A kind of preparation method of 2,4,4-trichloro-1,1,1-trifluorobutane

Abstract

The invention discloses a preparation method of 2,4,4-trichloro-1,1,1-trifluorobutane. The 2,4,4-trichloro-1,1,1-trifluorobutane is synthesized from raw materials 2,2-dichloro-1,1,1-trifluoroethane and chloroethylene in the presence of a telomerization catalyst, a catalytic addictive and a solvent, wherein the telomerization catalyst is copper chloride or cuprous chloride; and the catalytic addictive is 2,2-dipyridyl, pentamethyldiethylenetriamine, tri(2-pyridylmethyl)amine or tri(2-dimethylaminoethyl)amine; the solvent is acetonitrile, methanol or dimethyl sulfoxide. The invention provides a new synthesis route which is cheap and easily available in raw materials, and the synthesis route is mainly used for preparing the 2,4,4-trichloro-1,1,1-trifluorobutane.

Description

technical field

[0001] The invention relates to a preparation method of hydrofluorochloroalkane, in particular to a preparation method of 2,4,4-trichloro-1,1,1-trifluorobutane. Background technique

[0002] Due to the destruction of the ozone layer by the first and second generation blowing agents (fluorotrichloromethane CFC-11, fluorodichloroethane HCFC-141b, etc.), the use of the third generation blowing agents (1,1, 1,3,3-pentafluoropropane (HFC-245fa, etc.) will have a strong greenhouse effect. With the increasing impact of global warming on the earth's ecology, it is urgent to find green and environmentally friendly blowing agents.

[0003] 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336) can quickly add to OH radicals after being discharged into the atmosphere due to the double bond contained in the molecule, and through oxidation For degradation, the atmosphere has a short lifetime (20 days) and a low greenhouse effect value (GWP≈9). Its boiling point is close to room te...

Examples

Embodiment 1

[0016] Add 1.4 grams of copper chloride and 3.2 grams of 2,2-bipyridine to a 500 mL titanium alloy belt stirred autoclave, dissolve them in 20 mL of dimethyl sulfoxide, replace the air in the kettle with nitrogen, and inject 312 grams of R123 with nitrogen gas and 63 grams of vinyl chloride, the reaction temperature is 120°C, the reaction pressure is 1.2MPa, and the reaction time is 12 hours. After the reaction, the crude product is removed by atmospheric distillation to remove R123, R123 is recycled, and the vacuum distillation is continued to collect 2,4,4-trichloro- 1,1,1-Trifluorobutane, the conversion rate is 91.3%, and the selectivity is 87.6%.

[0017] Product structure characterization:

[0018] 1 H-NMR (500MHz, CDCl 3 ): δ2.66(m,1H), δ2.82(m,1H), δ4.37(m,1H), δ5.92(q,1H)

[0019] 13 C-NMR (500MHz, CDCl 3 ): δ44.52(s,1C), δ54.31(q,1C), δ68.53(s,1C), δ124.48(q,1C)

[0020] 19 F-NMR (500MHz, CDCl 3 ): δ-74.66(s,3F)

Embodiment 2～6

[0022] Examples 2-6 Prepare 2,4,4-trichloro-1,1,1-trifluorobutane according to the same preparation method as in Example 1, except that the reaction 2,2-difluorobutane in Example 1 Chlorine 1,1,1-trifluoroethane: vinyl chloride ratio is 2:1, while the telomerization ratios in Examples 2-6 are 1:1, 3:1, 5:1, 7:1, 10: 1. The reaction results of Examples 2-6 are shown in Table 1.

[0023] Table 1 Effect of telomerization ratio

[0024] Example

Embodiment 7～18

[0026] Examples 7-18 Prepare 2,4,4-trichloro-1,1,1-trifluorobutane according to the same preparation method as in Example 1, except that the reaction catalyst in Example 1 is copper chloride , and respectively ferric chloride, ferrous chloride, cupric chloride or cuprous chloride in the embodiment 7~18, the reaction can be carried out without adding solvent. The reaction results of Examples 7-18 are shown in Table 2.

[0027] Table 2 Catalyst and Catalytic Auxiliary Effect

[0028]

[0029]

technical field

[0001] The invention relates to a preparation method of hydrofluorochloroalkane, in particular to a preparation method of 2,4,4-trichloro-1,1,1-trifluorobutane. Background technique

[0002] Due to the destruction of the ozone layer by the first and second generation blowing agents (fluorotrichloromethane CFC-11, fluorodichloroethane HCFC-141b, etc.), the use of the third generation blowing agents (1,1, 1,3,3-pentafluoropropane (HFC-245fa, etc.) will have a strong greenhouse effect. With the increasing impact of global warming on the earth's ecology, it is urgent to find green and environmentally friendly blowing agents.

[0003] 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336) can quickly add to OH radicals after being discharged into the atmosphere due to the double bond contained in the molecule, and through oxidation For degradation, the atmosphere has a short lifetime (20 days) and a low greenhouse effect value (GWP≈9). Its boiling point is close to room te...

Examples

Embodiment 1

[0016] Add 1.4 grams of copper chloride and 3.2 grams of 2,2-bipyridine to a 500 mL titanium alloy belt stirred autoclave, dissolve them in 20 mL of dimethyl sulfoxide, replace the air in the kettle with nitrogen, and inject 312 grams of R123 with nitrogen gas and 63 grams of vinyl chloride, the reaction temperature is 120°C, the reaction pressure is 1.2MPa, and the reaction time is 12 hours. After the reaction, the crude product is removed by atmospheric distillation to remove R123, R123 is recycled, and the vacuum distillation is continued to collect 2,4,4-trichloro- 1,1,1-Trifluorobutane, the conversion rate is 91.3%, and the selectivity is 87.6%.

[0017] Product structure characterization:

[0018] 1 H-NMR (500MHz, CDCl 3 ): δ2.66(m,1H), δ2.82(m,1H), δ4.37(m,1H), δ5.92(q,1H)

[0019] 13 C-NMR (500MHz, CDCl 3 ): δ44.52(s,1C), δ54.31(q,1C), δ68.53(s,1C), δ124.48(q,1C)

[0020] 19 F-NMR (500MHz, CDCl 3 ): δ-74.66(s,3F)

Embodiment 2～6

[0022] Examples 2-6 Prepare 2,4,4-trichloro-1,1,1-trifluorobutane according to the same preparation method as in Example 1, except that the reaction 2,2-difluorobutane in Example 1 Chlorine 1,1,1-trifluoroethane: vinyl chloride ratio is 2:1, while the telomerization ratios in Examples 2-6 are 1:1, 3:1, 5:1, 7:1, 10: 1. The reaction results of Examples 2-6 are shown in Table 1.

[0023] Table 1 Effect of telomerization ratio

[0024] Example

Embodiment 7～18

[0026] Examples 7-18 Prepare 2,4,4-trichloro-1,1,1-trifluorobutane according to the same preparation method as in Example 1, except that the reaction catalyst in Example 1 is copper chloride , and respectively ferric chloride, ferrous chloride, cupric chloride or cuprous chloride in the embodiment 7~18, the reaction can be carried out without adding solvent. The reaction results of Examples 7-18 are shown in Table 2.

[0027] Table 2 Catalyst and Catalytic Auxiliary Effect

[0028]

[0029]

Images