CN105111066B - 3,5 dichlorobenzoyl chloride synthetic methods - Google Patents

3,5 dichlorobenzoyl chloride synthetic methods Download PDF

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Publication number
CN105111066B
CN105111066B CN201510475390.2A CN201510475390A CN105111066B CN 105111066 B CN105111066 B CN 105111066B CN 201510475390 A CN201510475390 A CN 201510475390A CN 105111066 B CN105111066 B CN 105111066B
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warming
reaction
chlorine
chloride
dichlorobenzoyl
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CN105111066A (en
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刘桂权
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LIANYUNGANG SUNLION CHEMICAL CO Ltd
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LIANYUNGANG SUNLION CHEMICAL CO Ltd
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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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  • Organic Chemistry (AREA)
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Abstract

The invention discloses a kind of 3, the synthetic method of 5 dichlorobenzoyl chlorides, comprise the following steps: m-phthaloyl chloride is put in reactor by (1), first it is warmed up to 90～130 DEG C, stirring is lower adds chlorosulfonic acid or oleum, it is incubated 8～10Hr in 150～170 DEG C, is finally warming up to 190～200 DEG C, insulation reaction 10～18 hours；(2) step (1) material is cooled to 50～60 DEG C, dropping thionyl chloride or phosphorus pentachloride, in 12～15Hr, material is warming up to 90～100 DEG C, and is incubated 12～15Hr and completes sulfonating chlorinating reaction；(3) step (2) material is warming up to 135～145 DEG C, is passed through 4th/2nd to five/5ths of chlorine total amount, then material is warming up to 175～185 DEG C is passed through remaining chlorine, insulation reaction 8～11 hours；(4) rectification under vacuum, the fraction collecting 155～160 DEG C obtains finished product.The whole course of reaction of the present invention completes in a still, it is to avoid middle separation process.After having reacted, through rectification isolated 3,5 dichlorobenzoyl chloride finished product, yield more than 85%, finished product content more than 97.0%.

Description

3,5 dichlorobenzoyl chloride synthetic methods
Technical field
The present invention relates to chemical field, be specifically related to 3,5 dichlorobenzoyl chloride synthetic methods.
Background technology
3,5 dichlorobenzoyl chlorides are of many uses, can prepare different material by differential responses, be mainly used in pesticide, Medicine, dyestuff etc..When being applied to pesticide, 3,5 one dichlorobenzoyl chlorides can be with methionine and ether thereof at sodium hydroxide solution environment Under, carry out benzoylation reaction, it is thus achieved that derivant can promote plant growing, improve plant situation, or make insecticide；Make For medicine intermediate, the different derivants of 3,5 one dichlorobenzoyl chlorides can treat various disease, such as, with hexamethylenamine and chlorine Changing the mixture reaction of hydrogen, can prepare the class medicine for the headache treating people, effect is the best, and pharmaceutical properties is stable, and Have no side effect；3,5. dichlorobenzoyl chloride can also be used to prepare tri-benzoyl nitrine as anti-balance diuretic；React with selenium Form product and be used for doing the photosensitizer of photo；Can be used to prepare the basic Methanamide of acetone；The most also it is used to prepare purine to spread out Biologic applications has bigger application development prospect in medical treatment, the derivant that especially it and aminoacid reaction generate.
The synthesis of 3,5 dichlorobenzoyl chlorides is typically with ortho-aminobenzoic acid as raw material, through superchlorination, diazonium-reduction, acyl The processes such as chlorination reaction, yield about 72%, and technological process is long, takies equipment many, produces waste water many, produce in production process Cost is the highest.
Summary of the invention
The technical problem to be solved in the present invention is to provide the synthetic method of a kind of 3,5 dichlorobenzoyl chlorides, whole reaction Process completes in a still, and no wastewater discharge, and yield is high.
The present invention is achieved through the following technical solutions:
The synthetic method of 3,5 dichlorobenzoyl chlorides, comprises the following steps:
(1) putting in reactor by m-phthaloyl chloride, be first warmed up to 90～130 DEG C, stirring is lower to add chlorosulfonic acid or sends out Cigarette sulphuric acid, is incubated 8～10Hr in 150～170 DEG C, is finally warming up to 190～200 DEG C, insulation reaction 10～18 hours；
(2) step (1) material is cooled to 50～60 DEG C, dropping thionyl chloride or phosphorus pentachloride, will in 12～15Hr Material is warming up to 90～100 DEG C, and be incubated 12～15Hr complete sulfonating chlorinating reaction；
(3) step (2) material is warming up to 135～145 DEG C, is passed through 4th/2nd to five/5ths of chlorine total amount, then Material is warming up to 175～185 DEG C and is passed through remaining chlorine, insulation reaction 8～11 hours；
(4) rectification under vacuum, the fraction collecting 155～160 DEG C obtains finished product.
Step (1) isophthaloyl chlorine is 1.0:1.0～1.10 with the mol ratio of chlorosulfonic acid or oleum.
Described oleum is the oleum of 65%.
Step (2) isophthaloyl chlorine is 1.0:1.0～1.15 with the mol ratio of thionyl chloride or phosphorus pentachloride.
Step (3) isophthaloyl chlorine is 7.5～8.0:1.0 with the mol ratio of chlorine.
Rectification under vacuum described in step (4), its vacuum is-0.080～-0.100MPa.
Chemical equation
(1) sulfonating reaction (chlorosulfonic acid)
Sulfonating reaction (oleum)
(2) sulfonating chlorinating reaction
(3) displacement reaction (SO2)
Displacement reaction (CO)
Primary raw material: (1) m-phthaloyl chloride；(2) chlorosulfonic acid or 65% oleum, preferentially select chlorosulfonic acid；(3) liquid Chlorine；(4) SO2Displacement reaction, CO displacement reaction catalyst: chlorine；(5) phosphorus pentachloride, thionyl chloride, preferentially selects protochloride Sulfone.
The present invention compared with prior art, has the advantage that
With m-phthaloyl chloride as raw material, through sulfonation, sulfonating chlorinating, SO2Displacement reaction, CO displacement reaction, prepare 3, 5 dichlorobenzoyl chlorides, whole course of reaction completes in a still, it is to avoid middle separation process.After having reacted, Jing Guojing Evaporate isolated 3,5 dichlorobenzoyl chloride finished products, yield more than 85%, finished product content more than 97.0%.
Detailed description of the invention
Embodiment 1
(1) in four-hole boiling flask, add m-phthaloyl chloride 101g, connect ball-type condenser, be first warmed up to 102 DEG C of stirrings Lower addition chlorosulfonic acid 63g, is slowly warmed up to 150 DEG C of insulation 10Hr, is the most slowly warmed up to 195 DEG C and is incubated 16 hours, completing Sulfonating reaction；
(2) material is cooled to 55 DEG C, drip thionyl chloride 68g, in 12～15Hr, material is warmed up to 95 DEG C, and protects Temperature 13Hr completes sulfonating chlorinating reaction；The hydrogen chloride of reaction generation, SO2Absorbed by water；
(3) temperature of charge being raised to about 138 DEG C, be slowly introducing chlorine 3.0 g, temperature is raised to 175 DEG C, continues to be passed through Chlorine 2.0 g(chlorine adds up to 5 g), is incubated 11 hours；Lower the temperature and treat decompression distillation,
(4) rectification under vacuum, slow band vacuum, vacuum is raised to-0.085MPa, when 142 DEG C, starts front-end volatiles, so After vacuum is raised to-0.090MPa, the fraction collecting 157 DEG C is finished product；Having steamed and obtained finished product about 89g, gas chromatogram is divided Analysis content 97.7%, yield is 85.5%.
Embodiment 2
(1) in four-hole boiling flask, add m-phthaloyl chloride 101g, connect ball-type condenser, be first warmed up to 110 DEG C of stirrings Lower addition chlorosulfonic acid 63g, is slowly warmed up to 157 DEG C of insulation 9.5Hr, is the most slowly warmed up to 195 DEG C and is incubated 16 hours, completing Sulfonating reaction；
(2) material is cooled to 50 DEG C, drips thionyl chloride 68g, in 12～15Hr, material is slowly warmed up to 90 DEG C, Insulation 15Hr completes sulfonating chlorinating reaction；The hydrogen chloride of reaction generation, SO2Absorbed by water；
(3) temperature of charge being raised to about 135 DEG C, be slowly introducing chlorine about 2.5 g, temperature is raised to 180 DEG C, continues logical Enter chlorine about 2.5 g(chlorine and add up to 5 g), be incubated 10.5 hours；Lower the temperature to be distilled,
(4) rectification under vacuum, vacuum rises to-0.085MPa, during temperature 142 DEG C, goes out front-end volatiles, and vacuum rises to- 0.090MPa, goes out finished product fraction and obtains finished product about 91.5g, gas chromatographic analysis content 97.2% during temperature 157 DEG C, yield is 88.0%。
Embodiment 3
(1) in four-hole boiling flask, add m-phthaloyl chloride 101g, connect ball-type condenser, be first warmed up to 120 DEG C of stirrings Lower addition chlorosulfonic acid 63g, is incubated 8.5Hr in 162 DEG C, is the most slowly warmed up to 195 DEG C and is incubated 16 hours, completing sulfonation anti- Should；
(2) material cooling to 55 DEG C, drip thionyl chloride 68g, be slowly warmed up to 98 DEG C, insulation 12Hr completes sulfonic acid chloride Change reaction；The hydrogen chloride of reaction generation, SO2Absorbed by water；
(3) temperature of charge being raised to about 140 DEG C, be slowly introducing chlorine about 2.8 g, temperature is raised to 180 DEG C, continues logical Enter chlorine about 2.2g(chlorine and add up to 5g), it is incubated 10 hours；Slow cooling, treats decompression distillation.
(4) rectification under vacuum, vacuum rises to-0.087MPa, during temperature 140 DEG C, goes out front-end volatiles, and vacuum rises to- 0.090MPa, goes out finished product during temperature 158 DEG C, has steamed and has obtained finished product about 91g, gas chromatographic analysis content 97.5%, and yield is 87.5%.

Claims (5)

  1. The synthetic method of 1.3,5 dichlorobenzoyl chlorides, it is characterised in that comprise the following steps:
    (1) putting in reactor by m-phthaloyl chloride, be first warmed up to 90～130 DEG C, stirring is lower adds chlorosulfonic acid or oleum Acid, is incubated 8～10Hr in 150～170 DEG C, is finally warming up to 190～200 DEG C, insulation reaction 10～18 hours；
    (2) step (1) material being cooled to 50～60 DEG C, dropping thionyl chloride or phosphorus pentachloride, by material in 12～15Hr Be warming up to 90～100 DEG C, and be incubated 12～15Hr complete sulfonating chlorinating reaction；
    (3) step (2) material is warming up to 135～145 DEG C, is passed through 4th/2nd to five/5ths of chlorine total amount, then by thing Material is warming up to 175～185 DEG C and is passed through remaining chlorine, insulation reaction 8～11 hours；
    (4) rectification under vacuum, the fraction collecting 155～160 DEG C obtains finished product；
    Step (3) isophthaloyl chlorine is 7.5～8.0:1.0 with the mol ratio of chlorine.
  2. The synthetic method of 3,5 dichlorobenzoyl chlorides the most as claimed in claim 1, it is characterised in that: isophthalic two in step (1) Formyl chloride is 1.0:1.0～1.10 with the mol ratio of chlorosulfonic acid or oleum.
  3. The synthetic method of 3,5 dichlorobenzoyl chlorides the most as claimed in claim 1 or 2, it is characterised in that: described oleum It it is the oleum of 65%.
  4. The synthetic method of 3,5 dichlorobenzoyl chlorides the most as claimed in claim 1, it is characterised in that: isophthalic two in step (2) Formyl chloride is 1.0:1.0～1.15 with the mol ratio of thionyl chloride or phosphorus pentachloride.
  5. The synthetic method of 3,5 dichlorobenzoyl chlorides the most as claimed in claim 1, it is characterised in that: described in step (4) Rectification under vacuum, its vacuum is-0.080～-0.100MPa.
CN201510475390.2A 2015-08-06 2015-08-06 3,5 dichlorobenzoyl chloride synthetic methods Active CN105111066B (en)

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Publication number Priority date Publication date Assignee Title
CN106349121B (en) * 2016-08-16 2018-08-17 上海绿麟达新材料科技有限公司 The preparation method of one kind 3,5- dichlorobenzoyl chlorides
CN107879930A (en) * 2017-05-10 2018-04-06 湖南比德生化科技股份有限公司 A kind of method that 3,5 dichlorobenzoyl chlorides are prepared with chlorobenzoyl chloride

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US3689546A (en) * 1969-03-05 1972-09-05 Rohm & Haas Preparation of aryl halides
US3869510A (en) * 1973-05-25 1975-03-04 Hooker Chemicals Plastics Corp Preparation of 3,5-dichlorobenzoyl chloride
CN103508880B (en) * 2013-10-09 2015-03-11 江西吉翔医药化工有限公司 Method for synthesizing 3,5-dichlorobenzoyl chloride
CN104016855B (en) * 2014-06-23 2015-06-24 江西吉翔医药化工有限公司 Synthesis method of 3,5-dichlorobenzoyl chloride

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