Method for preparing a halogenated olefin
(19)AUSTRALIAN PATENT OFFICE (54) Title Method for preparing a halogenated olefin (51)6 International Patent Classification(s) C07C 017/08 C07C 017/20 C07C 021/04 C07C 019/08 C07B 039/00 C07C 017/278 B01J 023/44 (21) Application No: 2002312773 (22) Application Date: 2002 .03.20 (87) WIPO No: WO02/076913 (30) Priority Data (31) Number (32) Date (33) Country 01/03908 2001 .03.22 FR (43) Publication Date : 2002.10.08 (43) Publication Journal Date : 2003 .03.27 (71) Applicant(s) SOLVAY (SOCIETE ANONYME) (72) Inventor(s) Mathieu, Veronique (-1-1) Application NoAU2002312773 A8(19)AUSTRALIAN PATENT OFFICE (54) Title Method for preparing a halogenated olefin (51)6 International Patent Classification(s) C07C 017/08 C07C 017/20 C07C 021/04 C07C 019/08 C07B 039/00 C07C 017/278 B01J 023/44 (21) Application No: 2002312773 (22) Application Date: 2002 .03.20 (87) WIPO No: WO02/076913 (30) Priority Data (31) Number (32) Date (33) Country 01/03908 2001 .03.22 FR (43) Publication Date : 2002.10.08 (43) Publication Journal Date : 2003 .03.27 (71) Applicant(s) SOLVAY (SOCIETE ANONYME) (72) Inventor(s) Mathieu, Veronique-1- Process for the preparation of a halogenated olefin by reaction of an alkyne and/or of an allene compound with a hydrogen halide in a liquid medium comprising at least one hydrohalogenation catalyst comprising at least one palladium compound. 1. A process for the preparation of a halogenated olefin by reaction of an alkyne and/or of an allene compound with a hydrogen halide in a liquid medium comprising at least
(a) one hydrohalogenation catalyst comprising at least one palladium compound; and (b) at least one organic solvent, chosen from organic nitriles, capable of dissolving the catalyst. 2. The process according to claim 1, in which the alkyne corresponds to the general formula (I)
[in-line-formulae]R1—C≡C—H[/in-line-formulae] in which R1 denotes an alkyl, aryl, carboxyl, ester or halogen group, and/or the allene compound corresponds to the general formula (II)
[in-line-formulae]R2R3C═C═CH2 (II)[/in-line-formulae] in which R2 and R3 independently denote a hydrogen, alkyl, aryl, carboxyl, ester or halogen group. 3. The process according to claim 1, in which 2-chloroprop-1-ene is prepared by reaction of methylacetylene and/or propadiene with hydrogen chloride. 4. The process according to claim 1, in which the palladium compound is chosen from complexes and salts comprising palladium in the 0 or 2 oxidation state. 5. The process according to claim 4, in which the palladium compound comprises palladium in the 2 oxidation state. 6. The process according to claim 5, in which the palladium compound is a salt chosen from palladium (II) acetate, palladium (II) nitrate, palladium (II) bromide or palladium (II) chloride. 7. The process according to claim 6, in which the palladium compound is palladium (II) chloride. 8. The process according to claim 1, in which the organic nitrile comprises 1,2,3 or 4 nitrile functionalities. 9. The process according to claim 8, in which the organic nitrile is adiponitrile. 10. The process according to claim 1, in which the pressure at which the reaction is carried out is from 1 to 5 bar and the temperature at which the reaction is carried out is from 100 to 160° C. 11. A Method for the preparation of 2-chloroprop-1-ene by reaction of a methylacetylene/propadiene mixture with hydrogen chloride in a liquid medium comprising at least one hydrochlorination catalyst comprising and at least one palladium compound, and at least one organic solvent chosen from organic nitriles, capable of dissolving the catalyst, in which method has the following stages:
(a) a methylacetylene/propadiene mixture is introduced into the liquid medium and (b) on conclusion of the reaction, 2-chloropropene is recovered, on the one hand, and a fraction comprising unreacted methylacetylene and unreacted propadiene is recovered, on the other hand, and (c) the fraction comprising unreacted methylacetylene and unreacted propadiene is recycled to stage (a) and wherein the molar ratio of methylacetylene to propadiene in the fraction comprising unreacted methylacetylene and unreacted propadiene is substantially identical to the initial molar ratio between these same constituents. 12. A process for the manufacture of a fluorinated compound, comprising
(a) preparing a halogenated precursor with the halogenated olefin, obtained by reacting an alkyne and/or of an allene compound with a hydrogen halide in a liquid medium comprising at least (a) one hydrohalogenation catalyst comprising at least one palladium compound; and (b) at least one organic solvent, chosen from organic nitriles, capable of dissolving the catalyst, (b) fluorinating the precursor obtained with a fluorinated reactant to form the fluorinated compound. 13. The process according to claim 12, in which the fluorinated compound is 1,1,1,3,3-penta-fluorobutane. 14. The process according to claim 12, wherein said halogenated olefin is 2-chloroprop-1-ene and said fluorinated reactant is hydrogen fluoride. 15. The process for the manufacture of a fluorinated compound comprising
(a) preparing a halogenated precursor with the halogenated olefin, obtained according to the method of claim 11 (b) fluorinating the precursor obtained with a fluorinated reactant, to form the fluorinated compound. 16. The process according to claim 1, wherein said halogenated olefin corresponds to the formula (III) or (IV)
[in-line-formulae]R1—XC═CH2 (III)[/in-line-formulae] [in-line-formulae]R2R3C═XC—CH3 (IV)[/in-line-formulae] R1 denotes an ailcyl, aryl, carboxyl, ester or halogen group, R2 and R3 independently denote a hydrogen, alkyl, aryl, carboxyl, ester or halogen group X is a halogen. 17. The process according to claim 1, wherein said hydrogen halide is hydrogen chloride. 18. The process according to claim 15, in which the alkyne corresponds to the general formula (I)
[in-line-formulae]R1—C≡C—H[/in-line-formulae] in which R1 denotes an alkyl, aryl, carboxyl, ester or halogen group, and/or the allene compound corresponds to the general formula (II) R2R3C═C═CH2(II) in which R2 and R3 independently denote a hydrogen, alkyl, aryl, carboxyl, ester or halogen group.