CN109251137A - The synthetic method of one kind 2,4- dichloroacetophenone - Google Patents
The synthetic method of one kind 2,4- dichloroacetophenone Download PDFInfo
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- CN109251137A CN109251137A CN201811073612.8A CN201811073612A CN109251137A CN 109251137 A CN109251137 A CN 109251137A CN 201811073612 A CN201811073612 A CN 201811073612A CN 109251137 A CN109251137 A CN 109251137A
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- dichloroacetophenone
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- synthetic method
- dichlorobenzene
- aceticanhydride
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses the synthetic methods of one kind 2,4- dichloroacetophenone, synthesize 2,4- dichloroacetophenone by electrophilic substitution reaction using m-dichlorobenzene and aceticanhydride as raw material.The present invention carries out the electrophilic substitution reaction by the way of reactive distillation, by adjusting the vacuum degree of reactive distillation column, controls reactive distillation column bottom temperature and carries out reactive distillation under optimal temperature conditions.Catalyst consumption, aceticanhydride unit consumption are reduced, production technology is simplified.
Description
Technical field
The present invention relates to Fine Organic Chemicals to synthesize field, and in particular to a kind of medicine intermediate 2,4- dichloroacetophenone
Synthetic method.
Background technique
2,4- dichloroacetophenones, English name: 2,4-Dichloroacetophenone, it is that a kind of important medicine is intermediate
Body is mainly used for synthetic antifunguses object ketoconazole.
The chemosynthesis reaction of 2,4- dichloroacetophenones is as described below:
Reaction equation
2004, Guo Yong China of Zhejiang University etc. delivered entitled " 2,4- dichloro-benzenes in " Chemical Reaction Engineering and technique "
The study on the synthesis of ethyl ketone " article.Reaction dissolvent, anhydrous AlCl are made using carbon disulfide in text3Make catalyst, chloroacetic chloride makees acyl
Agent controls interior temperature and electrophilic substitution reaction occurs under the conditions of 15 DEG C, can achieve higher selectivity and yield, but curing
Carbon has the security risks outstanding such as toxicity is big, inflammable, explosive, limits the application of the process program in the industrial production.It should
Technique uses the chloroacetic chloride with intense irritation smell to make acylating agent, and micro run, drip, leak can all cause production environment
It is exceedingly odious, it is easy replaced other environmental-friendly acylation process.
2010, Jiangsu Longchang Chemical Co., Ltd applied for " a kind of to utilize solid waste chlorobenzene coke tar for raw material 2,4- bis-
The production method of chloro-acetophenone " patent (CN101898947A).The patent describe one kind to mention from solid waste chlorobenzene coke tar
M-dichlorobenzene is taken, then m-dichlorobenzene carries out acylation reaction with chloroacetic chloride under the action of aluminum trichloride (anhydrous) and obtains 2,4- dichloro
The process program of acetophenone.Emphasis of the invention is, recycles m-dichlorobenzene from solid waste chlorobenzene tar, then with
The m-dichlorobenzene of recycling is that raw material produces 2,4- dichloroacetophenone.The patented technology fully utilize in chlorobenzene coke tar between two
Chlorobenzene solves the trouble and worry of m-dichlorobenzene, o-dichlorohenzene manufacturing enterprise, develops and uses by-product production extension product, reaches
The purpose of comprehensive utilization of resources is arrived.The patent does not provide the specific reaction result of m-dichlorobenzene electrophilic substitution reaction clear
Data.
2012, Jiangsu Longchang Chemical Co., Ltd applied for the patent of " production method of one kind 2,4- dichloroacetophenone "
(CN102675073A).The patent uses anhydrous AlCl3Make catalyst, aceticanhydride makees acylating agent, obtains by electrophilic substitution reaction
2,4- dichloroacetophenones.The emphasis of the patent is, using the m-dichlorobenzene in chlorinated aromatics waste as raw material production 2,4-
Dichloroacetophenone solves the handling problems of waste in benzene chlorination process, improves the utilization rate of chlorinated aromatics, reduces life
Production expense realizes the comprehensive utilization of solid waste resource, avoids the pollution to environment.The patent is anti-to m-dichlorobenzene parental materials
The specific reaction effect answered does not have specific data.
Summary of the invention
The technical problem to be solved by the present invention is to reduce anhydrous aluminum chloride unit consumption, aceticanhydride unit consumption is reduced, reduces synthesis 2,
The cost of material of 4- dichloroacetophenone.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that:
Electrophilic substitution reaction occurs in the case where anhydrous aluminum chloride makees catalysts conditions with aceticanhydride and synthesizes 2,4- dichloro for m-dichlorobenzene
Acetophenone.
Preferably, m-dichlorobenzene and aceticanhydride carry out electrophilic substitution reaction, the tower of rectifying column in the reaction flask with rectifying column
The acetic acid that top extraction reaction generates；The bed stuffing height of the rectifying column is equivalent to 5~30 pieces of theoretical plates.
Preferably, the mass ratio that feeds intake of m-dichlorobenzene and anhydrous aluminum chloride is 1:0.95~1.36.
It is further preferred that the mass ratio that feeds intake of m-dichlorobenzene and aceticanhydride is 1:1.1~5.5.
Preferably, it by adjusting the vacuum degree of rectifying column, controls temperature in reaction flask and is carried out under the conditions of 40~90 DEG C instead
Answer rectifying.
It is further preferred that the reflux ratio for controlling rectifying column in reactive distillation processes is 0.5~6:1.
Still further preferably, the reaction time is 6~15 hours.
Preferably, end of reaction improves the vacuum degree of reactive distillation system, and aceticanhydride excessive in reaction kettle is steamed from tower top
Out, it is applied after detection level.
The principle of the present invention is as described below:
Firstly, minor amount of water present in anhydrous aluminum chloride and reaction system occur metathesis reaction formed micro hydrogen chloride and
Aluminium hydroxide, hydrogen chloride react to form chloroacetic chloride and acetic acid with aceticanhydride；Then, chloroacetic chloride is under the action of anhydrous aluminum chloride, shape
At acetyl carbonium ion and stable aluminum tetrachloride anion；Finally, acetyl carbonium ion and m-dichlorobenzene are in anhydrous aluminum chloride
Catalytic action under occur electrophilic substitution reaction synthesize 2,4- dichloroacetophenone.
The processes such as anhydrous aluminum chloride hydrolysis, aceticanhydride decomposition are required no as acylating agent using chloroacetic chloride, it can be directly in nothing
The effect of water aluminium chloride is lower and m-dichlorobenzene carries out electrophilic substitution reaction and obtains 2,4- dichloroacetophenone, so chloroacetic chloride is more than aceticanhydride
It is easy and electrophilic substitution reaction occurs for m-dichlorobenzene.Usual situation needs more anhydrous aluminum chlorides as acylating agent using aceticanhydride
Inventory, more aceticanhydride inventorys, higher reaction temperature can be only achieved the effect of excess acetyl chloride.
The present invention introduces a kind of synthetic method of completely new 2,4- dichloroacetophenone.Firstly, by the way of reactive distillation
Electrophilic substitution reaction is carried out, the acetic acid separated that electrophilic substitution reaction is formed is gone out by reaction system by rectifying action, it in this way can be with
Guarantee that the concentration of m-dichlorobenzene in entire reaction system, anhydrous aluminum chloride, aceticanhydride all in highest level, avoids the acetic acid because of formation
Residual reduces the concentration of reaction raw materials in the reaction system, reduces reaction speed.It is reacted using reactive distillation mode,
It can use the reaction heat that electrophilic substitution reaction releases, achieve the purpose that comprehensive utilization of energy；Secondly, under condition of negative pressure into
Row reactive distillation controls reaction temperature near optimal temperature spot by negative-pressure operation.Reflux course is inherently a kind of
Violent mixing process can make up the reaction bad adverse effect to reaction of mixing effect, eliminate putting for mass transfer
Big effect；Finally, end of reaction, directly improves vacuum degree and recycles out excessive aceticanhydride and apply in next group, technical process
Succinctly.
The present invention is isolated the acetic acid that reaction generates using reaction rectification technique from reaction system, by optimization pair
Than that can achieve the purpose that for acetic acid and aceticanhydride to be effectively separated using the rectifying column of 5~30 pieces of theoretical plates.In an experiment
The separating effect of 5~30 pieces of theoretical plates can be reached using the glass spring circle filler of 100-1000mm.
The electrophilic substitution reaction is carried out by using reactive distillation mode, and the mass ratio of m-dichlorobenzene and aluminium chloride is 1:
Relatively good reaction effect can be reached between 0.95~1.36.The mass ratio that feeds intake of m-dichlorobenzene and aceticanhydride is in 1:1.1
~5.5 can guarantee the conversion ratio and selectivity of reaction.Although specific consersion unit has bigger difference, by adjusting
Reaction system vacuum degree, as long as temperature control system is formed reaction under conditions of 0.5~6:1 of reflux ratio at 40~90 DEG C in reacting
Acetic acid isolate reaction system in time and can guarantee to obtain satisfied reaction effect.It is anti-under the above-described reaction conditions by optimizing
Answering 6~15 hours can be by m-dichlorobenzene fully reacting.
The present invention has the advantage that
1, anhydrous aluminum chloride unit consumption is low, aceticanhydride unit consumption is low, fully utilizes the reaction heat of electrophilic substitution reaction；
2, reaction and rectifying are completed in the same equipment, and process is simple, and equipment investment is few, easy to operate.
Specific embodiment
The present invention is specifically described below by embodiment, but the present invention is not limited to these Examples.
Embodiment 1
Vinegar is put into the dry 500ml four-hole boiling flask for having agitating paddle, thermometer, constant pressure dropping funnel, rectifying column
Acid anhydride: 200.0g, anhydrous AlCl3: 100.0g.M-dichlorobenzene is added into constant pressure dropping funnel: 100.0g (98.3%,
0.6687mol).Four-hole boiling flask outer wall is kept the temperature with water-bath, sets water-bath hot water temperature as 55 DEG C.Stirring is opened, essence is opened
Top vacuum is evaporated, rectifying tower top vacuum degree >=0.085MPa is adjusted.It, slowly will be in constant pressure dropping funnel when interior temperature reaches 40 DEG C
M-dichlorobenzene is added dropwise in four-hole boiling flask, and time for adding was controlled at 0.5~1.0 hour.During dropwise addition, the top of the distillation column slowly goes out
Now flow back, the acetic acid that control 1~5:1 of reflux ratio extraction reaction is formed.It is added dropwise, water-bath hot water temperature is increased to 80~
It 90 DEG C, reduces top vacuum degree and regards tower during heat preservation in control four-hole boiling flask back flow reaction 8 hours under the conditions of 70~80 DEG C of temperature
Top temperature conditions produces the acetic acid to be formed.
Back flow reaction finishes, and improves reaction system vacuum degree to 0.09MPa or more, four-hole boiling flask outer wall is added with electric jacket
Heat recycles out excessive aceticanhydride in four-hole bottle under the conditions of controlling interior temperature less than 90 DEG C, next after the aceticanhydride detection level recycled out
It is applied when batch reaction.Recycling finishes, cooling, and toluene 200ml is added into four-hole boiling flask, is slowly added to 10% hydrochloric acid water
100~200ml of solution is dissolved.Dissolution finishes, and reaction solution is transferred in separatory funnel and carries out stratification.It has stood
Finish, divides to fall lower water.Upper toluene layer is transferred in 500ml three-necked flask, is greater than 0.085MPa in vacuum degree, temperature is less than
Toluene is recycled under the conditions of 85 DEG C.Recycling finishes, and obtains 2,4- dichloroacetophenone: 122.6 (97.9%, 0.635mol), calculates and receives
Rate: 95.0%.
Embodiment 2
Vinegar is put into the dry 500ml four-hole boiling flask for having agitating paddle, thermometer, constant pressure dropping funnel, rectifying column
Acid anhydride: 112.0g, anhydrous AlCl3: 95.0g.M-dichlorobenzene is added into constant pressure dropping funnel: 100.0g (98.3%,
0.6687mol).Four-hole boiling flask outer wall is kept the temperature with water-bath, sets water-bath hot water temperature as 55 DEG C.Stirring is opened, essence is opened
Top vacuum is evaporated, rectifying tower top vacuum degree >=0.085MPa is adjusted.It, slowly will be in constant pressure dropping funnel when interior temperature reaches 40 DEG C
M-dichlorobenzene is added dropwise in four-hole boiling flask, and time for adding was controlled at 0.5~1.0 hour.During dropwise addition, the top of the distillation column slowly goes out
Now flow back, the acetic acid that control 1~5:1 of reflux ratio extraction reaction is formed.It is added dropwise, water-bath hot water temperature is increased to 80~
It 90 DEG C, reduces top vacuum degree and regards tower during heat preservation in control four-hole boiling flask back flow reaction 8 hours under the conditions of 70~80 DEG C of temperature
Top temperature conditions produces the acetic acid to be formed.
Back flow reaction finishes, and improves reaction system vacuum degree to 0.09MPa or more, four-hole boiling flask outer wall is added with electric jacket
Heat recycles out excessive aceticanhydride in four-hole bottle under the conditions of controlling interior temperature less than 90 DEG C, next after the aceticanhydride detection level recycled out
It is applied when batch reaction.Recycling finishes, cooling, and toluene 200ml is added into four-hole boiling flask, is slowly added to 10% hydrochloric acid water
100~200ml of solution is dissolved.Dissolution finishes, and reaction solution is transferred in separatory funnel and carries out stratification.It has stood
Finish, divides to fall lower water.Upper toluene layer is transferred in 500ml three-necked flask, is greater than 0.085MPa in vacuum degree, temperature is less than
Toluene is recycled under the conditions of 85 DEG C.Recycling finishes, and obtains 2,4- dichloroacetophenone: 118.3 (95.9%, 0.600mol), calculates and receives
Rate: 89.8%.
Claims (8)
1. one kind 2, the synthetic method of 4- dichloroacetophenone, which is characterized in that m-dichlorobenzene and aceticanhydride are urged in anhydrous aluminum chloride
Electrophilic substitution reaction occurs under the conditions of agent and synthesizes 2,4- dichloroacetophenone.
2. a kind of synthetic method of 2,4- dichloroacetophenone according to claim 1, which is characterized in that with rectifying column
M-dichlorobenzene and aceticanhydride carry out electrophilic substitution reaction, the acetic acid that the overhead extraction reaction of rectifying column generates in reaction flask；The rectifying
The bed stuffing height of tower is equivalent to 5~30 pieces of theoretical plates.
3. a kind of synthetic method of 2,4- dichloroacetophenone according to claim 2, which is characterized in that m-dichlorobenzene and nothing
The mass ratio that feeds intake of water aluminium chloride is 1:0.95~1.36.
4. a kind of synthetic method of 2,4- dichloroacetophenone according to claim 3, which is characterized in that m-dichlorobenzene and vinegar
The mass ratio that feeds intake of acid anhydride is 1:1.1~5.5.
5. a kind of synthetic method of 2,4- dichloroacetophenone according to claim 4, which is characterized in that by adjusting rectifying
The vacuum degree of tower controls temperature in reaction flask and carries out reactive distillation under the conditions of 40~90 DEG C.
6. a kind of synthetic method of 2,4- dichloroacetophenone according to claim 5, which is characterized in that reactive distillation processes
The reflux ratio of middle control rectifying column is 0.5~6:1.
7. a kind of synthetic method of 2,4- dichloroacetophenone according to claim 5, which is characterized in that the reaction time 6
~15 hours.
8. a kind of synthetic method of 2,4- dichloroacetophenone according to claim 2, which is characterized in that end of reaction mentions
Aceticanhydride excessive in reaction kettle is steamed from tower top, is applied after detection level by the vacuum degree of high reactive distillation system.
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Cited By (3)
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| CN109721480A (en) * | 2018-11-14 | 2019-05-07 | 新昌县泰如科技有限公司 | The synthetic method of one kind 2,4- dichloroacetophenone |
| CN110922322A (en) * | 2019-11-01 | 2020-03-27 | 江苏隆昌化工有限公司 | Clean production method for improving reaction yield of 2, 4-dichloroacetophenone |
| CN113354520A (en) * | 2021-06-09 | 2021-09-07 | 江苏瑞恒新材料科技有限公司 | Synthetic method of 2, 4-dichloroacetophenone |
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| CN109721480A (en) * | 2018-11-14 | 2019-05-07 | 新昌县泰如科技有限公司 | The synthetic method of one kind 2,4- dichloroacetophenone |
| CN110922322A (en) * | 2019-11-01 | 2020-03-27 | 江苏隆昌化工有限公司 | Clean production method for improving reaction yield of 2, 4-dichloroacetophenone |
| CN113354520A (en) * | 2021-06-09 | 2021-09-07 | 江苏瑞恒新材料科技有限公司 | Synthetic method of 2, 4-dichloroacetophenone |
| CN113354520B (en) * | 2021-06-09 | 2022-04-19 | 江苏瑞恒新材料科技有限公司 | Synthetic method of 2, 4-dichloroacetophenone |
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