CN105461521B - The synthetic method of 2- chloroethyl propyl ethers - Google Patents
The synthetic method of 2- chloroethyl propyl ethers Download PDFInfo
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- CN105461521B CN105461521B CN201510926844.3A CN201510926844A CN105461521B CN 105461521 B CN105461521 B CN 105461521B CN 201510926844 A CN201510926844 A CN 201510926844A CN 105461521 B CN105461521 B CN 105461521B
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- Prior art keywords
- thionyl chloride
- added dropwise
- propyl ethers
- chloroethyl propyl
- synthetic method
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
Abstract
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of 2 chloroethyl propyl ether.The present invention uses efficient nucleophilic catalyst, using 2 positive propoxy ethyl alcohol and thionyl chloride as primary raw material, by the way that thionyl chloride is added dropwise, stringent control reaction rate obtains crude product by heating, heat preservation, solid caustic digestion excess thionyl chloride is directly added into after cooling and is neutralized, finally through 2 chloroethyl propyl ethers are obtained by filtration, purity is up to 99.5% or more, and yield is more than 98.8%, and water content is less than 0.1%.Compared with traditional handicraft, the present invention is generated without waste water, and purity and high income, water content is low, both economically and environmentally beneficial, is suitble to industrialized production.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of 2- chloroethyl propyl ethers.
Background technology
2- chloroethyl propyl ethers are to prepare one of important source material of herbicide pretilachlor, which is a kind of efficient, low
Poison, early stage wide spectrum rice field major choice sprouting stage herbicide, are widely used in field of rice cultivation.
Currently, preparing the 2- chloroethyl propyl ethers mainly using 2- positive propoxies ethyl alcohol as primary raw material, using different chlorinations
Agent carries out chlorine substitution reaction with it.Yang Jianping etc. (synthetic method of 2- positive propoxy chloroethanes, Zhejiang chemical industry, the 1999, the 30th
Volume, the 4th phase) using 2- positive propoxies ethyl alcohol and thionyl chloride as reaction raw materials, using composite catalyst, after reaction with 10%
Lye it is neutralized, to generate a large amount of organic wastewaters, product content 98.1%, yield 97%.Tong Guotong is special
A kind of preparation method of intermediate epichlorophdrin of herbicide pretilachlor is disclosed in sharp CN200810061878.0, and this method is with bis- (trichlorines
Methyl) carbonic ester be chlorinating agent, instead of chlorinating agents such as traditional chlorinated sulfoxide, phosphorus oxychloride, hydrogen chloride, in organic solvent condition
Under, using organic amine as catalyst, 2- chloroethyl propyl ethers are synthesized, since organic solvent is added, product must carry out distilation, from
And cause product yield relatively low, high energy consumption, and processing step is more, while bis- (trichloromethyl) carbonic esters (abbreviation triphosgene) price
It is higher, it is unfavorable for industrialization promotion.
With the fast development of pesticide industry, on the one hand, the demand of 2- chloroethyl propyl ethers constantly increases；On the other hand
Quality to 2- chloroethyl propyl ethers and environmental friendly higher requirements are also raised.The preparation work of traditional 2- chloroethyl propyl ethers
Skill, there are unstable product quality, yield is low, wastewater flow rate is big, technique is cumbersome the problems such as, cannot meet market to product
It is required that.Therefore, a kind of efficient, safe and environment-friendly 2- chloroethyl propyl ether synthesis technologies of exploitation have important practical significance.
Invention content
It is generated the object of the present invention is to provide a kind of simple for process, safe operation, without waste water, product purity and yield are promoted
The synthetic method of significant 2- chloroethyl propyl ethers.
The synthetic method of 2- chloroethyl propyl ethers of the present invention, includes the following steps：
(1) after mixing 2- positive propoxies ethyl alcohol and catalyst, excess thionyl chloride is added dropwise and is reacted, reaction process is put
Go out sulfur dioxide and hydrogen chloride gas；The catalyst is the compound containing alkylamino pyridine group；
The reaction principle of the present invention is as follows：
This reaction belongs to exothermic reaction, and reaction rate is increased with temperature constantly to be accelerated, and very sensitive to temperature, in chlorination
Reacting liquid temperature constantly increases during sulfoxide is added dropwise, since a large amount of sulfur dioxide and hydrogen chloride gas are released in the reaction,
Speed degree is released by tail gas and just can determine whether response situation, must be strictly controlled thionyl chloride during the reaction and speed is added dropwise
Degree, in a certain range by reaction temperature control, in order to avoid runaway reaction.
(2) thionyl chloride is added dropwise, heating, and up to no gas is released, then heat preservation, obtains crude product；
(3) after crude product cooling, solid base stirring is added, decomposes excess thionyl chloride, neutral 2- chloroethyls third is obtained by filtration
Base ether.
Wherein,
The catalyst is 4-dimethylaminopyridine or 4- pyrollidinopyridines.
The catalyst charge is the 0.1~0.5% of 2- positive propoxy ethyl alcohol quality.
The molar ratio of the 2- positive propoxies ethyl alcohol and thionyl chloride is 1:1.05~1.1.
Reaction temperature is maintained at 20~50 DEG C during thionyl chloride is added dropwise.
The thionyl chloride content is more than 98%, and wherein sulfonyl chlorinity is not more than 0.5%.
The thionyl chloride is added dropwise, and is warming up to 90~100 DEG C.
The soaking time is 2~4 hours.
The crude product is cooled to 30~50 DEG C.
The solid base is sodium hydroxide or potassium hydroxide.
Beneficial effects of the present invention are as follows：
The present invention passes through drop using efficient nucleophilic catalyst using 2- positive propoxies ethyl alcohol and thionyl chloride as primary raw material
Add thionyl chloride, strictly control reaction rate, obtains crude product by heating, heat preservation, solid caustic digestion mistake is directly added into after cooling
Amount thionyl chloride simultaneously neutralizes, and finally through 2- chloroethyl propyl ethers are obtained by filtration, up to 99.5% or more, yield is more than purity
98.8%, water content is less than 0.1%.Compared with traditional handicraft, the present invention is generated without waste water, and purity and high income, water content is low,
It is both economically and environmentally beneficial, it is suitble to industrialized production.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific implementation mode
The present invention is described further with reference to embodiments.
Embodiment 1
Take 100g 2- positive propoxies ethyl alcohol, 0.1g 4-dimethylaminopyridine that the reaction vessel with reflux condenser is added
In, constant pressure funnel is added in 120.1g thionyl chlorides (content 99.0%, sulfonyl chlorinity 0.1%), opens stirring, slowly
Thionyl chloride is added dropwise into reaction vessel, reaction process releases sulfur dioxide and hydrogen chloride gas, and speed is added dropwise in control thionyl chloride
Degree makes reacting liquid temperature be maintained at 25 DEG C ± 5 DEG C.
Thionyl chloride is added dropwise, and opens heating, and releasing rate according to reaction gas is gradually warming up to 90 DEG C, up to no gas
Body is released, and is continued heat preservation 2h and is obtained crude product；Crude product is cooled to 30 DEG C, solid sodium hydroxide stirring is directly added into, by thionyl chloride
It thoroughly decomposes, obtains neutral 2- chloroethyl propyl ethers 116.4g, after testing, product chromatographic content is 99.5%, and water content is
0.092%, yield 98.9%.
Embodiment 2
Take 100g 2- positive propoxies ethyl alcohol, 0.2g 4-dimethylaminopyridine that the reaction vessel with reflux condenser is added
In, constant pressure funnel is added in 122.5g thionyl chlorides (content 99.0%, sulfonyl chlorinity 0.1%), opens stirring, slowly
Thionyl chloride is added dropwise into reaction vessel, reaction process releases sulfur dioxide and hydrogen chloride gas, and speed is added dropwise in control thionyl chloride
Degree makes reacting liquid temperature be maintained at 35 DEG C ± 5 DEG C.
Thionyl chloride is added dropwise, and opens heating, and releasing rate according to reaction gas is gradually warming up to 95 DEG C, up to no gas
Body is released, and is continued heat preservation 3h and is obtained crude product；Crude product is cooled to 40 DEG C, solid sodium hydroxide stirring is directly added into, by thionyl chloride
It thoroughly decomposes, obtains neutral 2- chloroethyl propyl ethers 116.5g, after testing, product chromatographic content is 99.5%, and water content is
0.095%, yield is up to 99.0%.
Embodiment 3
Take 100g 2- positive propoxies ethyl alcohol, 0.3g 4- pyrollidinopyridines that the reaction vessel with reflux condenser is added
In, constant pressure funnel is added in 124.2g thionyl chlorides (content 99.0%, sulfonyl chlorinity 0.1%), opens stirring, slowly
Thionyl chloride is added dropwise into reaction vessel, reaction process releases sulfur dioxide and hydrogen chloride gas, and speed is added dropwise in control thionyl chloride
Degree makes reacting liquid temperature be maintained at 40 DEG C ± 5 DEG C.
Thionyl chloride is added dropwise, and opens heating, and releasing rate according to reaction gas is gradually warming up to 95 DEG C, up to no gas
Body is released, and is continued heat preservation 3h and is obtained crude product；Crude product is cooled to 45 DEG C, solid potassium hydroxide stirring is directly added into, by thionyl chloride
It thoroughly decomposes, obtains neutral 2- chloroethyl propyl ethers 116.7g, after testing, product chromatographic content is 99.6%, and water content is
0.091%, yield is up to 99.1%.
Embodiment 4
Take 100g 2- positive propoxies ethyl alcohol, 0.5g 4- pyrollidinopyridines that the reaction vessel with reflux condenser is added
In, constant pressure funnel is added in 125.2g thionyl chlorides (content 99.0%, sulfonyl chlorinity 0.1%), opens stirring, slowly
Thionyl chloride is added dropwise into reaction vessel, reaction process releases sulfur dioxide and hydrogen chloride gas, and speed is added dropwise in control thionyl chloride
Degree makes reacting liquid temperature be maintained at 45 DEG C ± 5 DEG C.
Thionyl chloride is added dropwise, and opens heating, and releasing rate according to reaction gas is gradually warming up to 95 DEG C, up to no gas
Body is released, and is continued heat preservation 4h and is obtained crude product；Crude product is cooled to 50 DEG C, solid potassium hydroxide stirring is directly added into, by thionyl chloride
It thoroughly decomposes, obtains neutral 2- chloroethyl propyl ethers 116.8g, after testing, product chromatographic content is 99.5%, and water content is
0.095%, yield is up to 99.2%.
Claims (3)
1. a kind of synthetic method of 2- chloroethyl propyl ethers, it is characterised in that include the following steps：
（1）After 2- positive propoxies ethyl alcohol and catalyst are mixed, excess thionyl chloride is added dropwise and is reacted, reaction process releases two
Sulfur oxide and hydrogen chloride gas；The catalyst is the compound containing alkylamino pyridine group, be 4-dimethylaminopyridine or
4- pyrollidinopyridines；The catalyst charge is the 0.1~0.5% of 2- positive propoxy ethyl alcohol quality, the 2- positive propoxies
The molar ratio of ethyl alcohol and thionyl chloride is 1:1.05~1.1；
（2）Thionyl chloride is added dropwise, heating, and up to no gas is released, then heat preservation, obtains crude product；
（3）After crude product cooling, solid base stirring is added, decomposes excess thionyl chloride, neutral 2- chloroethyl propyl ethers is obtained by filtration；
The thionyl chloride content is more than 98%, and wherein sulfonyl chlorinity is not more than 0.5%；
Reaction temperature is maintained at 20~50 DEG C during thionyl chloride is added dropwise；
The thionyl chloride is added dropwise, and is warming up to 90~100 DEG C；
The soaking time is 2~4 hours.
2. the synthetic method of 2- chloroethyl propyl ethers according to claim 1, it is characterised in that：The crude product is cooled to 30
~50 DEG C.
3. the synthetic method of 2- chloroethyl propyl ethers according to claim 1, it is characterised in that：The solid base is hydrogen-oxygen
Change sodium or potassium hydroxide.
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| CN109970522A (en) * | 2017-12-28 | 2019-07-05 | 山东侨昌化学有限公司 | A kind of deacidification technique in 2- chloroethyl propyl ether production process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284768A (en) * | 2008-05-29 | 2008-10-15 | 杭州职业技术学院 | Preparation method for intermediate epichlorophdrin of herbicide pretilachlor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284768A (en) * | 2008-05-29 | 2008-10-15 | 杭州职业技术学院 | Preparation method for intermediate epichlorophdrin of herbicide pretilachlor |
Non-Patent Citations (1)
| Title |
|---|
| 2-正丙氧基氯乙烷的合成开发;杨建萍等;《浙江化工》;19991231;第30卷(第4期);41-42 * |
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Address after: 255190 Yang Zhen, Zichuan District, Zibo City, Shandong Province Applicant after: Shandong Kaisheng New Materials Co.,Ltd. Address before: 255190 Yang Zhen, Zichuan District, Zibo City, Shandong Province Applicant before: SHANDONG KAISHENG NEW MATERIALS CO., LTD. |
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Inventor after: Zhang Taiming Inventor after: Li Guanghui Inventor after: Zhang Shanmin Inventor after: Bi Yixia Inventor after: Li Wenjuan Inventor after: Xie Shengbin Inventor after: Ma Tuanzhi Inventor before: Zhang Taiming Inventor before: Li Guanghui Inventor before: Zhang Shanmin Inventor before: Bi Yixia Inventor before: Li Wenjuan Inventor before: Xie Shengbin |
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