阅读说明：本技术 2-氯-1,4-二溴-1,1,2-三氟丁烷的合成方法 (Synthesis method of 2-chloro-1,4-dibromo-1,1,2-trifluorobutane ) 是由 邹小毛 侯文萧 许辉 王如军 张振国 赵宝修 史晋星 于 2019-10-24 设计创作，主要内容包括：本发明属于含氟精细化工领域,提供了一种2-氯-1,4-二溴-1,1,2-三氟丁烷的合成方法。具体是以1,2-二溴-1-氯-1,2,2-三氟乙烷为溶剂,使1,2-二溴-1-氯-1,2,2-三氟乙烷与乙烯在包含过氧化苯甲酸叔丁酯(TBPB)、过氧化苯甲酰(BPO)和过氧化十二酰(LPO)等自由基引发剂存在下反应。反应温度为70～130℃,优选反应温度90～120℃。引发剂加入量的摩尔比为1,2-二溴-1-氯-1,2,2-三氟乙烷：引发剂＝1:0.5％～1％。本发明降低了1,6-二溴-2-氯-1,1,2-三氟己烷的含量,具有清洁、安全、无需溶剂回收的优点,主要用于2-氯-1,4-二溴-1,1,2-三氟丁烷的合成。(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.)

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%.

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%.