WO2014110696A1 - Process for preparing solid (chlorine methylene) dimethyl ammonium chloride - Google Patents
Process for preparing solid (chlorine methylene) dimethyl ammonium chloride Download PDFInfo
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- WO2014110696A1 WO2014110696A1 PCT/CN2013/000225 CN2013000225W WO2014110696A1 WO 2014110696 A1 WO2014110696 A1 WO 2014110696A1 CN 2013000225 W CN2013000225 W CN 2013000225W WO 2014110696 A1 WO2014110696 A1 WO 2014110696A1
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- phthalic anhydride
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- ammonium chloride
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- the invention belongs to the technical field of chemical product preparation and relates to a preparation process of solid (chloromethylene) dimethyl ammonium chloride.
- Solid (chloromethylene) dimethyl ammonium chloride is a highly reactive reagent which allows the hydroxyl groups in alcohol, enol, phenol and carboxylic acid molecules to be replaced by chlorine to form the corresponding organic chloride; It is also possible to introduce an aldehyde group into the molecules of some compounds; it is also possible to convert a carboxylic acid into an active ester derivative thereof and the like, and has a wide range of uses.
- (chloromethylene) dimethyl ammonium chloride prepared by the reaction of thionyl chloride with hydrazine, hydrazine-dimethylformamide (DMF), has two forms: Type I is a liquid, The activity is lower, type II is solid, and activity is higher than type I.
- the conversion reaction of type I and type II is a reversible reaction, and sulfur dioxide is bonded to type I. To make the reaction to the right to obtain type II, it is necessary to remove S0 2 by high vacuum.
- the method has high requirements on the degree of vacuum. Once the degree of vacuum is lowered, due to the presence of sulfur dioxide, type II rapidly converts to type I, releasing heat, which causes decomposition of (chloromethylene) dimethylammonium chloride, which in turn generates a large amount of gas. Rapid exothermic, easy to cause explosion hazard; and the solid (chloromethylene) dimethyl ammonium chloride obtained by this method is easy to crystallize on the inner wall of the reactor, and the solid (chloromethylene) dimethyl chloride must be artificially used. The ammonium is scraped out to discharge, which not only reduces the production efficiency, but also increases the chance of the product being exposed to moisture in the air.
- the object of the present invention is to provide a preparation process of solid (chloromethylene) dimethyl ammonium chloride, which not only avoids environmental pollution caused by "one-pot method" of sulfur dioxide, but also avoids high vacuum forced release.
- the vacuum degree is high, the operation is unstable, and the discharge is difficult.
- the preparation process of the solid (chloromethylene) dimethyl ammonium chloride according to the present invention is to first acylate the raw material phthalic anhydride with thionyl chloride to obtain phthaloyl chloride, and phthaloyl chloride. N,N-dimethylformamide is reacted to obtain (chloromethylene) dimethyl ammonium chloride and phthalic anhydride, and the resulting phthalic anhydride is dissolved in an excess of hydrazine, hydrazine-dimethylformamide, and is obtained by solid-liquid separation. Solid (chloromethylene) dimethyl ammonium chloride.
- the invention is carried out in two steps:
- the phthaloyl chloride is reacted with hydrazine, hydrazine-dimethylformamide at a temperature of from 0 to 60 °C.
- the N,N-dimethylformamide is used in an amount of from 1.5 to 5 times the mass of the raw material phthalic anhydride, and the amount of hydrazine, hydrazine-dimethylformamide is excessive relative to the phthalic anhydride.
- the reason is that the solubility of phthalic anhydride in hydrazine and hydrazine-dimethylformamide is very large, and phthalic anhydride (ie, phthalic anhydride as a reactant) generated in the step (2) can be completely dissolved by using hydrazine and dimethyl-dimethylformamide.
- chloromethylene dimethylammonium chloride is almost insoluble in the hydrazine, hydrazine-dimethylformamide solution of phthalic anhydride, and is in a solid state, so that solid-liquid separation is carried out to obtain a solid (chloromethylene). Dimethyl ammonium chloride.
- the present invention is achieved by a stepwise reaction.
- the first step is the synthesis of phthaloyl chloride, which first removes sulfur dioxide, and the second step produces solid (chloromethylene) dimethyl ammonium chloride, while recovering phthalic anhydride.
- solid (chloromethylene) dimethyl ammonium chloride was obtained, and phthalic anhydride used as a raw material was regenerated. Solid (chloromethylene) dimethyl ammonium chloride can be obtained smoothly by a stepwise reaction and a phthalic anhydride.
- the solid content of the obtained (chloromethylene) dimethyl chloride hinge was 85.0%.
- reaction equation of the present invention is as follows:
- the sulfur dioxide is first released by the first step reaction, so that it is not necessary to forcibly remove the dioxane under high vacuum conditions.
- the sulphurization makes the reaction conditions mild and easy to carry out.
- the invention not only avoids the environmental pollution caused by the "one-pot method" of sulfur dioxide, but also avoids the problems of high vacuum degree, unstable operation and difficulty in discharging the high-vacuum forced removal of sulfur dioxide.
- the invention has safe and convenient operation. , easy to implement features.
- phthalic anhydride 60 g was added to a 1000 ml reaction flask, and 300 ml of thionyl chloride was slowly added dropwise. After the dropwise addition was completed, the reaction was started until no tail gas was generated, and excess thionyl chloride was distilled off under normal pressure, and phthaloyl chloride was distilled off under reduced pressure.
- the metered 100g N,N-dimethylformamide was put into a 500ml reaction flask, protected by high-purity nitrogen gas, and the stirring was started. Phthaloyl chloride was added dropwise to the reaction flask to adjust the reaction rate of the dropping rate to 55-60 ⁇ , after the addition is completed, stir at 55-60 ° C for 0.5 h, discharge to the filter, protect with high purity nitrogen, filter, filter cake washed with N, N-dimethylformamide to no phthalic anhydride, put Material packaging.
- the obtained solid (chloromethylene) dimethyl chloride hinge had a mass of 47.88 g and a mass percentage of 86.22%.
- phthalic anhydride 60 g was added to a 1000 ml reaction flask, and 300 ml of thionyl chloride was slowly added dropwise. After the dropwise addition was completed, the reaction was started until no tail gas was generated, and excess thionyl chloride was distilled off under normal pressure, and phthaloyl chloride was distilled off under reduced pressure.
- the metered 150g N,N-dimethylformamide was put into a 500ml reaction flask, and it was filled with high purity nitrogen gas.
- the stirring was started, and phthaloyl chloride was added dropwise to the reaction flask to adjust the reaction rate of the dropping rate to 45-50 ⁇ , after the addition is completed, stir at 40-45 ° C for 0.5 h, discharge to the filter, protect with high purity nitrogen, filter, filter cake washed with N, N-dimethylformamide to no phthalic anhydride, put Material packaging.
- the obtained solid (chloromethylene) dimethylammonium chloride had a mass of 46.21 g and a mass percentage of 87.15%.
- phthalic anhydride 60 g was added to a 1000 ml reaction flask, and 300 ml of thionyl chloride was slowly added dropwise. After the dropwise addition was completed, the reaction was started until no tail gas was generated, and excess thionyl chloride was distilled off under normal pressure, and phthaloyl chloride was distilled off under reduced pressure.
- the metered 180 g of N,N-dimethylformamide was placed in a 500 ml reaction flask, filled with high purity nitrogen gas, and stirred, and phthaloyl chloride was added dropwise to the reaction flask to adjust the reaction rate by controlling the dropping rate. 30-35 ° C, after the completion of the dropwise addition, stirring at 30-35 ° C for 0.5 h, discharge to the filter, high purity nitrogen protection, filtration, filter cake washed with N, N-dimethylformamide to no Phthalic anhydride, discharge packaging.
- the obtained solid (chloromethylene) dimethyl ammonium chloride has a mass of 47.21 g and a mass percentage of 85.22%.
- phthalic anhydride 60 g was added to a 1000 ml reaction flask, 300 ml of thionyl chloride was slowly added dropwise, and the addition was completed. Exhaust gas is generated, excess thionyl chloride is distilled off under normal pressure, and phthaloyl chloride is distilled off under reduced pressure.
- the metered 240 g of N,N-dimethylformamide was placed in a 500 ml reaction flask, and protected with high purity nitrogen gas, stirring was started, phthaloyl chloride was added dropwise to the reaction flask, and the reaction rate was controlled by adjusting the dropping rate. 20-25 ° C, after the completion of the dropwise addition, stirring at 20-25 ° C for 0.5 h, discharge to the filter, high purity nitrogen protection, filtration, filter cake washed with N, N-dimethylformamide to no Phthalic anhydride, discharge packaging.
- the obtained solid (chloromethylene) dimethylammonium chloride had a mass of 47.98 g and a mass percentage of 86.36%.
- phthalic anhydride 60 g was added to a 1000 ml reaction flask, and 300 ml of thionyl chloride was slowly added dropwise. After the dropwise addition was completed, the reaction was started until no tail gas was generated, and excess thionyl chloride was distilled off under normal pressure, and phthaloyl chloride was distilled off under reduced pressure.
- the metered 300 g of N,N-dimethylformamide was placed in a 500 ml reaction flask, and it was filled with high-purity nitrogen gas, stirred and stirred, and phthaloyl chloride was added dropwise to the reaction flask to adjust the drip acceleration control reaction.
- the temperature is 0-l (TC, after the addition is completed, the mixture is stirred at 0-10 ° C for 0.5 h, discharged to the filter, protected with high purity nitrogen, filtered, and the filter cake is washed with N,N-dimethylformamide until No phthalic anhydride, discharge packaging.
- the obtained solid (chloromethylene) dimethyl ammonium chloride had a mass of 45.29 g and a mass percentage of 87.55%.
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Abstract
A method for preparing solid (chlorine methylene) dimethyl ammonium chloride. The method comprises: carrying out acylating chlorination reaction on raw materials of phthalic anhydride and thionyl chloride to obtain o-phthaloyl chloride; o-phthaloyl chloride reacting with N,N-dimethylformamide to obtain (chlorine methylene) dimethyl ammonium chloride and phthalic anhydride; dissolving the generated phthalic anhydride in excessive N,N-dimethylformamide; and obtaining solid (chlorine methylene) dimethyl ammonium chloride through solid-liquid separation. The method discharges sulfur dioxide through the first step of reaction, so that sulfur dioxide does not need to be forcedly removed in a high vacuum condition, thereby making the reaction condition mild and the implementation easy.
Description
说 明 书 Description
固体 （氯亚甲基） 二甲基氯化铵的制备工艺 技术领域 Process for preparing solid (chloromethylene) dimethyl ammonium chloride
本发明属于化工产品制备技术领域， 涉及一种固体 （氯亚甲基） 二甲基氯化铵的制备工 艺。 The invention belongs to the technical field of chemical product preparation and relates to a preparation process of solid (chloromethylene) dimethyl ammonium chloride.
背景技术 Background technique
固体 （氯亚甲基） 二甲基氯化铵是一种具有强大反应活性的试剂， 它可以使醇、 烯醇、 酚和羧酸分子中的羟基被氯置换， 生成相应的有机氯化物； 也可以在一些化合物的分子中引 入醛基； 还可以使羧酸变成它的活性酯衍生物等， 具有广泛的用途。 Solid (chloromethylene) dimethyl ammonium chloride is a highly reactive reagent which allows the hydroxyl groups in alcohol, enol, phenol and carboxylic acid molecules to be replaced by chlorine to form the corresponding organic chloride; It is also possible to introduce an aldehyde group into the molecules of some compounds; it is also possible to convert a carboxylic acid into an active ester derivative thereof and the like, and has a wide range of uses.
现有技术中， 由氯化亚砜和 Ν,Ν-二甲基甲酰胺（DMF) 反应制得的 （氯亚甲基）二甲基 氯化铵， 有两种形态： I型为液体， 活性较低， II型为固体， 活性较 I型高。 I型与 II型的 转化反应为一可逆反应， 二氧化硫是键合于 I型中， 要使反应向右进行得到 II型， 需采用高 真空将 S02脱除。 In the prior art, (chloromethylene) dimethyl ammonium chloride prepared by the reaction of thionyl chloride with hydrazine, hydrazine-dimethylformamide (DMF), has two forms: Type I is a liquid, The activity is lower, type II is solid, and activity is higher than type I. The conversion reaction of type I and type II is a reversible reaction, and sulfur dioxide is bonded to type I. To make the reaction to the right to obtain type II, it is necessary to remove S0 2 by high vacuum.
反应方程式如下- 、 The reaction equation is as follows -
C1 C1— C1 C1—
I型 II型 Type I Type II
该法对真空度要求高， 一旦真空度降低， 由于二氧化硫的存在， II型迅速向 I型转化， 放出热量， 导致 （氯亚甲基） 二甲基氯化铵产生分解， 继而产生大量气体且急剧放热， 容易 造成爆炸危险； 并且该方法得到的固体 （氯亚甲基） 二甲基氯化铵易在反应器内壁上结晶， 必须采用人工将固体 （氯亚甲基） 二甲基氯化铵刮出， 才能出料， 不仅降低了生产效率， 也 增加了产品暴露在空气中接触水分的机会。 The method has high requirements on the degree of vacuum. Once the degree of vacuum is lowered, due to the presence of sulfur dioxide, type II rapidly converts to type I, releasing heat, which causes decomposition of (chloromethylene) dimethylammonium chloride, which in turn generates a large amount of gas. Rapid exothermic, easy to cause explosion hazard; and the solid (chloromethylene) dimethyl ammonium chloride obtained by this method is easy to crystallize on the inner wall of the reactor, and the solid (chloromethylene) dimethyl chloride must be artificially used. The ammonium is scraped out to discharge, which not only reduces the production efficiency, but also increases the chance of the product being exposed to moisture in the air.
发明内容 Summary of the invention
本发明的目的是提供一种固体（氯亚甲基）二甲基氯化铵的制备工艺，该工艺既避免了"一 锅法"产生的二氧化硫对环境的污染， 也避免了高真空强行脱除二氧化硫方法的真空度高、操 作不稳、 出料难的问题。 The object of the present invention is to provide a preparation process of solid (chloromethylene) dimethyl ammonium chloride, which not only avoids environmental pollution caused by "one-pot method" of sulfur dioxide, but also avoids high vacuum forced release. In addition to the sulfur dioxide method, the vacuum degree is high, the operation is unstable, and the discharge is difficult.
本发明所述的固体 （氯亚甲基） 二甲基氯化铵的制备工艺， 是先将原料苯酐与氯化亚砜 进行酰氯化反应得到邻苯二甲酰氯， 邻苯二甲酰氯再与 N，N-二甲基甲酰胺反应得到 （氯亚甲 基） 二甲基氯化铵与苯酐， 生成的苯酐溶解于过量的 Ν,Ν-二甲基甲酰胺中， 经固液分离得到
固体 （氯亚甲基） 二甲基氯化铵。 The preparation process of the solid (chloromethylene) dimethyl ammonium chloride according to the present invention is to first acylate the raw material phthalic anhydride with thionyl chloride to obtain phthaloyl chloride, and phthaloyl chloride. N,N-dimethylformamide is reacted to obtain (chloromethylene) dimethyl ammonium chloride and phthalic anhydride, and the resulting phthalic anhydride is dissolved in an excess of hydrazine, hydrazine-dimethylformamide, and is obtained by solid-liquid separation. Solid (chloromethylene) dimethyl ammonium chloride.
本发明是分两步进行的： The invention is carried out in two steps:
( 1 ) 邻苯二甲酰氯的合成- 将原料苯酐与氯化亚砜进行酰氯化反应得到邻苯二甲酰氯和二氧化硫， 按常规工艺进行 即可； 生产过程中产生的 so2经回收可套用于氯化亚砜的生产， 实现循环经济。 (1) Synthesis of phthaloyl chloride - acid chlorination of raw material phthalic anhydride with thionyl chloride to obtain phthaloyl chloride and sulfur dioxide, which can be carried out according to a conventional process; so 2 produced in the production process can be recycled In the production of thionyl chloride, a circular economy is realized.
(2) 固体 （氯亚甲基） 二甲基氯化铵的合成 - 将第一步得到的邻苯二甲酰氯与 N，N-二甲基甲酰胺反应得到 （氯亚甲基）二甲基氯化铵 与苯酐， 生成的苯酐溶解于过量的 N，N-二甲基甲酰胺， 固体 （氯亚甲基） 二甲基氯化铵经固 液分离得到。 (2) Synthesis of solid (chloromethylene) dimethyl ammonium chloride - The phthaloyl chloride obtained in the first step is reacted with N,N-dimethylformamide to give (chloromethylene) dimethyl The ammonium chloride and the phthalic anhydride are formed, and the phthalic anhydride formed is dissolved in an excess of N,N-dimethylformamide, and the solid (chloromethylene) dimethyl ammonium chloride is obtained by solid-liquid separation.
所述的邻苯二甲酰氯与 Ν,Ν-二甲基甲酰胺反应温度为 0-60°C。 The phthaloyl chloride is reacted with hydrazine, hydrazine-dimethylformamide at a temperature of from 0 to 60 °C.
所述的 N，N-二甲基甲酰胺的用量为原料苯酐质量的 1.5-5倍， Ν,Ν-二甲基甲酰胺的用量 相对于苯酐是过量的。 原因是苯酐在 Ν，Ν-二甲基甲酰胺中的溶解度非常大， 使用过量 Ν，Ν- 二甲基甲酰胺可以将步骤 （2) 生成的苯酐（即作为反应物投入的苯酐）全部溶解， 而（氯亚 甲基） 二甲基氯化铵在苯酐的 Ν,Ν-二甲基甲酰胺溶液中几乎不溶， 呈固体状态， 因而进行固 液分离， 可以得到固体 （氯亚甲基） 二甲基氯化铵。 The N,N-dimethylformamide is used in an amount of from 1.5 to 5 times the mass of the raw material phthalic anhydride, and the amount of hydrazine, hydrazine-dimethylformamide is excessive relative to the phthalic anhydride. The reason is that the solubility of phthalic anhydride in hydrazine and hydrazine-dimethylformamide is very large, and phthalic anhydride (ie, phthalic anhydride as a reactant) generated in the step (2) can be completely dissolved by using hydrazine and dimethyl-dimethylformamide. And (chloromethylene) dimethylammonium chloride is almost insoluble in the hydrazine, hydrazine-dimethylformamide solution of phthalic anhydride, and is in a solid state, so that solid-liquid separation is carried out to obtain a solid (chloromethylene). Dimethyl ammonium chloride.
本发明是通过分步反应实现的， 第一步是邻苯二甲酰氯的合成， 先将二氧化硫脱除， 第 二步生成固体（氯亚甲基）二甲基氯化铵， 同时回收苯酐。通过分步反应， 既得到了固体（氯 亚甲基） 二甲基氯化铵， 又将作为原料使用的苯酐重新生成。 通过分步反应和苯酐的媒介作 用可以顺利得到固体 （氯亚甲基） 二甲基氯化铵。 The present invention is achieved by a stepwise reaction. The first step is the synthesis of phthaloyl chloride, which first removes sulfur dioxide, and the second step produces solid (chloromethylene) dimethyl ammonium chloride, while recovering phthalic anhydride. By the stepwise reaction, solid (chloromethylene) dimethyl ammonium chloride was obtained, and phthalic anhydride used as a raw material was regenerated. Solid (chloromethylene) dimethyl ammonium chloride can be obtained smoothly by a stepwise reaction and a phthalic anhydride.
制得的固体 （氯亚甲基） 二甲基氯化铰的质量百分含量 85.0%。 The solid content of the obtained (chloromethylene) dimethyl chloride hinge was 85.0%.
本发明的反应方程式如下： The reaction equation of the present invention is as follows:
本发明具有如下的有益效果： The invention has the following beneficial effects:
本发明中通过第一步反应先将二氧化硫放出， 从而不需要在高真空条件下强行脱除二氧
化硫， 使得反应条件温和， 易于实施。 本发明既避免了"一锅法"产生的二氧化硫对环境的污 染， 也避免了高真空强行脱除二氧化硫方法的真空度高、 操作不稳、 出料难的问题， 本发明 具有操作安全、 方便， 易于实施的特点。 In the present invention, the sulfur dioxide is first released by the first step reaction, so that it is not necessary to forcibly remove the dioxane under high vacuum conditions. The sulphurization makes the reaction conditions mild and easy to carry out. The invention not only avoids the environmental pollution caused by the "one-pot method" of sulfur dioxide, but also avoids the problems of high vacuum degree, unstable operation and difficulty in discharging the high-vacuum forced removal of sulfur dioxide. The invention has safe and convenient operation. , easy to implement features.
具体实施方式 detailed description
下面结合实施例对本发明做进一步描述： The present invention will be further described below in conjunction with the embodiments:
实施例 1 Example 1
在 1000ml反应瓶中加入苯酐 60g， 缓慢滴加氯化亚砜 300ml， 滴加完毕， 升温反应至无 尾气产生， 常压蒸出过量氯化亚砜， 减压蒸出邻苯二甲酰氯。 60 g of phthalic anhydride was added to a 1000 ml reaction flask, and 300 ml of thionyl chloride was slowly added dropwise. After the dropwise addition was completed, the reaction was started until no tail gas was generated, and excess thionyl chloride was distilled off under normal pressure, and phthaloyl chloride was distilled off under reduced pressure.
将计量好的 100g N，N-二甲基甲酰胺投入到 500ml的反应瓶中，充高纯氮气保护，开启搅 拌， 向反应瓶中滴加邻苯二甲酰氯， 调节滴加速度控制反应温度为 55-60Ό , 滴加完毕， 于 55-60°C保温搅拌 0.5h， 放料至过滤器， 高纯氮保护， 过滤， 滤饼用 N，N-二甲基甲酰胺洗涤至 无苯酐， 放料包装。 得到的固体 （氯亚甲基） 二甲基氯化铰质量为 47.88g， 质量百分含量为 86.22%。 The metered 100g N,N-dimethylformamide was put into a 500ml reaction flask, protected by high-purity nitrogen gas, and the stirring was started. Phthaloyl chloride was added dropwise to the reaction flask to adjust the reaction rate of the dropping rate to 55-60Ό, after the addition is completed, stir at 55-60 ° C for 0.5 h, discharge to the filter, protect with high purity nitrogen, filter, filter cake washed with N, N-dimethylformamide to no phthalic anhydride, put Material packaging. The obtained solid (chloromethylene) dimethyl chloride hinge had a mass of 47.88 g and a mass percentage of 86.22%.
实施例 2 Example 2
在 1000ml反应瓶中加入苯酐 60g， 缓慢滴加氯化亚砜 300ml， 滴加完毕， 升温反应至无 尾气产生， 常压蒸出过量氯化亚砜， 减压蒸出邻苯二甲酰氯。 60 g of phthalic anhydride was added to a 1000 ml reaction flask, and 300 ml of thionyl chloride was slowly added dropwise. After the dropwise addition was completed, the reaction was started until no tail gas was generated, and excess thionyl chloride was distilled off under normal pressure, and phthaloyl chloride was distilled off under reduced pressure.
将计量好的 150g N,N-二甲基甲酰胺投入到 500ml的反应瓶中， 充高纯氮气保护， 开启搅 拌， 向反应瓶中滴加邻苯二甲酰氯， 调节滴加速度控制反应温度为 45-50Ό , 滴加完毕， 于 40-45°C保温搅拌 0.5h， 放料至过滤器， 高纯氮保护， 过滤， 滤饼用 N，N-二甲基甲酰胺洗涤至 无苯酐， 放料包装。 得到的固体 （氯亚甲基） 二甲基氯化铵质量为 46.21g， 质量百分含量为 87.15%。 The metered 150g N,N-dimethylformamide was put into a 500ml reaction flask, and it was filled with high purity nitrogen gas. The stirring was started, and phthaloyl chloride was added dropwise to the reaction flask to adjust the reaction rate of the dropping rate to 45-50Ό, after the addition is completed, stir at 40-45 ° C for 0.5 h, discharge to the filter, protect with high purity nitrogen, filter, filter cake washed with N, N-dimethylformamide to no phthalic anhydride, put Material packaging. The obtained solid (chloromethylene) dimethylammonium chloride had a mass of 46.21 g and a mass percentage of 87.15%.
实施例 3 Example 3
在 1000ml反应瓶中加入苯酐 60g， 缓慢滴加氯化亚砜 300ml， 滴加完毕， 升温反应至无 尾气产生， 常压蒸出过量氯化亚砜， 减压蒸出邻苯二甲酰氯。 60 g of phthalic anhydride was added to a 1000 ml reaction flask, and 300 ml of thionyl chloride was slowly added dropwise. After the dropwise addition was completed, the reaction was started until no tail gas was generated, and excess thionyl chloride was distilled off under normal pressure, and phthaloyl chloride was distilled off under reduced pressure.
将计量好的 180 g N,N-二甲基甲酰胺投入到 500ml的反应瓶中， 充高纯氮气保护， 开启 搅拌， 向反应瓶中滴加邻苯二甲酰氯， 调节滴加速度控制反应温度为 30-35°C， 滴加完毕， 于 30-35'C保温搅拌 0.5h， 放料至过滤器， 高纯氮保护， 过滤， 滤饼用 N，N-二甲基甲酰胺洗涤至 无苯酐， 放料包装。 得到的固体 （氯亚甲基） 二甲基氯化铵质量为 47.21g， 质量百分含量为 85.22% The metered 180 g of N,N-dimethylformamide was placed in a 500 ml reaction flask, filled with high purity nitrogen gas, and stirred, and phthaloyl chloride was added dropwise to the reaction flask to adjust the reaction rate by controlling the dropping rate. 30-35 ° C, after the completion of the dropwise addition, stirring at 30-35 ° C for 0.5 h, discharge to the filter, high purity nitrogen protection, filtration, filter cake washed with N, N-dimethylformamide to no Phthalic anhydride, discharge packaging. The obtained solid (chloromethylene) dimethyl ammonium chloride has a mass of 47.21 g and a mass percentage of 85.22%.
实施例 4 Example 4
在 1000ml反应瓶中加入苯酐 60g， 缓慢滴加氯化亚砜 300ml, 滴加完毕， 升温反应至无
尾气产生， 常压蒸出过量氯化亚砜， 减压蒸出邻苯二甲酰氯。 60 g of phthalic anhydride was added to a 1000 ml reaction flask, 300 ml of thionyl chloride was slowly added dropwise, and the addition was completed. Exhaust gas is generated, excess thionyl chloride is distilled off under normal pressure, and phthaloyl chloride is distilled off under reduced pressure.
将计量好的 240 g N，N-二甲基甲酰胺投入到 500ml的反应瓶中，充高纯氮气保护，开启 搅拌， 向反应瓶中滴加邻苯二甲酰氯， 调节滴加速度控制反应温度为 20-25°C， 滴加完毕， 于 20-25°C保温搅拌 0.5h， 放料至过滤器， 高纯氮保护， 过滤， 滤饼用 N，N-二甲基甲酰胺洗涤至 无苯酐， 放料包装。 得到的固体 （氯亚甲基） 二甲基氯化铵质量为 47.98g, 质量百分含量为 86.36%。 The metered 240 g of N,N-dimethylformamide was placed in a 500 ml reaction flask, and protected with high purity nitrogen gas, stirring was started, phthaloyl chloride was added dropwise to the reaction flask, and the reaction rate was controlled by adjusting the dropping rate. 20-25 ° C, after the completion of the dropwise addition, stirring at 20-25 ° C for 0.5 h, discharge to the filter, high purity nitrogen protection, filtration, filter cake washed with N, N-dimethylformamide to no Phthalic anhydride, discharge packaging. The obtained solid (chloromethylene) dimethylammonium chloride had a mass of 47.98 g and a mass percentage of 86.36%.
实施例 5 Example 5
在 1000ml反应瓶中加入苯酐 60g， 缓慢滴加氯化亚砜 300ml， 滴加完毕， 升温反应至无 尾气产生， 常压蒸出过量氯化亚砜， 减压蒸出邻苯二甲酰氯。 60 g of phthalic anhydride was added to a 1000 ml reaction flask, and 300 ml of thionyl chloride was slowly added dropwise. After the dropwise addition was completed, the reaction was started until no tail gas was generated, and excess thionyl chloride was distilled off under normal pressure, and phthaloyl chloride was distilled off under reduced pressure.
将计量好的 300 g N，N-二甲基甲酰胺投入到 500ml的反应瓶中， 充高纯氮气保护， 幵启 搅拌， 向反应瓶中滴加邻苯二甲酰氯， 调节滴加速度控制反应温度为 0-l(TC， 滴加完毕， 于 0-10°C保温搅拌 0.5h， 放料至过滤器， 高纯氮保护， 过滤， 滤饼用 N，N-二甲基甲酰胺洗涤至 无苯酐， 放料包装。 得到的固体 （氯亚甲基） 二甲基氯化铵质量为 45.29g， 质量百分含量为 87.55%。
The metered 300 g of N,N-dimethylformamide was placed in a 500 ml reaction flask, and it was filled with high-purity nitrogen gas, stirred and stirred, and phthaloyl chloride was added dropwise to the reaction flask to adjust the drip acceleration control reaction. The temperature is 0-l (TC, after the addition is completed, the mixture is stirred at 0-10 ° C for 0.5 h, discharged to the filter, protected with high purity nitrogen, filtered, and the filter cake is washed with N,N-dimethylformamide until No phthalic anhydride, discharge packaging. The obtained solid (chloromethylene) dimethyl ammonium chloride had a mass of 45.29 g and a mass percentage of 87.55%.
Claims
权 利 要 求 书 Claims
ι、 一种固体（氯亚甲基）二甲基氯化铰的制备工艺， 其特征在于： 先将原料苯酐与氯化 亚砜进行酰氯化反应得到邻苯二甲酰氯， 邻苯二甲酰氯再与 Ν,Ν-二甲基甲酰胺反应得到 （氯 亚甲基）二甲基氯化铵与苯酐， 生成的苯酐溶解于过量的 Ν,Ν-二甲基甲酰胺中， 经固液分离 得到固体 （氯亚甲基） 二甲基氯化铵。 Ip, a preparation process of a solid (chloromethylene) dimethyl chloride hinge, characterized in that: first, the raw material phthalic anhydride and sulfoxide are subjected to acid chloride reaction to obtain phthaloyl chloride, phthaloyl chloride Further reacting with hydrazine, hydrazine-dimethylformamide to obtain (chloromethylene) dimethyl ammonium chloride and phthalic anhydride, and the resulting phthalic anhydride is dissolved in an excess of hydrazine, hydrazine-dimethylformamide, and separated by solid-liquid separation. A solid (chloromethylene) dimethyl ammonium chloride was obtained.
2、 根据权利要求 1所述的固体（氯亚甲基）二甲基氯化铵的制备工艺， 其特征在于： 邻 苯二甲酰氯与 Ν,Ν-二甲基甲酰胺反应温度为 0-60°C。 2. The process for preparing solid (chloromethylene) dimethyl ammonium chloride according to claim 1, wherein: the reaction temperature of phthaloyl chloride with hydrazine and hydrazine-dimethylformamide is 0- 60 ° C.
3、根据权利要求 1或 2所述的固体（氯亚甲基）二甲基氯化铵的制备工艺，其特征在于: N，N-二甲基甲酰胺的用量为原料苯酐质量的 1.5-5倍。
The process for preparing solid (chloromethylene) dimethyl ammonium chloride according to claim 1 or 2, wherein the amount of N,N-dimethylformamide is 1.5- of the mass of the raw material phthalic anhydride. 5 times.
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| Title |
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| KIMURA, Y. ET AL.: "New Preparation Method for Vilsmeier Reagent and Related Imidoyl Chlorides.", TETRAHEDRON LETTERS, vol. 53, no. 9, 30 December 2011 (2011-12-30), pages 1116 - 1118 * |
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