WO2012067870A1

WO2012067870A1 - Process for making hydrohalocarbons and selected compounds

Info

Publication number: WO2012067870A1
Application number: PCT/US2011/059525
Authority: WO
Inventors: Mario Joseph Nappa; Ekaterina N. Swearingen; Sergei Rafailovich Sterlin
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2010-11-17
Filing date: 2011-11-07
Publication date: 2012-05-24
Also published as: RU2010147008A

Abstract

A process is disclosed for producing addition compound CCI₃CHXCCIYR, wherein X and Y are each independently selected from the group consisting of H, F, CI and Br, and R is a perhalogenated alkyl group, provided that CHX=CYR is not CF₃CH=CH₂. The process involves a liquid phase reaction of CCI₄ with CHX=CYR in the presence of an addition catalyst. New compounds disclosed include CCI₃CH₂CHCICF₂CF₃, CCI₃CH₂CFCICF₃ and CCI₃CHFCHCICF₃. These compounds are useful as intermediates for producing hydrofluorocarbons and hydrofluoroolefins.

Description

TITLE

PROCESS FOR MAKING HYDROHALOCARBONS AND SELECTED

COMPOUNDS BACKGROUND

Field of the Disclosure

This disclosure relates in general to the catalytical addition reactions of CCI with a hydrohaloolefin and compounds made thereby. Description of Related Art

Halogenated alkanes, such as CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons), have been employed in a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and

suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. They are also useful as intermediates to more highly fluorinated compositions such as HFCs (hydrofluorocarbons) and HFOs (hydrofluoroolefins). Due to the concerns of ozone depletion caused by some of the CFC and HCFC products, HFCs have replaced CFCs and HCFCs in a number of applications including using as refrigerants or foam expansion agents. HFOs have been regarded as good candidates to replace traditional CFCs, HCFCs and HFCs since they are both ozone- friendly and having low global warming potentials (GWPs). BRIEF SUMMARY OF THE DISCLOSURE

The present disclosure provides a liquid phase process to produce a product mixture comprising addition compound CCI3CHXCCIYR, wherein X and Y are each independently selected from the group consisting of H, F, CI and Br, and R is a perhalogenated alkyl group, provided that CHX=CYR is not CF₃CH=CH₂. The process comprises reacting CCI₄ with CHX=CYR in the presence of an addition catalyst.

New compounds provided in accordance with this disclosure include CCI3CH2CHCICF2CF3, CCI₃CH₂CFCICF₃ and CCI3CHFCHCICF3. These compounds are useful as intermediates for producing

hydrofluorocarbons and hydrofluoroolefins.

BRIEF SUMMARY OF THE DRAWINGS FIG. 1 - FIG. 1 is a graphical representation of the mass spectrum of CCI3CH2CHCICF2CF3.

FIG. 2A - FIG. 2A is a graphical representation of the ¹ H NMR spectrum of CCI3CH2CHCICF2CF3 around 4.56 ppm.

FIG. 2B - FIG. 2B is a graphical representation of the ¹ H NMR spectrum of CCl₃CH₂CHCICF₂CF₃ from 3.2 to 3.6 ppm.

FIG. 3A - FIG. 3A is a graphical representation of the ¹⁹F NMR spectrum

Of CCI3CH2CHCICF2CF3.

FIG. 3B - FIG. 3B is a detailed graphical representation of the ¹⁹F NMR spectrum of CCI3CH2CHCICF2CF3 around -1 15 ppm.

FIG. 3C - FIG. 3C is a detailed graphical representation of the ¹⁹F NMR spectrum of CCI3CH2CHCICF2CF3 around -123 ppm.

FIG. 4 - FIG. 4 is a graphical representation of the mass spectrum of CCI3CH2CFCICF3.

FIG. 5A - FIG. 5A is a graphical representation of the ¹ H NMR spectrum of CCI3CH2CFCICF3.

FIG. 5B - FIG. 5B is a detailed graphical representation of the ¹ H NMR spectrum of CCI₃CH₂CFCICF₃ from 3.45 to 3.85 ppm.

FIG. 6A - FIG. 6A is a graphical representation of the ¹⁹F NMR spectrum of CCI3CH2CFCICF3 around -83.8 ppm.

FIG. 6B - FIG. 6B is a graphical representation of the ¹⁹F NMR spectrum of CCI3CH2CFCICF3 around -128.3 ppm.

FIG. 7 - FIG. 7 is a graphical representation of the mass spectrum of CCI3CHFCHCICF3.

FIG. 8A - FIG. 8A is a graphical representation of the ¹ H NMR spectrum of CCIsCHFCHCICFsfrom 5.1 to 5.3 ppm.

FIG. 8B - FIG. 8B is a graphical representation of the ¹ H NMR spectrum of CCI₃CHFCHCICF₃from 4.56 to 4.92 ppm. FIG. 9A - FIG. 9A is a graphical representation of the ¹⁹F NMR spectrum of CCI3CHFCHCICF3 around -69.5 ppm.

FIG. 9B - FIG. 9B is a graphical representation of the ¹⁹F NMR spectrum of CCI3CHFCHCICF3 around -73.76 ppm.

FIG. 9C - FIG. 9C is a graphical representation of the ¹⁹F NMR spectrum of CCI3CHFCHCICF3 around -168.4 ppm.

FIG. 9D - FIG. 9D is a graphical representation of the ¹⁹F NMR spectrum of CCI3CHFCHCICF3 around -177.4 ppm. DETAILED DESCRIPTION

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. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.

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. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, use of "a" or "an" are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

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. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Disclosed is a liquid phase process comprising reacting CCI₄ with CHX=CYR in the presence of an addition catalyst to produce a product mixture comprising addition compound CCI₃CHXCCIYR, wherein X and Y are each independently selected from the group consisting of H, F, CI and Br, and R is a perhalogenated alkyl group, provided that CHX=CYR is not

The starting materials for the addition reactions in this disclosure, i.e., CCI₄ and CHX=CYR, can be synthesized by methods known in the art.

The term "alkyl", as used herein, either alone or in compound words such as "perhalogenated alkyl group", includes cyclic or acyclic and straight-chain or branched alkyl groups, such as, methyl, ethyl, n-propyl, /^'- propyl, or the different isomers thereof.

The term "perhalogenated alkyl group", as used herein, means an alkyl group wherein all hydrogens on carbon atoms have been substituted by halogens such as F, CI, Br and I. Examples of a perhalogenated alkyl group include -CCI3 and -CCI₂CCI₃.

The term "perfluorinated alkyl group", as used herein, means an alkyl group wherein all hydrogens on carbon atoms have been substituted by F. Examples of a perfluorinated alkyl group include -CF₃ and -CF₂CF₃.

The term "addition catalyst", as used herein, means a catalyst that can promote addition reactions.

In some embodiments of this invention, X and Y are each independently H or F and R is a perfluorinated alkyl group.

Examples of addition compound CCI3CHXCCIYR in this disclosure include CCI3CH2CHCICF2CF3, CCI₃CH₂CFCICF₃ and CCI3CHFCHCICF3. In some embodiments of this invention, CHX=CYR is

CH₂=CHCF₂CF₃ and the resulting product CCI₃CHXCCIYR is

CCI3CH2CHCICF2CF3.

In some embodiments of this invention, CHX=CYR is CH₂=CFCF₃ and the resulting product CCI3CHXCCIYR is CCI₃CH₂CFCICF₃.

In some embodiments of this invention, CHX=CYR is CHF=CHCF₃ and the resulting product CCI₃CHXCCIYR is CCI₃CHFCHCICF₃.

The addition reaction involving CCI₄ and CHX=CYR in this disclosure is based on a stoichiometry of 1 mole of CCI₄ per mole of CHX=CYR. In practice, an excess of CCI₄ may be used as desired.

Typically, the mole ratio of CCI₄ to CHX=CYR is about 1 :1 to about 10:1 .

The addition reaction process of this disclosure may be practiced by putting CCI₄ and CHX=CYR starting materials and the addition catalysts into a reaction vessel and then heating the mixture with agitation. The process may be carried out by either the batchwise or continuous system.

At the end of the addition reaction, the desired product

CCI₃CHXCCIYR may be recovered from the product mixture by

conventional methods. In some embodiments of this invention, the solid residues may be removed at the end of the addition reaction by

decantation or filtration and the desired product may be purified or recovered by distillation of the resulting liquid product mixture.

The addition compounds that comprise the products of this disclosure are useful as intermediates for producing hydrofluorocarbons and hydrofluoroolefins. Examples of producing hydrofluoroolefins using addition compounds of this disclosure is disclosed in Russian Patent

Application Number 2010147004 [FL1372] filed concurrently herewith, and hereby incorporated by reference in their entirety. Novel compounds provided herein include CCI₃CH₂CHCICF₂CF₃, which may be made by reacting CCI₄ with CH₂=CHCF₂CF₃ as demonstrated by Example 1 ;

CCI₃CH₂CFCICF₃, which may be made by reacting CCI₄ with CH₂=CFCF₃ as demonstrated by Example 2 and CCI₃CHFCHCICF₃, which may be made by reacting CCI with CHF=CHCF₃ as demonstrated by Example 3.

In some embodiments of this invention, the addition catalyst is a copper catalyst comprising cupric chloride and a suitable reductant. As used herein, cupric chloride can be either anhydrous (CuCI₂) or hydrated (e.g., CuCI₂ ^»2H₂O). In some embodiments of this invention, the amount of CuCI₂ ^»2H₂O used in the addition reactions is from about 0.5 to about 10 weight percent based on the total weight of the starting materials (i.e., CCI and CHX=CYR). In some embodiments of this invention, the amount of CuCI₂ ^»2H₂O used in the addition reactions is from about 1 to about 5 weight percent based on the total weight of the starting materials. In some embodiments of this invention, the amount of CuCI₂ used in the addition reactions is from about 0.4 to about 8 weight percent based on the total weight of the starting materials. In some embodiments of this invention, the amount of CuCI₂ used in the addition reactions is from about 0.8 to about 4 weight percent based on the total weight of the starting materials.

A suitable reductant in this disclosure is a reductant which can reduce Cu(ll) compounds (e.g, CuCI₂) to Cu(l) compounds (e.g, CuCI), but will not react with the starting materials CCI₄ and CHX=CYR under the reaction conditions in this disclosure. In some embodiments of this invention, about stoichiometric amount of the reductant is used in the addition reactions of this disclosure. In some embodiments of this invention, more than stoichiometric amount of the reductant is used in the addition reactions of this disclosure.

Examples of suitable reductants include hydrazine (N₂H ) and its derivatives such as monomethylhydrazine (CH₃(NH)NH₂) and 1 ,1 - dimethylhydrazine ((CH₃)₂NNH₂) et al., dithionites such as Na₂S₂O₄, K₂S₂O₄ and (NH₄)₂S₂O₄ et al., copper (zero valence, e.g, copper powder), manganese (zero valence) and iron (zero valence). In some embodiments of this invention, a low molecular weight nitrile such as acetonitrile and propionitrile can also be used as a suitable reductant.

Typically, a solvent is used together with the copper catalyst in this disclosure. In some embodiments of this invention, the solvent is a low molecular weight nitrile such as acetonitrile and propionitrile. In some embodiments of this invention, the solvent is an amide selected from the group consisting of dimethylformamide (DMF), dimethylacetamide and N- methylpyrrolidone. Optionally, a co-catalyst can be used together with the copper catalyst in the addition reactions of this disclosure. Suitable co-catalysts are those which can form coordination compounds with Cu(l) or Cu(ll). Examples of suitable co-catalysts for copper catalyst systems include bis(oxazoline)s, 2,2-bipyridine and their derivatives.

When the addition reaction in this disclosure is conducted in the presence of a copper catalyst, the temperature employed typically ranges from about 60° C to about 240° C. In some embodiments of this invention, the temperature employed in such addition reaction ranges from about 130° C to about 190° C. The pressure employed in the addition reaction is not critical. Typically, the addition reaction is conducted under autogenous pressure.

In some embodiments of this invention, the addition catalyst is an iron catalyst comprising iron and ferric chloride.

As used herein, ferric chloride can be either anhydrous (FeCI₃) or hydrated (e.g., FeCl3^»6H₂O). Iron used herein is metal iron having zero valence. In some embodiments of this invention, iron powder is used for the addition reaction. Typically, the molar ratio of iron to ferric chloride used in the addition reactions of this disclosure is from about 1 :1 to about 10:1 . In some embodiments of this invention, the total amount of iron and FeC used in the addition reaction is from about 5 to about 30 weight percent based on the amount of CCI₄.

Typically, a co-catalyst is used together with the iron catalyst in the addition reactions of this disclosure. In some embodiments of this invention, the co-catalyst is an alkyl or aryl phosphate such as triethyl phosphate, tributyl phosphate, phenyl diethyl phosphate, diethyl phosphate, dibutyl phosphate, phenyl phosphate, butyl phosphate and the like. Typically, the molar ratio of iron catalyst to phosphate co-catalyst is from about 2:1 to about 20:1 . In some embodiments of this invention, the molar ratio of iron catalyst to phosphate co-catalyst is from about 5:1 to about 10:1 .

Optionally, a solvent can be used together with the iron catalyst in this disclosure. In some embodiments of this invention, the starting material CCI₄ can also be used as a solvent. In some embodiments of this invention, the solvent is an inert chemical compound which does not react with other chemical compounds or catalysts during the reaction. Such inert solvent, if used, should boil at a temperature enabling separation from the unconverted starting materials CCI₄ and CHX=CYR and from the product CCI3CHXCCIYR.

When the addition reaction in this disclosure is conducted in the presence of an iron catalyst, the temperature employed typically ranges from about 60° C to about 240° C. In some embodiments of this invention, the temperature employed in such addition reaction ranges from about 130° C to about 190° C. The pressure employed in the addition reaction is not critical. Typically, the addition reaction is conducted under autogenous pressure.

The reactors, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the processes of embodiments of this invention may be constructed of materials resistant to corrosion. Typical materials of construction include TeflonTM and glass. Typical materials of construction also include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as MonelT nickel-copper alloys, HastelloyTM nickel-based alloys and, InconelTM nickel-chromium alloys, and copper-clad steel.

Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

EXAMPLES

The concepts described herein will be further described in the following examples, which do not limit the scope of the invention

described in the claims.

Example 1

Example 1 demonstrates that addition reaction of CCI₄ with

CF₃CF₂CH=CH2 in the presence of an iron catalyst generates addition compound CCI3CH2CHCICF2CF3. 3.5 g of iron powder, 3.5 g of tributyl phosphate, 2 g of FeCl3 and 76 g (0.5 mole) of CCI₄ were loaded into a 210 ml Hastelloy™ tube. The tube was cooled, evacuated and charged with 35 g (0.24 mole) of

CF₃CF₂CH=CH₂. The reaction mixture was warmed up to 130° C and kept at this temperature for 3 hrs. The product mixture was distilled to give desired product CCI3CH2CHCICF2CF3 (bp 105° C/100 mm Hg) with 75% yield. The product CCI3CH2CHCICF2CF3 was further characterized by mass and NMRs:

MS: 263, 245, 227, 207, 177, 1 19, 69.

1 H NMR (CDCI3): 3.26 ppm 1 H (J^H 16 d, J^H 7.5 d), 3.54 ppm 1 H (J^H

16 d, J^H 1 .6 d), 4.56 ppm 1 H (J^F 16 t, J^F = J^H 7.5 d, J^H 1 .6 d).

¹⁹F NMR (CDCI3): -80 ppm 3F (singlet), -1 15.1 ppm 1 F (J^F 273 d, J^H 7.5 d), -123.1 ppm 1 F (J^F 273 d, J^H 16 d).

Example 2

Example 2 demonstrates that addition reaction of CCI₄ with

CF₃CF=CH₂ in the presence of an iron catalyst generates addition compound CCI₃CH₂CFCICF₃.

7.5 g of iron powder, 7.35 g of tributyl phosphate, 4 g of FeC and 152 g (1 mole) of CCI₄ were loaded into a 400 ml Hastelloy™ tube. The tube was cooled, evacuated and charged with 51 g (0.447 mole) of

CF₃CF=CH₂. The reaction mixture was warmed up to 150° C and kept at this temperature for 3 hrs. The product mixture was distilled to give desired product CCI₃CH₂CFCICF₃ (bp 72° C/180 mm Hg) with 82.4% yield. The product CCI3CH2CFCICF3 was further characterized by mass and NMRs:

MS : 231 , 196, 135, 1 17, 69.

¹ H NMR (CDCI3): 1 H 3.78 ppm mult., 1 H 3.55 ppm mult..

¹⁹F NMR (CDCI3): 3F -83.8 ppm doublet J = 6.5Hz, 1 F -128.27 ppm mult..

Example 3

Example 3 demonstrates that addition reaction of CCI₄ with

CF₃CH=CHF in the presence of an iron catalyst generates addition compound CCI3CHFCHCICF3. 7.5 g of iron powder, 7.35 g of tributyl phosphate, 4 g of FeCh and 152 g (1 mole) of CCI₄ were loaded into a 400 ml Hastelloy™ tube. The tube was cooled, evacuated and charged with 51 g (0.447 mole) of CF₃CH=CHF. The reaction mixture was warmed up to 185° C and kept at this temperature for 6 hrs to give desired product CCI3CHFCHCICF3 with 15% yield. The product CCI3CHFCHCICF3 was further characterized by mass and NMRs: (CCl3CHFCHCICF₃ has two pairs of diastereomers: dl pair and meso form (diastereomers have identical NMR properties))

MS: 231 , 21 1 , 95, 1 17, 69.

dl pair: 5.2 ppm 1 H (J^F 45 d, J^H 6.5 d), 4.61 ppm 1 H (J^H 5.2, J^F 6.5); meso form: 5.18 ppm 1 H (J^F 45 d, J^H= 1 .1 d), 4.85 ppm 1 H (J^F 16, J^F 7.1 , J^H 1 .1 )

dl pair: -69.54 ppm 3F (J^F 20.7 d, J^H 6.5 d), -168.37 ppm 1 F (J^H 45 mult., J^H 6 mult, J^F 20.7 mult.);

meso form: -73.75 ppm 3F (J^F 6.5 d, J^H 1 .1 d); -177.37 ppm 1 F (J^H 45 mult., J^H 6.5 mult, J^F 16 mult.) Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to values stated in ranges include each and every value within that range.

Claims

CLAIM(S) What is claimed is:

1 . A liquid phase process comprising reacting CCI with CHX=CYR in the presence of an addition catalyst to produce a product mixture comprising addition compound CCI3CHXCCIYR, wherein X and Y are each independently selected from the group consisting of H, F, CI and Br, and R is a perhalogenated alkyl group, provided that CHX=CYR is not CF₃CH=CH₂.

2. The liquid phase process of claim 1 wherein said addition catalyst is a copper catalyst comprising cupric chloride and a suitable reductant.

3. The liquid phase process of claim 2 wherein said suitable reductant is selected from the group consisting of hydrazine and its

derivatives, dithionites, copper, manganese and iron.

4. The liquid phase process of claim 2 wherein a solvent is used

together with said copper catalyst.

5. The liquid phase process of claim 4 wherein said solvent is selected from the group consisting of acetonitrile, propionitrile,

dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

6. The liquid phase process of claim 2 wherein said reaction is

conducted at the temperature of from about 60° C to about 240° C.

7. The liquid phase process of claim 1 wherein said addition catalyst is an iron catalyst comprising iron and ferric chloride.

8. The liquid phase process of claim 7 wherein said ferric chloride is FeCI₃.

9. The liquid phase process of claim 7 wherein a co-catalyst is used together with said iron catalyst and wherein said co-catalyst is an alkyl or aryl phosphate.

10. The liquid phase process of claim 9 wherein said co-catalyst is selected from the group consisting of triethyl phosphate, tributyl phosphate, phenyl diethyl phosphate, diethyl phosphate, dibutyl phosphate, phenyl phosphate and butyl phosphate.

1 1 . The liquid phase process of claim 7 wherein said reaction is

conducted at the temperature of from about 60° C to about 240° C.

12. The liquid phase process of claim 1 wherein X and Y are each independently H or F and R is a perfluorinated alkyl group.

13. The liquid phase process of claim 1 wherein said CHX=CYR is CH2=CHCF₂CF₃ and said addition compound CCI₃CHXCCIYR is CCI3CH2CHCICF2CF3.

14. The liquid phase process of claim 1 wherein said CHX=CYR is CH₂=CFCF₃ and said addition compound CCI3CHXCCIYR is CCI3CH2CFCICF3.

15. The liquid phase process of claim 1 wherein said CHX=CYR is CHF=CHCF₃ and said addition compound CCI3CHXCCIYR is

CCI3CHFCHCICF3.

16. The liquid phase process of claim 1 further comprising recovering said addition compound CCI3CHXCCIYR from the product mixture.

17. The liquid phase process of claim 16 wherein said addition

compound CCI3CHXCCIYR is recovered from the product mixture by distillation.

18. A compound of the formula CCI3CH2CHCICF2CF3.

19. A compound of the formula CCI₃CH₂CFCICF₃.

20. A compound of the formula CCI3CHFCHCICF3.