Process for Preparing (Z)-1,1,1,4,4,4-Hexafluoro-2-Butene

1 . A process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising reacting hexachlorobutadiene with hydrofluoric acid in the presence of a transition metal catalyst, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

2 . The process of claim 1 , wherein the transition metal catalyst is selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.

3 . The process of claim 1 , wherein the transition metal catalyst is tantalum (V) chloride.

4 . The process of claim 1 , wherein the transition metal catalyst is niobium (V) chloride or niobium (IV) chloride.

5 . The process of claim 1 , wherein the transition metal catalyst is a mixture of a tantalum catalyst and a niobium catalyst.

6 . The process of claim 1 , wherein a molar excess of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene.

7 . The process of claim 1 , wherein the process is performed a temperature of from about 110° C. to about 135° C.

8 . The process of claim 1 , wherein the process comprises:

i) adding the transition metal catalyst to the hydrofluoric acid to form a first mixture; and

ii) adding the hexachlorobutadiene to the first mixture to form a second mixture.

9 . The process of claim 8 , wherein the first mixture is heated to a temperature of from about 110° C. to about 140° C.

10 . The process of claim 9 , further comprising cooling the first mixture to a temperature of from about −10° C. to about 10° C. prior to performing step ii).

11 . The process of claim 10 , further comprising heating the second mixture to a temperature of from about 110° C. to about 140° C.

12 . A process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising:

i) adding tantalum (V) chloride to hydrofluoric acid to form a first mixture;

ii) heating the first mixture to a temperature of from about 110° C. to about 120° C.;

iii) cooling the first mixture to a temperature of from about −10° C. to about 10° C.;

iv) adding hexachlorobutadiene to the first mixture to form a second mixture; and

v) heating the second mixture to a temperature of from about 110° C. to about 120° C.

13 . A process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising:

i) adding niobium (V) chloride to hydrofluoric acid to form a first mixture;

ii) heating the first mixture to a temperature of from about 125° C. to about 135° C.;

iii) cooling the first mixture to a temperature of from about −10° C. to about 10° C.;

iv) adding hexachlorobutadiene to the first mixture to form a second mixture; and

v) heating the second mixture to a temperature of from about 125° C. to about 135° C.

14 . The process of claim 12 , wherein a molar excess of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene.

15 . The process of claim 1 , wherein the process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene is performed in the absence of an additional solvent component.

16 . The process of claim 1 , further comprising reacting the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene with a base in the presence of an alkali metal halide and a quaternary (C 4-12 alkyl)ammonium salt to form perfluorobut-2-yne.

17 . The process of claim 16 , wherein the base is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, and mixtures thereof.

18 . The process of claim 16 , wherein the alkali metal halide is sodium chloride.

19 . The process of claim 16 , wherein the quaternary (C 4-12 alkyl)ammonium salt is selected from the group consisting of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium hydrogen sulfate, trioctylmethylammonium chloride, trioctylmethylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, and tetradodecylammonium chloride.

20 . The process of claim 16 , wherein about 1 to about 1.5 molar equivalents of base is used based on one molar equivalent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

21 . The process of claim 16 , further comprising reacting the perfluorobut-2-yne with hydrogen in the presence of a hydrogenation catalyst to form 1,1,1,4,4,4-hexafluoro-2-butene.

22 . The process of claim 21 , wherein the hydrogenation catalyst is Lindlar's catalyst.

23 . The process of claim 21 , wherein greater than about 95% of the 1,1,1,4,4,4-hexafluoro-2-butene is (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

24 . The process of claim 21 , wherein the process of preparing 1,1,1,4,4,4-hexafluoro-2-butene is performed in the absence of an additional solvent component.

25 . The process of claim 1 , wherein greater than about 99.5 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

26 . A process of preparing a composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene, comprising:

i) reacting hexachlorobutadiene with hydrofluoric acid in the presence of tantalum (V) chloride to form a first composition comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

ii) reacting the first composition with sodium hydroxide in the presence of sodium chloride and trioctylmethylammonium chloride to form a second composition comprising perfluorobut-2-yne; and

iii) reacting the second composition in the presence of a hydrogenation catalyst to form the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

27 . A process of preparing a composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene, comprising:

i) reacting hexachlorobutadiene with hydrofluoric acid in the presence of niobium (IV) chloride to form a first composition comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;

ii) reacting the first composition with sodium hydroxide in the presence of sodium chloride and trioctylmethylammonium salt chloride to form a second composition comprising perfluorobut-2-yne; and

iii) reacting the second composition in the presence of a hydrogenation catalyst to form the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

28 . A composition, comprising:

i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and

ii) one or more additional compounds selected from the group consisting of:

1,1,1,3,3,3-hexafluoropropane;

1,1,1,2,2,4,4,4-octafluorobutane;

1,1,1,4,4,4-hexafluorobutane;

1,2-dichloro-1,1,2,2-tetrafluoroethane;

2-chloro-1,1,1-trifluoroethane;

2-chloro-1,1,1,2,4,4,4-heptafluorobutane;

2-chloro-1,1,1,3,4,4,4-heptafluorobutane;

2-chloro-1,1,1,3,3-pentafluoropropane;

1-chloro-1,1,3,3,3-pentafluoropropane;

(E)-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene;

1,2-dichloro-3,3,4,4-tetrafluorocyclobut-1-ene;

2-chloro-1,1,1,4,4,4-hexafluorobutane;

2,2-dichloro-1,1,1-trifluoroethane;

1,2-dichloro-1,1,2-trifluoroethane;

1,2-dichloro-1,1,3,3,3-pentafluoropropane;

(E)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene;

1,1,2-trichloro-1,2,2-trifluoroethane;

(Z)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene;

1,2-dichloro-3,3,3-trifluoroprop-1-ene;

(Z)-1,2-dichloro-1,1,4,4,4-pentafluorobut-2-ene;

2,2-dichloro-1,1,1,4,4,4-hexafluorobutane;

dl-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane;

meso-2,3-dichloro-1,1,1,4,4,4-hexafluorobutane;

1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene;

2,3-dichloro-1,1,1,3-tetrafluoropropane;

1,2-dichloro-1,1,2,4,4,4-hexafluorobutane;

1,2,2-trichloro-1,1-difluoroethane;

1,1,1-trichloro-2,2-difluoroethane;

1,1,2,2-tetrachloro-1,2-difluoroethane;

1,1,1,2-tetrachloro-2,2-difluoroethane;

1,2,3-trichloro-1,1,4,4,4-pentafluorobutane; and

1,1,2,3-tetrachloro-4,4,4-trifluorobut-1-ene;

wherein the composition comprises greater than about 98 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

29 . A composition, comprising:

i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and

ii) one or more additional compounds selected from the group consisting of:

2-chloro-1,1,1,2,4,4,4-heptafluorobutane;

(E)-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene;

1,2-dichloro-3,3,4,4-tetrafluorocyclobut-1-ene;

1,2-dichloro-1,1,3,3,3-pentafluoropropane; and

1,1,2-trichloro-1,2,2-trifluoroethane;

wherein the composition comprises greater than about 98 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.

30 . A composition, comprising:

i) perfluorobut-2-yne; and

ii) one or more additional compounds selected from the group consisting of:

1,1,1,3,3,3-hexafluoropropane;

1,1,1,2,4,4,4-heptafluorobut-2-ene;

(E)-1,1,1,4,4,4-hexafluorobutene;

1,1,1,2,2,4,4,4-octafluorobutane;

1,1,1,4,4,4-hexafluorobutane;

1,2-dichloro-1,1,2,2-tetrafluoroethane;

2-chloro-1,1,1-trifluoroethane;

(Z)-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene;

1-chloro-3,3,4,4,4-pentafluotobut-1-yne;

1-chloro-3,3,4,4,4-pentafluorobut-2-yne;

(Z)-1,2-dichloro-1,1,4,4,4-pentafluorobut-2-ene;

1,2-dichloro-3,3,4,4,4-pentafluorobut-1-ene

2-chloro-1,1,1,2,4,4,4-heptafluorobutane;

2-chloro-1,1,1,3,4,4,4-heptafluorobutane;

2-chloro-1,1,1,3,3-pentafluoropropane;

1-chloro-1,1,3,3,3-pentafluoropropane;

(E)-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene;

2-chloro-1,1,1,4,4,4-hexafluorobutane;

2,2-dichloro-1,1,1-trifluoroethane;

1,2-dichloro-1,1,2-trifluoroethane;

1,2-dichloro-1,1,3,3,3-pentafluoropropane;

(E)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene;

1,1,2-trichloro-1,2,2-trifluoroethane;

(Z)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene;

1-chloro-3,3,3-trifluoroprop-1-yne;

1,2-dichloro-3,3,3-trifluoroprop-1-ene;

(Z)-1,2-dichloro-1,1,4,4,4-pentafluorobut-2-ene;

1-chloro-1,1,2,4,4,4-hexafluorobut-2-ene;

2-chloro-1,3,3,3-tetrafluoroprop-1-ene;

1,1,3,3,3-pentafluoroprop-1-ene; and

2-chloro-1,1,3,3,3-pentafluoroprop-1-ene;

wherein the composition comprises greater than about 99 mole percent perfluorobut-2-yne.

31 . A composition, comprising:

i) perfluorobut-2-yne; and

ii) one or more additional compounds selected from the group consisting of:

2-chloro-1,1,1,2,4,4,4-heptafluorobutane;

(E)-2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene; and

1,1,2-trichloro-1,2,2-trifluoroethane;

wherein the composition comprises greater than about 99 mole percent perfluorobut-2-yne.

32 . A composition, comprising:

i) (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and

ii) one or more additional compounds selected from the group consisting of:

1,1,1,3,3,3-hexafluoropropane;

(E)-1,1,1,4,4,4-hexafluorobutene;

1,1,1,2,2,4,4,4-octafluorobutane;

1,2-dichloro-1,1,2,2-tetrafluoroethane;

3-chloro-1,1,1-trifluoropropane;

4-chloro-1,1,1,2,2-pentafluorobutane;

2-chloro-1,1,1,2,4,4,4-heptafluorobutane;

2-chloro-1,1,1,3,4,4,4-heptafluorobutane;

2-chloro-1,1,1,3,3-pentafluoropropane;

1-chloro-1,1,3,3,3-pentafluoropropane;

2-chloro-1,1,1,4,4,4-hexafluorobutane;

1,2-dichloro-1,1,3,3,3-pentafluoropropane;

1,2-dichloro-3,3,3-trifluoroprop-1-ene;

1-chloro-3,3,3-trifluoro-propene;

1-chloro-1,1,2,4,4,4-hexafluorobut-2-ene;

1-chloro-1,1,4,4,4-pentafluorobutane;

2-chloro-1,1,1,3-tetrafluoropropane; and

1,1,1,3,3-pentafluoropropane;

wherein the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene.

33 . A composition, comprising:

i) (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and

ii) one or more additional compounds selected from the group consisting of:

2-chloro-1,1,1,2,4,4,4-heptafluorobutane; and

1,2-dichloro-1,1,3,3,3-pentafluoropropane;

wherein the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene.