阅读说明：本技术 以离子液体为溶剂合成0-(3-氯-2-丙烯基)羟胺的绿色工艺 (Green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by taking ionic liquid as solvent ) 是由 楚庆岩 刁统贺 王鸣 孙圆 商芳芳 杨海玉 崔洪友 于 2019-11-29 设计创作，主要内容包括：本发明具体涉及一种以离子液体为溶剂合成0-(3-氯-2-丙烯基)羟胺的绿色工艺。将丁酮肟、离子液体BmimOH和碱金属氢氧化物混合,在釜式反应器中加热,并带有管式反应器强化反应,达到一定温度后滴加1,3-二氯丙烯反应,反应完毕后萃取；将得到的萃取液脱除溶剂后加盐酸调节pH至中性,室温搅拌反应,反应结束后加入NaOH溶液调节pH＝9-10,将反应溶液脱除溶剂即得到0-(3-氯-2-丙烯基)羟胺。本发明合成的0-(3-氯-2-丙烯基)羟胺的产率＞95.7％,纯度≥99％,反应条件容易实现,离子液体BmimOH可回收循环利用,不产生污染环境的副产物。(The invention particularly relates to a green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by taking ionic liquid as a solvent. Mixing butanone oxime, ionic liquid BmimOH and alkali metal hydroxide, heating in a kettle-type reactor, carrying out enhanced reaction by using a tubular reactor, dropwise adding 1, 3-dichloropropene for reaction after reaching a certain temperature, and extracting after the reaction is finished; and removing the solvent from the obtained extract, adding hydrochloric acid to adjust the pH value to be neutral, stirring at room temperature for reaction, adding a NaOH solution to adjust the pH value to be 9-10 after the reaction is finished, and removing the solvent from the reaction solution to obtain the 0- (3-chloro-2-propenyl) hydroxylamine. The yield of the synthesized 0- (3-chloro-2-propenyl) hydroxylamine is more than 95.7 percent, the purity is more than or equal to 99 percent, the reaction condition is easy to realize, the ionic liquid BmimOH can be recycled, and no by-product polluting the environment is generated.)

1. A green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by taking ionic liquid as a solvent is characterized by comprising the following steps: the method comprises the following steps:

(1) mixing butanone oxime, ionic liquid BmimOH and alkali metal hydroxide, heating, dropwise adding 1, 3-dichloropropene, reacting, and extracting after the reaction is finished;

(2) and removing the solvent from the obtained extract, adding hydrochloric acid to adjust the pH value to be neutral, stirring at room temperature for reaction, adding a NaOH solution to adjust the pH value to be 9-10 after the reaction is finished, and removing the solvent from the reaction solution to obtain the 0- (3-chloro-2-propenyl) hydroxylamine.

2. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as a solvent according to claim 1, which is characterized in that: the alkali metal hydroxide in step (1) is one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, or francium hydroxide.

3. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as a solvent according to claim 1, which is characterized in that: the molar ratio of the butanone oxime to the ionic liquid BmimOH is 1:0.003-1:0.03, the molar ratio of the butanone oxime to the alkali metal hydroxide is 1:0.6-1:1.5, and the molar ratio of the butanone oxime to the 1, 3-dichloropropene is 1:0.4-1: 1.6.

4. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as a solvent according to claim 1, which is characterized in that: and (2) when the temperature is heated to 40-80 ℃ in the step (1), dropwise adding 1, 3-dichloropropene, and reacting for 0.5-2.5h, wherein the reactor adopted in the reaction is a kettle type reactor with a tubular reactor.

5. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as a solvent according to claim 1, which is characterized in that: after the reaction in the step (1) is finished, the extraction is as follows: after the reaction is finished, cooling to room temperature, and extracting the reaction liquid by using ether; and (2) drying the obtained extract with anhydrous sodium sulfate, distilling under reduced pressure to remove the solvent, adding hydrochloric acid with the mass fraction of 36% into the dried solution to adjust the pH to 7, stirring at room temperature for reaction for 3-6h, dissolving the product in ethyl acetate after the reaction is finished, adding a NaOH solution to adjust the pH to 9-10, and removing the solvent from the reaction solution to obtain the 0- (3-chloro-2-propenyl) hydroxylamine.

6. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as a solvent according to claim 5, which is characterized in that: and (2) after the reaction liquid in the step (1) is extracted by diethyl ether, distilling the extract at the lower layer of the diethyl ether at the temperature of 35-60 ℃ under reduced pressure to remove impurities, and obtaining the ionic liquid BmimOH for recycling.

7. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as a solvent according to any one of claims 1 to 6, which comprises the following steps: the preparation method of the ionic liquid BmimOH comprises the following steps: dissolving N-methylimidazole in acetonitrile, heating, adding bromobutane, carrying out reflux reaction, and carrying out reduced pressure distillation on a product to obtain ionic liquid BmimBr; dissolving the obtained ionic liquid BmimBr with dichloromethane, adding alkali metal hydroxide to react at room temperature, filtering the reactant, performing rotary evaporation on the obtained filtrate to remove the solvent, extracting with diethyl ether, and performing vacuum drying to obtain the ionic liquid BmimOH.

8. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as solvent according to claim 7, which is characterized in that: the molar ratio of the N-methylimidazole to the bromobutane is 1:0.5-1:1.5, the volume ratio of the acetonitrile to the bromobutane is 1:0.4-1:1.6, and the molar ratio of the ionic liquid BmimBr to the dichloromethane is 1:4-1: 12.

9. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as solvent according to claim 7, which is characterized in that: the alkali metal hydroxide is lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide or francium hydroxide, and the molar ratio of the usage amount of the alkali metal hydroxide to the ionic liquid BmimBr is 1:0.4-1: 1.5.

10. The green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by using ionic liquid as solvent according to claim 7, which is characterized in that: the preparation method of the ionic liquid BmimOH comprises the following steps: dissolving N-methylimidazole in acetonitrile, heating to 50-90 ℃, adding bromobutane, carrying out magnetic stirring reflux reaction for 9-16h, and carrying out reduced pressure distillation on the product at 75 ℃ to obtain ionic liquid BmimBr; dissolving the obtained ionic liquid BmimBr with dichloromethane, adding alkali metal hydroxide to react for 10-18h at room temperature, filtering the reactant, performing rotary evaporation on the obtained filtrate to remove the solvent, extracting with diethyl ether, and performing vacuum drying for 5-12h to obtain the ionic liquid BmimOH.

Technical Field

The invention relates to a synthesis process of 0- (3-chloro-2-propenyl) hydroxylamine, in particular to a green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by taking ionic liquid as a solvent.

Background

0- (3-chloro-2-propenyl) hydroxylamine is an important intermediate for clethodim and can be widely used for synthesizing other cyclohexenone oxime herbicides, such as Tralkoxydim (Tepraloxydim), Cycloxydim (cyclooxydim), Tralkoxydim (Tralkoxydim), Butroxydim, clethodim (Clefoxidim) and the like. China is a big agricultural country, and in order to meet the increasing needs of agricultural products such as grains, cotton, oil plants, fruits, vegetables and the like, the agricultural land area is ensured, and the yield of the agricultural land area is mainly increased. In addition, pesticides are widely used in health care and other fields. The 0- (3-chloro-2-propenyl) hydroxylamine belongs to an alkoxyamine compound, and the compound is an organic synthesis intermediate with wide application and high price. The alkoxy amine compound can be used as an alkyl amination reagent, introduces alkoxy amine groups into ketone compounds (particularly steroids) in organic synthesis and new drug production, can be used as an intermediate for drug production, and can also be used as an intermediate in the fields of new drugs and new pesticide creation. The synthesis research of the 0- (3-chloro-2-propenyl) hydroxylamine has certain guiding significance for the synthesis of the alkoxy amine compound, so the synthesis research has certain value and practical significance.

Ionic liquids are media and soft functional materials that have been developed in recent years based on green sustainable concepts. The organic phase-change material has special performances of wider liquid range, non-volatility, adjustable physical and chemical properties, wider electrochemical window and the like, and is widely applied as a reaction medium and a catalyst for organic synthesis, a solvent and an extracting agent for scientific separation, an electrochemical electrolyte and the like. With the rapid development of society, the ecological environment problem is increasingly serious. The original treatment method of pollution before treatment can not meet the requirements of social development, so that the new concept of environmental protection for preventing pollution from being generated from the source leads to the rise of green chemistry. The ionic liquid is a brand new medium and soft functional material developed under the framework of green chemistry in recent years, has the characteristics of non-volatility, wide liquid path, strong dissolution, high thermal stability, adjustability, cyclic utilization and the like, and shows good application prospect in the fields of multiphase separation, chemical reaction and the like. There are various forms of cations and anions constituting the ionic liquid, and the properties of the ionic liquid can be adjusted by modifying the cations or changing the anions. At present, the research of designing a group with a specific end or a series of specific properties on an ionic liquid to be a functionalized ionic liquid and applying the functionalized ionic liquid to a specific chemical reaction has become an important direction for the development of the ionic liquid. At present, most of the application reports of the room-temperature ionic liquid are focused on the research application of the acidic functionalized ionic liquid as a reaction medium and a catalyst, and relatively few reports are provided about the application of the basic ionic liquid.

The existing process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine mainly comprises the following steps: 1. acetonitrile and ethanol are used as starting materials to synthesize the 0- (3-chlorine-2-propenyl) hydroxylamine. 2. Hydroxyl phthalimide is used as a starting material to synthesize the 0- (3-chloro-2-propenyl) hydroxylamine. 3. Ethyl acetate is used as a starting material to synthesize 0- (3-chloro-2-propenyl) hydroxylamine. The process 1 is that a large amount of hydrogen chloride gas is led into toluene solution of acetonitrile and absolute ethyl alcohol and stirred for 22h, then hydroxylamine hydrochloride water solution is dripped under the condition of-10 ℃ to-5 ℃, and the stirring is carried out until an organic layer is separated, thus forming the compound of ethyl acetylhydroxamate. The yield was 93.9%. Then tetrabutylammonium bromide is used as a phase transfer catalyst to react with 1, 3-dichloropropene to obtain 0- (3-chloro-2-propenyl) hydroxylamine with the yield of 87.5 percent. The method uses a large amount of hydrogen chloride gas, has serious pollution and corrosion, uses a relatively expensive phase transfer catalyst, and is not beneficial to industrialization in the aspects of cost and environmental protection. The N-hydroxyphthalimide used in the process 2 is mainly synthesized by the reaction of hydroxylamine and phthalic anhydride, phthaloyl chloride or ethyl phthalate in sodium ethoxide or other media. The method has the advantages of multiple reaction steps, long route and low economic benefit. The process 3 is that ethyl acetate and hydroxylamine hydrochloride react in NaOH aqueous solution at normal temperature l h, 1, 3-dichloropropene is then dripped, stirring and refluxing are carried out for 2.5h at 60 ℃, the cooling is carried out to the room temperature, standing and layering are carried out, an upper layer organic phase is collected, anhydrous magnesium sulfate is used for drying, and then the solvent is removed under reduced pressure, so that the 0- (3-chloro-2-propenyl) hydroxylamine is obtained.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by taking ionic liquid as a solvent, the yield of the synthesized 0- (3-chloro-2-propenyl) hydroxylamine is more than 95.7 percent, the purity is more than or equal to 99 percent, the reaction conditions of the process are easy to realize, the ionic liquid BmimOH can be recycled, and no by-product polluting the environment is generated.

The invention relates to a green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by taking ionic liquid as a solvent, which comprises the following steps:

(1) mixing butanone oxime, ionic liquid BmimOH and alkali metal hydroxide, heating, dropwise adding 1, 3-dichloropropene, reacting, and extracting after the reaction is finished;

(2) and removing the solvent from the obtained extract, adding hydrochloric acid to adjust the pH value to be neutral, stirring at room temperature for reaction, adding a NaOH solution to adjust the pH value to be 9-10 after the reaction is finished, and removing the solvent from the reaction solution to obtain the 0- (3-chloro-2-propenyl) hydroxylamine.

Wherein:

the alkali metal hydroxide in step (1) is also one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide or francium hydroxide.

The molar ratio of the butanone oxime to the ionic liquid BmimOH is 1:0.003-1:0.03, preferably 1:0.009-1: 0.02. The molar ratio of butanone oxime to alkali metal hydroxide is 1:0.6 to 1:1.5, preferably 1:0.9 to 1: 1.2. The molar ratio of butanone oxime to 1, 3-dichloropropene is from 1:0.4 to 1:1.6, preferably from 1:0.8 to 1: 1.3.

When the temperature in the step (1) is heated to 40-80 ℃, preferably 50-65 ℃, 1, 3-dichloropropene begins to be dripped, the reaction is carried out for 0.5-2.5h, preferably 0.8-2h, and the reactor adopted by the reaction is preferably a kettle type reactor with a tubular reactor, namely, the reaction is heated in the kettle type reactor and is provided with the tubular reactor to strengthen the reaction.

Preferably, the extraction in step (1) after the reaction is completed is: after the reaction is finished, cooling to room temperature, and extracting the reaction liquid by using ether; and (2) drying the obtained extract by using anhydrous sodium sulfate, distilling under reduced pressure to remove the solvent, adding hydrochloric acid with the mass fraction of 36% into the dried solution to adjust the pH to be 7, stirring at room temperature for reaction for 3-6h, dissolving the product in ethyl acetate after the reaction is finished, adding a NaOH solution to adjust the pH to be 9-10, and removing the solvent from the reaction solution to obtain the 0- (3-chloro-2-propenyl) hydroxylamine.

And (2) after the reaction liquid in the step (1) is extracted by diethyl ether, distilling the extract at the lower layer of the diethyl ether at the temperature of 35-60 ℃ under reduced pressure to remove impurities, and obtaining the ionic liquid BmimOH for recycling.

Wherein: the preparation method of the ionic liquid BmimOH comprises the following steps: dissolving N-methylimidazole in acetonitrile, heating, adding bromobutane, carrying out reflux reaction, and carrying out reduced pressure distillation on a product to obtain ionic liquid BmimBr; dissolving the obtained ionic liquid BmimBr with dichloromethane, adding alkali metal hydroxide to react at room temperature, filtering the reactant, performing rotary evaporation on the obtained filtrate to remove the solvent, extracting with diethyl ether, and performing vacuum drying to obtain the ionic liquid BmimOH.

As a preferable technical scheme, the preparation method of the ionic liquid BmimOH comprises the following steps: dissolving N-methylimidazole in acetonitrile, heating to 50-90 ℃, adding bromobutane, carrying out magnetic stirring reflux reaction for 9-16h, and carrying out reduced pressure distillation on the product at 75 ℃ to obtain ionic liquid BmimBr; dissolving the obtained ionic liquid BmimBr with dichloromethane, adding alkali metal hydroxide to react for 10-18h at room temperature, filtering the reactant, performing rotary evaporation on the obtained filtrate to remove the solvent, extracting with diethyl ether, and performing vacuum drying for 5-12h to obtain the ionic liquid BmimOH.

The molar ratio of N-methylimidazole to bromobutane is from 1:0.5 to 1:1.5, preferably from 1:0.8 to 1: 1.2. The volume ratio of acetonitrile to bromobutane is 1:0.4 to 1:1.6, preferably 1:0.6 to 1: 1.3. The molar ratio of the ionic liquid BmimBr to the dichloromethane is 1:4 to 1:12, preferably 1:6 to 1: 10.

The alkali metal hydroxide is lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide or francium hydroxide, and the molar ratio of the used amount to the ionic liquid BmimBr is 1:0.4-1:1.5, preferably 1:0.6-1: 1.2.

As a preferred technical scheme, the green process for synthesizing the 0- (3-chloro-2-propenyl) hydroxylamine by taking the ionic liquid as the solvent comprises the following steps:

1. preparation of ionic liquids

(1) Preparation of ionic liquid BmimBr: dissolving N-methylimidazole in acetonitrile, heating to 50-90 ℃, adding bromobutane, carrying out magnetic stirring reflux reaction for 9-16h, and carrying out reduced pressure distillation on the product at 75 ℃ to obtain ionic liquid BmimBr.

(2) Preparation of ionic liquid BmimOH: dissolving the obtained ionic liquid BmimBr with dichloromethane, adding a proper amount of alkali metal hydroxide to react for 10-18h at room temperature, filtering the reactant, rotatably evaporating the obtained filtrate to remove the solvent, extracting for 3 times with diethyl ether, and then drying in vacuum for 5-12h to obtain the ionic liquid BmimOH.

2. Preparation of 0- (3-chloro-2-propenyl) hydroxylamine

Mixing butanone oxime, ionic liquid BmimOH and alkali metal hydroxide in a kettle type reactor, heating, carrying out enhanced reaction in a tubular reactor, beginning to drop 1, 3-dichloropropene after reaching a certain temperature, reacting for several hours, cooling to room temperature, extracting for 3 times by using diethyl ether, drying the obtained extract by using anhydrous sodium sulfate, distilling under reduced pressure to remove a solvent, adding hydrochloric acid with the mass fraction of 36% into the dried solution to adjust the pH to be 7, stirring at the room temperature for reaction for 3-6 hours, dissolving the product in a proper amount of ethyl acetate after the reaction is finished, adding a NaOH solution to adjust the pH to be 9-10, and removing the solvent from the reaction solution to obtain the 0- (3-chloro-2-propenyl) hydroxylamine.

3. Recovery of ionic liquid BmimOH

And (3) distilling the ether lower-layer extract in the step (2) at the temperature of 35-60 ℃ under reduced pressure to remove impurities such as water and the like, thus obtaining the ionic liquid BmimOH for recycling.

Compared with the prior art, the invention has the following advantages:

the invention provides a green process for synthesizing 0- (3-chloro-2-propenyl) hydroxylamine by taking ionic liquid as a solvent, wherein the ionic liquid BmimOH is taken as the solvent and a catalyst, butanone oxime, alkali metal hydroxide and 1, 3-dichloropropene are taken as raw materials, the yield of the 0- (3-chloro-2-propenyl) hydroxylamine synthesized by the process is more than 95.7 percent, the purity is more than or equal to 99 percent, the reaction condition of the process is easy to realize, the ionic liquid BmimOH can be recycled, and no by-product polluting the environment is generated.

Detailed Description

The present invention will be further described with reference to the following examples.