CN107721812B - Method for preparing chloroisoamylene from decaether - Google Patents
Method for preparing chloroisoamylene from decaether Download PDFInfo
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- CN107721812B CN107721812B CN201710919377.0A CN201710919377A CN107721812B CN 107721812 B CN107721812 B CN 107721812B CN 201710919377 A CN201710919377 A CN 201710919377A CN 107721812 B CN107721812 B CN 107721812B
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- C07C17/00—Preparation of halogenated hydrocarbons
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Abstract
The invention discloses a method for preparing chloroisoamylene from decaether, which comprises the following steps: 1) adding water into decaether, stirring and cooling to-5 deg.C; 2) dripping thionyl chloride at normal pressure to enable decaether to generate chlorination reaction with the decaether to obtain chloroisoamylene and sulfur dioxide gas; the preparation method prepares the carbon decaether into the chloroisoamylene through chlorination, so that the carbon decaether which is a byproduct in the production process of the carbon pentadecenol is utilized, and considerable economic benefit and social benefit are realized.
Description
The technical field is as follows:
the invention relates to a method for preparing chloroisoamylene from decaether.
Background art:
chloroisopentene, a mixture of 1-chloro-3-methyl-2-butene (1-chloroisopentene) and 3-chloro-3-methyl-1-butene (3-chloroisopentene), is a very useful intermediate in fine chemical engineering, and can be hydrolyzed to produce a mixture of 3-methyl-2-buten-1-ol (isopentenol) and 2-methyl-3-buten-2-ol (methylbutenol). The prenol is mainly used for reacting with trimethyl orthoacetate or ethyl orthoacetate to synthesize methyl ester or ethyl ester of cardia acid, and is an important raw material for preparing the key intermediate of pyrethroid, namely homocis-permethrin. Methyl butenol is mainly used as a raw material for producing methyl heptenone, and can also be used for synthesizing DV-chrysanthemic acid or chrysanthemic ester, isophytol, vitamin A, carotenoid, terpene series perfume intermediate and the like.
The existing preparation method of chloro isoamylene is to prepare the chloro isoamylene by addition reaction of hydrogen chloride gas and isoprene. The addition reaction of hydrogen chloride and isoprene simultaneously produces 1-chloro-3-methyl-2-butene (1-chloroisoamylene) and 3-chloro-3-methyl-1-butene (3-chloroisoamylene).
2-methyl-3-buten-2-ol is isomerized to produce isopentenol in the presence of a protonic acid catalyst such as phosphoric acid and the like, and a dehydration reaction is carried out between a small amount of associated alcohols to obtain decaether as a by-product, wherein the decaether is 1, 1-dimethylallyl 3-methyl-2-butenyl ether or di (3-methyl-2-butenyl) ether, and the method comprises the following steps: intermolecular dehydration of 2-methyl-3-buten-2-ol and isopentenol gives 1, 1-dimethallyl 3-methyl-2-butenyl ether, and intermolecular dehydration of isopentenol gives di (3-methyl-2-butenyl) ether. The reaction formula is as follows:
the carbon decaether as a byproduct is difficult to be utilized in industrial production, and resource waste is caused.
The invention content is as follows:
the invention aims to solve the problems in the prior art, and provides a method for preparing chloroisoamylene from decaether by re-chlorination, so that the decaether serving as a byproduct in the production process of the pentadecenol is utilized, and considerable economic and social benefits are realized.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing chloroisoamylene from decaether, comprising the following steps: 1) adding water into decaether, stirring and cooling to-5 deg.C; 2) and (3) dropwise adding thionyl chloride into the deca-carbonate to enable the deca-carbonate to perform chlorination reaction with the deca-carbonate to obtain chloroisoamylene and sulfur dioxide gas.
Further, the decaether is 1, 1-dimethylallyl 3-methyl-2-butenyl ether, bis (3-methyl-2-butenyl) ether or a mixture of 1, 1-dimethylallyl 3-methyl-2-butenyl ether and bis (3-methyl-2-butenyl) ether.
Further, the mass ratio of the decaether to water is 10-20: 1.
Further, the molar ratio of the decaether to the dropwise added thionyl chloride is 1: 0.4-0.5.
Further, the thionyl chloride was uniformly added dropwise to the decaether over 0.5 hour.
Further, the reaction temperature is kept at-5-10 ℃ in the chlorination reaction process.
Further, the heat preservation time in the chlorination reaction process is 0.5-3 h.
Further, thionyl chloride was added dropwise to the decaether at normal pressure to cause chlorination reaction of the decaether therewith.
Further, the preparation was carried out in a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and an air-guide tube.
The invention has the beneficial effects that: the invention relates to a method for preparing chloroisoamylene from decaether, which comprises the following steps: 1) adding water into decaether, stirring and cooling to-5 deg.C; 2) dripping thionyl chloride at normal pressure to enable decaether to generate chlorination reaction with the decaether to obtain chloroisoamylene and sulfur dioxide gas; the preparation method prepares the carbon decaether into the chloroisoamylene through chlorination, so that the carbon decaether which is a byproduct in the production process of the carbon pentadecenol is utilized, and considerable economic benefit and social benefit are realized.
The specific implementation mode is as follows:
the following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
A method for preparing chloroisoamylene from decaether, comprising the following steps: 1) adding water into decaether, stirring and cooling to-5 deg.C; 2) and (3) dropwise adding thionyl chloride into the deca-carbon ether to perform chlorination reaction with the deca-carbon ether to obtain chloroisoamylene, namely a mixture of 1-chloro-3-methyl-2-butene (1-chloroisoamylene) and 3-chloro-3-methyl-1-butene (3-chloroisoamylene) and sulfur dioxide gas. The mass ratio of the decaether to water is 10-20: 1, the molar ratio of the decaether to the dropwise added thionyl chloride is 1: 0.4-0.5, the thionyl chloride is uniformly dropwise added into the decaether within 0.5 hour, the reaction temperature is kept at-5-10 ℃ in the chlorination reaction process, the heat preservation time in the chlorination reaction process is 0.5-3 hours, and the preferable method is to dropwise add the thionyl chloride into the decaether under normal pressure so that the decaether and the decaether are subjected to chlorination reaction.
The preparation process is preferably completed in a four-neck flask with a stirrer, a thermometer, a dropping funnel and an air duct, so that the stirring, the temperature control, the dropping of thionyl chloride and the collection of sulfur dioxide gas are facilitated. The decaether is 1, 1-dimethylallyl 3-methyl-2-butenyl ether, di (3-methyl-2-butenyl) ether or a mixture of 1, 1-dimethylallyl 3-methyl-2-butenyl ether and di (3-methyl-2-butenyl) ether in any proportion.
The reaction formula is as follows:
example 1
154.0g (1mol) of 1, 1-dimethylallyl 3-methyl-2-butenyl ether is added into a 500ml four-neck flask with a stirrer, a thermometer, a dropping funnel and an air duct, 7.7g of water is added, stirring and cooling are carried out to-5 ℃, then 59.5g (0.5mol) of thionyl chloride is added dropwise, the dropping is completed within 0.5 hour, the temperature is controlled to be-5-3 ℃, heat preservation is carried out for 2 hours continuously, standing and layering are carried out, a water layer is discarded, an organic layer is collected, 206.4g of chloroisoamylene is obtained, and the yield is 98.7%.
Example 2
In a 500ml four-neck flask with a stirrer, a thermometer, a dropping funnel and an air duct, 154.0g (1mol) of bis (3-methyl-2-butenyl) ether is added, 15.4g of water is added, the mixture is stirred and cooled to-5 ℃, 59.5g (0.5mol) of thionyl chloride is added dropwise, the dropping is completed within about 0.5 hour, the temperature is controlled to be between 0 and 10 ℃, the heat preservation is continued for 0.5 hour, the mixture is kept still for layering, a water layer is discarded, an organic layer is collected, 204.6g of chloroisoamylene is obtained, and the yield is 97.9%.
Example 3
54.0g of 1, 1-dimethylallyl 3-methyl-2-butenyl ether and 100.0g (total 1mol) of bis (3-methyl-2-butenyl) ether are added into a 500ml four-neck flask with a stirrer, a thermometer, a dropping funnel and an air duct, 10.0g of water is added, the mixture is stirred and cooled to-5 ℃, 47.6g (0.4mol) of thionyl chloride is added dropwise, the mixture is dripped out after about 0.5 hour, the temperature is controlled between 0 and 10 ℃, the mixture is kept for 3 hours, the mixture is kept still and layered, a water layer is discarded, an organic layer is collected, 164.1g of chloroisoamylene is obtained, and the yield is 78.5%.
Claims (8)
1. A method for preparing chloroisoamylene from decaether is characterized by comprising the following steps: 1) adding water into decaether, stirring and cooling to-5 deg.C; 2) dropwise adding thionyl chloride into the deca-carbon ether to enable the deca-carbon ether to perform chlorination reaction with the deca-carbon ether to obtain chloroisoamylene and sulfur dioxide gas; the decaether is 1, 1-dimethylallyl 3-methyl-2-butenyl ether, bis (3-methyl-2-butenyl) ether or a mixture of 1, 1-dimethylallyl 3-methyl-2-butenyl ether and bis (3-methyl-2-butenyl) ether.
2. The process of claim 1 for the preparation of chloroisoamylene from decaether characterized by: the mass ratio of the decaether to water is 10-20: 1.
3. The process of claim 1 for the preparation of chloroisoamylene from decaether characterized by: the molar ratio of the carbon decaether to the dropwise added thionyl chloride is 1: 0.4-0.5.
4. A process for the preparation of chloroisoamylene from decaether according to claim 3, wherein: the thionyl chloride was added dropwise uniformly to the decaether over 0.5 hour.
5. The process of claim 1 for the preparation of chloroisoamylene from decaether characterized by: and keeping the reaction temperature at-5-10 ℃ in the chlorination reaction process.
6. The process of claim 1 for the preparation of chloroisoamylene from decaether characterized by: the heat preservation time in the chlorination reaction process is 0.5-3 h.
7. The process of claim 1 for the preparation of chloroisoamylene from decaether characterized by: thionyl chloride is added dropwise to the deca-ether at normal pressure to cause chlorination reaction between the deca-ether and the deca-ether.
8. The process of claim 1 for the preparation of chloroisoamylene from decaether characterized by: the preparation process is completed in a four-neck flask with a stirrer, a thermometer, a dropping funnel and an air duct.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1351039A (en) * | 1970-10-05 | 1974-04-24 | Hoffmann La Roche | Process for the manufacture of 1-chloro-3-methyl-2-butene |
| CN1196039A (en) * | 1995-07-11 | 1998-10-14 | 埃勒夫阿托化学有限公司 | Method for preparing alpha, omega-bromochloroalkanes |
| CN102633594A (en) * | 2012-03-27 | 2012-08-15 | 巨化集团公司 | Method for synthesizing triphenylchloromethane by using triphenylmethyl alkyl ether |
| CN105111039A (en) * | 2015-09-02 | 2015-12-02 | 南通天泽化工有限公司 | Preparation method of chloroisopentene |
| CN105481634A (en) * | 2015-12-16 | 2016-04-13 | 绍兴明业化纤有限公司 | Preparing method for chloro-isopentene |
-
2017
- 2017-09-30 CN CN201710919377.0A patent/CN107721812B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1351039A (en) * | 1970-10-05 | 1974-04-24 | Hoffmann La Roche | Process for the manufacture of 1-chloro-3-methyl-2-butene |
| CN1196039A (en) * | 1995-07-11 | 1998-10-14 | 埃勒夫阿托化学有限公司 | Method for preparing alpha, omega-bromochloroalkanes |
| CN102633594A (en) * | 2012-03-27 | 2012-08-15 | 巨化集团公司 | Method for synthesizing triphenylchloromethane by using triphenylmethyl alkyl ether |
| CN105111039A (en) * | 2015-09-02 | 2015-12-02 | 南通天泽化工有限公司 | Preparation method of chloroisopentene |
| CN105481634A (en) * | 2015-12-16 | 2016-04-13 | 绍兴明业化纤有限公司 | Preparing method for chloro-isopentene |
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