阅读说明：本技术 用于制备z-1,1,1,4,4,4-六氟丁-2-烯的方法以及用于制备其的中间体 (Process for preparing Z-1,1,1,4,4, 4-hexafluorobut-2-ene and intermediates useful for preparing same ) 是由 彭晟 A·C·西弗特 于 2020-04-03 设计创作，主要内容包括：本公开提供了用于制备Z-1,1,1,4,4,4-六氟丁-2-烯的方法以及用于制备其的中间体。一种用于制备2-氯-1,1,1,4,4,4-六氟丁烷的方法包括使1,1,2,4,4-五氯丁-1,3-二烯与HF在液相中接触。一种用于制备E-1,1,1,4,4,4-六氟丁-2-烯的方法包括使2-氯-1,1,1,4,4,4-六氟丁烷与碱接触。一种用于制备2,3-二氯-1,1,1,4,4,4-六氟丁烷的方法包括使E-1,1,1,4,4,4-六氟丁-2-烯与氯源和催化剂接触。一种用于制备1,1,1,4,4,4-六氟-2-丁炔的方法包括使2,3-二氯-1,1,1,4,4,4-六氟丁烷与碱接触。一种用于制备Z-1,1,1,4,4,4-六氟丁-2-烯的方法包括使1,1,1,4,4,4-六氟-2-丁炔与氢气和催化剂接触。(The present disclosure provides processes for the preparation of Z-1,1,1,4,4, 4-hexafluorobut-2-ene and intermediates useful for the preparation thereof. A process for preparing 2-chloro-1, 1,1,4,4, 4-hexafluorobutane comprises contacting 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene with HF in the liquid phase. A process for preparing E-1, 1,1,4,4, 4-hexafluorobut-2-ene comprises contacting 2-chloro-1, 1,1,4,4, 4-hexafluorobutane with a base. A process for preparing 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane comprises contacting E-1, 1,1,4,4, 4-hexafluorobut-2-ene with a chlorine source and a catalyst. A process for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne comprises contacting 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane with a base. A process for preparing Z-1,1,1,4,4, 4-hexafluorobut-2-ene comprises contacting 1,1,1,4,4, 4-hexafluoro-2-butyne with hydrogen and a catalyst.)

1. A process for the preparation of Z-1,1,1,4,4, 4-hexafluoro-2-butene comprising:

(a) contacting 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene with HF in the liquid phase in the presence of a catalyst to produce a product mixture comprising 2-chloro-1, 1,1,4,4, 4-hexafluorobutane;

(b) contacting 2-chloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product mixture comprising E-1, 1,1,4,4, 4-hexafluoro-2-butene;

(c) contacting E-1, 1,1,4,4, 4-hexafluoro-2-butene with a chlorine source in the presence of a catalyst to produce a product mixture comprising 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane;

(d) contacting 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product mixture comprising 1,1,1,4,4, 4-hexafluoro-2-butyne; and

(e) contacting 1,1,1,4,4, 4-hexafluoro-2-butyne with hydrogen to produce a product mixture comprising Z-1,1,1,4,4, 4-hexafluoro-2-butene.

2. The process of claim 1, wherein 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene is prepared by contacting trichloroethylene in the presence of a catalyst.

3. The process of claim 2, further comprising recovering trichloroethylene from the product mixture and recycling the recovered trichloroethylene.

4. The process of claim 1, wherein 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene is prepared by contacting chlorotrifluoroethylene and pentachloroethane in the presence of a catalyst.

5. The process of claim 4, further comprising recovering trichloroethylene from the product mixture and recycling the recovered trichloroethylene.

6. The process of claim 2 or claim 4, wherein the catalyst for the preparation of 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene comprises iron.

7. The process of claim 2 or claim 4, wherein the catalyst for the preparation of 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene comprises copper.

8. The process of claim 1, further comprising recovering 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene from the product mixture, and recycling the recovered 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene to step (a).

9. The process of claim 1, wherein the catalyst in step (a) is a metal halide.

10. The process of claim 1, wherein step (b) is carried out in the presence of a phase transfer catalyst.

11. The process of claim 1, wherein step (c) is carried out in the gas phase in the presence of a gas phase catalyst.

12. The process of claim 1, wherein step (c) is carried out in the liquid phase in the presence of a liquid phase catalyst.

13. The process of claim 1, wherein step (d) is carried out in the presence of a phase transfer catalyst.

14. The method of claim 1, wherein step (c) is performed by photoinitiation.

15. The process of claim 1, wherein step (e) is carried out in the presence of an alkyne-to-alkene catalyst.

16. The method of claim 15, wherein the alkyne-to-alkene catalyst comprises palladium.

17. The method of claim 15 or 16, wherein the alkyne-to-alkene catalyst comprises a support selected from alumina, silicon carbide, or titanium silicate.

18. The method of claim 15, wherein the alkyne-to-alkene catalyst is a palladium catalyst dispersed at a concentration of 100ppm to 5000ppm on alumina, silicon carbide, or titanium silicate with Ag or lanthanide poisons.

19. The process of any one of claims 1-18, further comprising recovering 2-chloro-1, 1,1,4,4, 4-hexafluorobutane from step (a).

20. The process of any one of claims 1-19, further comprising recovering E-1, 1,1,4,4, 4-hexafluoro-2-butene from step (b).

21. The process of any one of claims 1-20, further comprising recovering 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane from step (c).

22. The process of any one of claims 1-21, further comprising recovering 1,1,1,4,4, 4-hexafluoro-2-butyne from step (d).

23. The process of any one of claims 1-22, further comprising recovering Z-1,1,1,4,4, 4-hexafluoro-2-butyne from step (e).

24. A process for the preparation of Z-1,1,1,4,4, 4-hexafluoro-2-butene comprising:

(a) contacting 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene with HF in the liquid phase in the presence of a catalyst to produce a product mixture comprising 2-chloro-1, 1,1,4,4, 4-hexafluorobutane; and

(b) contacting 2-chloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product mixture comprising E-1, 1,1,4,4, 4-hexafluoro-2-butene.

25. The process of claim 24, wherein 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene is prepared by contacting trichloroethylene in the presence of a catalyst.

26. The process of claim 25, further comprising recovering trichloroethylene from said product mixture and recycling said recovered trichloroethylene.

27. The process of claim 24, wherein 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene is prepared by contacting chlorotrifluoroethylene and pentachloroethane in the presence of a catalyst.

28. The process of claim 27, further comprising recovering trichloroethylene from said product mixture and recycling said recovered trichloroethylene.

29. The process of claim 25 or claim 27, wherein the catalyst for preparing 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene comprises iron.

30. The process of claim 25 or claim 27, wherein the catalyst for preparing 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene comprises copper.

31. The process of claim 24, further comprising recovering 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene from the product mixture, and recycling the recovered 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene to step (a).

32. The process of claim 24, wherein the catalyst in step (a) is a metal halide.

33. The process of claim 24, wherein step (b) is carried out in the presence of a phase transfer catalyst.

Technical Field

The disclosure herein relates to a process for the preparation of Z-1,1,1,4,4, 4-hexafluoro-2-butene and intermediates useful in the preparation thereof. The present disclosure also provides processes for preparing 2-chloro-1, 1,1,4,4, 4-hexafluorobutane, E-1, 1,1,4,4, 4-hexafluoro-2-butene, and 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane.

Background

Over the last several decades, various industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide range of applications, including their use as refrigerants, cleaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, aerosol propellants, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particle removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. In finding alternatives to these versatile compounds, many industries have turned to the use of Hydrofluorocarbons (HFCs). HFCs have zero ozone depletion potential and are therefore unaffected by current regulatory phase-out due to the montreal protocol.

In addition to the ozone depletion problem, global warming is another environmental problem in many of these applications. Thus, there is a need for compositions that meet both low ozone depletion standards and have low global warming potentials. It is believed that certain hydrofluoroolefins meet both goals. Accordingly, there is a need to provide intermediates useful in the preparation of hydrofluoroolefins and processes for the preparation of chlorine-free hydrofluoroolefins. These materials have no ozone depletion potential and have a lower global warming potential.

Is incorporated by reference

All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. In case of conflict, the present patent application, including any definitions herein, will control.

Disclosure of Invention

The present disclosure provides a process for the preparation of hydrofluoroolefins Z-1,1,1,4,4, 4-hexafluorobut-2-ene (Z-HFO-1336mzz or Z-1336 mzz). The process comprises (a) contacting 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene with HF in the liquid phase in the presence of a fluorination catalyst to produce a product mixture comprising 2-chloro-1, 1,1,4,4, 4-hexafluorobutane; (b) contacting 2-chloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product mixture comprising E-1, 1,1,4,4, 4-hexafluorobut-2-ene (E-HFO-1336mzz or E-1336 mzz); (c) contacting E-1, 1,1,4,4, 4-hexafluorobut-2-ene with a chlorine source to produce a product mixture comprising 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane; (d) contacting 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product mixture comprising 1,1,1,4,4, 4-hexafluoro-2-butyne; and (e) contacting 1,1,1,4,4, 4-hexafluoro-2-butyne with hydrogen in the presence of a catalyst to produce a product mixture comprising Z-1,1,1,4,4, 4-hexafluoro-2-butene.

In some embodiments, 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (HCC-2320az, 2320az) is prepared according to a process that includes dimerization of Trichloroethylene (TCE). The process for preparing 2320az includes contacting TCE in the presence of a catalyst to prepare a product mixture comprising 2320 az.

In some embodiments, dimerization of TCE to pentachloroethane (CCl)₃CHCl₂HCC-120), which accelerates the dimerization process.

In certain embodiments, 2320az is prepared with a selectivity of at least 80%; in some embodiments, the selectivity is greater than 90% or greater than 95% or greater than 99% or greater than 99.5%. In certain embodiments, 2320az is recovered from the product mixture. In some embodiments, unreacted TCE is recovered and recycled. In some embodiments, the pentachloroethane is recovered and recycled.

In some embodiments, 2-chloro-1, 1,1,4,4, 4-hexafluorobutane (HCFC-346mdf or 346mdf) is prepared by contacting 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (HCC-2320az or 2320az) with Hydrogen Fluoride (HF) in the liquid phase in the presence of a catalyst to prepare a mixture comprising 346 mdf.

In the process of the present disclosure, 346mdf is contacted with a base to produce E-1, 1,1,4,4, 4-hexafluoro-2-butene (E-1336 mzz).

In some embodiments, 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane (CF)₃CHClCHClCF₃) (HCFC-336mdd, 336mdd) by reacting E-1336mzz with chlorine (Cl) in the liquid or vapor phase, optionally in the presence of a catalyst₂) Contacted or contacted with a photoinitiator to prepare a mixture comprising 336 mdd.

In some embodiments, 336mdd is used in a process for preparing 1,1,1,4,4, 4-hexafluoro-2-butyne, the process comprising contacting 336mdd with a base. In some embodiments, 1,1,1,4,4, 4-hexafluoro-2-butyne is recovered and then reacted with hydrogen to form Z-1,1,1,4,4, 4-hexafluoro-2-butene.

The present disclosure also provides compositions prepared according to the methods disclosed herein.

Detailed Description

As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

By "recovery" is meant sufficient isolation of the desired product to make it useful for its intended use, as starting material for subsequent reaction steps, or in the case of recovery of E-1, 1,1,4,4, 4-hexafluoro-2-butene or Z-1,1,1,4,4, 4-hexafluoro-2-butene, as, for example, a refrigerant or foam expansion agent or solvent or fire extinguishing agent or electronic gas.

The details of the recovery step will depend on the compatibility of the product mixture with the reaction conditions of the subsequent reaction step. For example, if the product is prepared in a reaction medium that is different or incompatible with the subsequent reaction step, the recovery step can include separating the desired product from the product mixture comprising the reaction medium. This separation can occur simultaneously with the contacting step when the desired product is volatile under the reaction conditions. Volatilization of the desired product can constitute separation and thus recovery of the desired product. If the vapor contains other materials intended to be separated from the desired product, the desired product can be separated, for example, by selective distillation.

The step for recovering the desired product from the product mixture preferably comprises separating the desired product from the catalyst or other components used to prepare the desired product or product mixture prepared in the process.

The present disclosure provides, inter alia, methods for preparing E-1336mzz and Z-1336 mzz. The starting material may comprise 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene, which may be prepared from trichloroethylene, a process as described herein.

Preparation of 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (2320az)

1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (HCC-2320az or 2320az) may be prepared according to the present disclosure by dimerization of Trichloroethylene (TCE). In some embodiments, a process for preparing a product mixture comprising 2320az is provided, the process comprising contacting TCE with a dimerization catalyst at an elevated temperature.

In some embodiments, the dimerization catalyst comprises iron. The iron dimerization catalyst may comprise metallic iron from any source, including combinations of sources, and may be or may comprise iron powder, iron wire, iron mesh, or iron filings. The iron catalyst may also comprise an iron salt, such as ferric chloride or ferrous chloride (FeCl, respectively)₃Or FeCl₂)。

In some embodiments, the dimerization catalyst comprises copper. The copper dimerization catalyst may comprise metallic copper from any source, including combinations of sources, and may be or may comprise, for example, copper powder or copper wire. The copper catalyst may also comprise cuprous or cupric salts, such as cuprous chloride or cupric chloride (CuCl or CuCl, respectively)₂)。

The process is preferably carried out in an anhydrous environment. For example, when ferric chloride is used, the ferric chloride is preferably anhydrous.

In some embodiments, the dimerization catalyst has a particular concentration relative to the moles of TCE reactant used. Thus, in some embodiments where the catalyst comprises a metallic iron catalyst, the weight ratio of Fe wire (or Fe powder) catalyst to TCE is from about 0.0001 to about 1. In other embodiments, the weight ratio of iron catalyst to TCE is from about 0.01 to about 1.

In some embodiments, the dimerization catalyst comprises ferric chloride, and the weight ratio of ferric chloride to TCE is from about 0.00001 to about 1. For example, the weight ratio of ferric chloride to TCE is about 0.00001 to about 0.002, and in another example, the weight ratio is about 0.00005 to about 0.001. In another example, the weight ratio of ferric chloride to TCE is about 0.0001 to about 1, and in another example, the weight ratio of ferric chloride to TCE is about 0.00015 to about 1.

In some embodiments, trichloroethylene is contacted with a dimerization catalyst and pentachloroethane. Pentachloroethane (HCC-120) accelerates the reaction to produce a product mixture containing 2320 az. In certain embodiments, the weight ratio of HCC-120 to TCE is about 0.001 to about 1. In other embodiments, the weight ratio of HCC-120 to TCE is about 0.005 to about 1.

Dimerization of the TCE is carried out at elevated temperatures, for example, at temperatures in the range of about 210 ℃ to about 235 ℃. The temperature may be greater than 200 ℃. The temperature may be less than 245 ℃.

The pressure is usually autogenous.

The contact (residence) time is generally about 0.5 to 10 hours.

In some embodiments, the conversion of TCE is at least 15%, or at least 30%, or at least 50%. In some embodiments, the selectivity of 2320az is at least 80%, or at least 85%, or at least 90%.

Byproducts of the dimerization reaction may include tetrachloroethane isomers, tetrachlorobutadiene isomers, hexachlorobutene isomers, trichloroethylene oligomers. The product mixture comprising 2320az may further comprise E-1, 1, 2, 3, 4-pentachloro-1, 3-butadiene or Z-1,1, 2, 3, 4-pentachloro-1, 3-butadiene. . Thus, in one embodiment, there is a composition comprising 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene, E-1, 1, 2, 3, 4-pentachlorobutane-1, 3-diene, and Z-1,1, 2, 3, 4-pentachlorobutane-1, 3-diene.

The process may also include recovering 2320az from the product mixture prior to using the recovered 2320az as a starting material in a process for preparing, for example, EHCFC-346mdf, HFO-E-1336mzz, HCFC-336mdd, 1,1,1,4,4, 4-hexafluoro-2-butyne, and HFO-Z-1336mzz as described herein.

The process for recovering 2320az from the product mixture may include one or any combination of purification techniques known in the art, such as distillation. By "recovering" 2320az from the product mixture, a product is prepared comprising at least 95% or at least 97% or at least 99% 2320 az.

In certain embodiments, the process for preparing 2320az may further comprise recovering trichloroethylene from the product mixture and recycling the recovered trichloroethylene to the dimerization process as described herein.

In certain embodiments, the process for making 2320az may further comprise recovering hexachlorobutene isomers from the product mixture and recycling the recovered hexachlorobutene isomers to the dimerization process as described herein.

In certain embodiments, the process for preparing 2320az may further comprise recovering pentachloroethane from the product mixture and recycling the recovered pentachloroethane to the dimerization process as described herein.

Other products, if present, such as E-1, 1, 2, 3, 4-pentachloro-1, 3-butadiene and Z-1,1, 2, 3, 4-pentachloro-1, 3-butadiene may also be recovered.

Preparation of 2-chloro-1, 1,1,4,4, 4-hexafluorobutane (HCFC-346mdf)

According to the process provided herein, a process is provided that includes contacting 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (2320az) with HF in the liquid phase in the presence of a catalyst to produce a product mixture comprising HCFC-346mdf (346 mdf).

Fluorination catalysts useful in the liquid phase process of the present invention include those derived from lewis acid catalysts such as metal halides. The halide may be selected from fluoride, chloride and bromide, or combinations thereof. The metal halide may be a transition metal halide or other metal halide. Transition metal chlorides include halides of titanium, zirconium, hafnium, tantalum, niobium, tin, molybdenum, tungsten, and antimony. Other suitable metal halide catalysts include boron trichloride, boron trifluoride, and arsenic trifluoride.

In some embodiments, the liquid phase fluorination can be in a reaction zone comprising a reaction vessel of any size suitable for the scale of the reactionIs carried out in (1). In some embodiments, the reaction zone is a reaction vessel constructed of a corrosion resistant material. In some embodiments, these materials include alloys such as nickel-based alloys such asAvailable under the trademark Special Metals Corp(hereinafter referred to as) Commercially available nickel-chromium alloys are available or available under the trademark NI-CHROMIUM from Special Metals Corp (New Hartford, New York)Commercially available nickel-copper alloys or fluoropolymer lined vessels. In other embodiments, the reaction vessel may be made of other materials of construction, including stainless steel (particularly austenitic stainless steel) and copper clad steel.

The molar ratio of HF to 2320az is in some embodiments from about 1 to about 35. In other embodiments, the molar ratio of HF to 2320az is about 1 to about 25.

In some embodiments, the fluorination process is conducted at an elevated temperature, for example at a temperature in the range of from 50 ℃ to 160 ℃. In some embodiments, the temperature may be greater than 100 ℃. In other embodiments, the temperature may be less than 150 ℃.

In some embodiments, the fluorination process is carried out at a pressure in the range of from 0psi to 600psi (0MPa to 4.1 MPa).

In some embodiments, the residence time of the fluorination process may be from about 1 to about 25 hours. In other embodiments, the residence time of the fluorination process may be from about 2 to about 10 hours. In other embodiments, the residence time of the fluorination process may be from 4 to about 6 hours.

In some embodiments, the product mixture comprising 346mdf may further comprise one or more of 1, 2-dichloro-1, 1,4,4, 4-pentafluorobutane, Z-1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene, E-1, 1,1,4,4, 4-hexafluoro-2-butene, and 1, 1-dichloro-2, 2, 4,4, 4-pentafluorobutane. In one embodiment, there is a composition comprising 2-chloro-1, 1,1,4,4, 4-hexafluorobutane (346mdf), 1, 2-dichloro-1, 1,4,4, 4-pentafluorobutane (345mfd), Z-1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene (Z-1326mxz), E-1, 1,1,4,4, 4-hexafluoro-2-butene (E-1336mzz), and 1, 1-dichloro-2, 2, 4,4, 4-pentafluorobutane (345 mfc).

In some embodiments, the product mixture is a composition comprising 346mdf, the composition comprises 1,1,1,4,4, 4-hexafluorobutane (356mff), 1,1, 1-trifluoro-2-trifluoromethylbutane (356mzz), Z-1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene (Z-1326mxz), E-1, 1,1,4,4, 4-hexafluoro-2-chloro-2-butene (E-1326mxz), Z-1,1,1,4,4, 4-hexafluoro-2, 3-dichlorobutene (Z-1316mxx), and E-1, 1,1,4,4, 4-hexafluoro-2, 3-dichlorobutene (E-1316 mxx). In one embodiment, the 346mdf containing product mixture comprises greater than 0 wt.% and less than 2 wt.% each of 356mff and 356mmz and greater than 0 wt.% and less than 3 wt.% of Z-1326mxz, Z-1316mxx, and E-1316mxx, and greater than 0 wt.% and less than 5 wt.% of E-1326 mxz. The compositions are useful for preparing E-1, 1,1,4,4, 4-hexafluoro-2-butene (E-1336mzz) as described herein.

In some embodiments, 346mdf is produced at a selectivity of greater than 90%, 92%, 94%, 95%, 96%, 97%, 98%, or 99% relative to other products.

The process can further include recovering 346mdf from the product mixture comprising 346 mdf. The method for recovering 346mdf includes one or any combination of purification techniques known in the art, such as distillation. By "recovering" 346mdf from the product mixture, a product comprising 346mdf comprising at least 98.5% or at least 99% or at least 99.5% 346mdf is prepared.

In certain embodiments, the process for preparing 346mdf can further comprise recovering 2320az from the product mixture, and recycling the recovered 2320az to the fluorination process as described herein.

In some embodiments, a process for preparing 346mdf as disclosed herein comprises (a') contacting trichloroethylene in the presence of a dimerization catalyst to prepare a product mixture comprising 2320 az; (a) contacting 2320az produced in step (a') with hydrogen fluoride in the liquid phase in the presence of a fluorination catalyst to produce a product mixture comprising 346 mdf. Optionally, 2320az is recovered after step (a') and before step (a).

In some embodiments, a process for preparing 346mdf as disclosed herein comprises (a') contacting trichloroethylene in the presence of a dimerization catalyst and pentachloroethane to prepare a product mixture comprising 2320 az; (a) contacting 2320az produced in step (a') with hydrogen fluoride in the liquid phase in the presence of a fluorination catalyst to produce a product mixture comprising 346 mdf. Optionally, 2320az is recovered after step (a') and before step (a).

Variations of the method elements in steps (a') and (a) are disclosed above. Before step (a) is carried out, the purity of 2320az is generally at least 97%.

(E) Preparation of (E) -1,1,1,4,4, 4-hexafluorobut-2-ene (E-1336mzz)

Also provided herein is a method comprising contacting 346mdf with a base to form a product mixture comprising E-1336 mzz. An effective amount of base is added to convert 346mdf to E-1336 mzz.

In some embodiments, the base is selected from the group consisting of lithium hydroxide, lithium oxide, sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, rubidium hydroxide, rubidium oxide, cesium hydroxide, cesium oxide, calcium hydroxide, calcium oxide, strontium hydroxide, strontium oxide, barium hydroxide, and barium oxide. In some embodiments, the base is potassium hydroxide. In some embodiments, the base is sodium hydroxide. In some embodiments, the base is in an aqueous solution. In some embodiments, the concentration of the base in the aqueous solution is from about 4M to about 12M.

In some embodiments, the process is carried out in the presence of a phase transfer catalyst. In some embodiments, the phase transfer catalyst is selected from the group consisting of quaternary ammonium salts, heterocyclic ammonium salts, organophosphonium salts, and nonionic compounds. In some embodiments, the phase transfer catalyst is selected from the group consisting of benzyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltrioctylammonium chloride, methyltributylammonium chloride, methyltrioctylammonium chloride, dimethyldiphenylphosphonium iodide, methyltriphenoxyphosphonium iodide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, hexadecyltributylphosphonium bromide, and DL-alpha-tocopheryl methoxypolyethylene glycol succinate. In some embodiments, the phase transfer catalyst is methyltrioctylammonium chloride.

In some embodiments, the base is sodium hydroxide and the phase transfer catalyst is methyltrioctylammonium chloride.

In some embodiments, the product mixture further comprises hexafluoroisobutylene (1336mt), 1,1,1,4,4, 4-hexafluorobutane (356mff), E-1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene (1335lzz), and Z-CF₃CH＝CHCF₃One or more of (a). In some embodiments, E-CF is produced in about 95% or greater yield₃CH＝CHCF₃. In some embodiments, the E-CF is produced at a selectivity of about 99 mol% or more relative to the other components of the mixture₃CH＝CHCF₃。

In one embodiment, the product mixture is a mixture comprising E-1336mzz and greater than 0% and less than 1% each of Z-1336mzz and 1,1,1,4,4, 4-hexafluorobutane (356mff), and greater than 0% and less than 0.5% by weight of 1,1, 1-trifluoro-2-trifluoromethylbutene (1336mt, CF₃(CF₃)C＝CH₂) And more than 0% and less than 0.2% by weight of 1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene (1335lzz, CF₂ClCH＝CHCF₃) The composition of (1).

In one embodiment, the product mixture is a mixture comprising E-1336mzz and a total of greater than 0% and less than 1% by weight of Z-and E-1, 1, 2, 4,4, 4-hexafluorobutene (Z-and E-1336mzy, CF₂HCF＝CHCF₃) And Z-and E-1, 1,1,4,4, 4-hexafluoro-2-chloro-2-butene (Z-and E-1326mxz) in a total amount of more than 0% by weight and less than 0.5% by weight, and0.2% by weight of Z-and E-1, 1,1,4, 4-pentafluoro-2-chlorobutene (Z-and E-1335mxz, CF)₂HCH＝CClCF₃) And more than 0% and less than 0.2% by weight in total of Z-and E-1, 1,1,4, 4-pentafluoro-3-chlorobutene (Z-and E-1335mzx, CF)₂HCCl＝CHCF₃) The composition of (1).

In one embodiment, the product mixture is a mixture comprising E-1336mzz and greater than 0% and less than 1% each by weight of 1,1,1,4,4, 4-hexafluorobutane (356mff, CF)₃CH₂CH₂CF₃)1, 1, 1-trifluoro-2-trifluoromethylbutane (356mmz, (CF)₃)₂CHCH₃) And 1,1,4,4, 4-pentafluoro-2-methylbut-1-ene (1345cm, CF)₃C(CH₃)＝CF₂) And more than 0% and less than 0.1% by weight in total of Z-and E-1, 1,1,4,4, 4-hexafluoro-2-chloro-2-butene (Z-and E-1326mxz), and more than 0% and less than 0.1% by weight in total of Z-and E-1, 1,1,4,4, 4-hexafluoro-2, 3-dichlorobutene (Z-and E-1316mxx, CF)₃CCl＝CClCF₃) The composition of (1).

In some embodiments of the methods provided herein, E-1336mzz is recovered from the product mixture.

Preparation of HCFC-336mdd

Reaction of E-1336mzz with a chlorine source produces a mixture comprising 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane (CF)₃CHClCHClCF₃HCFC-336mdd) is a chlorination process in which a chlorine source is reacted with E-1336mzz to produce a product mixture comprising the desired HCFC-336mdd product. The process can be carried out in the liquid phase, liquid medium or gas phase, each preferably in the presence of a chlorination catalyst or under photoinitiation. An example of a liquid medium is the E-1336mzz reactant itself.

Photoinitiation is carried out in a suitable photoinitiating apparatus comprising a light source, a chlorine source (Cl)₂) And E-1336mzz (material to be chlorinated), as described, for example, in WO 2006/069108 a 1.

Examples of suitable chlorination catalysts include lewis acids such as transition metal chlorides or aluminum chloride.

The catalyst used in the chlorination process in the liquid phase may be selected from the group consisting of ferric chloride, chromium chloride, aluminum chloride, cupric chloride, and combinations of two or more of these. The catalyst used in the chlorination process in the gas phase may be selected from the group consisting of ferric chloride, chromium chloride, aluminum chloride, cupric chloride, and combinations of two or more of these supported on carbon.

The temperature and pressure conditions for the chlorination process are preferably selected to be effective in producing HCFC-336mdd with high selectivity. When the process is carried out in a liquid phase, such as that provided by E-1336mzz, the process is preferably carried out in a closed pressurizable reactor, the pressure of which is sufficient to maintain the liquid state. The pressure within the reactor may be autogenous or elevated. When the process is carried out in a liquid medium by purging unreacted chlorine and distilling off unreacted E-1336mzz, the desired product HCFC-336mdd may be recovered from the reactor. The catalyst can be filtered off if it is present in a sufficiently high concentration that it precipitates out of the product mixture before or during or after distillation. Alternatively, the catalyst may remain in the distillation bottoms.

Tubular reactors can be used to carry out the process in the gaseous state (phase). A chlorination catalyst, such as a lewis acid, may be placed within the reactor for effective contact with the E-1336mzz and chlorine source simultaneously fed to the reactor at a temperature and residence time effective to produce the desired HCFC-336mdd reaction product with the desired selectivity. The temperature of the chlorination process is maintained by applying heat to the reactor. Preferably, the temperature of the process is in the range of 100 ℃ to 200 ℃. The pressure in the tubular reactor is preferably about 0.1MPa to 1 MPa. HCFC-336mdd may be recovered from the product mixture by distillation.

The chlorine source may be selected from chlorine, N-chlorosuccinimide, tert-butyl hypochlorite, oxalyl chloride and sulfuryl chloride.

In one embodiment, the reaction of E-1336mzz with a chlorine source is carried out in the presence of a chlorination catalyst, and the chlorine source is chlorine gas (Cl)₂). In one embodiment, the reaction of E-1336mzz with a chlorine source is carried out in the absence of a chlorination catalyst, and the chlorine source is chlorine gas (Cl)₂)。

In one embodiment, the reaction of E-1336mzz with a chlorine source is initiated photo-initiated in the presence of ultraviolet radiation, and the chlorine source is chlorine gas.

In one embodiment, the reaction of E-1336mzz with a chlorine source is carried out in the absence of a chlorination catalyst, and the chlorine source is N-chlorosuccinimide, tert-butyl hypochlorite, oxalyl chloride, or sulfuryl chloride.

The process may also include recovering HCFC-336mdd from the product mixture to reduce other components in the product mixture. The process for recovering HCFC-336mdd may include one or any combination of purification techniques known in the art such as distillation. A product comprising at least 98.5% or at least 99% or at least 99.5% HCFC-336mdd is prepared by "recovering" HCFC-336mdd from the product mixture. In some embodiments, E-1336mzz may be recovered and recycled into the process or used for another purpose.

The chlorination of E-1336mzz preferably provides selectivity to HCFC-336mdd of at least 85%, more preferably at least 90%, and most preferably at least 95%, whether the reaction is carried out in the liquid phase or the vapor phase.

The product mixture comprising 336mdd may also comprise HCFC-336mfa (2, 2-dichloro-1, 1,1,4,4, 4-hexafluorobutane, CF₃CCl₂CH₂CF₃) And HCFC-326mda (2, 3, 3-trichloro-1, 1,1,4,4, 4-trifluoropropane, CF₃CHClCCl₂CF₃) Which can be recovered from the product mixture. Alternatively, HCFC-336mfa and/or HCFC-326mda may remain in the product mixture and proceed to subsequent steps to produce hexafluoro-2-butyne.

In certain embodiments, the process for preparing 336mdd can further comprise recovering unconverted E-1336mzz from the chlorination product mixture, and recycling the recovered E-1336mzz to the chlorination process as described herein.

In some embodiments, unconverted E-1336mzz is recovered from the product mixture. In some embodiments, E-1336mzz may be and be used for another purpose, such as a blowing agent or a heat transfer fluid.

Preparation of 1,1,1,4,4, 4-hexafluoro-2-butyne

The present disclosure also provides a process comprising contacting HCFC-336mdd with a base to produce a catalyst comprising 1,1,1,4,4, 4-hexafluoro-2-butyne (CF) in a dehydrochlorination reaction₃C≡CCF₃) The product mixture of (1). The base is preferably an alkaline aqueous medium. The reaction step is preferably carried out in the presence of a catalyst. Preferably, the alkaline aqueous medium comprises an aqueous solution of an alkali metal hydroxide or alkali metal halide salt or other base. Preferably, the catalyst is a phase transfer catalyst. As used herein, phase transfer catalyst is intended to mean a substance that facilitates the transfer of ionic compounds between an organic phase and an aqueous phase. In this step, the organic phase comprises the HCFC-336mdd reactant and the aqueous phase comprises the basic aqueous medium. Phase transfer catalysts facilitate the reaction of these dissimilar and incompatible components.

Although various phase transfer catalysts may function in different ways, their mechanism of action does not determine their utility in the present invention, provided that the phase transfer catalyst favors dehydrochlorination reactions.

Preferred phase transfer catalysts are alkyl quaternary ammonium salts. In some embodiments, at least one alkyl group of the alkyl quaternary ammonium salt comprises at least 8 carbons. Examples of quaternary alkyl ammonium salts in which the three alkyl groups contain at least 8 carbon atoms include trioctylmethylammonium chloride.336 is a commercially available phase transfer catalyst comprising trioctylmethylammonium chloride. Examples of quaternary alkyl ammonium salts in which the four alkyl groups contain at least 8 carbon atoms include tetraoctylammonium salts. The anion of such salts may be a halide such as chloride or bromide, hydrogen sulfate or any other commonly used anion. The alkyl quaternary ammonium salt comprises tetraoctyl ammonium chloride, tetraoctyl ammonium bisulfate, tetraoctyl ammonium bromide, methyl trioctyl ammonium chloride, methyl trioctyl ammonium bromide, tetradecyl ammonium chloride, and tetradecylAmmonium bromide and tetradodecylammonium chloride. According to such embodiments, the phase transfer catalyst and reaction conditions are effective to achieve conversion of HCFC-336mdd, preferably at least 50%/hour.

In other embodiments, the alkyl group of the alkyl quaternary ammonium salt comprises from 4 to 10 carbon atoms and the nonionic surfactant is present in the aqueous alkaline medium. According to such embodiments, the phase transfer catalyst and reaction conditions are effective to achieve conversion of HCFC-336mdd, preferably at least 20%/hour. The alkyl quaternary ammonium anion in which the alkyl group contains 4 to 10 carbon atoms may be a halide such as chloride or bromide, hydrogen sulfate or any other commonly used anion. The above-described alkyl quaternary ammonium salts may be used in this embodiment, provided that their alkyl groups contain from 4 to 10 carbon atoms. Specific additional salts include tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium hydrogen sulfate.

Preferred nonionic surfactants include ethoxylated nonylphenols or ethoxylated C₁₂-C₁₅A straight chain aliphatic alcohol. Nonionic surfactants useful in the present invention include those available from Stepan Company (Northfield, IL)N25-9 and10。

in some embodiments, the quaternary alkylammonium salts are added in an amount of 0.5 to 2 mole% of HCFC-336 mdd. In other embodiments, the quaternary alkylammonium salts are added in an amount of 1 to 2 mole% of HCFC-336 mdd. In other embodiments, the quaternary alkylammonium salts are added in an amount of 1 to 1.5 mole% of HCFC-336 mdd. In some embodiments, the quaternary alkylammonium salt is added in an amount of 1 to 1.5 mole% of HCFC-336mdd, and the weight of nonionic surfactant added is 1 to 2 times the weight of the quaternary alkylammonium salt. These amounts apply to each of the above-described embodiments of the alkyl quaternary ammonium salt used.

In some embodiments, the reaction is preferably carried out at a temperature of about 60 ℃ to 90 ℃, most preferably at 70 ℃.

The basic aqueous medium is a liquid (e.g., solution, dispersion, emulsion, suspension, or the like) that is primarily an aqueous liquid having a pH in excess of 7. In some embodiments, the basic aqueous solution has a pH in excess of 8. In some embodiments, the basic aqueous solution has a pH in excess of 10. In some embodiments, the basic aqueous solution has a pH of 10 to 13. In some embodiments, the basic aqueous solution comprises a small amount of a water-miscible or immiscible organic liquid. In some embodiments, the liquid in the basic aqueous solution is at least 90% water. In some embodiments, the water is tap water; in other embodiments, the water is deionized or distilled.

The base is selected from the group consisting of hydroxides, oxides, carbonates or phosphates of alkali metals, alkaline earth metals and mixtures thereof. In some embodiments, the base is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, and mixtures thereof.

These embodiments of the basic aqueous medium and base apply to all of the phase change catalysts, amounts, and reaction conditions described above. The selectivity of formation of 1,1,1,4,4, 4-hexafluoro-2-butyne is preferably at least 85%.

In some embodiments, the dehydrochlorination of 336mdd to 1,1,1,4,4, 4-hexafluoro-2-butyne is carried out in the presence of an alkali metal halide salt. The alkali metal may be sodium or potassium. The halide may be chloride or bromide. The preferred alkali metal halide salt is sodium chloride. Without being bound by any particular theory, it is believed that the alkali metal halide salt stabilizes the phase transfer catalyst. Although the dehydrochlorination reaction itself produces alkali metal chlorides, particularly sodium chloride, if sodium hydroxide is used as the base, the addition of additional sodium chloride provides additional effects that increase the yield of 1,1,1,4,4, 4-hexafluoro-2-butyne. In some embodiments, the alkali metal halide is added in an amount of about 25 to about 100 equivalents per mole of phase transfer catalyst. In other embodiments, the alkali metal halide is added in an amount of about 30 to about 75 equivalents per mole of phase transfer catalyst. In other embodiments, the alkali metal halide is added in an amount of about 40 to about 60 equivalents per mole of phase transfer catalyst. These amounts apply to each of the above alkyl quaternary ammonium salts.

The product 1,1,1,4,4, 4-hexafluoro-2-butyne (b.p. -25 ℃) can be recovered from the product mixture by distillation, in which butyne is evaporated from the aqueous medium and can then be condensed. In addition, the product mixture may also comprise 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene (HCFO-1326, Z-isomer, E-isomer, or mixtures thereof), which may be separated from the product mixture and recycled to a process comprising contacting HCFC-336mdd with a base to produce a catalyst comprising CF in a dehydrochlorination reaction₃C≡CCF₃The method step of (1).

Preparation of Z-1,1,1,4,4, 4-hexafluoro-2-butene

The present disclosure also provides a hydrogenation process comprising contacting 1,1,1,4,4, 4-hexafluoro-2-butyne with hydrogen to produce a product mixture comprising Z-1,1,1,4,4, 4-hexafluoro-2-butene (Z-1336 mzz). The process is preferably carried out in the presence of an alkyne-to-alkene catalyst.

In some embodiments, the hydrogenation of 1,1,1,4,4, 4-hexafluoro-2-butyne is carried out in the liquid phase as a batch process.

In some embodiments, the hydrogenation of 1,1,1,4,4, 4-hexafluoro-2-butyne is carried out in the gas phase as a continuous process.

In some embodiments, the alkyne-to-alkene catalyst is a palladium catalyst, such as silver and/or lanthanide doped palladium dispersed on alumina or titanium silicate. The loading of palladium dispersed on alumina or titanium silicate is relatively low. In some embodiments, the palladium loading is from about 100ppm to about 5000 ppm. In other embodiments, the palladium loading is from about 200ppm to about 5000 ppm. In some embodiments, the target catalyst is doped with at least one of silver, cerium, or lanthanum. In some embodiments, the molar ratio of cerium or lanthanum to palladium is from about 2: 1 to about 3: 1. In some embodiments, the molar ratio of silver to palladium is about 0.5: 1.0.

Other embodiments of the alkyne to alkene catalyst are lindlar catalysts, which are heterogeneous palladium catalysts supported on calcium carbonate supports, which have been deactivated or conditioned with lead compounds. The lead compound may be lead acetate, lead oxide, or any other suitable lead compound. In some embodiments, the catalyst is prepared by reducing a palladium salt in the presence of a calcium carbonate slurry, followed by addition of a lead compound. In some embodiments, the palladium salt is palladium chloride.

In other embodiments, the lindlar catalyst is further inactivated or conditioned with quinoline. The amount of palladium on the support is typically about 5% by weight, but may be any catalytically effective amount. In other embodiments, the amount of supported palladium in the lindlar catalyst is greater than 5 wt%. In other embodiments, the amount of palladium on the support may be from about 5% to about 1% by weight.

In some embodiments, the amount of catalyst used is from about 0.5% to about 4% by weight of the amount of 1,1,1,4,4, 4-hexafluoro-2-butyne. In other embodiments, the amount of catalyst used is from about 1% to about 3% by weight of the amount of butyne. In other embodiments, the amount of catalyst used is from about 1% to about 2% by weight of the amount of butyne.

In some embodiments, the reacting step is a batch reaction and is carried out in the presence of a solvent. In one such embodiment, the solvent is an alcohol. Typical alcohol solvents include ethanol, isopropanol, and n-propanol. In other embodiments, the solvent is a fluorocarbon or hydrofluorocarbon. Typical fluorocarbons or hydrofluorocarbons include 1,1,1, 2, 2, 3, 4, 5, 5, 5-decafluoropentane and 1,1, 2, 2, 3, 3, 4-heptafluorocyclopentane.

In some embodiments, the reaction of 1,1,1,4,4, 4-hexafluoro-2-butyne with hydrogen is preferably fed in portions with no more than about 100psi (0.69MPa) increase in vessel pressure per addition. In other embodiments, the addition of hydrogen is controlled such that the pressure in the vessel does not increase by more than about 50psi (0.35MPa) per addition. In some embodiments, after sufficient hydrogen has been consumed in the hydrogenation reaction to convert at least 50% of the butyne to Z-1336mzz, hydrogen may be added in greater increments in the remainder of the reaction. In other embodiments, hydrogen may be added in greater increments to the remainder of the reaction after sufficient hydrogen has been consumed in the hydrogenation reaction to convert at least 60% of the butynes to the desired butenes. In other embodiments, hydrogen may be added in greater increments to the remainder of the reaction after sufficient hydrogen has been consumed in the hydrogenation reaction to convert at least 70% of the butynes to the desired butenes. In some embodiments, a larger hydrogen addition increment may be 300psi (2.07 MPa). In other embodiments, a larger hydrogen addition increment may be 400psi (2.76 MPa).

In some embodiments, the molar ratio is about 1 mole of hydrogen to about 1 mole of 1,1,1,4,4, 4-hexafluoro-2-butyne. In other embodiments, the molar ratio of hydrogen to butyne is from about 0.9 moles to about 1.3 moles. In other embodiments, hydrogen is added in an amount of about 0.95 moles of hydrogen to about 1.1 moles of butyne. In other embodiments, hydrogen is added in an amount of about 0.95 moles of hydrogen to about 1.03 moles of butyne.

In some embodiments, the hydrogenation is carried out at ambient temperature (15 ℃ to 25 ℃). In other embodiments, the hydrogenation is carried out at above ambient temperature. In other embodiments, the hydrogenation is carried out at sub-ambient temperatures. In other embodiments, the hydrogenation is carried out at a temperature of less than about 0 ℃.

In one embodiment of the continuous process, a mixture of 1,1,1,4,4, 4-hexafluoro-2-butyne and hydrogen is passed through a reaction zone containing a catalyst. A reaction vessel such as a metal tube filled with a catalyst may be used to form the reaction zone. In some embodiments, the molar ratio of hydrogen to butyne is about 1: 1. In other embodiments of the continuous process, the molar ratio of hydrogen to butyne is less than 1: 1. In other embodiments, the molar ratio of hydrogen to butyne is about 0.67: 1.0.

In some embodiments of the continuous process, the reaction zone is maintained at ambient temperature. In other embodiments of the continuous process, the reaction zone is maintained at a temperature of 30 ℃. In other embodiments of the continuous process, the reaction zone is maintained at a temperature of about 40 ℃.

In some embodiments of the continuous process, the flow rates of 1,1,1,4,4, 4-hexafluoro-2-butyne and hydrogen are maintained to provide a residence time in the reaction zone of about 30 seconds. In other embodiments of the continuous process, the flow rates of butyne and hydrogen are maintained to provide a residence time in the reaction zone of about 15 seconds. In other embodiments of the continuous process, the flow rates of butyne and hydrogen are maintained to provide a residence time in the reaction zone of about 7 seconds.

It will be appreciated that by increasing the flow rate of 1,1,1,4,4, 4-hexafluoro-2-butyne and hydrogen into the reaction zone, the residence time in the reaction zone is reduced. This will increase the amount of butyne that is hydrogenated per unit time as the flow rate increases. Since hydrogenation is exothermic, it may be desirable to provide an external source of cooling to the reaction zone at higher flow rates to maintain the desired temperature, depending on the length and diameter of the reaction zone and its heat removal capability.

Preferably the conditions of the contacting step (including the choice of catalyst) are selected to produce Z-1336mzz with a selectivity of at least 85%, more preferably at least 90%, and most preferably at least 95%.

In some embodiments, after the batch or continuous hydrogenation process is complete, Z-1336mzz may be recovered by any conventional means, including, for example, fractional distillation. Unconverted hexafluoro-2-butyne can be recovered and recycled to the hydrogenation process. In other embodiments, Z-1336mzz is of sufficient purity to not require further purification steps after the batch or continuous hydrogenation process is completed.

Examples

Material

Trichloroethylene, chlorine, ferric chloride, TaCl₅Pentachloroethane (HCC-120), tetra-n-butylammonium bromide (TBAB), trioctylmethylammonium chloride (C: (C-120))336) NaOH and lindlar catalysts were purchased from Sigma Aldrich, st. Hydrogen fluoride is available from Synquest Labs, inc., Alachua, FL.10 nonionic surfactants are available from Stepan Company, Northfield, IL.

Use of5975GC, RESTEK Rtx-1 column for GC analysis of examples 1-4.

Example 1: preparation of 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (HCC-2320az)

Trichloroethylene (100g, 0.76mol) was added to a solution containing 30mg of anhydrous FeCl₃In the oscillating tube of (1). The reaction mixture was heated at 230 ℃ for 2 hours. The reactor contents were cooled to room temperature and analyzed by GC to determine conversion and selectivity. The results are provided in table 1.

Example 2: preparation of 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (HCC-2320az)

Trichloroethylene (100g, 0.76mol) was added to a shaker tube containing 1g of iron wire. The reaction mixture was heated at 230 ℃ for 2 hours. The reactor contents were cooled to room temperature and analyzed by GC to determine conversion and selectivity. The results are provided in table 1.

Example 3: preparation of 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (HCC-2320az)

Trichloroethylene (100g, 0.76mol) was added to a solution containing 20mg of anhydrous FeCl₃And 1g HCC-120. The reaction mixture was heated at 230 ℃ for 2 hours. The reactor contents were cooled to room temperature and analyzed by GC to determine conversion and selectivity. The results are provided in table 1.

Example 4: preparation of 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene (HCC-2320az)

Trichloroethylene (100g, 0.76mol) was added to a shaker tube containing 1g of iron wire and 1g of HCC-120. The reaction mixture was heated at 230 ℃ for 2 hours. The reactor contents were cooled to room temperature and analyzed by GC to determine conversion and selectivity. The results are provided in table 1.

TABLE 1 dimerization of trichloroethylene to 2320az

Examples	Catalyst and process for preparing same	Time (hours)	Conversion/selectivity (%)
				1	FeCl3(30mg)	16	26.9/81.6
2	Fe wire (1g)	8	28.0/86.7
				3	FeCl3(20mg)/HCC-120(1g)	2	35.4/84.3
4	Fe filament (1g)/HCC-120(1g)	2	32.3/87.4

As can be seen from Table 1, when FeCl is used₃Or Fe wire catalyst, the presence of HCC-120 increased the conversion of trichloroethylene to 2320 az.

Example 5: preparation of 2-chloro-1, 1,1,4,4, 4-hexafluorobutane (HCFC-346mdf)

Adding TaCl₅(12.5g) added to 210mLC reactor, then HF (49g) was added. The reaction mixture was heated to 150 ℃ for 1 hour and cooled to 0 ℃. HCC-2320az (26g) was added to the reactor and the reaction was heated back to 130 ℃. The reaction rate is indicated by the increase in pressure. Horizontal shut-off pressure means that the reaction is complete. After water treatment and phase separation, the product mixture was analyzed by GC and showed 100% conversion of the starting material and 98% selectivity to the product HCFC-346 mdf.

_{3 3}Example 6: preparation of E-CFCH ═ CHCF (E-1336mzz)

At Room Temperature (RT) at 0.27g of methyltrioctylammonium chloride ((R))336) Aqueous NaOH (6mL, 0.06mol) was added to 346mdf (10g, 0.05mol) and water (6.8mL) in the presence of water. After addition, the reaction temperature was raised to 70 ℃ and the reaction was monitored using gas chromatography. After 2 hours, 7.2g of product E-CF were collected in a dry ice separator₃CH＝CHCF₃(E-1336mzz) (E-1336mzz selectivity 99.4%, yield 95.4%).

_{3 3}Example 7: preparation of E-CFCH ═ CHCF (E-1336mzz)

Aqueous KOH (6mL, 0.06mol) was added to 346mdf (10g, 0.05mol) and water (6.8mL) at Room Temperature (RT). After addition, the reaction temperature was raised to 70 ℃ and the reaction was monitored using gas chromatography. After 2 hours, 7.6g of product E-1336mzz were collected in a dry ice separator (E-1336mzz selectivity 99.5%, yield 96%).

The product composition is shown in table 2 below, and contains greater than 99% E-1336 mzz.

TABLE 2 product composition

Product of	％
		E-1336mzz(E-CF3CH＝CHCF3)	＞99
Z-1336mzz(Z-CF3CH＝CHCF3)	＜0.4
		1336mt(CF3(CF3)C＝CH2)	＜0.2
356mff(CF3CH2CH2CF3)	＜0.4
		1335lzz(CF2ClCH＝CHCF3)	Trace (< 0.1)

_{3 3}Comparative example: preparation of E-CFCH ═ CHCF (E-1336mzz)

Aqueous NaOH (6mL, 0.06mol) was added to 346mdf (10g, 0.05mol) and water (6.8mL) at Room Temperature (RT). After addition, the reaction temperature was raised to 70 ℃ and the reaction was monitored using gas chromatography. After 2 hours, 0.1g of product E-CF was collected in a dry ice separator₃CH＝CHCF₃(E-1336mzz) (yield: < 1%).

Example 8: liquid phase preparation of 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane (HCFC-336mdd)

In this example, E-1336mzz was catalyzed and thermally chlorinated in the liquid phase to produce HCFC-336 mdd. A lewis acid catalyst is used.

In the liquid phase reaction inC, in a reactor. The liquid medium is the E-1336mzz reactant. When used, the catalyst is present in the liquid phase. The reactor contents were transferred to a drum and analyzed by GC to determine conversion and selectivity. The HCFC-336mdd was recovered from the reaction by purging unreacted chlorine, distilling off unreacted E-1336mzz and filtering off the catalyst. The reaction conditions and results are given in table 3.

TABLE 3 liquid phase thermal chlorination of E-1336mzz

For each of examples 8-1 to 8-6, inIn a C reactor, in FeCl₃、CrCl₃、AlCl₃Or CuCl₂E-1336mzz (20g, 0.122mol) and chlorine (8.65g, 0.122mol) were heated to the temperature in the presence of catalyst (0.4g, 0.0025mol) for the stated time. The temperatures and the times are provided in table 3.

For examples 8-7 and 8-8, E-1336mzz (20g, 0.122mol) and chlorine were reactedGas (8.65g, 0.122mol) in 210mLC reactor was heated to the temperature described in table 3 (temperature described in table 3) for 2 hours. No catalyst is present.

Comparison of the results of examples 8-1 to 8-8 shows that the reaction is preferably carried out in the presence of a catalyst and at a temperature of at least 130 ℃ or at least 150 ℃.

Example 9: gas phase production of 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane (HCFC-336mdd)

The gas phase reaction method comprises the following steps: pickling the acid-washed2cc (1.10g) of ferric chloride on carbon was charged toIn a tube (0.5 inch OD, 15 inches long, 0.34 inch wall thickness). The reactor was heated to 125 ℃ in a Lindberg furnace and CF3CH ═ CHCF₃(E-1336mzz) was fed at a rate of 2.42 ml/hr-4.83 ml/hr, and chlorine gas was fed at a rate of 6.2sccm (standard cubic centimeter per minute) -13.0sccm through a vaporizer controlled at 80 ℃. During the run, the temperature was raised to 175 ℃. All of the following experiments were conducted at 49psig to 51psig (0.34MPa to 0.35 MPa). Use of6890 GC/5973 MS andPC2618 5％the reactor effluent was analyzed on-line by CBK-D/60/806 m.times.2 mm ID 1/8 "OD packed column purged with helium at 30 sccm. HCFC-336mdd is recovered by distillation.

The data are shown in table 4. Samples were taken at hourly intervals.

TABLE 4 gas phase chlorination of E-1336mzz

In Table 4, 236fa (HFC-1, 1,1, 3, 3, 3-hexafluoropropane) and 123(HCFC-2, 2-dichloro-1, 1, 1-trifluoroethane) are impurities in the reactor feed.

The reaction conditions provide a residence time of 27 to 29 seconds at a reactor temperature of 175 deg.c, giving high selectivity in the preparation of HCFC-336 mdd.

Example 10: preparation of 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane (HCFC-336mdd)

In this example, the reaction is photoinitiated.

A 50 gallon (190L) stirred reaction vessel was equipped with a chromatography column, overhead condenser, dip tube and quartz optical trap with cooling jacket. The trap was fitted with a 450 watt mercury arc lamp bulb.

The reactor was charged with 158kg of E-1336mzz, and the liquid was cooled to 0 ℃. The stirrer was run at 100rpm and the overhead condenser was cooled to about-20 ℃ and the lamp was turned on. The temperature and pressure were controlled using the feed rate and 69kg of chlorine gas was slowly added to the system through the dip tube over 51 hours. Liquid reaction temperatures and pressures were not allowed to exceed 10 ℃ and 1psig (0.07MPa), respectively.

After the chlorine addition was complete, the lamp was turned off and the solution was allowed to warm to room temperature. The system was vented to the environment through a caustic scrubber and the crude reaction mixture was inventoried into a storage vessel. The crude reaction mixture was slowly added via a dip tube to a reactor equipped with a bottom drain valve and containing 80 gallons (300L) of 10% K by mixing 3 batches of the resulting crude reaction mixture (663Kg/422L)₂HPO₄/KH₂PO₄The recovery of HCFC-336mdd was carried out in a 200 gallon (750L) stirred vessel of aqueous solution. After the addition was complete, the mixture was stirred vigorously for 3 hours, and then stirring was stopped. The lower organic phase was then decanted from the reactor using conductivity measurements to determine the change in phase. The resulting neutralized organic oil was a water white liquid and had a pH of 5-6, which was passed through a molecular sieve bed to dry it and stored for final purification. The isolated chemical yield of more than 7 batches was 98%. The resulting GC analysis (% FID) was 93.5% of the two 336mdd diastereomers (336mdd-dl and 336mdd-meso), the remainder being determined as 6% of the bulk unknown, presumably oligomers of product/starting material, and the selectivity of the reaction thus being 93.5%. Final purification was accomplished by distillation.

Example 11 preparation of 1,1,1,4,4, 4-hexafluoro-2-butyne

HCFC-336mdd was prepared using the vapor phase process described in example 9 to provide an HCFC-336mdd selectivity of 99.4% according to the specific information in Table 4.

At room temperature under336(0.53g, 0.001325mol), which is trioctylmethylammonium chloride, aqueous NaOH (22mL, 0.22mol) was added to HCFC-336mdd (23.5g, 0.1mol) and water (5.6 mL). After addition, the reaction temperature was raised to 70 ℃ and the reaction was monitored using gas chromatography. The reaction was completed after 2 hours, and 14g of 1,1,1,4,4, 4-hexafluoro-2-butyne product (conversion: 100%; yield: 86%) was collected in a dry ice trap. The butyne is purified by distillation.

Example 12: preparation of Z-1,1,1,4,4, 4-hexafluoro-2-butene

The 1,1,1,4,4, 4-hexafluoro-2-butyne prepared according to example 11 was reacted with hydrogen to prepare the desired Z-isomer of 1,1,1,4,4, 4-hexafluoro-2-butene by the following procedure: 5g of Lindelian (CaCO poisoned with lead)₃Loaded with 5% Pd) catalyst was charged to a 1.3L shaking gas cylinder. 480g (2.96 mol) of hexafluoro-2-butaneThe alkyne is charged into the oscillating cylinder. The reactor was cooled (-78 ℃) and vented. After the cylinder had warmed to room temperature, H was slowly added in increments not exceeding Δ P ═ 50psi (0.35MPa)₂. A total of 3 moles of H₂Added to the reactor. Gas chromatography analysis of the crude product showed that the mixture was composed of CF₃C≡CCF₃(0.236%), trans-isomer E-CF₃CH＝CHCF₃(0.444%), saturated CF₃CH₂CH₂CF₃(1.9％)、CF₂CHCl, impurity from the starting butyne (0.628%), cis isomer Z-CF₃CH＝CHCF₃(96.748%) composition.

Distillation of the crude product afforded 287g (59% yield) of 100% pure cis-CF₃CH＝CHCF₃(bp. 33.3 ℃ C.). MS: 164[ MI]，145[M-19]，95[CF₃CH＝CH]，69[CF₃]。NMR ¹H: 6.12ppm (multiplet),¹⁹f: -60.9ppm (triplet J ═ 0.86 Hz). The selectivity of the reaction to the Z-isomer was 96.98%. The Z-isomer is recovered by distillation.

Other embodiments

1. The present disclosure provides a process for preparing Z-1,1,1,4,4, 4-hexafluorobut-2-ene, the process comprising: (a) contacting 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene with HF in the liquid phase in the presence of a fluorination catalyst to produce a product comprising 2-chloro-1, 1,1,4,4, 4-hexafluorobutane; (b) contacting 2-chloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product comprising E-1, 1,1,4,4, 4-hexafluoro-2-butene; (c) contacting E-1, 1,1,4,4, 4-hexafluoro-2-butene with a chlorine source to produce a product comprising 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane; (d) contacting 2, 3-dichloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product mixture comprising 1,1,1,4,4, 4-hexafluoro-2-butyne; and (e) contacting 1,1,1,4,4, 4-hexafluoro-2-butyne with hydrogen to produce a product comprising Z-1,1,1,4,4, 4-hexafluoro-2-butene.

2. The process of embodiment 1 may also include contacting chlorotrifluoroethylene in the presence of a dimerization catalyst to produce a product mixture comprising 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene.

3. The process of embodiment 1 may also include contacting chlorotrifluoroethylene and pentachloroethane in the presence of a dimerization catalyst to produce a product mixture comprising 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene.

4. A product mixture comprising 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene and trichloroethylene may be prepared according to the process of embodiment 2 or 3.

5. The process of embodiment 4 may also include recovering trichloroethylene and recycling the trichloroethylene to the process of embodiment 2.

6. The dimerization catalyst of any of embodiments 2 through 5 may comprise iron or copper.

7. The process of any of embodiments 2-6 may further comprise recovering 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene from the product mixture and recycling the recovered 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene to step (a).

8. In the method of any of embodiments 2-7, the dimerization catalyst comprises metallic iron.

9. In the method of any of embodiments 2-7, the dimerization catalyst comprises ferric chloride.

10. In the method of any of embodiments 2-7, the dimerization catalyst comprises metallic copper.

11. In the process of any of embodiments 2-7, the dimerization catalyst comprises cuprous chloride or cupric chloride.

12. In the process of any embodiment 3, the weight ratio of pentachloroethane to trichloroethylene is from about 0.001 to about 1 or from about 0.005 to about 1.

13. In the method of any of the preceding embodiments 1-12, the fluorination catalyst of step (a) is a lewis acid catalyst.

14. In the process of any of the preceding embodiments 1-13, the molar ratio of HF to 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene in step (a) is from about 1 to about 35.

15. In the process of any of the preceding embodiments 1-14, the product mixture of step (a) comprises 1, 2-dichloro-1, 1,4,4, 4-pentachlorobutane.

16. In the method of any of the foregoing embodiments 1-15, the base of step (b) is selected from the group consisting of lithium hydroxide, lithium oxide, sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, rubidium hydroxide, rubidium oxide, cesium hydroxide, cesium oxide, calcium hydroxide, calcium oxide, strontium hydroxide, strontium oxide, barium hydroxide, and barium oxide.

17. In the method of any of the foregoing embodiments 1-16, step (b) is carried out in the presence of a phase transfer catalyst.

18. In the method of embodiment 17, the phase transfer catalyst is selected from the group consisting of quaternary ammonium salts, heterocyclic ammonium salts, organophosphonium salts and nonionic compounds.

19. In the method of any one of the preceding embodiments 1-18, step (c) is carried out in the liquid phase.

20. In the method of any one of the preceding embodiments 1-18, step (c) is carried out in the gas phase.

21. In the method of any of the foregoing embodiments 1-20, the chlorine source in step (c) is chlorine gas.

22. In the process of any of the preceding embodiments 1-21, the base is the basic aqueous medium in step (d).

23. In the method of any of the preceding embodiments 1-22, step (d) is carried out in the presence of a phase transfer catalyst.

24. In the method of any one of the preceding embodiments 1-23, step (d) is carried out in the presence of an alkali metal halide salt.

25. In the method of any of the preceding embodiments 1-24, the catalyst in step (e) is an alkyne-to-alkene catalyst.

26. In the method of embodiment 25, the alkyne-to-alkene catalyst is a palladium catalyst doped with silver and/or a lanthanide, dispersed on alumina or titanium silicate.

27. In the process of embodiment 26, the palladium loading is from 100ppm to 5000 ppm.

28. In the method of embodiment 26 or 27, the target catalyst is doped with at least one of silver, cerium, or lanthanum.

29. In the method of embodiment 25, the alkyne-to-alkene catalyst is a lindlar catalyst.

30. In any of the foregoing embodiments 1-29, the process further comprises recovering 2-chloro-1, 1,1,4,4, 4-hexafluorobutane from the product mixture of step (a) prior to step (b) or recovering E-1, 1,1,4,4, 4-hexafluoro-2-butene from the product mixture of step (b) prior to step (c) or recovering 2, 3-dichloro-1, 1,1,4,4, 4-4-hexafluorobutane from the product mixture of step (c) prior to step (d) or recovering 1,1,1,4,4, 4-hexafluoro-2-butynylhexafluorobutane from the product mixture of step (d) prior to step (E) or recovering Z-1 from the product mixture of step (E), 1,1,4,4, 4-hexafluoro-2-butene.

31. The present disclosure provides a process for preparing E-1, 1,1,4,4, 4-hexafluorobut-2-ene, the process comprising: (a) contacting 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene with HF in the liquid phase in the presence of a fluorination catalyst to produce a product comprising 2-chloro-1, 1,1,4,4, 4-hexafluorobutane; and (b) contacting 2-chloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product comprising E-1, 1,1,4,4, 4-hexafluoro-2-butene.

32. The present disclosure provides a process for preparing Z-1,1,1,4,4, 4-hexafluorobut-2-ene, the process comprising: (a) contacting 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene with HF in the liquid phase in the presence of a fluorination catalyst to produce a product comprising 2-chloro-1, 1,1,4,4, 4-hexafluorobutane; and (b) contacting 2-chloro-1, 1,1,4,4, 4-hexafluorobutane with a base to produce a product comprising E-1, 1,1,4,4, 4-hexafluoro-2-butene.

33. The process of embodiment 32 may also include contacting chlorotrifluoroethylene in the presence of a dimerization catalyst to produce a product mixture comprising 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene.

34. The process of embodiment 32 may also include contacting chlorotrifluoroethylene and pentachloroethane in the presence of a dimerization catalyst to produce a product mixture comprising 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene.

35. A product mixture comprising 1,1, 2, 4, 4-pentachlorobutane-1, 3-diene and trichloroethylene may be prepared according to the process of embodiment 33 or 34.

36. The process of embodiment 35 may further comprise recovering trichloroethylene and recycling the trichloroethylene to the process of embodiment 2.

37. A dimerization catalyst according to any of embodiments 33-36 may comprise iron or copper.

38. The process of any of embodiments 33-37 can further comprise recovering 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene from the product mixture and recycling the recovered 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene to step (a).

39. In the method of any of embodiments 33-38, the dimerization catalyst comprises metallic iron.

40. In the method of any of embodiments 33-38, the dimerization catalyst comprises ferric chloride.

41. In the method of any of embodiments 33-38, the dimerization catalyst comprises metallic copper.

42. In the method of any of embodiments 33-38, the dimerization catalyst comprises cuprous chloride or cupric chloride.

43. In the process of any embodiment 34, the weight ratio of pentachloroethane to trichloroethylene is from about 0.001 to about 1 or from about 0.005 to about 1.

44. In the method of any of the preceding embodiments 32-43, the fluorination catalyst of step (a) is a Lewis acid catalyst.

45. In the process of any of the preceding embodiments 32-44, the molar ratio of HF to 1,1, 2, 4, 4-pentachlorobutan-1, 3-diene in step (a) is from about 1 to about 35.

46. In the process of any preceding embodiment 32-45, the product mixture of step (a) comprises 1, 2-dichloro-1, 1,4,4, 4-pentachlorobutane.

47. In the method of any one of the preceding embodiments 32-46, the base of step (b) is selected from the group consisting of lithium hydroxide, lithium oxide, sodium hydroxide, sodium oxide, potassium hydroxide, potassium oxide, rubidium hydroxide, rubidium oxide, cesium hydroxide, cesium oxide, calcium hydroxide, calcium oxide, strontium hydroxide, strontium oxide, barium hydroxide, and barium oxide.

48. In the method of any one of the preceding embodiments 32-47, step (b) is carried out in the presence of a phase transfer catalyst.

49. In the method of embodiment 48, the phase transfer catalyst is selected from the group consisting of quaternary ammonium salts, heterocyclic ammonium salts, organophosphonium salts, and nonionic compounds.

It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It will be understood by those of ordinary skill in the art to which the invention relates that any feature described herein in relation to any particular aspect and/or embodiment of the invention may be combined with one or more of any other feature of any other aspect and/or embodiment of the invention described herein, as appropriate, with modifications to ensure compatibility of the combination. Such combinations are considered part of the invention contemplated by this disclosure.