CN103626645A - Method for increasing yield of dichloro diphenyl ether ketone - Google Patents
Method for increasing yield of dichloro diphenyl ether ketone Download PDFInfo
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- CN103626645A CN103626645A CN201310602723.4A CN201310602723A CN103626645A CN 103626645 A CN103626645 A CN 103626645A CN 201310602723 A CN201310602723 A CN 201310602723A CN 103626645 A CN103626645 A CN 103626645A
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- reactor
- diphenyl ether
- dichloro
- ether ketone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
Abstract
The invention discloses a method for increasing the yield of dichloro diphenyl ether ketone. The method comprises the steps of firstly dissolving dichloro diphenyl ether into an organic solvent, adding into an open carbon steel reactor, starting a brumagin-type stirrer in the reactor for mixing, and controlling the interior temperature of the carbon steel reactor to be 10-15 DEG C; adding anhydrous aluminum chloride as a catalyst into the reactor, cooling down, and then dripping acetyl chloride into the reactor so as to keep the temperature to be 15-20 DEG C; after dripping, preserving heat for 2-2.5 hours to finish the reaction; cooling down the reactor to be 5-10 DEG C, discharging the cooled material to a hydrolyzing kettle for hydrolysis to remove the anhydrous aluminum chloride catalyst; and washing the hydrolyzed reaction liquid, then desolventizing, decolorizing, crystallizing, centrifuging, and carrying out air drying so as to obtain the finished product. The dosing weight ratio of the organic solvent to the dichloro diphenyl ether to the anhydrous aluminum chloride catalyst to the acetyl chloride is (28-30):10:(1-3):(3.3-3.7). The method has the advantage of effectively increasing the yield.
Description
Technical field
The present invention relates to the preparation field of medicine intermediate and pesticide intermediate, in particular a kind of method that improves dichloro-diphenyl ether ketone yield.
Background technology
Dichloro-diphenyl ether ketone is the important intermediate of agricultural bactericide difenoconazole, Dumb imidazoles, tricyclazole etc., yet, in existing dichloro-diphenyl ether ketone production process, mainly contain following shortcoming: reaction conversion ratio is low, production cost is high, and aluminum trichloride (anhydrous) consumption is large, and three wastes discharging of waste liquid amount is large.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of reaction conditions gentle, transformation efficiency is high, and catalyst levels is few, and production cost is low, the method for the raising dichloro-diphenyl ether ketone yield that three waste discharge is few simultaneously.
The present invention is achieved by the following technical solutions:
A method that improves dichloro-diphenyl ether ketone yield, comprises the steps:
(1) dichloro-diphenyl ether be dissolved in to organic solvent and add in carbon steel open type reactor, four symmetrical baffle plates are installed in reactor, the boolean Ma Jinshi agitator of opening in reactor stirs, and agitator speed is 85～150 revs/min, and to control carbon steel reactor temperature be 10～15 ℃;
(2) in reactor, add Catalyzed by Anhydrous Aluminium Chloride agent, by the chilled brine passing in reactor external jacket, lower the temperature, then in reactor, drip Acetyl Chloride 98Min., control rate of addition and make between temperature keeps 15～20 ℃;
(3) drip and finish rear insulation 2～2.5 hours, finish reaction; Reactor is progressively cooled to 5～10 ℃ and discharge to hydrolysis kettle reaction solution is hydrolyzed, remove Catalyzed by Anhydrous Aluminium Chloride agent;
(4) reaction solution after hydrolysis, again through washing, precipitation, decolouring, crystallization, centrifugal, air-dry, obtains dichloro-diphenyl ether ketone finished product;
In above-mentioned steps, the weight ratio that feeds intake of organic solvent, dichloro-diphenyl ether, Catalyzed by Anhydrous Aluminium Chloride agent and Acetyl Chloride 98Min. is: 28～30:10:1～3:3.3～3.7.
As aforesaid method preferably, described organic solvent is anhydrous ethylene dichloride.
As aforesaid method preferably, in described step (1), agitator speed is 130 revs/min.
As aforesaid method preferably, described Catalyzed by Anhydrous Aluminium Chloride agent is highly active Catalyzed by Anhydrous Aluminium Chloride agent, granularity is at 10～20 orders.
The present invention has the following advantages compared to existing technology:
The present invention is by improving reactor structure, optimize ingredient proportion and controlling temperature of reaction, time etc., and reaction conditions is gentle, has reduced catalyst levels, has improved reaction conversion ratio, reduced production cost, and three waste discharge is few.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The present invention is as follows to the texture improvement of reactor: according to GB/T25027-2010 customization carbon steel open type reactor, at reactor inwall, install four symmetrical baffle plate additional simultaneously, apolegamy 7.5kw level Four Flame-Proof Three-Phase Induction Motors, the cycloidal planetary gear speed reducer that supporting speed ratio is 11 and corresponding frame; Agitator is the boolean Ma Jinshi agitator of supporting machinery sealing, preferentially select that Chang Zhoutang village acid proof enamel factory or Wuxi Xiao Xing chemical enamel company limited or Linyi Guang Hong industrial enamel equipment company limited produce double-deck and every layer are the enamel boolean Ma Jinshi agitator of six leaves, adopt this boolean Ma Jinshi agitator can make to stir more abundant, coordinate four baffle plates to change the sense of rotation of reactant, augmenting response thing contact efficiency, further strengthened mixing effect, reactant reaction speed is accelerated.
Embodiment 1
A method that improves dichloro-diphenyl ether ketone yield, comprises the steps:
(1) in the carbon steel open type reactor of drying, add after 400kg dichloro-diphenyl ether and the anhydrous ethylene dichloride 1200kg of organic solvent, the boolean Ma Jinshi agitator of opening in reactor stirs, agitator speed is 130 revs/min, and to control carbon steel reactor temperature be 10～15 ℃;
(2) in reactor, add highly active Catalyzed by Anhydrous Aluminium Chloride agent 100kg, granularity is at 10～20 orders, by the chilled brine passing in reactor external jacket, lower the temperature, then in the high groove position of reactor, drip Acetyl Chloride 98Min. 130kg, control rate of addition and make between temperature keeps 15～20 ℃;
(3) drip and to finish rear insulation 2～2.5 hours, during sampling carry out middle control analysis, according to analytical results, add raw material or catalyzer, finish reaction; Reactor is progressively cooled to 5～10 ℃ and discharge to hydrolysis kettle to be hydrolyzed to reaction solution, remove Catalyzed by Anhydrous Aluminium Chloride agent, reactor rinses with anhydrous ethylene dichloride, and washing fluid is incorporated to the reaction solution solution of anhydrating, the logical steam negative pressure of reacting kettle jacketing is dried, in order to the lower batch of operation that feeds intake;
(4) reaction solution after hydrolysis, again through washing, precipitation, decolouring, crystallization, centrifugal, air-dry, obtains dichloro-diphenyl ether ketone finished product 465kg;
The finished product that it makes: white crystals, content: >=98.5%, moisture content :≤0.5%, industrialization yield reaches 97.90%.And to the specification of quality of finished product dichloro-diphenyl ether ketone be: content >=98.0%, moisture content≤0.5%, the finished product dichloro-diphenyl ether ketone that visible the present embodiment makes can reach its specification of quality completely.
Wherein, yield refers at chemical reaction or relevant chemical industry and produces the product production of actual production of Zhong， input unit quantity raw material acquisition and the ratio of the product production of Theoretical Calculation.In the present embodiment, the yield computation process of dichloro-diphenyl ether ketone finished product is as follows:
Chemical equation is:
239.08 281.05
400×99.5% 465×98.5%
Wherein, the molecular weight of dichloro-diphenyl ether is 239.08, and the molecular weight of dichloro-diphenyl ether ketone is 281.05; Content >=99.5% of dichloro-diphenyl ether during suitability for industrialized production.
The yield of the dichloro-diphenyl ether ketone finished product that the present embodiment obtains is:
Embodiment 2
In the present embodiment, the weight that feeds intake of the anhydrous ethylene dichloride of organic solvent, dichloro-diphenyl ether, Catalyzed by Anhydrous Aluminium Chloride agent and Acetyl Chloride 98Min. is respectively: 1120kg, 400kg, 40kg, 122kg, agitator speed is 85 revs/min, all the other steps, with embodiment 1, finally make dichloro-diphenyl ether ketone finished product 460kg.
The finished product that it makes: white crystals, content: >=98.0%, moisture content :≤0.5%.Industrialization yield reaches 96.35%.
After the same method, the yield that calculates the dichloro-diphenyl ether ketone finished product that the present embodiment obtains is:
Embodiment 3
In the present embodiment, the weight that feeds intake of the anhydrous ethylene dichloride of organic solvent, dichloro-diphenyl ether, Catalyzed by Anhydrous Aluminium Chloride agent and Acetyl Chloride 98Min. is respectively: 1160kg, 400kg, 120kg, 148kg, agitator speed is 150 revs/min, all the other steps, with embodiment 1, finally make dichloro-diphenyl ether ketone finished product 466kg.
The finished product that it makes: white crystals, content: >=98.5%, moisture content :≤0.5%.Industrialization yield reaches 98.11%.
After the same method, the yield that calculates the dichloro-diphenyl ether ketone finished product that the present embodiment obtains is:
From above-described embodiment, a kind of method that improves dichloro-diphenyl ether ketone yield provided by the invention, the dichloro-diphenyl ether ketone finished product making all meets specification of quality, and yield all reaches more than 96%, by optimization, improve reactor structure, optimize ingredient proportion and control temperature of reaction, time etc., reaction conditions is gentle, has effectively improved dichloro-diphenyl ether ketone yield, reduced catalyst levels, thereby reduced production cost, and three waste discharge is few, is suitable for applying on a large scale.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. a method that improves dichloro-diphenyl ether ketone yield, is characterized in that, comprises the steps:
(1) dichloro-diphenyl ether be dissolved in to organic solvent and add in carbon steel open type reactor, four symmetrical baffle plates are installed in reactor, the boolean Ma Jinshi agitator of opening in reactor stirs, and agitator speed is 85～150 revs/min, and to control carbon steel reactor temperature be 10～15 ℃;
(2) in reactor, add Catalyzed by Anhydrous Aluminium Chloride agent, by the chilled brine passing in reactor external jacket, lower the temperature, then in reactor, drip Acetyl Chloride 98Min., control rate of addition and make between temperature keeps 15～20 ℃;
(3) drip and finish rear insulation 2～2.5 hours, finish reaction; Reactor is progressively cooled to 5～10 ℃ and discharge to hydrolysis kettle reaction solution is hydrolyzed, remove Catalyzed by Anhydrous Aluminium Chloride agent;
(4) reaction solution after hydrolysis, again through washing, precipitation, decolouring, crystallization, centrifugal, air-dry, obtains dichloro-diphenyl ether ketone finished product;
In above-mentioned steps, the weight ratio that feeds intake of organic solvent, dichloro-diphenyl ether, Catalyzed by Anhydrous Aluminium Chloride agent and Acetyl Chloride 98Min. is: 28～30:10:1～3:3.3～3.7.
2. a kind of method that improves dichloro-diphenyl ether ketone yield as claimed in claim 1, is characterized in that, described organic solvent is anhydrous ethylene dichloride.
3. a kind of method that improves dichloro-diphenyl ether ketone yield as claimed in claim 1, is characterized in that, in described step (1), agitator speed is 130 revs/min.
4. a kind of method that improves dichloro-diphenyl ether ketone yield as claimed in claim 1, is characterized in that, described Catalyzed by Anhydrous Aluminium Chloride agent is highly active Catalyzed by Anhydrous Aluminium Chloride agent, and granularity is at 10～20 orders.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876811A (en) * | 2015-02-09 | 2015-09-02 | 周保东 | Purification method of 2-chloro-4-(4-chlorophenoxy)acetophenone |
| CN113816838A (en) * | 2021-08-05 | 2021-12-21 | 宁夏瑞泰科技股份有限公司 | Synthetic method of 2-chloro-4- (4-chlorophenoxy) -acetophenone |
| CN113861004A (en) * | 2021-11-03 | 2021-12-31 | 山东潍坊双星农药有限公司 | Catalytic synthesis method of difenoconazole intermediate difenone |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113816838A (en) * | 2021-08-05 | 2021-12-21 | 宁夏瑞泰科技股份有限公司 | Synthetic method of 2-chloro-4- (4-chlorophenoxy) -acetophenone |
| CN113861004A (en) * | 2021-11-03 | 2021-12-31 | 山东潍坊双星农药有限公司 | Catalytic synthesis method of difenoconazole intermediate difenone |
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