CN107805198A - The synthetic method of 3,5 dichlorobenzoyl chlorides - Google Patents
The synthetic method of 3,5 dichlorobenzoyl chlorides Download PDFInfo
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- CN107805198A CN107805198A CN201711060569.7A CN201711060569A CN107805198A CN 107805198 A CN107805198 A CN 107805198A CN 201711060569 A CN201711060569 A CN 201711060569A CN 107805198 A CN107805198 A CN 107805198A
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- reaction
- triphosgene
- chloride
- chloroformyls
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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
- C07C51/62—Preparation of carboxylic acid halides by reactions not involving the carboxylic acid halide group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of 3,5 dichlorobenzoyl chlorides of synthesis, using the triphosgene that stability is high, quantity of three wastes is few as chlorinating agent, first by benzenedisulfonic acid between chlorobenzoyl chloride and obtained 5 chloroformyls of oleum progress sulfonating reaction；Triphosgene is added through benzene-disulfo-chloride between obtained 5 chloroformyls of catalytic chlorination reaction；Finally removal sulfur dioxide displacement reaction obtains 3,5 dichlorobenzoyl chlorides under the catalytic action of chlorine.The present invention, as chlorinating agent, has the advantages of process conditions are gentle, simple to operate safe, while product yield high, byproduct and three wastes yield are few using triphosgene；Meanwhile the factors such as raw material proportioning, triphosgene dosage, temperature, time are optimized, process conditions are gentle, have preferable economic benefit and social benefit, are suitable for industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of 3,5 dichlorobenzoyl chlorides, more particularly to one kind is using triphosgene as chlorinating agent
3,5 dichlorobenzoyl chlorides synthesis technique.
Background technology
At present industrially conventional 3,5- dichlorobenzoyl chloride synthetic methods be through sulfur trioxide or oleum sulfonation, then
Benzene-disulfo-chloride between raw material 5- chloroformyls is made in chlorination through chlorinating agent such as phosphorus pentachloride or phosphorous oxychloride, and raw material is again by higher
At a temperature of lead to chlorine and slough sulfur dioxide, while chlorination obtains 3,5- dichlorobenzoyl chlorides.Phosphorus pentachloride is monitored danger
Chemicals, molecular weight is big and unit consumption is high, while the monitored hazardous chemical POCl3 of accessory substance equimolar amounts is, it is necessary to return
Receive and utilize processing.In addition, the density and boiling point of by-product phosphorus trichloride are higher, it is difficult to be thoroughly separated off from product, cause
The yield and product content of three step removal sulfur dioxide chlorination reactions decline.Also there are the three wastes in this technique and equipment corrosion is serious, raw
The problems such as producing security difference (reference：Niu Binbo, study on the synthesis [D] the Hebei University of Technology of 3,5- dichlorobenzoyl chlorides,
2015.), so the technique for improving existing 3,5- dichlorobenzoyl chlorides has important industrial value.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of 3,5 safe and environment-friendly dichlorobenzoyl chlorides.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
3,5- dichlorobenzoyl chloride synthetic methods, using the triphosgene that stability is high, quantity of three wastes is few as chlorinating agent, first
By benzenedisulfonic acid between chlorobenzoyl chloride and the obtained 5- chloroformyls of oleum progress sulfonating reaction；Triphosgene is added through catalytic chlorination
Benzene-disulfo-chloride between 5- chloroformyls is made in reaction；Finally removal sulfur dioxide displacement reaction obtains 3,5- under the catalytic action of chlorine
Dichlorobenzoyl chloride.
Further, the temperature of sulfonating reaction is 170 DEG C -185 DEG C, and the time of sulfonating reaction is 14~16 hours.
Further, the mass ratio of chlorobenzoyl chloride and oleum is 3~5:1.
Further, the temperature of catalytic chlorination reaction is less than 120 DEG C；The time of catalytic chlorination reaction is 5~7 hours.
Further, the mass ratio of triphosgene and chlorobenzoyl chloride is 1:20~25.
Further, the temperature of removal sulfur dioxide displacement reaction is 160 ± 10 DEG C；The time of removal sulfur dioxide displacement reaction
For 14~16 hours.
Further, in removal sulfur dioxide displacement reaction, it is passed through Cl2Temperature be 140 ± 10 DEG C.
Compared with prior art, the present invention has following advantages：
1st, there is the advantages of process conditions are gentle, simple to operate safe, while product is received as chlorinating agent using triphosgene
Rate is high, and byproduct and three wastes yield are few；
2nd, the factors such as raw material proportioning, triphosgene dosage, temperature, time are optimized, process conditions are gentle, and product yield is high,
With preferable economic benefit and social benefit, it is suitable for industrial production.
Brief description of the drawings
Fig. 1 is the process chart being related in embodiment one.
Embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.
Such as Fig. 1,3,5- dichlorobenzoyl chloride synthetic methods, comprise the following steps that：
Step 1, chlorobenzoyl chloride is added into reaction bulb, while oleum is added dropwise, be slowly warming up to 170 DEG C -185 DEG C,
Insulation 14~16 hours；
Step 2, step 1 products therefrom add triphosgene powder, backflow insulation 5~7 hours at less than 120 DEG C；
Step 3, product are warming up to 140 ± 10 DEG C, are passed through a small amount of Cl2As catalyst, 160 ± 10 DEG C are continuously heating to,
Insulation 14~16 hours；
Step 4, slowly depressurize, after the sulfur dioxide for reclaiming residual, be evaporated under reduced pressure recovery leading portion 3- chlorobenzoyls.
Step 5, continue to be evaporated under reduced pressure to finished product 3,5- dichlorobenzoyl chlorides.
In above-mentioned steps, excessive sulfur trioxide blows out reaction system with nitrogen after reaction.
In above-mentioned steps, hydrogen chloride, sulfur dioxide and phosgene etc. caused by reaction need to carry out absorption processing.
In above-mentioned steps, product 3,5- dichlorobenzoyl chlorides are reclaimed by being evaporated under reduced pressure, by gas chromatographic analysis content.
Embodiment one：
Raw material chlorobenzoyl chloride 220g is added into reaction bulb, oleum 50g, while slowly heating is slowly added dropwise.Heating
To 160 DEG C, after reacting 12h, product 3,5- disulfobenzene formyl chlorides are obtained, excessive sulfur trioxide is blown out with nitrogen to be absorbed.3,
5- disulfobenzenes formyl chloride adds triphosgene powder 10g, backflow insulation 6h, obtains product 3,5- disulfonic acid chlorides at 120 DEG C or so
Base chlorobenzoyl chloride.3,5- disulfonyl chloro chlorobenzoyl chlorides heat up in reaction bulb, while are passed through a small amount of Cl2, it is continuously heating to 180
DEG C, final product 3 is obtained after reacting certain time, 5- dichlorobenzoyl chlorides, is evaporated under reduced pressure simultaneously sampling analysis.Product yield reaches
94.1%.
Embodiment two：
Raw material chlorobenzoyl chloride 150g is added into reaction bulb, oleum 50g, while slowly heating is slowly added dropwise.Heating
To 170 DEG C, after reacting 14h, product 3,5- disulfobenzene formyl chlorides are obtained, excessive sulfur trioxide is blown out with nitrogen to be absorbed.3,
5- disulfobenzenes formyl chloride adds triphosgene powder 15g, backflow insulation 8h, obtains product 3,5- disulfonic acid chlorides at 120 DEG C or so
Base chlorobenzoyl chloride.3,5- disulfonyl chloro chlorobenzoyl chlorides heat up in reaction bulb, while are passed through a small amount of Cl2, it is continuously heating to 170
DEG C, final product 3 is obtained after reacting certain time, 5- dichlorobenzoyl chlorides, is evaporated under reduced pressure simultaneously sampling analysis.Product yield reaches
83.3%.
Claims (7)
1. synthesize the method for 3,5- dichlorobenzoyl chlorides, it is characterised in that comprise the following steps：
Step 1, chlorobenzoyl chloride and oleum are subjected to the step of benzenedisulfonic acid between 5- chloroformyls is made in sulfonating reaction,
Step 2, by benzenedisulfonic acid between 5- chloroformyls and triphosgene through benzene-disulfo-chloride between the obtained 5- chloroformyls of catalytic chlorination reaction
The step of,
Step 3, under the catalytic action of chlorine, benzene-disulfo-chloride removal sulfur dioxide between 5- chloroformyls is entered into line replacement and reacts to obtain
The step of target product,
2. the method as described in claim 1, it is characterised in that in step 1, the temperature of sulfonating reaction is 170 DEG C -185 DEG C, sulphur
The time for changing reaction is 14~16 hours.
3. the method as described in claim 1, it is characterised in that in step 1, the mass ratio of chlorobenzoyl chloride and oleum is 3
~5:1.
4. the method as described in claim 1, it is characterised in that in step 2, the temperature of catalytic chlorination reaction is less than 120 DEG C；Urge
The time for changing chlorination reaction is 5~7 hours.
5. the method as described in claim 1, it is characterised in that the mass ratio of triphosgene and chlorobenzoyl chloride is 1:20~25.
6. the method as described in claim 1, it is characterised in that in step 3, the temperature for replacing reaction is 160 ± 10 DEG C；Displacement
The time of reaction is 14~16 hours.
7. the method as described in claim 1, it is characterised in that in step 3, be passed through Cl2Temperature be 140 ± 10 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711060569.7A CN107805198A (en) | 2017-11-02 | 2017-11-02 | The synthetic method of 3,5 dichlorobenzoyl chlorides |
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| CN201711060569.7A CN107805198A (en) | 2017-11-02 | 2017-11-02 | The synthetic method of 3,5 dichlorobenzoyl chlorides |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909088A (en) * | 2020-08-04 | 2020-11-10 | 浙江工业大学 | Utilizing BTC/Ph3Method for preparing isoquinoline hydrochloride intermediate and Rho kinase inhibitor by PO chloro system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3689546A (en) * | 1969-03-05 | 1972-09-05 | Rohm & Haas | Preparation of aryl halides |
| CN103508880A (en) * | 2013-10-09 | 2014-01-15 | 江西吉翔医药化工有限公司 | Method for synthesizing 3,5-dichlorobenzoyl chloride |
| CN104016855A (en) * | 2014-06-23 | 2014-09-03 | 江西吉翔医药化工有限公司 | Synthesis method of 3,5-dichlorobenzoyl chloride |
-
2017
- 2017-11-02 CN CN201711060569.7A patent/CN107805198A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3689546A (en) * | 1969-03-05 | 1972-09-05 | Rohm & Haas | Preparation of aryl halides |
| CN103508880A (en) * | 2013-10-09 | 2014-01-15 | 江西吉翔医药化工有限公司 | Method for synthesizing 3,5-dichlorobenzoyl chloride |
| CN104016855A (en) * | 2014-06-23 | 2014-09-03 | 江西吉翔医药化工有限公司 | Synthesis method of 3,5-dichlorobenzoyl chloride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909088A (en) * | 2020-08-04 | 2020-11-10 | 浙江工业大学 | Utilizing BTC/Ph3Method for preparing isoquinoline hydrochloride intermediate and Rho kinase inhibitor by PO chloro system |
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