CN103073408A - Preparation method of dichlorodiphenylene ether ketone - Google Patents

Preparation method of dichlorodiphenylene ether ketone Download PDF

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Publication number
CN103073408A
CN103073408A CN2013100031503A CN201310003150A CN103073408A CN 103073408 A CN103073408 A CN 103073408A CN 2013100031503 A CN2013100031503 A CN 2013100031503A CN 201310003150 A CN201310003150 A CN 201310003150A CN 103073408 A CN103073408 A CN 103073408A
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China
Prior art keywords
dichloro
diphenyl ether
ether ketone
preparation method
reaction
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CN2013100031503A
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Chinese (zh)
Inventor
吕欢欢
马文元
张兴华
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扬州市天平化工厂有限公司
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Priority to CN2013100031503A priority Critical patent/CN103073408A/en
Publication of CN103073408A publication Critical patent/CN103073408A/en

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Abstract

The invention discloses a preparation method of dichlorodiphenylene ether ketone. The method includes the steps as follows: (1) condensation reaction: adding p-chlorophenol and a sodium hydroxide solution into a reactor to prepare phenoxide; dehydrating and adding a copper acetate catalyst, assistants and m-dichlorobenzene; and subjecting phenoxide to a condensation reaction with m-dichlorobenzene under the effects of the copper acetate catalyst and the assistants to prepare dichlordiphenyl ether; (2) acylation reaction: dissolving the prepared dichlordiphenyl ether in a solvent, and then subjecting dichlordiphenyl ether to an acylation reaction under the catalysis of an anhydrous aluminum trichloride catalyst to generate dichlorodiphenylene ether ketone. The preparation method has the advantages of short and simple synthetic route, mild reaction conditions, high conversion rate, low production cost, little discharge of three wastes, and high waste liquor recycling rate.

Description

The preparation method of dichloro-diphenyl ether ketone

Technical field

The present invention relates to the preparation field of medicine intermediate, particularly relate to a kind of preparation method of dichloro-diphenyl ether ketone.

Background technology

Dichloro-diphenyl ether ketone is agricultural bactericide , Openmouthedness imidazoles, the important intermediate of tricyclazole etc.Yet mainly there is following shortcoming in the synthetic dichloro-diphenyl ether ketone of prior art: synthetic route is long and complicated, severe reaction conditions, and low conversion rate, production cost is high, and three waste discharge is large, and the waste liquid recovery utilization rate is low.

Summary of the invention

It is short and simple that the technical problem that the present invention mainly solves provides a kind of synthetic route, and reaction conditions is gentle, and transformation efficiency is high, and production cost is low, and three waste discharge is few, the preparation method of the dichloro-diphenyl ether ketone that the waste liquid recovery utilization rate is high.

For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of preparation method of dichloro-diphenyl ether ketone is provided, may further comprise the steps:

(1) condensation reaction: add para-chlorophenol in the reactor and sodium hydroxide solution is made phenates, add neutralized verdigris catalyzer, auxiliary agent and Meta Dichlorobenzene after the dehydration, be warming up to 148 ~ 152 ℃, described phenates under described neutralized verdigris catalyzer and promoter effect with Meta Dichlorobenzene generation condensation reaction, reaction 45 ~ 50 h, then remove the neutralized verdigris catalyzer, reclaim unreacted Meta Dichlorobenzene, rectifying obtains dichloro-diphenyl ether;

(2) acylation reaction: the dichloro-diphenyl ether that makes is dissolved in the organic solvent; add the Catalyzed by Anhydrous Aluminium Chloride agent; be cooled to less than-10 ℃, then drip Acetyl Chloride 98Min., drip and finish; the control temperature is 0 ~ 2 ℃; insulation 3 ~ 5 h finish reaction, and reaction solution is hydrolyzed; remove the Catalyzed by Anhydrous Aluminium Chloride agent, cooling obtains dichloro-diphenyl ether ketone finished product.

In a preferred embodiment of the present invention, the weight ratio of described para-chlorophenol, sodium hydroxide solution, neutralized verdigris catalyzer, auxiliary agent and Meta Dichlorobenzene is 1:1 ~ 1.5:0.1 ~ 0.4:0.2 ~ 0.6:3 ~ 4.

In a preferred embodiment of the present invention, the weight ratio of described organic solvent, dichloro-diphenyl ether, Catalyzed by Anhydrous Aluminium Chloride agent and Acetyl Chloride 98Min. is 10 ~ 15:2 ~ 4:1 ~ 3:1.

In a preferred embodiment of the present invention, described sodium hydroxide solution is that mass percent concentration is 40 ~ 60% sodium hydroxide solution.

In a preferred embodiment of the present invention, described auxiliary agent is diethyl acetamide.

In a preferred embodiment of the present invention, described organic solvent is ethylene dichloride, methylene dichloride or acetone.

The invention has the beneficial effects as follows: synthetic route of the present invention is short and simple, and reaction conditions is gentle, and transformation efficiency is high, and production cost is low, and three waste discharge is few, and the waste liquid recovery utilization rate is high.

Embodiment

The below is described in detail preferred embodiment of the present invention, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made more explicit defining.

Embodiment 1

A kind of preparation method of dichloro-diphenyl ether ketone may further comprise the steps:

(1) condensation reaction: add para-chlorophenol 225 kg and mass percent concentration is that 50% sodium hydroxide solution, 300 kg make phenates to 3000 L reactors, then adding toluene 720 kg backflow dewaters, 107 ℃ of reflux temperature controls, dewater and finish to steam except toluene, steam to 115 ℃ of end of interior temperature, be cooled to room temperature and add neutralized verdigris catalyzer 50 kg, diethyl acetamide 100 kg and Meta Dichlorobenzene 800 kg, be warming up to 148 ℃, be incubated 48 h, survey transformation efficiency 96% qualified, be cooled to the room temperature press filtration, remove the neutralized verdigris catalyzer, filter cake washes with water, discards waste water layer, the oil reservoir underpressure distillation, the recycling use Meta Dichlorobenzene steams to 180 ℃ of interior temperature, cools to 70 ℃ and changes rectifying still over to, rectifying high vacuum remove portion diethyl acetamide and unreacted Meta Dichlorobenzene get the dichloro-diphenyl ether more than 98%;

(2) acylation reaction: dichloro-diphenyl ether 300 kg that make are dissolved among ethylene dichloride organic solvent 1200 kg; stir lower Catalyzed by Anhydrous Aluminium Chloride agent 200 kg that add; be cooled to less than-10 ℃, then drip Acetyl Chloride 98Min. 100 kg from header tank, the control temperature of reaction is less than-5 ℃; drip and finish; the control temperature is 0 ℃, is incubated 4 h, surveys transformation efficiency more than 98%; impurity is qualified less than 0.2%; with the reaction solution hydrolysis, among suction ice sour water 1600 kg, leave standstill after the stirring; remove waste acid water; the washing oil reservoir is removed the Catalyzed by Anhydrous Aluminium Chloride agent to neutral, removes the ethylene dichloride solvent; cooling is dried and is namely made dichloro-diphenyl ether ketone finished product.

Make dichloro-diphenyl ether ketone finished product outward appearance: white crystals, content: 〉=98%, moisture content :≤0.5%.

Embodiment 2

A kind of preparation method of dichloro-diphenyl ether ketone may further comprise the steps:

(1) condensation reaction: add para-chlorophenol 225 kg and mass percent concentration is that 50% sodium hydroxide solution, 225 kg make phenates to 3000 L reactors, then adding toluene 700 kg backflow dewaters, 105 ℃ of reflux temperature controls, dewater and finish to steam except toluene, steam to 115 ℃ of end of interior temperature, be cooled to room temperature and add neutralized verdigris catalyzer 22.5 kg, diethyl acetamide 45 kg and Meta Dichlorobenzene 675 kg, be warming up to 150 ℃, be incubated 45 h, survey transformation efficiency 96% qualified, be cooled to the room temperature press filtration, remove the neutralized verdigris catalyzer, filter cake washes with water, discards waste water layer, the oil reservoir underpressure distillation, the recycling use Meta Dichlorobenzene steams to 180 ℃ of interior temperature, cools to 60 ℃ and changes rectifying still over to, rectifying high vacuum remove portion diethyl acetamide and unreacted Meta Dichlorobenzene get the dichloro-diphenyl ether more than 98%;

(2) acylation reaction: dichloro-diphenyl ether 200 kg that make are dissolved among ethylene dichloride organic solvent 1000 kg; stir lower Catalyzed by Anhydrous Aluminium Chloride agent 100 kg that add; be cooled to less than-10 ℃, then drip Acetyl Chloride 98Min. 100 kg from header tank, the control temperature of reaction is less than-5 ℃; drip and finish; the control temperature is 1 ℃, is incubated 3 h, surveys transformation efficiency more than 98%; impurity is qualified less than 0.2%; with the reaction solution hydrolysis, among suction ice sour water 1400 kg, leave standstill after the stirring; remove waste acid water; the washing oil reservoir is removed the Catalyzed by Anhydrous Aluminium Chloride agent to neutral, removes the ethylene dichloride solvent; cooling is dried and is namely made dichloro-diphenyl ether ketone finished product.

Make dichloro-diphenyl ether ketone finished product outward appearance: white crystals, content: 〉=98%, moisture content :≤0.5%.

Embodiment 3

A kind of preparation method of dichloro-diphenyl ether ketone may further comprise the steps:

(1) condensation reaction: add para-chlorophenol 225 kg and mass percent concentration is that 50% sodium hydroxide solution, 337.5 kg make phenates to 3000 L reactors, then adding toluene 750 kg backflow dewaters, 110 ℃ of reflux temperature controls, dewater and finish to steam except toluene, steam to 115 ℃ of end of interior temperature, be cooled to room temperature and add neutralized verdigris catalyzer 90 kg, diethyl acetamide 135 kg and Meta Dichlorobenzene 900 kg, be warming up to 152 ℃, be incubated 50 h, survey transformation efficiency 96% qualified, be cooled to the room temperature press filtration, remove the neutralized verdigris catalyzer, filter cake washes with water, discards waste water layer, the oil reservoir underpressure distillation, the recycling use Meta Dichlorobenzene steams to 180 ℃ of interior temperature, cools to 80 ℃ and changes rectifying still over to, rectifying high vacuum remove portion diethyl acetamide and unreacted Meta Dichlorobenzene get the dichloro-diphenyl ether more than 98%;

The weight ratio of described organic solvent, dichloro-diphenyl ether, Catalyzed by Anhydrous Aluminium Chloride agent and Acetyl Chloride 98Min. is 10 ~ 15:2 ~ 4:1 ~ 3:1.

(2) acylation reaction: dichloro-diphenyl ether 400 kg that make are dissolved among ethylene dichloride organic solvent 1500 kg; stir lower Catalyzed by Anhydrous Aluminium Chloride agent 300 kg that add; be cooled to less than-10 ℃, then drip Acetyl Chloride 98Min. 100 kg from header tank, the control temperature of reaction is less than-5 ℃; drip and finish; the control temperature is 2 ℃, is incubated 5 h, surveys transformation efficiency more than 98%; impurity is qualified less than 0.2%; with the reaction solution hydrolysis, among suction ice sour water 1600 kg, leave standstill after the stirring; remove waste acid water; the washing oil reservoir is removed the Catalyzed by Anhydrous Aluminium Chloride agent to neutral, removes the ethylene dichloride solvent; cooling is dried and is namely made dichloro-diphenyl ether ketone finished product.

Make dichloro-diphenyl ether ketone finished product outward appearance: white crystals, content: 〉=98%, moisture content :≤0.5%.

Synthetic route of the present invention is short and simple, and reaction conditions is gentle, and transformation efficiency is high, and production cost is low, and three waste discharge is few, and the waste liquid recovery utilization rate is high.

The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention to do, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.

Claims (6)

1. the preparation method of a dichloro-diphenyl ether ketone is characterized in that, may further comprise the steps:
(1) condensation reaction: add para-chlorophenol in the reactor and sodium hydroxide solution is made phenates, add neutralized verdigris catalyzer, auxiliary agent and Meta Dichlorobenzene after the dehydration, be warming up to 148 ~ 152 ℃, described phenates under described neutralized verdigris catalyzer and promoter effect with Meta Dichlorobenzene generation condensation reaction, reaction 45 ~ 50 h, then remove the neutralized verdigris catalyzer, reclaim unreacted Meta Dichlorobenzene, rectifying obtains dichloro-diphenyl ether;
(2) acylation reaction: the dichloro-diphenyl ether that makes is dissolved in the organic solvent; add the Catalyzed by Anhydrous Aluminium Chloride agent; be cooled to less than-10 ℃, then drip Acetyl Chloride 98Min., drip and finish; the control temperature is 0 ~ 2 ℃; insulation 3 ~ 5 h finish reaction, and reaction solution is hydrolyzed; remove the Catalyzed by Anhydrous Aluminium Chloride agent, cooling obtains dichloro-diphenyl ether ketone finished product.
2. the preparation method of dichloro-diphenyl ether ketone according to claim 1 is characterized in that, the weight ratio of described para-chlorophenol, sodium hydroxide solution, neutralized verdigris catalyzer, auxiliary agent and Meta Dichlorobenzene is 1:1 ~ 1.5:0.1 ~ 0.4:0.2 ~ 0.6:3 ~ 4.
3. the preparation method of dichloro-diphenyl ether ketone according to claim 1 is characterized in that, the weight ratio of described organic solvent, dichloro-diphenyl ether, Catalyzed by Anhydrous Aluminium Chloride agent and Acetyl Chloride 98Min. is 10 ~ 15:2 ~ 4:1 ~ 3:1.
4. the preparation method of dichloro-diphenyl ether ketone according to claim 1 is characterized in that, described sodium hydroxide solution is that mass percent concentration is 40 ~ 60% sodium hydroxide solution.
5. the preparation method of dichloro-diphenyl ether ketone according to claim 1 is characterized in that, described auxiliary agent is diethyl acetamide.
6. the preparation method of dichloro-diphenyl ether ketone according to claim 1 is characterized in that, described organic solvent is ethylene dichloride, methylene dichloride or acetone.
CN2013100031503A 2013-01-06 2013-01-06 Preparation method of dichlorodiphenylene ether ketone CN103073408A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103626645A (en) * 2013-11-22 2014-03-12 绩溪县昌盛化工科技有限公司 Method for increasing yield of dichloro diphenyl ether ketone
CN104876811A (en) * 2015-02-09 2015-09-02 周保东 Purification method of 2-chloro-4-(4-chlorophenoxy)acetophenone

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EP0065485B1 (en) * 1981-05-12 1990-04-18 Ciba-Geigy Ag Arylphenyl ether derivatives as microbicides, process for their preparation and their application
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103626645A (en) * 2013-11-22 2014-03-12 绩溪县昌盛化工科技有限公司 Method for increasing yield of dichloro diphenyl ether ketone
CN103626645B (en) * 2013-11-22 2015-10-28 绩溪县昌盛化工科技有限公司 A kind of method improving yield of dichloro diphenyl ether ketone
CN104876811A (en) * 2015-02-09 2015-09-02 周保东 Purification method of 2-chloro-4-(4-chlorophenoxy)acetophenone
CN104876811B (en) * 2015-02-09 2016-07-13 周保东 The method of purification of 3,4 '-dichloro phenylene ether ketone

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Application publication date: 20130501