system of 0.5g, 30% sodium nitrite solution dropwise dripping 276g under the conditions of 80 DEG C carries out the 4th reaction.4th reacts complete sucking filtration obtains 3,5-dichlorobenzoic acid solid.Then by 3,5-dichlorobenzoic acid solid joins and carries out the 5th complete first air-distillation of reaction response at 80 DEG C in the thionyl chloride of 350g and go out thionyl chloride, then the distillation that carries out reducing pressure obtains 3, and (distill is liquid to 5-dichlorobenzoyl chloride.Fusing point is 28 DEG C, and winter, solvent crystallization was solid) 181.3g, content 98.6%, total recovery 86.8%.
Embodiment
3
In the four-hole bottle of 1000mL, add the ortho-aminobenzoic acid of 137g and the acetic anhydride of 120g, at 120 DEG C, carry out the first reaction, obtain 2-acetaminobenzoic acid.First reaction terminates, and adds the glacial acetic acid of 300g in above-mentioned four-hole bottle, and the chlorine being slowly introducing 150g after stirring at 40 DEG C carries out the second reaction.Second reaction terminate after, by four-hole bottle product take out, carry out sucking filtration, wash 3,5-bis-chloro-2-acetaminobenzoic acid solid.Then by 3, the addition of 5-bis-chloro-2-acetaminobenzoic acid solid carries out the 3rd reaction to 36.5% hydrochloric acid of 400g, and reaction temperature is 130 DEG C, and course of reaction constantly distills out the acetic acid of generation, obtains 3, chloro-2 amino benzoic Acid of 5-bis-.Then the product that 3rd reacts joins 36.5% hydrochloric acid of the isopropanol of 120g, 400g, and in the copper sulfate mixed system of 0.5g, 30% sodium nitrite solution dropwise dripping 276g under the conditions of 80 DEG C carries out the 4th reaction.4th reacts complete sucking filtration obtains 3,5-dichlorobenzoic acid solid.Then by 3,5-dichlorobenzoic acid solid joins in the thionyl chloride of 350g and carries out the 5th reaction at 80 DEG C, reacts complete first air-distillation and goes out thionyl chloride, then the distillation that carries out reducing pressure obtains 3, and (distill is liquid to 5-dichlorobenzoyl chloride.Fusing point is 28 DEG C, and crystallization in winter is solid) 179.6g, content 98.0%, total recovery 84.9%.
Embodiment
4
In the four-hole bottle of 1000mL, add the ortho-aminobenzoic acid of 137g and the acetic anhydride of 120g, at 120 DEG C, carry out the first reaction, obtain 2-acetaminobenzoic acid.First reaction terminates, and adds the glacial acetic acid of 200g in above-mentioned four-hole bottle, and the chlorine being slowly introducing 150g after stirring at 50 DEG C carries out the second reaction.Second reaction terminate after, by four-hole bottle product take out, carry out sucking filtration, wash 3,5-bis-chloro-2-acetaminobenzoic acid solid.Then by 3, the addition of 5-bis-chloro-2-acetaminobenzoic acid solid carries out the 3rd reaction to 36.5% hydrochloric acid of 400g, and reaction temperature is 120 DEG C, and course of reaction constantly distills out the acetic acid of generation, obtains 3, chloro-2 amino benzoic Acid of 5-bis-.Then the product that 3rd reacts joins 36.5% hydrochloric acid of the isopropanol of 120g, 400g, and in the copper sulfate mixed system of 0.5g, 30% sodium nitrite solution dropwise dripping 276g under the conditions of 80 DEG C carries out the 4th reaction.4th reacts complete sucking filtration obtains 3,5-dichlorobenzoic acid solid.Then by 3,5-dichlorobenzoic acid solid joins in the thionyl chloride of 350g and carries out the 5th reaction at 80 DEG C, reacts complete first air-distillation and goes out thionyl chloride, then the distillation that carries out reducing pressure obtains 3, and the liquid-solid body of 5-dichlorobenzoyl chloride, (distilling is liquid.Fusing point is 28 DEG C, and summer is liquid, and crystallization in winter is solid) 184.3g, content 96.3%, total recovery 85.6%.
Embodiment
5
In the four-hole bottle of 1000mL, add the ortho-aminobenzoic acid of 137g and the acetic anhydride of 120g, at 120 DEG C, carry out the first reaction, obtain 2-acetaminobenzoic acid.First reaction terminates, and adds the glacial acetic acid of 500g in above-mentioned four-hole bottle, and the chlorine being slowly introducing 150g after stirring at 40 DEG C carries out the second reaction.Second reaction terminate after, by four-hole bottle product take out, carry out sucking filtration, wash 3,5-bis-chloro-2-acetaminobenzoic acid solid.Then by 3, the addition of 5-bis-chloro-2-acetaminobenzoic acid solid carries out the 3rd reaction to 36.5% hydrochloric acid of 400g, and reaction temperature is 120 DEG C, and course of reaction constantly distills out the acetic acid of generation, obtains 3, chloro-2 amino benzoic Acid of 5-bis-.Then the product that 3rd reacts joins 36.5% hydrochloric acid of the isopropanol of 120g, 400g, and in the copper sulfate mixed system of 0.5g, 30% sodium nitrite solution dropwise dripping 276g under the conditions of 100 DEG C carries out the 4th reaction.4th reacts complete sucking filtration obtains 3,5-dichlorobenzoic acid solid.Then by 3,5-dichlorobenzoic acid solid joins in the thionyl chloride of 300g and carries out the 5th reaction at 80 DEG C, reacts complete first air-distillation and goes out thionyl chloride, then the distillation that carries out reducing pressure obtains 3, and (solid, distill is liquid to 5-dichlorobenzoyl chloride.Fusing point is 28 DEG C, and crystallization in winter is solid) 181.2g, content 97.5%, total recovery 85.2%.
Embodiment
6
In the four-hole bottle of 1000mL, add the ortho-aminobenzoic acid of 137g and the acetic anhydride of 120g, at 120 DEG C, carry out the first reaction, obtain 2-acetaminobenzoic acid.First reaction terminates, and adds the glacial acetic acid of 500g in above-mentioned four-hole bottle, and the chlorine being slowly introducing 150g after stirring at 40 DEG C carries out the second reaction.Second reaction terminate after, by four-hole bottle product take out, carry out sucking filtration, wash 3,5-bis-chloro-2-acetaminobenzoic acid solid.Then by 3, the addition of 5-bis-chloro-2-acetaminobenzoic acid solid carries out the 3rd reaction to 36.5% hydrochloric acid of 400g, and reaction temperature is 110 DEG C, and course of reaction constantly distills out the acetic acid of generation, obtains 3, chloro-2 amino benzoic Acid of 5-bis-.Then the product that 3rd reacts joins 36.5% hydrochloric acid of the isopropanol of 120g, 200g, and in the copper sulfate mixed system of 0.5g, 30% sodium nitrite solution dropwise dripping 276g under the conditions of 80 DEG C carries out the 4th reaction.4th reacts complete sucking filtration obtains 3,5-dichlorobenzoic acid solid.Then by 3,5-dichlorobenzoic acid solid joins in the thionyl chloride of 200g and carries out the 5th reaction at 100 DEG C, reacts complete first air-distillation and goes out thionyl chloride, carry out decompression distillation again and obtain 3,5-dichlorobenzoyl chloride solid 182.1g, content 96.3%, total recovery 84.6%.
Claims (10)
1. one kind 3, the preparation method of 5-dichlorobenzoyl chloride, it is characterised in that comprise the following steps:
(1) first reaction: ortho-aminobenzoic acid and acetic anhydride prepare 2-acetaminobenzoic acid；
(2) second reactions: 2-acetaminobenzoic acid and chlorine reaction prepare 3,5-bis-chloro-2-acetaminobenzoic acid；
(3) the 3rd reactions: 3,5-bis-chloro-2-acetaminobenzoic acid and hydrochloric acid reaction prepare 3,5-bis-chloro-2-amino benzoic Acid；
(4) the 4th reactions: 3,5-bis-chloro-2-amino benzoic Acid and sodium nitrite, hydrochloric acid, isopropanol reaction prepare 3,5-Dichloro-benzoic acid；
(5) the 5th reactions: 3,5-Dichloro-benzoic acid and thionyl chloride reaction, obtain 3,5-dichlorobenzoyl chloride.
The most according to claim 1, preparation method, it is characterised in that the second reaction, with glacial acetic acid as solvent.
Preparation method the most according to claim 1 or claim 2, it is characterised in that the 4th reaction, uses copper sulfate as catalyst.
Preparation method the most according to claim 3, it is characterised in that follow the tracks of extent of reaction by liquid chromatographic detection.
Preparation method the most according to claim 4, it is characterised in that
First reaction: liquid chromatograph impurity peaks reaches less than 0.3%, stopped reaction；
Second reaction: liquid chromatograph 2-acetaminobenzoic acid does not turns peak and reaches less than 0.1%, stopped reaction；
3rd reaction: liquid chromatograph 3,5-bis-chloro-2-acetaminobenzoic acid does not turns peak and reaches less than 0.1%, stopped reaction；
4th reaction: liquid chromatograph 3,5-bis-chloro-2-amino benzoic Acid does not turns peak and reaches less than 0.1%, stopped reaction；
5th reaction: liquid chromatograph 3,5-Dichloro-benzoic acid does not turns peak and reaches less than 0.1%, stopped reaction.
Preparation method the most according to claim 5, it is characterised in that
The reaction temperature of the first reaction is 100-150 DEG C；
The reaction temperature of the second reaction is 40-50 DEG C;
The reaction temperature of the 3rd reaction is 110-130 DEG C；
The reaction temperature of the 4th reaction is 80-100 DEG C；
The reaction temperature of the 5th reaction is 80-100 DEG C.
Preparation method the most according to claim 6, it is characterised in that
The reaction temperature of the first reaction is 120 DEG C；
The reaction temperature of the second reaction is 40 DEG C；
The reaction temperature of the 3rd reaction is 120 DEG C；
The reaction temperature of the 4th reaction is 80 DEG C；
The reaction temperature of the 5th reaction is 80 DEG C.
Preparation method the most according to claim 7, it is characterised in that
3rd reaction: in hydrochloric acid, hydrogen chloride is 2-3:1 with the mol ratio of 3,5-bis-chloro-2-acetaminobenzoic acid；
4th reaction: in hydrochloric acid, hydrogen chloride, sodium nitrite, the mol ratio of 3,5-bis-chloro-2-amino benzoic Acid are 1.2:1:1.
Preparation method the most according to claim 8, it is characterised in that
3rd reaction: in hydrochloric acid, hydrogen chloride is 2.5:1 with the mol ratio of 3,5-bis-chloro-2-acetaminobenzoic acid.
Preparation method the most according to claim 9, it is characterised in that
In step 3, the mass concentration of hydrochloric acid is 36.5%；In step 4, the mass concentration of hydrochloric acid is 36.5%, and the mass concentration of sodium nitrite solution is 30%.
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Cited By (3)
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| CN110835308A (en) * | 2018-08-15 | 2020-02-25 | 海利尔药业集团股份有限公司 | Preparation method of halogenated o-aminobenzoic acid |
| CN113912487A (en) * | 2021-11-23 | 2022-01-11 | 山东研峰新材料科技有限公司 | Synthesis method of 2, 5-bis-halogenated benzoic acid |
| CN114805051A (en) * | 2021-08-03 | 2022-07-29 | 浙江宇龙生物科技股份有限公司 | Method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer |
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| CN114805051B (en) * | 2021-08-03 | 2023-08-15 | 浙江宇龙生物科技股份有限公司 | Method for preparing 2, 4-dichlorobenzoic acid from propiconazole 4-H isomer |
| CN113912487A (en) * | 2021-11-23 | 2022-01-11 | 山东研峰新材料科技有限公司 | Synthesis method of 2, 5-bis-halogenated benzoic acid |
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