阅读说明：本技术 一种1-（4-氯苯基）-3-丁烯-1-醇的生产方法 (Production method of 1- (4-chlorphenyl) -3-butene-1-ol ) 是由 杨志 李劲 陈月佳 刘志刚 吴同文 朱梦鑫 范敏琪 张磊 林炳安 陈璐 于 2018-06-26 设计创作，主要内容包括：本发明涉及一种1-(4-氯苯基)-3-丁烯-1-醇的生产方法,包括以下几个步骤,在反应釜内,加入水、粉碎好的对氯苯甲醛、催化剂,快速搅拌,室温下滴加3-氯丙烯,滴加时间5-7小时,滴完后保温2小时,反应完成后抽滤,滤液分层取下层,干燥后得油状透明液体1-(4-氯苯基)-3-丁烯-1-醇,含量95％-95.9％,收率93％-95％,其中对氯苯甲醛和3-氯丙烯的摩尔比为1∶1.05-1.08,对氯苯甲醛和锌粉的摩尔比为1∶0.5-1.01,催化剂质量为对氯苯甲醛质量的0.4-0.7％,反应温度为15-30℃,反应时间7-9小时,收率93-95％。本发明收率高,生产成本低,不需要无水无氧条件下操作,不需要处理易燃有机溶剂,不需要保护底物或反应物上活泼氢,反应速度和反应选择性高,安全性好,符合绿色环保理念。(The invention relates to a method for producing 1- (4-chlorphenyl) -3-butylene-1-alcohol, which comprises the following steps of adding water, crushed p-chlorobenzaldehyde and a catalyst into a reaction kettle, quickly stirring, dropwise adding 3-chloropropene at room temperature for 5-7 hours, preserving heat for 2 hours after dropwise adding, carrying out suction filtration after reaction is finished, taking a lower layer from filtrate in layers, drying to obtain oily transparent liquid 1- (4-chlorphenyl) -3-butylene-1-alcohol with the content of 95-95.9 percent and the yield of 93-95 percent, wherein the molar ratio of the p-chlorobenzaldehyde to the 3-chloropropene is 1: 1.05-1.08, the molar ratio of the p-chlorobenzaldehyde to zinc powder is 1: 0.5-1.01, the mass of the catalyst is 0.4-0.7 percent of the mass of the p-chlorobenzaldehyde, the reaction temperature is 15-30 ℃, the reaction time is 7-9 hours, and the yield is 93-95%. The method has the advantages of high yield, low production cost, no need of operation under anhydrous and anaerobic conditions, no need of processing flammable organic solvents, no need of protecting active hydrogen on substrates or reactants, high reaction speed and reaction selectivity, good safety and accordance with the concept of environmental protection.)

1. A production method of 1- (4-chlorphenyl) -3-butene-1-ol is characterized in that: the production method comprises the following steps:

1) adding water, the crushed p-chlorobenzaldehyde, zinc powder and a catalyst into a reaction kettle, quickly stirring, dropwise adding 3-chloropropene at room temperature for 5-7 hours, and preserving heat for 2 hours after dropwise adding;

2) sampling and analyzing, carrying out suction filtration after the reaction is finished, taking the lower layer from the filtrate by layers, and drying to obtain oily transparent liquid 1- (4-chlorphenyl) -3-butene-1-ol;

wherein the molar ratio of the p-chlorobenzaldehyde to the 3-chloropropene is 1: 1.05-1.08, the mass of the catalyst is 0.4-0.7% of that of the p-chlorobenzaldehyde, the molar ratio of the p-chlorobenzaldehyde to the zinc powder is 1: 0.5-1.01, and the chemical reaction formula of the reaction is as follows:

2. the process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 1, characterized in that: the catalyst is cuprous chloride, and the chemical reaction formula of the reaction is as follows:

3. the process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 1, characterized in that: the catalyst is indium chloride, and the chemical reaction formula of the reaction is as follows:

4. the process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 1, characterized in that: the catalyst is a mixture of cuprous chloride and indium chloride in any ratio.

5. The process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 1, characterized in that: the reaction solvent is water, and the water adopts ordinary tap water, soft water and hard water, and does not need an organic solvent; the zinc powder is superfine zinc powder.

6. The process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 1, characterized in that: the p-chlorobenzaldehyde is required to be crushed into particles with the granularity of more than 400 meshes.

7. The process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 5, characterized in that: the zinc powder adopts 400-mesh and 600-mesh particles.

8. The process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 1, characterized in that: the reaction temperature required for the reaction is room temperature and is controlled between 15 and 30 ℃.

9. The process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 1, characterized in that: the molar ratio of the p-chlorobenzaldehyde to the zinc powder is 1: 0.8.

10. The process for the production of 1- (4-chlorophenyl) -3-buten-1-ol according to claim 2, characterized in that: the mass of the cuprous chloride is 0.5 percent of that of the p-chlorobenzaldehyde.

Technical Field

The invention relates to the field of bactericides, and in particular relates to a production method of 1- (4-chlorphenyl) -3-butene-1-ol.

Background

The cyproconazole is an excellent triazole bactericide developed by Swiss and mountain Dow company, and has the characteristics of high efficiency, low toxicity, broad spectrum and the like. Is a sterol demethylation inhibitor, and has prophylactic and therapeutic effects. It is effective on powdery mildew, rust fungi, spore, coracocephalosporium, septoria, and Venturia fungi of cereal crops, coffee, beet, fruit trees, and grape. When the composition is mixed with other bactericides, the composition can well prevent and treat the eyespot disease, the leaf spot disease and the net spot disease of cereals. The lasting period for preventing and controlling wheat rust is 4-6 weeks, and the period for preventing and controlling powdery mildew is 3-4 weeks. Powdery mildew of cereals, fruit trees and grapes, leaf spot of peanuts and beets, apple scab and white rot of peanuts.

1- (4-chlorphenyl) -3-buten-1-ol is an important intermediate of cyproconazole, the synthesis process of the 1- (4-chlorphenyl) -3-buten-1-ol is described in more detail in Chinese patent CN101857576B, fine chemical intermediate 2010, volume 40, phase 5 (authors: Tongyun and Wumei) and chemical reagent 2010, volume 32, phase 10 (authors: Lihongbo, etc.), the synthesis of the 1- (4-chlorphenyl) -3-buten-1-ol is mainly prepared by Grignard reaction of allyl chloride or allyl bromide and p-chlorobenzaldehyde, and a common reaction solvent is diethyl ether or tetrahydrofuran.

The Grignard reaction refers to the nucleophilic addition reaction of the carbonyl group of an aldehyde ketone with an organomagnesium reagent, and is one of the most important reactions for the formation of new carbon-carbon bonds. However, the organic magnesium reagent is generally highly sensitive to water and air, and needs to be operated under anhydrous and anaerobic conditions, the used solvent diethyl ether or tetrahydrofuran has low flash point, is flammable and explosive, has large dosage in the reaction, is not good in reaction initiation, is easy to generate material flushing or explosion danger, and is not guaranteed in production safety of enterprises.

Therefore, how to provide a method for producing 1- (4-chlorphenyl) -3-buten-1-ol which is economical, environment-friendly, safe and stable is a problem to be solved urgently by the technical personnel in the field. To solve this problem, the invention is particularly proposed.

Disclosure of Invention

The invention aims to provide a production method of 1- (4-chlorphenyl) -3-butene-1-ol, which replaces an organic solvent with water, is economic, environment-friendly, safe and stable, is simple and convenient to operate, avoids using the organic solvent, reduces the environment-friendly treatment pressure, ensures the safety in the reaction process, obviously reduces the production cost, and is suitable for industrial production.

The invention is realized by the following technical scheme:

a process for the production of 1- (4-chlorophenyl) -3-buten-1-ol, said process comprising the steps of:

3) adding water, the crushed p-chlorobenzaldehyde, zinc powder and a catalyst into a reaction kettle, quickly stirring, dropwise adding 3-chloropropene at room temperature for 5-7 hours, and preserving heat for 2 hours after dropwise adding;

4) sampling and analyzing, carrying out suction filtration after the reaction is finished, taking the lower layer from the filtrate by layers, and drying to obtain oily transparent liquid 1- (4-chlorphenyl) -3-butene-1-ol;

wherein the molar ratio of the p-chlorobenzaldehyde to the 3-chloropropene is 1: 1.05-1.08, the mass of the catalyst is 0.4-0.7% of that of the p-chlorobenzaldehyde, the molar ratio of the p-chlorobenzaldehyde to the zinc powder is 1: 0.5-1.01, and the chemical reaction formula of the reaction is as follows:

preferably, the catalyst is cuprous chloride, and the chemical reaction formula of the reaction is as follows:

preferably, the catalyst is indium chloride, and the reaction has the following chemical reaction formula:

preferably, the catalyst is a mixture of cuprous chloride and indium chloride in any ratio.

Preferably, the reaction solvent is water, and the water is common tap water, soft water or hard water and does not need an organic solvent; the zinc powder is superfine zinc powder.

Preferably, the p-chlorobenzaldehyde is crushed into 400 mesh size.

Preferably, the zinc powder adopts 400-600 mesh particles.

Further, the reaction temperature required for the reaction is room temperature, and is controlled at 15-30 ℃.

Furthermore, the molar ratio of the p-chlorobenzaldehyde to the zinc powder is 1: 0.8.

Furthermore, the mass of the cuprous chloride is 0.5 percent of that of the p-chlorobenzaldehyde.

By the method, oily transparent liquid 1- (4-chlorphenyl) -3-butene-1-ol is obtained after drying, the content is 95-95.9 percent, and the yield is 93-95 percent.

The beneficial technical effects are as follows:

compared with the traditional Grignard Reaction, the Barbier Reaction (Barbier Reaction) adopted by the invention has the advantages of high yield, economy, low production cost, no need of operation under anhydrous and anaerobic conditions, no need of processing flammable organic solvents, no need of protecting active hydrogen on substrates or reactants, Reaction speed and Reaction selectivity improvement, safer Reaction, reduction of pollution of the solvents to the environment and the like, and conforms to the concept and requirements of environmental protection.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments, which are not intended to limit the invention, and all embodiments that are compatible with the solution of the present invention are within the scope of the present invention: