GB805816A - Dehydrochlorination process - Google Patents
Dehydrochlorination processInfo
- Publication number
- GB805816A GB805816A GB2253955A GB2253955A GB805816A GB 805816 A GB805816 A GB 805816A GB 2253955 A GB2253955 A GB 2253955A GB 2253955 A GB2253955 A GB 2253955A GB 805816 A GB805816 A GB 805816A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dcb
- give
- chloroprene
- tcb
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/19—Halogenated dienes
- C07C21/20—Halogenated butadienes
- C07C21/21—Chloroprene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
1:2:3-Trichlorobutane is converted into hydrogen chloride and chloroprene precursors, i.e. 1:2-dichlorobutene-2, 2:3-dichlorobutene-1 and 1:3-dichlorobutene-2 (hereinafter called 1:2-DCB-2 &c.), by heating in the presence of the hydrochloride or a quaternary ammonium chloride salt derived from an amine, the amine having a pK value of 3.0 to 9.0 and a boilingpoint at atmospheric pressure of 110 DEG to 250 DEG C. (pK value being defined as log10 1/K , where K is the product of the concentration of the ammonium and hydroxyl ions divided by the total concentration of unionized material present as either the free base or hydrate). The catalyst is preferably derived from a tertiary amine, e.g. alpha- and gamma-picolines, 2:4:6-collidine, the amine hydrochlorides advantageously being used. These may be formed in situ, by addition of the free amine to the reaction mixture which combines with hydrogen chloride liberated. The reaction is preferably conducted at 150 DEG to 220 DEG C., under pressure when necessary, and an inert solvent such as diphenyl ether or chloronaphthalene may be employed. Preferably, the reaction mixture contains at least 25 per cent by weight of catalyst and the reaction is carried out continuously by withdrawing product and adding fresh 1:2:3-trichlorobutane to keep the volume of the reaction mixture approximately constant. The continuous process may be effected using a fractionating column, the dichlorobutene products being obtained as distillates. The process may be combined with the preparation of chloroprene by the chlorination of butane, butene-1 or butene-2 to 1:2:3- and 2:2:3-trichlorobutanes, the former, pure or admixed with the latter, being treated according to the present invention and the chloroprene precursors so formed being dehydrochlorinated to give chloroprene, and the 2:2:3-trichlorobutane being dehydrochlorinated directly to give chloroprene. The chloroprene precursor 1:2-DCB-2 is advantageously isomerized to 2:3-DCB-1, by heat alone or under the influence of copper or a copper chloride catalyst, before being converted into chloroprene by, for example, uncatalysed pyrolysis at 450 DEG to 650 DEG C. In examples: (1) 1:2:3-trichlorobutane (1:2:3-TCB) and quinoline (pK 8.8; b.p. 238 DEG C.) are refluxed in a fractionating column to give 2:3-DCB-1 and 1:2-DCB-2; (2) N-ethyl-piperidine (pK 3.0; b.p. 131 DEG C.) replaces the quinoline of (1), the product containing additionally some 1:3-DCB-2; (3) 1:2:3-TCB containing some 2:2:3:3-tetrachlorobutane is treated as in (1) with pyridine hydrochloride (pyridine has pK 8.6; b.p. 115 DEG C.) to give 1:2-DCB-2 and 2:3-DCB-1; (4) a mixture of 1:2:3-TCB and 2:2:3-TCB is treated as in (1) to give the required 2:3-DCB-1 and 1:2-DCB-2 and unwanted 2:3-DCB-2; (5) 1:2:3-TCB containing some 1:2:3:4-tetrachlorobutane is treated as in (1) with sym-collidine (pK 6.9; b.p. 172 DEG C.) to give 1:2-DCB-2 and 2:3-DCB-1; (6) a mixture as in (3) is treated as in (1) with cyclohexylamine (pK 3.4; b.p. 134 DEG C.) to give 1:2-DCB-2 and 2:3-DCB-1; (7) 1:2:3-TCB and tributylamine hydrochloride (tributylamine has pK 3.2; b.p. 214 DEG C.) give 1:2-DCB-2, 2:3-DCB-1, and 1:3-DCB-2 with some 3:4-DCB-1 and other dichlorobutenes, 1-chlorobutadiene and chloroprene; (8) 1:2:3-TCB and a -picoline hydrochloride (a -picoline has pK 8.1; b.p. 128 DEG C.) give the products of (7); (9) the mixture of (3) and a -picoline give 1:2-DCB-2, 2:3-DCB-1, 1:3-DCB-2 and some 1:3-DCB-1 and chloroprene; (10) the mixture of (3) with gamma-picoline (pK 7.8; b.p. 143 DEG C.) gives 1:2-DCB-2 and 2:3-DCB-1; (11) 1:2:3-TCB with 5-ethyl-2-methylpyridine (pK about 8; b.p. 174 DEG C.) gives 2:3-DCB-1, 1:2-DCB-2 and some chloroprene; and (12) 1:2:3-TCB and 1-methylpyridinium chloride give 1:2-DCB-2, 2:3-DCB-1, 1:3-DCB-2 and some 3:4-DCB-1, chloroprene and 1-chlorobutadiene. The Provisional Specification refers to the use of any amine catalyst, used as such or as an acid salt or quaternary ammonium compound; and provides an additional example wherein a mixture of 1:2:3-TCB and 2:2:3:3-tetrachlorobutane is refluxed with N-ethylpiperidine to give 1:2-DCB-2 and 2:3 - DCB - 1. Specification 805,817 is referred to.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2253955A GB805816A (en) | 1955-08-05 | 1955-08-05 | Dehydrochlorination process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2253955A GB805816A (en) | 1955-08-05 | 1955-08-05 | Dehydrochlorination process |
Publications (1)
Publication Number | Publication Date |
---|---|
GB805816A true GB805816A (en) | 1958-12-10 |
Family
ID=10181045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB2253955A Expired GB805816A (en) | 1955-08-05 | 1955-08-05 | Dehydrochlorination process |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB805816A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3338980A (en) * | 1962-09-20 | 1967-08-29 | Montedison Spa | Process for the preparation of fluorolefines by pyrolysis |
CN112919416A (en) * | 2021-03-26 | 2021-06-08 | 华东理工大学 | Method for preparing hydrogen chloride by catalyzing organic amine hydrochloride pyrolysis |
CN115401060A (en) * | 2022-08-24 | 2022-11-29 | 浙江红狮环保股份有限公司 | Method for removing chlorine content in organic hazardous waste |
-
1955
- 1955-08-05 GB GB2253955A patent/GB805816A/en not_active Expired
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3338980A (en) * | 1962-09-20 | 1967-08-29 | Montedison Spa | Process for the preparation of fluorolefines by pyrolysis |
CN112919416A (en) * | 2021-03-26 | 2021-06-08 | 华东理工大学 | Method for preparing hydrogen chloride by catalyzing organic amine hydrochloride pyrolysis |
CN112919416B (en) * | 2021-03-26 | 2023-09-05 | 华东理工大学 | Method for preparing hydrogen chloride by catalyzing pyrolysis of organic amine hydrochloride |
CN115401060A (en) * | 2022-08-24 | 2022-11-29 | 浙江红狮环保股份有限公司 | Method for removing chlorine content in organic hazardous waste |
CN115401060B (en) * | 2022-08-24 | 2023-11-14 | 浙江红狮环保股份有限公司 | Method for removing chlorine content from organic hazardous waste |
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