KR20150061638A - Dehydrochlorination of chlorinated reactants to produce 1,1,1,4,4,4-hexafluoro-2-butyne - Google Patents

Abstract

Reacting HCFC-336 with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkyl ammonium salt comprising at least one alkyl group having 8 or more carbon atoms, and recovering the hexafluoro-2-butyne, , And a conversion rate of 1,1,4,4,4-hexafluorobutane of 50% or more per hour is disclosed. Reacting HCFC-336 with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkyl ammonium salt having an alkyl group of 4 to 10 carbon atoms and combinations thereof and a nonionic surfactant, and recovering hexafluoro-2-butyne Wherein the conversion of dichloro-1,1,1,4,4,4-hexafluorobutane to hexafluoro-2-butyne is greater than or equal to 20% per hour, the conversion of hexafluoro-2-butyne A manufacturing method is also disclosed.

Description

DEHYDROCHLORINATION OF CHLORINATED REACTANTS TO PRODUCE 1,1,1,4,4,4-HEXAFLUORO < RTI ID = 0.0 > (1,1,1,4,4,4-hexafluoro-2-butyne) < / RTI > -2-BUTYNE}

FIELD OF THE INVENTION The present invention relates generally to a process for the synthesis of fluorinated olefins and fluorinated alkynes.

The fluorocarbon industry has been exploring alternative refrigerants for ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) that have been phased out as a result of the Montreal Protocol for decades. Solutions for many applications have been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, foam blowing agents and propellants. These new compounds, for example HFC-134a and HFC-125, which are the most widely used HFC refrigerants, and HFC-134a and HFC-245fa, which are blowing agents, have an ozone depletion index of zero and, as a result of the Montreal Protocol, Are not affected by the phased withdrawal by.

In addition to the problem of ozone depletion, global warming is another environmental issue in many of these applications. Thus, there is a need for compositions that meet both low global warming indices as well as low ozone depletion standards. It is believed that certain hydrofluoroolefins meet two objectives. Therefore, there is a need for a process for producing halogenated hydrocarbons and fluoroolefins that does not contain chlorine and which also has a low global warming index. Some hydrofluoroolefins have been found to meet this objective. One such olefin is 1,1,1,4,4,4-hexafluoro-2-butene. There is a need for an efficient synthesis method for such compounds.

Reacting a chlorinated reagent with an aqueous solution of an alkali metal hydroxide in the presence of a phase transfer catalyst. In one embodiment, the chlorinated reactant comprises chlorofluorobutane or chlorofluorobutene. In one embodiment, the chlorinated reactant comprises HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), HCFC-336mfa (2,2- , 1,1,4,4,4-hexafluorobutane) or HCFO-1326mxz (E- or Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene) to be. As used herein, HCFC-336 is meant to include either or both of the aforementioned HCFC-336 isomers. In one embodiment, the phase transfer catalyst is a quaternary alkyl ammonium salt. In one embodiment, the quaternary alkyl ammonium salt has at least one alkyl group having at least 8 carbon atoms, the method comprising recovering hexafluoro-2-butyne, wherein the dichloro-1,1,1,4,4 , And the conversion rate of 4-hexafluorobutane is 50% or more per hour.

Reacting the chlorinated reactant with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkyl ammonium salt having an alkyl group of 4 to 10 carbon atoms and combinations thereof and a nonionic surfactant and recovering hexafluoro-2-butyne Wherein the conversion of the chlorinated reagent to hexafluoro-2-butyne is 20% or more per hour.

The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims.

Reacting the chlorinated reactant with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkyl ammonium salt comprising at least one alkyl group having 8 or more carbon atoms and recovering hexafluoro-2-butyne, , And a conversion rate of 1,1,4,4,4-hexafluorobutane of 50% or more per hour is disclosed.

Reacting the chlorinated reactant with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkyl ammonium salt having an alkyl group of 4 to 10 carbon atoms and combinations thereof and a nonionic surfactant and recovering hexafluoro-2-butyne Wherein the conversion of the chlorinated reagent to hexafluoro-2-butyne is 20% or more per hour.

Many alternatives and embodiments are described above and are merely illustrative and not restrictive. After reading this specification, it is understood by those skilled in the art that other modes and embodiments are possible without departing from the scope of the present invention.

Any one or more of the other features and advantages of the embodiments will become apparent from the detailed description and the claims that follow. In addition, individual features and elements of the embodiments disclosed herein may be used individually, in conjunction, or in combination with each other, whether individually described, claimed or exemplified below.

As used herein, the designation HCFC-336 without positional isomers includes HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane) or HCFC- -336 mfa (2,2-dichloro-1,1,1,4,4-hexafluorobutane). As used herein, the nomenclature HCFC-1326mxz without stereochemistry is E-or Z-HCFC-1326mxz (E-1,1,1,4,4,4-hexafluoro-2- 2-butene or Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene).

HCFC-336 is potentially available through a number of routes and is of interest as a potential precursor to 1,1,1,4,4,4-hexafluoro-2-butene. HCFC-336 can be prepared by hydrogenation of CFC-1316mxx or by chlorination of HFC-356mff. Two dehydrochlorination will provide hexafluoro-2-butyne, which is readily hydrogenated to provide cis-1,1,1,4,4,4-hexafluoro-2-butene . The first dehydrochlorination seems to be straightforward, but in classical organic chemistry dehydrochlorination of vinyl chloride to form acetylene requires very harsh bases, such as sodium in liquid ammonia, which are very strong bases. Higher molecular weight polyfluorinated vinyl chlorides have been reported to be dehydrohalogenated to alkynes using aqueous bases at temperatures from 100 to 120 占 폚 up to 200 or 250 占 폚. However, at these temperatures, hexafluoro-2-butyne will have too high a vapor pressure in the reactor and will be prone to decomposition.

It has been shown that using a basic aqueous solution with a quaternary alkylammonium salt as a phase transfer catalyst can dehydrochlorinate either HCFC-336mdd or HCFC-336mfa twice at temperatures well below 100 ° C.

As used herein, phase transfer catalyst means a material that promotes the migration of an ionic compound from the aqueous phase or from the solid phase to the organic phase. The phase transfer catalyst promotes the reaction of these dissimilar and incompatible components. Although various phase transfer catalysts can function in different ways, their mechanism of action is not critical to their utility in the present invention, as long as the phase transfer catalyst promotes the dehydrochlorination reaction.

The phase transfer catalyst as used herein is a quaternary alkyl ammonium salt wherein the alkyl group is an alkyl chain having 4 to 10 carbon atoms. In one embodiment, the quaternary alkylammonium salt is trioctylmethylammonium chloride (Aliquat 336). The anion of the salt may be a halide such as chloride or bromide, a hydrogen sulfate, or any other commonly used anion.

In another embodiment, the quaternary alkylammonium salt is tetraoctylammonium chloride. In another embodiment, the quaternary alkylammonium salt is tetraoctylammonium hydrogensulfate.

Other compounds, which are considered as phase transfer catalysts in other applications, including crown ethers, cryptands, or nonionic surfactants alone, do not significantly affect the conversion rate or rate of the dehydrochlorination reaction in the same manner.

In another embodiment, either of the HCFC-336mdd or HCFC-336mfa is reacted with a quaternary alkylammonium salt wherein the alkyl group is an alkyl chain having 4 or more carbon atoms and further with a nonionic surfactant at a temperature much lower than 100 ° C using a basic aqueous solution One can be dehydrochlorinated twice. An example of such a quaternary alkylammonium salt is tetrabutylammonium chloride.

In one embodiment, the nonionic surfactant is ethoxylated nonylphenol or ethoxylated C12-C15 linear aliphatic alcohol. Suitable non-ionic surfactants include Bio-soft N25-9 and Makon (R) 10 from Stepan Company.

In one embodiment, the quaternary alkyl ammonium salt is selected from the group consisting of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium hydrogensulfate, methyltrioctylammonium chloride , Methyltrioctylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, and tetradodecylammonium chloride.

The dehydrochlorination of HCFC-336 can be effected by quaternary alkylammonium salts in which the alkyl group is an alkyl chain having at least one alkyl chain containing at least 8 alkyl chains. In another embodiment, the quaternary alkylammonium salt has three alkyl chains of 8 or more carbon atoms, for example, a trioctylmethylammonium salt. In another embodiment, the quaternary alkylammonium salt is a tetraoctylammonium salt. The anion of the salt may be a halide such as chloride or bromide, a hydrogen sulfate, or any other commonly used anion.

In one embodiment, the quaternary alkylammonium salt is added in an amount of from 0.5 mol% to 2.0 mol% of HCFC-336. In another embodiment, the quaternary alkylammonium salt is added in an amount of 1 mole% to 2 mole% of HCFC-336. In another embodiment, the quaternary alkylammonium salt is added in an amount of 1 mole% to 1.5 mole% of HCFC-336. In one embodiment, the quaternary alkylammonium salt is added in an amount of 1 mole% to 1.5 mole% of HCFC-336, and the weight of the nonionic surfactant added is 1.0 to 2.0 times the weight of the quaternary alkylammonium salt.

In one embodiment, the reaction is carried out at a temperature of about 60 to 90 < 0 > C. In another embodiment, the reaction is carried out at 70 < 0 > C.

As used herein, a basic aqueous solution is a liquid (such as a solution, dispersion, emulsion, or suspension) that is an aqueous liquid having a pH of more than about 7. In some embodiments, the basic aqueous solution has a pH of greater than 8. In some embodiments, the basic aqueous solution has a pH greater than 10. In some embodiments, the basic aqueous solution has a pH of 10-13. In some embodiments, the basic aqueous solution contains a small amount of organic liquid which may be miscible or immiscible with water. In some embodiments, the liquid medium in the basic aqueous solution is at least 90% water. In one embodiment, the water is tap water; In another embodiment, water is deionized water or distilled water.

The base in the basic aqueous solution is selected from the group consisting of hydroxides, oxides, carbonates, or phosphates of alkali metals and alkaline earth metals, and mixtures thereof. In one embodiment, bases that may be used include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, or mixtures thereof.

The hydrofluorochloroolefin HCFC-1326mxz is, in some schemes, an impurity for the synthesis of 1,1,1,4,4,4-hexafluoro-2-butene, which is of interest as a foam expansion agent . In other possible schemes, this can be an intermediate. One synthetic method of HCFC-1326mxz is via hydrogenation of 1,1,1,4,4,4-hexafluoro-2,3-dichloro-2-butene. Whatever the synthesis method, typically a mixture of Z- and E-stereoisomers for the double bond is obtained. Unfortunately, it exhibits considerably high toxicity, so it is desirable to convert it into a useful product in high yield, whether formed as an impurity or as an intermediate. Dehydrochlorination will provide hexafluoro-2-butyne, which can be hydrogenated to provide 1,1,1,4,4,4-hexafluoro-2-butene. In classical organic chemistry, the dehydrochlorination of vinyl chloride to form acetylene requires very harsh conditions, such as sodium in liquid ammonia, which are very strong bases. Higher molecular weight polyfluorinated vinyl chlorides have been reported to be dehydrohalogenated to alkynes using aqueous bases at temperatures from 100 to 120 占 폚 up to 200 or 250 占 폚. However, at these temperatures, hexafluoro-2-butyne will have too high a vapor pressure in the reactor and will be prone to decomposition.

And E-1,1,1,4,4,4-hexafluoro-2-chloro-2- (4-methoxyphenyl) propane as a phase transfer catalyst at a temperature significantly lower than 100 < 0 > C using a basic aqueous solution, Butene can be dehydrochlorinated.

As used herein, phase transfer catalyst means a material that promotes the migration of an ionic compound from the aqueous phase or from the solid phase to the organic phase. The phase transfer catalyst promotes the reaction of these dissimilar and non-compatible components. Although various phase transfer catalysts can function in different ways, their mechanism of action is not critical to their utility in the present invention, as long as the phase transfer catalyst promotes the dehydrochlorination reaction.

The phase transfer catalyst as used herein is a quaternary alkylammonium salt wherein the alkyl group is an alkyl chain of 4 to 12 carbon atoms. In one embodiment, the quaternary alkylammonium salt is a tetrabutylammonium salt. The anion of the salt may be a halide such as chloride or bromide, a hydrogen sulfate, or any other commonly used anion.

In another embodiment, the quaternary alkylammonium salt is trioctylmethylammonium chloride (Aliquat 336). In another embodiment, the quaternary alkylammonium salt is tetraoctylammonium chloride. In another embodiment, the quaternary alkylammonium salt is tetraoctylammonium hydrogensulfate.

Other compounds, usually considered as phase transfer catalysts in other applications, including crown ethers, creptadoes, or non-ionic surfactants alone, do not significantly affect the conversion rate or rate of the dehydrochlorination reaction in the same manner.

The Z- and E-isomers of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene exhibit significantly different reactivities to dehydrochlorination and are effective as phase transfer catalysts in this reaction The requirements for acting are different. Z-isomer

CF ₃ CCl = CHCF ₃

Can be effected by a quaternary alkylammonium salt in which the alkyl group is an alkyl chain having 4 to 12 carbon atoms. The anion of the salt may be a halide such as chloride or bromide, a hydrogen sulfate, or any other commonly used anion. In one embodiment, the quaternary alkylammonium salt is a tetrabutylammonium salt. In another embodiment, the quaternary alkylammonium salt is a tetrahexylammonium salt. In another embodiment, the quaternary alkylammonium salt is a tetraoctylammonium salt. In another embodiment, the quaternary alkylammonium salt is a trioctylmethylammonium salt.

The dehydrochlorination of the E-isomer of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene is carried out in the presence of a quaternary alkyl group wherein the alkyl group is an alkyl chain having at least one alkyl chain having at least 8 carbon atoms It can be affected by ammonium salts. In another embodiment, the quaternary alkylammonium salt has three alkyl chains of 8 or more carbon atoms, for example, a trioctylmethylammonium salt. In another embodiment, the quaternary alkylammonium salt is a tetraoctylammonium salt. In another embodiment, the quaternary ammonium salt is a tetradecyl ammonium salt. In another embodiment, the quaternary alkylammonium salt is a tetradodecylammonium salt. The anion of the salt may be a halide such as chloride or bromide, a hydrogen sulfate, or any other commonly used anion.

In another embodiment, the dehydrochlorination of the E-isomer of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene is carried out in such a manner that the alkyl group is an alkyl chain of 4 to 12 carbon atoms By the alkylammonium salts, and by the presence of non-ionic surfactants. The nonionic surfactant can be ethoxylated nonylphenol, and ethoxylated C12 to C15 linear aliphatic alcohol. Suitable non-ionic surfactants include Bio-Soft N25-9 and Macon (R) 10 from Stefan Company.

In one embodiment, the quaternary alkylammonium salt is added in an amount of from 0.5 mol% to 2.0 mol% of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene. In another embodiment, the quaternary alkyl ammonium salt is added in an amount of 1 mole% to 2 mole% of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene. In another embodiment, the quaternary alkylammonium salt is added in an amount of from 1 mole% to 1.5 mole% of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene.

In one embodiment, the dehydrochlorination of Z- or E-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene is carried out in the presence of an alkali metal halide salt. In one embodiment, the alkali metal is sodium or potassium. In one embodiment, the halide is chloride or bromide. In one embodiment, the alkali metal halide salt is sodium chloride. Without wishing to be bound by any particular theory, it is believed that the alkali metal halide salt stabilizes the phase transfer catalyst. The dehydrochlorination reaction itself produces an alkali metal chloride, in particular sodium hydroxide when sodium hydroxide is used as the base, but the addition of a separate sodium chloride provides an additional effect of increasing the yield of hexafluoro-2-butyne do.

The addition of the alkali metal halide salt also reduces the amount of fluoride ion measured in the water exiting the reaction. Without wishing to be bound by any particular theory, it is believed that the presence of the fluoride can be achieved by the use of 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene, or hexafluoro-2- Is believed to result from the decomposition of any one of the butene products.

In some samples, the amount of fluoride ion found in water exiting from dehydrochlorination is about 6000 ppm. In some instances, the use of 30 to 60 equivalents of sodium chloride per mole of phase transfer catalyst reduces the amount of fluoride ion in the effluent water to 2000 ppm. In one embodiment, the alkali metal halide is added in an amount of 25 to 100 equivalents per mole of the phase transfer catalyst. In another embodiment, the alkali metal halide is added in an amount of 30 to 75 equivalents per mole of the phase transfer catalyst. In another embodiment, the alkali metal halide is added in an amount of 40 to 60 equivalents per mole of the phase transfer catalyst.

In one embodiment, the reaction is carried out at a temperature of about 60 to 90 < 0 > C. In another embodiment, the reaction is carried out at 70 < 0 > C.

As used herein, a basic aqueous solution is a liquid (such as a solution, dispersion, emulsion, or suspension) that is an aqueous liquid having a pH of more than about 7. In some embodiments, the basic aqueous solution has a pH of greater than 8. In some embodiments, the basic aqueous solution has a pH greater than 10. In some embodiments, the basic aqueous solution has a pH of 10-13. In some embodiments, the basic aqueous solution contains a small amount of organic liquid which may be miscible or immiscible with water. In some embodiments, the liquid medium in the basic aqueous solution is at least 90% water. In one embodiment, the water is tap water; In another embodiment, water is deionized water or distilled water.

The base in the basic aqueous solution is selected from the group consisting of hydroxides, oxides, carbonates, or phosphates of alkali metals and alkaline earth metals, and mixtures thereof. In one embodiment, bases that may be used include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, or mixtures thereof.

As used herein, the terms "comprise," " comprise, "" comprising," " comprising, "" having ", or & It is intended to cover. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to such elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus It is possible. Moreover, unless expressly stated to the contrary, "or" does not mean " comprehensive " or " exclusive " For example, the condition A or B is satisfied by either: A is true (or exists), B is false (or not present), A is false (or nonexistent) (Or present), A and B are both true (or present).

Also, the use of the indefinite article ("a" or "an") is used to describe the elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the present invention. It should be understood that these techniques include one or at least one, and singular forms also include plural forms, unless the number is expressly meant to be singular.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In the event of conflict, the present specification, including definitions, will control. Also, the materials, methods, and embodiments are illustrative only and not intended to be limiting.

Example

The concepts described herein will be further described in the following examples, which are not intended to limit the scope of the invention as set forth in the claims.

Tetrabutylammonium hydrogensulfate, tetra-n-butylammonium bromide (TBAB), tetra-n-butylammonium hydrogen sulfate, trioctylmethylammonium chloride (Aliquat TM 336), tetraoctylammonium chloride (TOAC) (TOAHS) and tributylmethylammonium bromide (TBMAB) are available from Sigma Aldrich, St. Louis, Missouri, USA. Bio-Soft (R) N25-9 and Macon (R) 10 are available from Stefan Company, Northfield, Ill.; 1326 is available from Synquest Labs, Inc. < RTI ID = 0.0 >

Legend

HCFC-336mfa is CF ₃ CCl ₂ CH ₂ CF ₃

HCFC-336mdd is CF ₃ CHClCHClCF ₃

HCFC-1326mxy is CF ₃ CCl = CHCF ₃

HFB is CF ₃ C≡CCF ₃

Example 1

Example 1 demonstrates the conversion of 336 m dd to hexafluorobutene in the presence of aliquat 336.

NaOH aqueous solution (22 mL, 0.22 mol) was added at room temperature to 336 mdd (23.5 g, 0.1 mol) and water (5.6 mL) in the presence of Aliquat 占 336 (0.53 g, 0.001325 mol). After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 2 hours the reaction was complete and 14 g of product (conversion: 100%; yield: 86%) were collected on a dry ice trap.

Example 2

Example 2 demonstrates the conversion of 336 mfa to hexafluoro-2-butyne in the presence of aliquat 336.

NaOH aqueous solution (22 mL, 0.22 mol) is added at room temperature to 336 mfa (23.5 g, 0.1 mol) and water (5.6 mL) in the presence of Aliquat 占 336 (0.53 g, 0.001325 mol). After addition, the reaction temperature is raised to 70 < 0 > C and the reaction is monitored using gas chromatography. After 2 hours the reaction is complete and hexafluorobutene is collected in a dry ice trap.

Example 3

Example 3 demonstrates the conversion of 336 mfa to hexafluoro-2-butyne in the presence of tetrabutylammonium chloride and a nonionic surfactant.

A solution of NaOH (22 mL, 0.22 mol) was added at room temperature to a solution of 336 mfa (23.5 g, 0.1 mol) and water (5.6 mL) in the presence of tetrabutylammonium bromide (0.45 g, 0.001325 mol) ). After addition, the reaction temperature is raised to 70 < 0 > C and the reaction is monitored using gas chromatography. After 4.5 hours the reaction is complete and hexafluorobutene is collected in a dry ice trap.

Comparative Example 1

NaOH aqueous solution (23 mL, 0.23 mol) is added to a mixture of HCFC-336mfa (23.5 g, 0.1 mol) and water (18 mL) at 37 ° C. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 31 hours, 0.36 g of hexafluoro-2-butyne (conversion: 2.2%; yield: 2.2%) was collected in the dry ice trap.

Comparative Example 2

Aqueous solution of NaOH (10 mL, 0.10 mol) is added to a mixture of HCFC-336mfa (11.8 g, 0.05 mol) and water (18 mL) at 37 ° C in the presence of 15-crown-5 (0.65 g, 0.003 mol). After addition, the reaction temperature is raised to 70 < 0 > C and the reaction is monitored using gas chromatography. The reaction does not complete after 30 hours. 1.16 g of hexafluoro-2-butyne (conversion: 14%; yield: 14%) is collected in a dry ice trap.

Comparative Example 3

NaOH aqueous solution (22 mL, 0.22 mol) is added to HCFC-336mfa (23 g, 0.1 mol) and water (18 mL) at 37 ° C in the presence of Macon (R) 10 (0.7 g). After addition, the reaction temperature is raised to 70 < 0 > C and the reaction is monitored using gas chromatography. The reaction does not complete after 22 hours. 1.09 g of hexafluoro-2-butyne (conversion: 17%; yield: 6.8%) was collected in a dry ice trap.

Example 4

Aqueous NaOH solution (12 mL, 0.12 mol) was added to a mixture of Z-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of tetra- n-butylammonium bromide (0.45 g, 0.001325 mol) Respectively. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 1 hour the reaction was complete and 15.4 g of product (conversion: 100%; yield: 95%) were collected in the dry ice trap.

Example 5

A mixture of Z-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of tetra-n-butylammonium hydrogen sulphate (0.43 g, 0.001325 mol) Lt; / RTI > After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 1 hour the reaction was complete and 11 g of product (conversion: 100%; yield: 71%) was collected on a dry ice trap.

Example 6

Was added to a mixture of Z-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of Aliquat 占 336 (0.53 g, 0.001325 mol) Respectively. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 1 hour the reaction was complete and 15.6 g of product (conversion: 100%; yield: 96%) were collected in the dry ice trap.

Example 7

Aqueous solution of NaOH (12 mL, 0.12 mol) was added to a mixture of E-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of Aliquat 占 336 (0.53 g, 0.001325 mol) Respectively. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 1 hour the reaction was complete and 15.8 g of product (conversion: 100%; yield: 98%) were collected in the dry ice trap.

Example 8

NaOH aqueous solution (12 mL, 0.12 mol) was added to a mixture of E-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of tetra- n-butylammonium bromide (0.45 g, 0.001325 mol) Respectively. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. The reaction was not completed after 7 hours. 12.6 g of product (conversion: 78%; yield: 78%) were collected on a dry ice trap.

Example 9

A mixture of E-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of tetra-n-butylammonium hydrogen sulphate (0.43 g, 0.001325 mol) Lt; / RTI > After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. The reaction was not completed after 7 hours. 12.6 g of product (conversion: 77%; yield: 77%) were collected in a dry ice trap.

Example 10

Aqueous NaOH solution (12 mL, 0.12 mol) was added to a mixture of E-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of tetraoctylammonium bromide (0.72 g, 0.001325 mol) at 42 ° C. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After six and a half hours the reaction was complete. 15.6 g of product (conversion: 100%; yield: 95%) were collected in a dry ice trap.

Example 11

Aqueous NaOH solution (12 mL, 0.12 mol) was added to a mixture of E-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of tetraoctylammonium chloride (0.43 g, 0.001325 mol) at 42 ° C. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After five and a half hours, 15.2 g of the product (conversion: 95%; yield: 93%) were collected in the dry ice trap.

Example 12

Aqueous NaOH solution (12 mL, 0.12 mol) was added to a mixture of E-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of tetra- n-butylammonium chloride (0.37 g, 0.001325 mol) Respectively. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 23 hours, 14.8 g of product (conversion: 90%; yield: 87%) were collected in the dry ice trap.

Example 13

Aqueous NaOH solution (12 mL, 0.12 mol) was added to a mixture of E-1326 (20 g, 0.1 mol) and water (18 mL) in the presence of tributylmethylammonium chloride (0.31 g, 0.001325 mol) at 42 ° C. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 23 hours, 8 g of product (conversion: 59%; yield: 49%) were collected in the dry ice trap.

Example 14

A solution of NaOH (12 mL, 0.12 mol) was added to ZE-1326 (20 g, 0.10 mol) in the presence of tetrabutylammonium bromide (0.45 g, 0.001325 mol) and BioSoft (R) N25-9 mol) and water (18 mL). After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. The reaction was completed after 5 hours. 13 g of product (conversion: 100%; yield: 80%) were collected in a dry ice trap.

Example 15

A solution of NaOH in water (12 mL, 0.12 mol) was added to ZE-1326 (20 g, 0.1 mol) in the presence of tetrabutylammonium bromide (0.45 g, 0.001325 mol) (18 mL). After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. The reaction was completed after 5 hours. 11.2 g of the product (conversion: 100%; yield: 69%) were collected in a dry ice trap.

Example 16

A solution of 10 M NaOH (12 mL, 0.12 mol) was added to a solution of ZE-1326 (20 g, 0.1 mol) in the presence of NaCl (2.3 g, 0.0393 mol) and Aliquat (R) 336 (0.53 g, 0.001325 mol) ) And water (18 mL) over 30 min. When the addition was complete, the reaction temperature was increased to 70 ° C after addition and the reaction was monitored using gas chromatography. After 1 hour and 20 minutes the reaction was complete and a layer of water was submitted for analysis of the fluoride (wt.%).

Example 17

A solution of NaOH (12 mL, 0.12 mol) was added to a solution of ZE-1326 (20 g, 0.1 mol) in the presence of NaCl (4.6 g, 0.0786 mol) and Aliquat (R) 336 (0.53 g, 0.001325 mol) Was added to water (18 mL) over 30 min. When the addition was complete, the reaction temperature was increased to 70 ° C after addition and the reaction was monitored using gas chromatography. After 1 hour and 20 minutes the reaction was complete and a layer of water was submitted for analysis of the fluoride (wt.%).

Example 18

A solution of NaOH (12 mL, 0.12 mol) was added to a solution of ZE-1326 (20 g, 0.1 mol) in the presence of NaCl (3.45 g, 0.0590 mol) and Aliquat (R) 336 (0.53 g, 0.001325 mol) Was added to a mixture of water (18 mL) over 30 min. When the addition was complete, the reaction temperature was increased to 70 ° C after addition and the reaction was monitored using gas chromatography. After 2 hours the reaction was complete and a layer of water was submitted for analysis of fluoride (wt.%).

Comparative Example 4

NaOH aqueous solution (12 mL, 0.12 mol) was added to a mixture of ZE-1326 (20 g, 0.1 mol) and water (18 mL) at 37 ° C. After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. After 31 hours, 0.36 g of product (conversion: 2.2%; yield: 2.2%) was collected in the dry ice trap.

Comparative Example 5

Aqueous NaOH solution (6 mL, 0.06 mol) was added to a mixture of ZE-1326 (10 g, 0.05 mol) and water (18 mL) in the presence of 15-crown-5 (0.65 g, 0.003 mol) After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. The reaction was not completed after 30 hours. 1.16 g of product (conversion: 14%; yield: 14%) was collected on a dry ice trap.

Comparative Example 6

NaOH aqueous solution (12 mL, 0.12 mol) was added to a mixture of ZE-1326 (20 g, 0.1 mol) and water (18 mL) at 37 ° C in the presence of Macon (R) 10 (0.7 g). After the addition, the reaction temperature was raised to 70 < 0 > C and the reaction was monitored using gas chromatography. The reaction was not complete after 22 hours. 1.09 g of product (conversion: 17%; yield: 6.8%) was collected on a dry ice trap.

[Table 1]

It is to be understood that not all of the acts described above in the general description or the examples are required, that some of the specified acts may not be required, and that one or more additional actions in addition to those described may be performed. Also, the order in which actions are listed is not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. It should be understood, however, that any feature (s) capable of generating or clarifying benefits, advantages, solutions to problems, and any benefit, advantage, or solution may be of particular importance to any or all of the claims , It shall not be construed as a required or essential feature.

It is to be understood that certain features may be resorted to and described in connection with the separate embodiments for clarity and in combination with a single embodiment. Conversely, various features described in connection with a single embodiment for the sake of simplicity may also be provided separately or in any subcombination. In addition, references to ranges of values include all values within that range.

Claims (16)

Reacting the chlorinated reactant with an aqueous solution of an alkali metal hydroxide in the presence of a phase transfer catalyst comprising at least one alkyl group having at least 8 carbon atoms and recovering the hexafluoro-2-butyne, Wherein the conversion of 1,1,4,4,4-hexafluorobutane is 50% or more per hour. The process according to claim 1, wherein the phase transfer catalyst is a quaternary alkylammonium salt and the phase transfer catalyst has three or more alkyl groups having 8 or more carbon atoms. The process according to claim 1, wherein the quaternary alkylammonium salt is methyl trioctylammonium chloride. The method of claim 1, wherein the basic aqueous solution is prepared from a base 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, Lt; RTI ID = 0.0 > of hexafluoro-2-butyne. ≪ / RTI > The process of claim 1, wherein the chlorinated reactant is chlorofluorobutane or chlorofluorobutene. 2. The process of claim 1 wherein the chlorinated reactant is selected from the group consisting of HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), HCFC-336mfa (2,2- 1,1,1,4,4,4-hexafluorobutane) or HCFO-1326mxz (E- or Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene ). ≪ / RTI > Reacting the chlorinated reactant with an aqueous solution of an alkali metal hydroxide in the presence of a quaternary alkyl ammonium salt having an alkyl group of 4 to 10 carbon atoms and combinations thereof and a nonionic surfactant and recovering hexafluoro-2-butyne Wherein the conversion of dichloro-1,1,1,4,4,4-hexafluorobutane to hexafluoro-2-butyne is greater than or equal to 20% per hour, the conversion of hexafluoro-2-butyne Gt; 9. The process according to claim 8, wherein the nonionic surfactant is selected from the group consisting of ethoxylated nonylphenol and ethoxylated C12-C15 aliphatic alcohols. The process of claim 8, wherein the quaternary alkylammonium salt is selected from the group consisting of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium hydrogen sulfate, 2-butyne, which is at least one of ammonium chloride, methyltrioctylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, and tetradodecylammonium chloride. 9. The process according to claim 8, wherein the quaternary alkylammonium salt is a tetrabutylammonium salt. 9. The process according to claim 8, wherein the quaternary alkylammonium salt is a trioctylmethylammonium salt. 9. The method of claim 8, wherein the basic aqueous solution is prepared from a base 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, Lt; RTI ID = 0.0 > of hexafluoro-2-butyne. ≪ / RTI > 7. The process of claim 6, wherein the quaternary alkylammonium salt is a tetrabutylammonium salt and the nonionic surfactant is ethoxylated nonylphenol. The process according to claim 8, wherein the chlorinated reactant is chlorofluorobutane or chlorofluorobutene. 9. The process of claim 8 wherein the chlorinated reactant is selected from the group consisting of HCFC-336mdd (2,3-dichloro-1,1,1,4,4,4-hexafluorobutane), HCFC-336mfa (2,2- 1,1,1,4,4,4-hexafluorobutane) or HCFO-1326mxz (E- or Z-1,1,1,4,4,4-hexafluoro-2-chloro-2-butene ). ≪ / RTI > 9. The process according to claim 1 or 8, wherein the step of reacting the chlorinated reagent takes place in the presence of an alkali metal halide.