CN112707790A - Synthesis method of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane - Google Patents
Synthesis method of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane Download PDFInfo
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- CN112707790A CN112707790A CN201911017134.3A CN201911017134A CN112707790A CN 112707790 A CN112707790 A CN 112707790A CN 201911017134 A CN201911017134 A CN 201911017134A CN 112707790 A CN112707790 A CN 112707790A
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- dibromo
- chloro
- trifluorobutane
- trifluoroethane
- ethylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
Abstract
The invention belongs to the field of fluorine-containing fine chemical engineering, and provides a synthetic method of 2-chloro-1,4-dibromo-1,1, 2-trifluorobutane. Specifically, 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane is used as a solvent, and 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane is reacted with ethylene in the presence of a radical initiator such as tert-butyl peroxybenzoate (TBPB), Benzoyl Peroxide (BPO), and Lauroyl Peroxide (LPO). The reaction temperature is 70-130 ℃, and the preferable reaction temperature is 90-120 ℃. The molar ratio of the added amount of the initiator is 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane: the initiator is 1: 0.5-1%. The method reduces the content of 1, 6-dibromo-2-chloro-1, 1, 2-trifluorohexane, has the advantages of cleanness, safety and no need of solvent recovery, and is mainly used for synthesizing 2-chloro-1,4-dibromo-1,1, 2-trifluorobutane.
Description
The technical field is as follows:
the invention relates to the field of fluorine-containing fine chemical engineering, and provides a synthetic method of 2-chloro-1,4-dibromo-1,1, 2-trifluorobutane.
Background art:
2-chloro-1,4-dibromo-1,1,2-trifluorobutane (1,2-chloro-1,4-dibromo-1,1,2-trifluorobutane) is an important fluorine-containing organic intermediate, and can be used in the fields of pesticides, materials, medicines and the like. In the prior art, the preparation method of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane is reported as follows: that is, 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane is reacted with ethylene using a radical initiator to produce 2-chloro-1,4-dibromo-1,1, 2-trifluorobutane.
Chinese patent CN 104093755 discloses that a mixture of tert-butyl peroxypivalate and 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane is used as a radical initiator to react ethylene with 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane in 1,1,1,3, 3-pentafluorobutane at 120 ℃ for 4 hours, and the 2-chloro-1,4-dibromo-1,1,2-trifluorobutane is obtained after vacuum distillation. U.S. Pat. No. 2003181615 discloses a process for the preparation of ethylene by reacting 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane at 60 ℃ for 2 hours using tert-butanol as solvent and bis (4-tert-butylcyclohexyl) -carboxydicarbonate as radical initiator. Bruce e e.smart 2002 reports a process for preparing 2-chloro-1,4-dibromo-1,1,2-trifluorobutane by reacting ethylene with 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane at 80 ℃ for 8 hours using benzoyl peroxide as a radical initiator and distilling.
The invention content is as follows:
the invention aims to provide a preparation method of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane, which reduces the content of 1, 6-dibromo-2-chloro-1, 1, 2-trifluorohexane.
The technical scheme adopted by the invention is as follows:
1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane is reacted with ethylene in the presence of a radical initiator using 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane as a solvent.
The initiator comprises tert-butyl peroxybenzoate (TBPB), Benzoyl Peroxide (BPO), and Lauroyl Peroxide (LPO).
The molar ratio of the added amount of the initiator is 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane: the initiator is 1: 0.5-1%.
The reaction temperature is 70-130 ℃.
The preferable reaction temperature is 90-120 ℃.
The introduction mode of the ethylene is high-pressure introduction or liquid nitrogen cooling introduction.
The molar ratio of the introduced amount of ethylene is 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane: ethylene-1: 0.7 to 1.
The synthesis method of the 2-chloro-1,4-dibromo-1,1,2-trifluorobutane is rectified to obtain the 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane and the 2-chloro-1,4-dibromo-1,1,2-trifluorobutane with the purity of more than 99%.
The invention provides a synthetic method for preparing 2-chloro-1,4-dibromo-1,1,2-trifluorobutane without a solvent.
The invention has the advantages of no solvent recovery, cleanness, low cost and safety.
Detailed Description
Example 1: synthesis of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane
160g (0.579mol) of 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane and 1.12g (5.79mmol) of t-butyl peroxybenzoate were charged in a 300mL autoclave, and 16g (0.570mol) of ethylene was charged. Magnetic stirring, heating to 120 deg.C, and reacting for 4 h. Cooling in ice water bath, and discharging residual ethylene gas. After the reaction is finished, rectifying operation is carried out. The GC analysis showed that the 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane content was 47.85% and the conversion was 48.63%. The content of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane was 42.46%, and the yield was 41.38%. The content of 1, 6-dibromo-2-chloro-1, 1, 2-trifluorohexane was 2.34%.
Example 2: synthesis of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane
160g (0.579mol) of 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane and 1.12g (5.79mmol) of t-butyl peroxybenzoate were charged in a 300mL autoclave, and 12g (0.428mol) of ethylene was charged. Magnetic stirring, heating to 120 deg.C, and reacting for 4 h. Cooling in ice water bath, and discharging residual ethylene gas. After the reaction is finished, rectifying operation is carried out. GC analysis showed that the 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane content was 40.10% and the conversion was 42.04%. The content of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane was 46.25%, and the yield was 60.81%. The content of 1, 6-dibromo-2-chloro-1, 1, 2-trifluorohexane was 1.89%.
Example 3: synthesis of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane
160g (0.579mol) of 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane and 2.31g (5.79mmol) of lauroyl peroxide were charged into a 300mL autoclave, and 16g (0.570mol) of ethylene was charged. Magnetic stirring, heating to 100 deg.C, and reacting for 4 h. Cooling in ice water bath, and discharging residual ethylene gas. After the reaction is finished, rectifying operation is carried out. GC analysis showed that the 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane content was 54.51% and the conversion was 40.80%. The content of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane was 32.87%, and the yield was 32.26%. The content of 1, 6-dibromo-2-chloro-1, 1, 2-trifluorohexane was 6.73%.
Example 4: synthesis of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane
160g (0.579mol) of 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane and 1.12g (5.79mmol) of benzoyl peroxide were charged into a 300mL autoclave, and 16g (0.570mol) of ethylene was charged. Magnetic stirring, heating to 120 deg.C, and reacting for 4 h. Cooling in ice water bath, and discharging residual ethylene gas. After the reaction is finished, rectifying operation is carried out. The content of 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane was 49.67% by GC analysis, and the conversion was 43.28%. The content of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane was 39.64%, and the yield was 38.42%. The content of 1, 6-dibromo-2-chloro-1, 1, 2-trifluorohexane was 6.50%.
Example 5: synthesis of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane
160g (0.579mol) of 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane and 1.12g (mol) of t-butyl peroxybenzoate were charged in a 300mL autoclave, and 32.50g (1.158mol) of ethylene was charged. Magnetic stirring, heating to 120 deg.C, and reacting for 4 h. Cooling in ice water bath, and discharging residual ethylene gas. After the reaction is finished, rectifying operation is carried out. GC analysis showed that the 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane content was 42.99% and the conversion was 40.80%. The content of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane was 26.89%, and the yield was 24.31%. The content of 1, 6-dibromo-2-chloro-1, 1, 2-trifluorohexane was 23.85%.
Claims (8)
- A process for synthesizing 2-chloro-1,4-dibromo-1,1,2-trifluorobutane, characterized by reacting 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane with ethylene in the presence of a radical initiator using 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane as a solvent.
- 2. The method for synthesizing 2-chloro-1,4-dibromo-1,1,2-trifluorobutane according to claim 1, wherein the initiator comprises t-butyl peroxybenzoate (TBPB), Benzoyl Peroxide (BPO) and Lauroyl Peroxide (LPO).
- 3. The process for synthesizing 2-chloro-1,4-dibromo-1,1,2-trifluorobutane according to claim 1, wherein the molar ratio of the amount of the initiator added to the 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane is the initiator: 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane: 0.5% -1%: 1.
- 4. the method for synthesizing 2-chloro-1,4-dibromo-1,1,2-trifluorobutane according to claim 1, wherein the reaction temperature is 70 to 130 ℃.
- 5. The method for synthesizing 2-chloro-1,4-dibromo-1,1,2-trifluorobutane according to claim 4, wherein the optimal reaction temperature is 90 to 120 ℃.
- 6. The process for the synthesis of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane according to claim 1, wherein the ethylene is introduced by high-pressure introduction or liquid nitrogen cooling introduction.
- 7. The process for synthesizing 2-chloro-1,4-dibromo-1,1,2-trifluorobutane according to claim 1, wherein the molar ratio of 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane to the introduced amount of ethylene is 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane: ethylene-1: 0.7 to 1.
- 8. The process for the synthesis of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane according to claim 1, wherein the process for the synthesis of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane is rectified to obtain 1, 2-dibromo-1-chloro-1, 2, 2-trifluoroethane and 2-chloro-1,4-dibromo-1,1,2-trifluorobutane having a purity of more than 99%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS247548B1 (en) * | 1985-09-11 | 1987-01-15 | Zdenek Chvatal | Method of fluorohalogenbutanes preparation |
| EP1289915A2 (en) * | 2000-06-13 | 2003-03-12 | Hydro-Quebec | Bromosulphonated fluorinated crosslinkable elastomers based on vinylidene fluoride having very low tg and method for preparing same |
| CN104093755A (en) * | 2011-12-14 | 2014-10-08 | 霍尼韦尔国际公司 | Process, properties, and applications of graft copolymers |
-
2019
- 2019-10-24 CN CN201911017134.3A patent/CN112707790A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS247548B1 (en) * | 1985-09-11 | 1987-01-15 | Zdenek Chvatal | Method of fluorohalogenbutanes preparation |
| EP1289915A2 (en) * | 2000-06-13 | 2003-03-12 | Hydro-Quebec | Bromosulphonated fluorinated crosslinkable elastomers based on vinylidene fluoride having very low tg and method for preparing same |
| US20030181615A1 (en) * | 2000-06-13 | 2003-09-25 | Ameduri Bruno Michel | Bromosulphonated fluorinated cross-linkabke elastomers based on vinylidene fluoride having low t9 and processes for their preparation |
| CN104093755A (en) * | 2011-12-14 | 2014-10-08 | 霍尼韦尔国际公司 | Process, properties, and applications of graft copolymers |
Non-Patent Citations (1)
| Title |
|---|
| TARRANT, PAUL ETAL.: ""Free radical additions involving fluorine compounds. II. The addition of 1-chloro-1,2-dibromo-1,2,2-trifluoroethane to some hydrocarbon olefins"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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