WO2012067872A1

WO2012067872A1 - Process for making hydrohalocarbons and selected compound

Info

Publication number: WO2012067872A1
Application number: PCT/US2011/059536
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: RU2010147009A

Abstract

A process is disclosed for producing addition compound CHCI₂CHXCCIYR, wherein X and Y are each independently selected from the group consisting of H, F, CI and Br, and R = H or a perhalogenated alkyl group. The process involves a liquid phase reaction of CHCI₃ with CHX=CYR in the presence of an addition catalyst. New compound disclosed is CHCI₂CH₂CHCICF₃. It is useful as an intermediate for producing hydrofluorocarbons and hydrofluoroolefins.

Description

TITLE

PROCESS FOR MAKING HYDROHALOCARBONS AND SELECTED

COMPOUND BACKGROUND

Field of the Disclosure

This disclosure relates in general to the catalytical addition reactions of CHCI₃ with a hydrohaloolefin and compound 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 CHCI2CHXCCIYR, wherein X and Y are each independently selected from the group consisting of H, F, CI and Br, and R = H or a perhalogenated alkyl group. The process comprises reacting CHCI3 with CHX=CYR in the presence of an addition catalyst.

New compound provided in accordance with this disclosure is CHCI2CH2CHCICF3. It is useful as an intermediate for producing

hydrofluorocarbons and hydrofluoroolefins such as CF₃CH=CHCF₂H. BRIEF SUMMARY OF THE DRAWINGS

FIG. 1 - FIG. 1 is a graphical representation of the mass spectrum of CHCI2CH2CHCICF3.

FIG. 2A - FIG. 2A is a graphical representation of the ¹ H NMR spectrum of CHCI2CH2CHCICF3.

FIG. 2B - FIG. 2B is a detailed graphical representation of the

CHCI2CH2CHCICF3 ¹ H NMR spectrum around 5.9 ppm.

FIG. 2C - FIG. 2C is a detailed graphical representation of the

CHCI2CH2CHCICF3 ¹ H NMR spectrum around 4.4 ppm.

FIG. 2D - FIG. 2D is a detailed graphical representation of the

CHCI2CH2CHCICF3 ¹ H NMR spectrum around 2.8 ppm.

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

Of CHCI2CH2CHCICF3.

FIG. 3B - FIG. 3B is a detailed graphical representation of the

CHCI2CH2CHCICF3 ¹⁹F NMR spectrum around -75 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 CHCI3 with CHX=CYR in the presence of an addition catalyst to produce a product mixture comprising addition compound CHCI2CHXCCIYR, wherein X and Y are each independently selected from the group consisting of H, F, CI and Br, and R = H or a perhalogenated alkyl group.

The starting materials for the addition reactions in this disclosure, i.e., CHCI3 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 -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 selected from the group consisting of H, F and CI. In some embodiments of this invention, CHX=CYR is selected from the group consisting of CH₂=CH₂, CH₂=CHCF₃, CH₂=CHCF₂CF₃, CH₂=CFCF₃ and CHF=CHCF₃.

Examples of addition compound CHCI₂CHXCCIYR in this

disclosure include CHCI₂CH₂CH₂CI, CHCI₂CH₂CHCICF₃,

CHCI₂CH₂CHCICF₂CF₃, CHCI₂CH₂CCIFCF₃ and CHCI₂CHFCHCICF₃.

In some embodiments of this invention, CHX=CYR is CH₂=CHCF₃ and the resulting product CHCI₂CHXCCIYR is CHCI₂CH₂CHCICF₃.

In some embodiments of this invention, CHX=CYR is CH₂=CH₂ and the resulting product CHCI₂CHXCCIYR is CHCI₂CH₂CH₂CI.

The addition reaction involving CHCI₃ and CHX=CYR in this disclosure is based on a stoichiometry of 1 mole of CHCI₃ per mole of CHX=CYR. In practice, an excess of CHCI₃ may be used as desired.

Typically, the mole ratio of CHCI₃ to CHX=CYR is about 1 :1 to about 10:1 .

The addition reaction process of this disclosure may be practiced by putting CHCI₃ 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

CHCI₂CHXCCIYR 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 compound provided herein is CHCI2CH2CHCICF3, which may be made by reacting CHCI3 with CH₂=CHCF₃ as demonstrated by Example 1 .

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 (CuCy or hydrated (e.g., CuCI₂*2H₂O). In some embodiments of this invention, the amount of CuCl2*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., CHCI₃ and CHX=CYR). In some embodiments of this invention, the amount of CuCl2*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, CuCy to Cu(l) compounds (e.g, CuCI), but will not react with the starting materials CHCI₃ 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 Na₂S₂O , K₂S2O₄ and (NH₄)₂S2O₄ et al., copper (zero valence, e.g, copper powder), manganese (zero valence), and iron (zero valence, e.g, iron powder). 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 (FeCIs) 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 FeCI₃ used in the addition reaction is from about 5 to about 30 weight percent based on the amount of CHCI3.

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 CHCIs 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 CHCIs and CHX=CYR and from the product CHCI₂CHXCCIYR.

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, InconelT 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 CHCI₃ with CF₃CH=CH₂ in the presence of an iron catalyst generates addition compound CHCI₂CH₂CHCICF₃.

7.5 g of iron powder, 7.35 g of tributyl phosphate, 4 g of FeCI₃ and 144 g (1 .2 mole) of CHCI₃ were loaded into a 400 ml Hastelloy™ tube. The tube was cooled, evacuated and charged with 57.6 g (0.6 mole) of CF₃CH=CH₂. The reaction mixture was warmed up to 185° C and kept at this temperature for 3 hrs. The product mixture was distilled to give 87 g of desired product CHCI₂CH₂CHCICF₃ (b.p. 122-124° C/atmospheric pressure) with 67.7% yield. The product CHCI₂CH₂CHCICF₃ was further characterized by mass and NMR:

MS: 179 [M-CI], 159 [M-CI-HF], 143 [CHCI₂CH₂CI], 1 17

[CF₃CHCICH₂], 109 [CHCI₂CH₂CH], 83 [CHCI₂], 69 [CF₃].

¹ H NMR (CDCIs): (CCI₂H^aCH₂ ^bCH^cCICF₃) 1 H^a 5.93 ppm d (9.9Hz) of d (3.2Hz), 2H^b 2.75 ppm mult, 1 H^c 4.37 ppm mult.

1⁹F NMR (CDCIs): -75.1 ppm d (6.5Hz).

Example 2

Example 2 demonstrates that addition reaction of CHCI3 with CF₃CH=CH₂ in the presence of a copper catalyst generates addition compound CHCI₂CH₂CHCICF₃.

21 .25 g of CuCI₂'2H₂O, 13.5 g of phenylhydrazine, 75 ml of acetonitrile and 360 g (3 moles) of CHCI₃ were loaded into a 1 L

Hastelloy™ autoclave. The autoclave was cooled, evacuated and charged with 120 g of CF₃CH=CH₂. The reaction mixture was warmed up to 185° C and kept at this temperature for 20 hrs. The yield of CF₃CCI₂CH₂CHCICF₃ was 30%. Example 3

Example 3 demonstrates that addition reaction of CHCI3 with CH₂=CH₂ in the presence of an iron catalyst generates addition compound CHCI2CH2CH2CI .

7.5 g of iron powder, 4.35 g of tributyl phosphate, 4 g of FeCl3 and

144 g (1 .2 mole) of CHCI₃ were loaded into a 400 ml Hastelloy™ tube. The tube was cooled, evacuated and charged with 22.4 g (0.8 mole) of CH₂=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 CHCI₂CH₂CH₂CI (b.p. 88° C/150 mm Hg) with 54% yield.

Example 4

Example 4 demonstrates that addition reaction of CHCI3 with CF₃CH=CH₂ in the presence of a copper catalyst generates addition compound CHCI₂CH₂CHCICF₃.

A mixture of CHCI₃ (78 g, 0.661 mole), CF₃CH=CH₂ (12.6 g,

0.131 mole), CH₃CN (10 ml) and CuCI₂ ^»2H₂O (2.2 g, 13 mmol) was shaken in a 100 ml steel autoclave at 170° C for 18 hrs. The distillation of the resulting product mixture gave 0.3 g of CF₃CH=CH₂, 68.1 g of fraction I (b.p. 55-95° C/atmospheric pressure) containing 95 mole % of CHCI3 and 5 mole % (3.4 g) of CHCI₂CH₂CHCICF₃, and 18.9 g of fraction II (35-108° C/35 mm Hg) containing 80% (15.1 g) of CHCI₂CH₂CHCICF₃. The conversion rate of CF₃CH=CH₂ is about 97%, and the yield of

CHCI₂CH₂CHCICF₃ is 68.7%. Further distillation gave an analytical sample having boiling point of 127-128° C under atmospheric pressure.

Example 5

Example 5 demonstrates that addition reaction of CHCI3 with CF₃CH=CH₂ in the presence of a copper catalyst generates addition compound CHCI₂CH₂CHCICF₃.

A mixture of CHCI₃ (77.5 g, 0.651 mole), CF₃CH=CH₂ (13.4 g, 0.139 mole), CH₃CN (10 ml), CuCI₂-2H₂O (2.2 g, 13 mmol) and 0.83 g copper powder (13 mmol) was shaken in a 100 ml steel autoclave at 170° C for 18 hrs. The distillation of the resulting product mixture gave 2 g of CF₃CH=CH₂, 71 g of fraction I (b.p. 55-98° C/atmospheric pressure) containing 96.3 mole % of CHCI₃ and 3.7 mole % of CHCI₂CH₂CHCICF₃, and 17 g of fraction II (38-120°/38-40 mm Hg) containing 68.6% of CHCI2CH2CHCICF3. The conversion rate of CF₃CH=CH₂ is about 85%, and the yield of CHCI₂CH₂CHCICF₃ is 56%.

Example 6

Example 6 demonstrates that addition reaction of CHCI3 with

CH₂=CH₂ in the presence of a copper catalyst generates addition compound CHCI₂CH₂CH₂CI.

A mixture of CHCI₃ (80 g, 0.678 mole), CH₃CN (10 ml), CuCI₂-2H₂O (2.2 g, 13 mmol), 0.8 g copper powder (13 mmol), 2,2'-bipyridine (2.8 g, 14 mmol) and 3.4 g of CH₂=CH₂ was shaken in a 100 ml steel autoclave at 170° C for 1 1 hrs. The distillation of the resulting product mixture gave a fraction having boiling point of 125-150° C under atmospheric pressure. Further distillation of this fraction gave 19 g (96% purity) of

CHCI₂CH₂CH₂CI (b.p. 69-71 °/65 mm Hg).

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 CHCI₃ with CHX=CYR in the presence of an addition catalyst to produce a product mixture comprising addition compound CHCI₂CHXCCIYR, wherein X and Y are each independently selected from the group consisting of H, F, CI and Br, and R = H or a perhalogenated alkyl group.

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 said CHX=CYR is selected from the group consisting of CH₂=CH₂, CH₂=CHCF₃, CH₂=CHCF₂CF₃, CH₂=CFCF₃ and CHF=CHCF₃.

13. The liquid phase process of claim 1 wherein said CHX=CYR is CH₂=CHCF₃ and said addition compound CHCI₂CHXCCIYR is

CHCI₂CH₂CHCICF₃.

14. The liquid phase process of claim 1 wherein said CHX=CYR is CH₂=CH₂ and said addition compound CHCI₂CHXCCIYR is CHCI2CH2CH2CI .

15. The liquid phase process of claim 1 further comprising recovering said addition compound CHCI₂CHXCCIYR from the product mixture.

16. The liquid phase process of claim 15 wherein said addition

compound CHCI₂CHXCCIYR is recovered from the product mixture by distillation.

17. A compound of the formula CHCI₂CH₂CHCICF₃.