Process for production of iodofluoroalkane compounds

Abstract

The present invention relates to a process for producing an iodofluoroalkane compound comprising the steps of: a) contacting a fluoroolefin with hydrogen iodide to form a stream A comprising the iodofluoroalkane compound and unreacted hydrogen iodide, b) separating the stream A into a first stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted hydrogen iodide, c) recycling the stream B2 to step a).

Description

[0001] This application is a divisional application of a patent application with application number 202180028072.5, application date February 17, 2021, priority date February 19, 2020, and invention name “Method for producing iodofluoroalkane compounds”. Technical Field

[0002] The present invention relates to a process for producing halogenated alkane compounds. In particular, the present invention relates to a process for producing iodofluoroalkane compounds. Background Art

[0003] Due to the reactivity of the iodine atom, iodofluoro compounds are important synthetic intermediates for the manufacture of pharmaceutical products, plant protection products, fire extinguishing agents and products for the treatment of various substrates, in particular substrates intended for electronic applications.

[0004] Iodofluorinated compounds are also used in the refrigeration field or in air conditioning equipment. From WO 2006 / 112 881, compositions comprising CF are known which are intended for use in refrigerant compositions, refrigeration systems, compositions based on swelling agents, aerogel propellants, etc. 3 Composition of I and HFC-152A.

[0005] Furthermore, patent application FR 2794456 discloses a process for preparing trifluoroiodomethane or pentafluoroiodoethane. Furthermore, FR 2745286 discloses a process for preparing trifluoroiodomethane.

[0006] By using more suitable reagents or operating conditions, the process for producing iodofluoro compounds can be improved both in terms of reaction conversion and selectivity as well as in terms of environmental impact.

[0007] The object of the present invention is to address all or some of the disadvantages observed in the prior art processes.

[0008] Invention I

[0009] Summary of Invention I

[0010] The present invention relates to a process for producing iodofluoroalkane compounds, comprising the following steps:

[0011] a) contacting a fluoroolefin with hydrogen iodide to form a stream A comprising said iodofluoroalkane compound and unreacted hydrogen iodide,

[0012] b) separating the stream A into a first stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted hydrogen iodide,

[0013] c) Recirculating stream B2 into step a).

[0014] According to a preferred embodiment, the hydrogen iodide is anhydrous.

[0015] According to a preferred embodiment, the fluoroolefin is anhydrous.

[0016] The fact that the process is carried out under anhydrous conditions makes it possible to obtain better reaction conversion and / or selectivity. Anhydrous operating conditions also allow for limiting corrosion of the installations.

[0017] According to a preferred embodiment, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0018] According to another preferred embodiment, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5-C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0019] According to another preferred embodiment, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0020] According to a preferred embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom; or

[0021] The iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above; or

[0022] The iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0023] According to a preferred embodiment, the fluoroolefin is selected from CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CF 2 =CF 2 , CH 3 -CF=CH 2 , CH 3 -CH=CHF、CH 2 F-CH=CH 2 , CH 3 -CF=CHF、CH 2 F-CF=CH 2 , CH 3 -CH=CF 2 , CH 2 F-CH=CHF, CHF 2 -CH=CH 2 , CH 3 -CF=CF 2 , CH 2 F-CF=CHF、CHF 2 -CF=CH 2 , CH 2 F-CH=CF 2 , CHF 2 -CH=CHF、CF 3 -CH=CH 2 , CH 2 F-CF=CF 2 , CHF 2 -CF=CHF、CF 3 -CF=CH 2 , CHF 2 -CH=CF 2 CF 3 -CH=CHF, CHF 2 -CF=CF 2 CF 3 -CF=CHF、CF 3 -CH=CF 2 CF 3 -CF=CF 2 ; preferably selected from CF 2 =CH 2 CF 2 =CHF, CF2 =CF 2 CF 3 -CH=CH 2 CF 3 -CF=CH 2 CF 3 -CH=CHF、CF 3 -CF=CHF、CF 3 -CF=CF 2 .

[0024] According to a preferred embodiment, the iodofluoroalkane compound is selected from CH 2 F-CH 2 I. CHFI-CH 3 , CHF 2 -CH 2 I. CF 2 I-CH 3 , CH 2 F-CHFI, CHF 2 -CHFI, CF 2 I-CH 2 F. CHF 2 -CF 2 I. CH 3 -CHF-CH 2 I. CH 3 -CFI-CH 3 , CH 3 -CH 2 -CHFI, CH 3 -CHI-CH 2 F, CH 2 F-CH 2 -CH 2 I. CH 3 -CHF-CHFI, CH 3 -CFI-CH 2 F, CH 2 F-CHF-CH 2 I. CH 3 -CH 2 -CF 2 I. CH 3 -CHI-CHF 2 , CH 2 F-CH 2 -CHFI, CH 2 F-CHI-CH 2 F. CHF 2 -CH 2 -CH 2 I. CH 3 -CHF-CF2 I、CH 3 -CFI-CHF 2 、CH 2 F-CHF-CHFI、CH 2 F-CFI-CH 2 F、CHF 2 -CHF-CH 2 I、CH 2 F-CH 2 -CF 2 I、CH 2 F-CHI-CHF 2 、CHF 2 -CH 2 -CHFI、CF 3 -CH 2 -CH 2 I、CF 3 -CHI-CH 3 、CH 2 F-CHF-CF 2 I、CH 2 F-CFI-CHF 2 、CHF 2 -CHF-CHFI、CF 3 -CHF-CH 2 I、CF 3 -CFI-CH 3 、CHF 2 -CH 2 -CF 2 I、CHF 2 -CHI-CHF 2 、CF 3 -CH 2 -CHFI、CF 3 -CHI-CH 2 F、CHF 2 -CHF-CF 2 I、CHF 2 -CFI-CHF 2 、CF 3 -CHF-CHFI、CF 3 -CFI-CH 2 F、CF 3 -CH 2 -CF 2 I、CF 3 -CHI-CHF 2 、CF 3 -CHF-CF 2 I、CF 3 -CFI-CHF 2; preferably selected from CHF 2 -CH 2 I. CF 2 I-CH 3 , CHF 2 -CHFI, CF 2 I-CH 2 F. CHF 2 -CF 2 I. CF 3 -CH 2 -CH 2 I. CF 3 -CHI-CH 3 CF 3 -CHF-CH 2 I. CF 3 -CFI-CH 3 CF 3 -CH 2 -CHFI, CF 3 -CHI-CH 2 F. CF 3 -CHF-CHFI, CF 3 -CFI-CH 2 F. CF 3 -CHF-CF 2 I. CF 3 -CFI-CHF 2 .

[0025] According to a preferred embodiment, step a) is:

[0026] -CF 2 =CH 2 Convert to CF 2 I-CH 3 ;or

[0027] -CF 2 =CHF to CF 2 I-CH 2 F; or

[0028] -CF 2 =CF 2 Convert to CHF 2 -CF 2 I; or

[0029] -CF 3 -CH=CH 2 Convert to CF 3 -CH 2 -CH 2 I; or

[0030] -CF3 -CF=CH 2 Convert to CF 3 -CFI-CH 3 ;or

[0031] -CF 3 -CH=CHF is converted to CF 3 -CH 2 -CHFI; or

[0032] -CF 3 -CF = CHF to CF 3 -CHF-CHFI; or

[0033] -CF 3 -CF=CF 2 Convert to CF 3 -CHF-CF 2 I.

[0034] According to a preferred embodiment, the fluoroolefin has a boiling point below 100° C. at atmospheric pressure.

[0035] According to a preferred embodiment, step a) is carried out in the gas phase in the presence of a catalyst selected from the following: oxides, oxyhalides or halides of metals of columns 4 to 12 of the periodic table or of metals selected from Li, Na, K, Cs, Mg, Ca, Al and Sb.

[0036] According to a preferred embodiment, step a) is carried out at a temperature of 150°C to 700°C.

[0037] According to a preferred embodiment, step a) is carried out in liquid phase in the presence of a solvent S1 and a catalyst selected from alkali metal or alkaline earth metal salts.

[0038] According to a preferred embodiment, step a) is carried out in the presence of a solvent S1 having a boiling point of 20°C to 250°C.

[0039] Detailed description of invention I

[0040] The present invention relates to a process for producing iodofluoroalkane compounds. Specifically, the process comprises contacting a fluoroolefin with hydrogen iodide to form a stream A comprising the iodofluoroalkane compound and unreacted hydrogen iodide.

[0041] Preferably, the process further comprises the step of separating the compounds contained in stream A. The process may further comprise the step of recycling the starting reagents.

[0042] Therefore, the process comprises the following steps:

[0043] a) contacting a fluoroolefin with hydrogen iodide to form a stream A comprising said iodofluoroalkane compound and unreacted hydrogen iodide,

[0044] b) separating the stream A into a first stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted hydrogen iodide,

[0045] c) Recirculating stream B2 into step a).

[0046] Step a) of the process

[0047] Step a) of the process requires contacting a fluoroolefin with hydrogen iodide (HI).

[0048] The fluoroolefin preferably has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0049] The term "alkyl" refers to a monovalent group derived from a linear or branched alkane comprising a specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane comprising a specified number of carbon atoms. The term "alkenyl" refers to a monovalent group comprising a specified number of carbon atoms and at least one carbon-carbon double bond. The term "cycloalkenyl" refers to a monovalent group derived from a cycloalkene comprising at least one carbon-carbon double bond in its cyclic portion and a specified number of carbon atoms. The term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon comprising a specified number of carbon atoms.

[0050] Preferably, the alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl groups are not substituted by functional groups other than fluorine. However, the groups may include several fluorine atoms on their carbon chains, for example, the groups may contain 1-10 fluorine atoms, preferably 1-5 fluorine atoms.

[0051] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0052] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0053] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0054] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2, R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0055] Alternatively, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0056] The fluoroolefin may have the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0057] The fluoroolefin may have the formula (I) (R 1)(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F, and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0058] The fluoroolefin may have the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 are independently selected from H and F for each unit n, and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0059] In particular, the fluoroolefin is selected from CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CF 2 =CF 2 , CH 3-CF=CH 2 、CH 3 -CH=CHF、CH 2 F-CH=CH 2 、CH 3 -CF=CHF、CH 2 F-CF=CH 2 、CH 3 -CH=CF 2 、CH 2 F-CH=CHF、CHF 2 -CH=CH 2 、CH 3 -CF=CF 2 、CH 2 F-CF=CHF、CHF 2 -CF=CH 2 、CH 2 F-CH=CF 2 、CHF 2 -CH=CHF、CF 3 -CH=CH 2 、CH 2 F-CF=CF 2 、CHF 2 -CF=CHF、CF 3 -CF=CH 2 、CHF 2 -CH=CF 2 、CF 3 -CH=CHF、CHF 2 -CF=CF 2 、CF 3 -CF=CHF、CF 3 -CH=CF 2 、CF 3 -CF=CF 2 。

[0060] More particularly, the fluoroolefin is selected from CF 2 =CH 2 、CF 2 =CHF、CF 2 =CF 2 、CF 3 -CH=CH 2 、CF 3 -CF=CH 2 、CF 3 -CH=CHF、CF 3 -CF=CHF、CF 3 -CF=CF 2 。

[0061] Preferably, step a) is carried out in the presence of an anhydrous fluoroolefin. The term "anhydrous" means here that the fluoroolefin contains less than 500 ppm of water, advantageously less than 250 ppm, preferably less than 100 ppm of water, more preferentially less than 50 ppm of water, in particular less than 25 ppm of water, more particularly less than 10 ppm, preferably less than 5 ppm of water; preferably, the fluoroolefin is free of water. The use of anhydrous fluoroolefins in the present process makes it possible to avoid the formation of impurities (reaction by-products, polymers derived from fluoroolefins, etc.).

[0062] The fluoroolefin may have a boiling point of less than 100°C at atmospheric pressure. Advantageously, the fluoroolefin has a boiling point of less than 75°C at atmospheric pressure. Preferably, the fluoroolefin has a boiling point of less than 50°C at atmospheric pressure. More preferentially, the fluoroolefin has a boiling point of less than 25°C at atmospheric pressure. In particular, the fluoroolefin has a boiling point of less than 10°C at atmospheric pressure.

[0063] In step a), the fluoroolefin is contacted with hydrogen iodide (HI). Preferably, the hydrogen iodide is also anhydrous. The term "anhydrous" means here that the hydrogen iodide contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the hydrogen iodide is free of water. The use of anhydrous hydrogen iodide in the present process also prevents the formation of impurities as mentioned above. The use of anhydrous fluoroolefins and anhydrous hydrogen iodide makes it possible to achieve particularly advantageous selectivities on an industrial scale.

[0064] Preferably, hydrogen iodide is contacted with the fluoroolefin in a stoichiometric amount or in excess thereof, for example, the HI / fluoroolefin molar ratio is 1-50, preferably 2-25, in particular 5-20.

[0065] Preferably, hydrogen iodide is prepared by using hydrogen gas (H 2 ) and iodine (I 2 ). In particular, hydrogen iodide is prepared by contacting anhydrous hydrogen gas with anhydrous iodine. The term "anhydrous" refers to the same definition as mentioned above for hydrogen iodide.

[0066] Alternatively, hydrogen iodide may be deficient relative to the fluoroolefin. In this case, the streams A and B2 comprise the unreacted fluoroolefin instead of unreacted hydrogen iodide. The compound recycled to step a) is therefore a fluoroolefin.

[0067] As mentioned above, step a) results in the formation of a stream A comprising said iodofluoroalkane compound and unreacted hydrogen iodide.

[0068] The iodofluoroalkane compound formed preferably has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0069] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0070] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0071] According to a preferred embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0072] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0073] According to another preferred embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0074] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0075] The iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0076] The iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0077] In particular, the iodofluoroalkane compound is selected from CH 2 F-CH 2 I. CHFI-CH 3 , CHF 2 -CH 2 I. CF 2 I-CH 3 , CH 2 F-CHFI, CHF 2 -CHFI, CF 2 I-CH 2 F. CHF 2 -CF 2 I. CH 3 -CHF-CH 2 I. CH 3 -CFI-CH 3 , CH 3 -CH 2 -CHFI, CH 3 -CHI-CH 2 F, CH 2 F-CH 2 -CH 2 I. CH 3 -CHF-CHFI, CH 3 -CFI-CH 2 F, CH 2 F-CHF-CH 2 I. CH 3 -CH 2 -CF 2 I. CH 3 -CHI-CHF 2 , CH2 F-CH 2 -CHFI、CH 2 F-CHI-CH 2 F、CHF 2 -CH 2 -CH 2 I、CH 3 -CHF-CF 2 I、CH 3 -CFI-CHF 2 、CH 2 F-CHF-CHFI、CH 2 F-CFI-CH 2 F、CHF 2 -CHF-CH 2 I、CH 2 F-CH 2 -CF 2 I、CH 2 F-CHI-CHF 2 、CHF 2 -CH 2 -CHFI、CF 3 -CH 2 -CH 2 I、CF 3 -CHI-CH 3 、CH 2 F-CHF-CF 2 I、CH 2 F-CFI-CHF 2 、CHF 2 -CHF-CHFI、CF 3 -CHF-CH 2 I、CF 3 -CFI-CH 3 、CHF 2 -CH 2 -CF 2 I、CHF 2 -CHI-CHF 2 、CF 3 -CH 2 -CHFI、CF 3 -CHI-CH 2 F、CHF 2 -CHF-CF 2 I、CHF 2 -CFI-CHF 2 、CF 3 -CHF-CHFI、CF 3 -CFI-CH 2 F、CF 3-CH 2 -CF 2 I. CF 3 -CHI-CHF 2 CF 3 -CHF-CF 2 I. CF 3 -CFI-CHF 2 .

[0078] More particularly, the iodofluoroalkane is selected from CHF 2 -CH 2 I. CF 2 I-CH 3 , CHF 2 -CHFI, CF 2 I-CH 2 F. CHF 2 -CF 2 I. CF 3 -CH 2 -CH 2 I. CF 3 -CHI-CH 3 CF 3 -CHF-CH 2 I. CF 3 -CFI-CH 3 CF 3 -CH 2 -CHFI, CF 3 -CHI-CH 2 F. CF 3 -CHF-CHFI, CF 3 -CFI-CH 2 F. CF 3 -CHF-CF 2 I. CF 3 -CFI-CHF 2 .

[0079] In a particularly preferred embodiment, step a) of the production process is

[0080] -CF 2 =CH 2 Convert to CF 2 I-CH 3 ;or

[0081] -CF 2 =CHF to CF 2 I-CH 2 F; or

[0082] -CF 2 =CF 2Convert to CHF 2 -CF 2 I; or

[0083] -CF 3 -CH=CH 2 Convert to CF 3 -CH 2 -CH 2 I; or

[0084] -CF 3 -CF=CH 2 Convert to CF 3 -CFI-CH 3 ;or

[0085] -CF 3 -CH=CHF is converted to CF 3 -CH 2 -CHFI; or

[0086] -CF 3 -CF = CHF to CF 3 -CHF-CHFI; or

[0087] -CF 3 -CF=CF 2 Convert to CF 3 -CHF-CF 2 I.

[0088] Step a) can be carried out in the liquid phase or in the gas phase.Step a) can be carried out in the presence or absence of a catalyst.

[0089] When step a) is carried out in the gas phase, step a) may be carried out in the presence of a catalyst. Preferably, the catalyst is selected from oxides, oxyhalides or halides of metals of columns 4 to 12 of the periodic table or of metals selected from Li, Na, K, Cs, Mg, Ca, Al and Sb.

[0090] Preferably, the catalyst is a chromium oxide (chromium oxide), a chromium oxyfluoride (chromium oxyfluoride) or a chromium fluoride (chromium fluoride). The chromium oxyfluoride preferably has a fluorine content of 10% to 50% by weight, preferably 20% to 50% by weight, in particular 30% to 50% by weight. The fluorine content is measured ionically or by weight change of the catalyst or by any other quantitative method known to those skilled in the art. The chromium oxyfluoride or chromium fluoride catalyst preferably has a fluorine content of 15 to 100% by weight. 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2The specific surface area was measured on a Micromeritics Gemini 2360 machine using a standard 5-point method (BET method).

[0091] When the catalyst is chromium oxide, chromium oxyfluoride or chromium fluoride, it may further contain 0.5 wt% to 10 wt% of a promoter relative to the total weight of the catalyst. The promoter is selected from Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb and Mg.

[0092] When the metal is selected from Li, Na, K, Cs, Mg, Ca, Al and Sb, the anion bound to the metal is F - , Cl - ,I - or CO 3 2- Preferably, the catalyst is NaI or KI. The catalyst preferably has a molecular weight of -20-1000 m 2 / g, especially 20-300m 2 / g specific surface area.

[0093] The catalyst may be deposited on a porous support. The porous support may be selected from activated carbon, graphite, alumina and alumina fluoride.

[0094] When the metal of the catalyst is selected from Li, Na, K, Cs, Mg, Ca, Al and Sb, the catalyst content is 1 wt% to 30 wt% relative to the fluoroolefin.

[0095] When the catalyst is selected from the oxides, oxyhalides or halides of metals of columns 4 to 12 of the periodic table, it may be activated before being used in step a). For example, the catalyst may be activated in the presence of oxygen, air, hydrogen iodide or HF or a mixture thereof.

[0096] The catalyst may also deactivate over time. Thus, step a) may be carried out in the presence of oxygen or air or an oxygen-nitrogen mixture. If oxygen is used in step a), it is present in an amount of 0.005 mol% to 10 mol% relative to the molar amount of fluoroolefin.

[0097] The catalyst may also be regenerated after the process is carried out. The regeneration step may comprise contacting the catalyst with a stream of oxygen or air at a temperature of from 200°C to 700°C.

[0098] Alternatively, step a) can be carried out in the gas phase in the absence of a catalyst.

[0099] In the gas phase, step a) is carried out at a temperature of 150°C to 700°C, preferably 250°C to 600°C.

[0100] Regardless of whether step a) is carried out in the gas phase in the presence or absence of a catalyst, the pressure in this step is from 0.1 bar to 30 bar, preferably from 1 bar to 20 bar, in particular from 1 bar to 15 bar.

[0101] Alternatively, step a) is carried out in the liquid phase. Preferably, when step a) is carried out in the liquid phase, it is carried out in the presence of solvent S1. Preferably, solvent S1 is anhydrous. The term "anhydrous" herein means that solvent S1 contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferably less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the solvent S1 is free of water.

[0102] Solvent S1 has a boiling point of 0°C-250°C, preferably 20°C-250°C, and particularly 20°C-200°C. The solvent S1 is selected from acetic acid, CCl 4 , chloroform, dichloromethane, sulfolane, tetramethylene sulfone, N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone, and mixtures thereof.

[0103] The temperature for carrying out step a) is 50°C to 280°C, preferably 50°C to 250°C.

[0104] Preferably, step a) is carried out in the liquid phase in the presence of a catalyst selected from alkali metal or alkaline earth metal salts. Preferably, the catalyst is an alkali metal salt. Any alkali metal iodide may be used, but preferably sodium iodide or potassium iodide is used. The ratio between the catalyst and the fluoroolefin is 1-20, preferably 1-10. The catalyst preferably has 20-1000 m 2 / g, especially 20-300m 2 The catalyst may be deposited on a porous support. The porous support may be selected from activated carbon, graphite, alumina and alumina fluoride. When the metal of the catalyst is selected from Li, Na, K, Cs, Mg, Ca, Al and Sb, the catalyst content is 1 wt% to 30 wt% relative to the fluoroolefin.

[0105] As mentioned above, step a) makes it possible to obtain a stream A comprising said iodofluoroalkane compound and unreacted hydrogen iodide. Stream A may also comprise other compounds such as impurities, reaction by-products or even unreacted fluoroolefin.

[0106] For example, when the fluoroolefin is CF 2 =CH 2 When, except CF 2 I-CH3 In addition, logistics A may also include CHF 2 -CH 2 I. When the fluoroolefin is CF 2 =CHF, except for CF 2 I-CH 2 In addition to F, logistics A can also include CF 3 -CHFI. When the fluoroolefin is CF 3 -CH=CH 2 When, except CF 3 -CH 2 -CH 2 In addition to I, logistics A can also include CF 3 -CHI-CH 3 When the fluoroolefin is CF 3 -CF=CH 2 When, except CF 3 -CFI-CH 3 In addition, logistics A can also include CF 3 -CHF-CH 2 I. When the fluoroolefin is CF 3 -CH=CHF, except CF 3 -CH 2 - In addition to CHFI, logistics A can also include CF 3 -CHI-CH 2 F. When the fluoroolefin is CF 3 -CF=CHF, except CF 3 In addition to CHF-CHFI, logistics A can also include CF 3 -CFI-CH 2 F. When the fluoroolefin is CF 3 -CF=CF 2 When, except CF 3 -CHF-CF 2 In addition to I, logistics A can also include CF 3 -CFI-CHF 2 .

[0107] According to another embodiment, the process may be carried out in the presence of a mixture of fluoroolefins as defined above resulting in the production of a mixture of iodofluoroalkane compounds in said stream A and in said stream B1.

[0108] Step b) of the process

[0109] Said stream A is then separated to form a first stream B1 comprising said iodofluoroalkane compounds and a stream B2 comprising unreacted hydrogen iodide. Said stream B1 and said stream B2 may both contain impurities, reaction by-products or even unreacted fluoroolefins. In this case, stream B1 is subjected to a further purification step to obtain a stream B1 comprising said purified iodofluoroalkane compounds. Preferably, after the separation and possible purification steps, the content of said iodofluoroalkane compounds in said stream B1 is greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, in particular greater than 98%, more particularly greater than 99%.

[0110] Said stream A is preferably separated and / or purified by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent or a combination thereof.

[0111] The stream A can also be separated or purified by contacting it with an adsorbent. The adsorbent can be a molecular sieve or a zeolite having pore openings with an average diameter of 3-11 angstroms, advantageously 4-10 angstroms, preferably 5-10 angstroms.

[0112] Step c) of the process

[0113] Step c) of the process comprises recycling stream B2 to step a). This recycling step improves the overall yield of the process (better conversion) and saves expensive reagents (and catalysts), while minimizing environmental impact. Without this recycling step, unreacted hydrogen iodide would have to be incinerated, thereby increasing the carbon footprint of the process.

[0114] If stream B1 comprises unreacted fluoroolefin, this can be removed from stream B1 and also recycled to step a).

[0115] The process can be carried out continuously or in a batch or semi-batch manner.

[0116] Preferably, in order to avoid corrosion problems, the reactor in which step a) is carried out is made of a material comprising a base layer made of material M1 and an inner layer made of material M2.

[0117] Advantageously, the material M2 comprises at least 40% by weight of nickel relative to the total weight of the material M2. Preferably, the material M2 comprises at least 45% by weight of nickel relative to the total weight of the material M2, more preferentially at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel.

[0118] Material M2 may also include a chromium content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % relative to the total weight of material M2.

[0119] Material M2 may also include molybdenum in an amount less than 35 wt. %, advantageously less than 30 wt. %, preferably less than 20 wt. %, more preferentially less than 15 wt. %, in particular less than 10 wt. %, more particularly less than 5 wt. % relative to the total weight of material M2.

[0120] Preferably, the material M2 is or

[0121] According to a preferred embodiment, material M1 comprises at least 70 wt. % iron, advantageously at least 75 wt. %, preferably at least 80 wt. %, more preferentially at least 85 wt. %, in particular at least 90 wt. %, more particularly at least 95 wt. % iron relative to the total weight of material M1.

[0122] The material M1 may also include less than 2% by weight, advantageously less than 1.5% by weight, preferably less than 1% by weight, more preferentially less than 0.75% by weight, in particular less than 0.5% by weight, more particularly less than 0.2% by weight, preferably less than 0.1% by weight of carbon relative to the total weight of the material M1. More particularly, the material M1 may include 0.01% by weight to 0.2% by weight of carbon based on the total weight of the material M1.

[0123] Preferably, the base layer and the inner layer are attached to each other by hot or cold plating, hot or cold rolling, or welding.

[0124] The present invention includes the following embodiments.

[0125] Item 1. A process for producing an iodofluoroalkane compound, comprising the following steps:

[0126] a) contacting a fluoroolefin with hydrogen iodide to form a stream A comprising said iodofluoroalkane compound and unreacted hydrogen iodide,

[0127] b) separating the stream A into a first stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted hydrogen iodide,

[0128] c) Recirculating stream B2 into step a).

[0129] 2. A process as described in item 1, characterized in that the hydrogen iodide is anhydrous.

[0130] 3. A process as described in any one of the preceding clauses, characterized in that the fluoroolefin is anhydrous.

[0131] 4. A process as described in any one of the preceding items, characterized in that the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0132] 5. A process as described in any one of the preceding items 1 to 4, characterized in that the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0133] 6. A process as described in any one of the preceding items 1 to 4, characterized in that the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0134] 7. A process as described in item 4, characterized in that the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 As defined in item 4 or in the process as described in item 5, characterized in that the iodofluoroalkane compound has formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 As defined in item 5 or in the process as described in item 6, characterized in that the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R 4 ), where R1 , R 2 , R 3 and R 4 As defined in item 6.

[0135] 8. A process as described in any one of the preceding items 1 to 4, characterized in that the fluoroolefin is selected from CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CF 2 =CF 2 , CH 3 -CF=CH 2 , CH 3 -CH=CHF、CH 2 F-CH=CH 2 , CH 3 -CF=CHF、CH 2 F-CF=CH 2 , CH 3 -CH=CF 2 , CH 2 F-CH=CHF, CHF 2 -CH=CH 2 , CH 3 -CF=CF 2 , CH 2 F-CF=CHF、CHF 2 -CF=CH 2 , CH 2 F-CH=CF 2 , CHF 2 -CH=CHF、CF 3 -CH=CH 2 , CH 2 F-CF=CF 2 , CHF 2 -CF=CHF、CF 3 -CF=CH 2 , CHF 2 -CH=CF 2 CF 3 -CH=CHF, CHF 2 -CF=CF 2 CF 3 -CF=CHF、CF 3 -CH=CF 2 CF 3 -CF=CF 2 ; preferably selected from CF 2 =CH 2 CF2 =CHF, CF 2 =CF 2 CF 3 -CH=CH 2 CF 3 -CF=CH 2 CF 3 -CH=CHF、CF 3 -CF=CHF、CF 3 -CF=CF 2 .

[0136] 9. A process as described in the preceding item, characterized in that the iodofluoroalkane compound is selected from CH 2 F-CH 2 I. CHFI-CH 3 , CHF 2 -CH 2 I. CF 2 I-CH 3 , CH 2 F-CHFI, CHF 2 -CHFI, CF 2 I-CH 2 F. CHF 2 -CF 2 I. CH 3 -CHF-CH 2 I. CH 3 -CFI-CH 3 , CH 3 -CH 2 -CHFI, CH 3 -CHI-CH 2 F, CH 2 F-CH 2 -CH 2 I. CH 3 -CHF-CHFI, CH 3 -CFI-CH 2 F, CH 2 F-CHF-CH 2 I. CH 3 -CH 2 -CF 2 I. CH 3 -CHI-CHF 2 , CH 2 F-CH 2 -CHFI, CH 2 F-CHI-CH 2 F. CHF 2 -CH 2 -CH 2 I. CH3 -CHF-CF 2 I、CH 3 -CFI-CHF 2 、CH 2 F-CHF-CHFI、CH 2 F-CFI-CH 2 F、CHF 2 -CHF-CH 2 I、CH 2 F-CH 2 -CF 2 I、CH 2 F-CHI-CHF 2 、CHF 2 -CH 2 -CHFI、CF 3 -CH 2 -CH 2 I、CF 3 -CHI-CH 3 、CH 2 F-CHF-CF 2 I、CH 2 F-CFI-CHF 2 、CHF 2 -CHF-CHFI、CF 3 -CHF-CH 2 I、CF 3 -CFI-CH 3 、CHF 2 -CH 2 -CF 2 I、CHF 2 -CHI-CHF 2 、CF 3 -CH 2 -CHFI、CF 3 -CHI-CH 2 F、CHF 2 -CHF-CF 2 I、CHF 2 -CFI-CHF 2 、CF 3 -CHF-CHFI、CF 3 -CFI-CH 2 F、CF 3 -CH 2 -CF 2 I、CF 3 -CHI-CHF 2 、CF 3 -CHF-CF 2 I、CF 3-CFI-CHF 2 ; preferably selected from CHF 2 -CH 2 I. CF 2 I-CH 3 , CHF 2 -CHFI, CF 2 I-CH 2 F. CHF 2 -CF 2 I. CF 3 -CH 2 -CH 2 I. CF 3 -CHI-CH 3 CF 3 -CHF-CH 2 I. CF 3 -CFI-CH 3 CF 3 -CH 2 -CHFI, CF 3 -CHI-CH 2 F. CF 3 -CHF-CHFI, CF 3 -CFI-CH 2 F. CF 3 -CHF-CF 2 I. CF 3 -CFI-CHF 2 .

[0137] 10. A process as described in any one of the preceding items 1 to 3, characterized in that step a) further involves:

[0138] -CF 2 =CH 2 Convert to CF 2 I-CH 3 ;or

[0139] -CF 2 =CHF to CF 2 I-CH 2 F; or

[0140] -CF 2 =CF 2 Convert to CHF 2 -CF 2 I; or

[0141] -CF 3 -CH=CH 2 Convert to CF 3 -CH 2 -CH 2I; or

[0142] -CF 3 -CF=CH 2 Convert to CF 3 -CFI-CH 3 ;or

[0143] -CF 3 -CH=CHF is converted to CF 3 -CH 2 -CHFI; or

[0144] -CF 3 -CF = CHF to CF 3 -CHF-CHFI; or

[0145] -CF 3 -CF=CF 2 Convert to CF 3 -CHF-CF 2 I.

[0146] 11. A process as described in any one of the preceding items, characterized in that the fluoroolefin has a boiling point below 100°C at atmospheric pressure.

[0147] 12. A process as described in any of the preceding items, characterized in that step a) is carried out in the gas phase and in the presence of a catalyst selected from the following: oxides, oxyhalides or halides of metals of columns 4 to 12 of the Periodic Table or of metals selected from Li, Na, K, Cs, Mg, Ca, Al and Sb.

[0148] 13. Process as described in any of the preceding items, characterized in that step a) is carried out at a temperature of 150°C to 700°C.

[0149] 14. The process as described in any one of the preceding items 1 to 10, characterized in that step a) is carried out in liquid phase in the presence of a solvent S1 and a catalyst selected from alkali metal or alkaline earth metal salts.

[0150] 15. A process as described in the preceding item, characterized in that step a) is carried out in the presence of a solvent S1 having a boiling point of 20°C to 250°C. Example

[0151] Example 1

[0152] 250 mL of sulfolane and 0.1 mol of sodium iodide were introduced into a 500 mL Hastelloy C276 reactor equipped with a stirrer, a heating device and a temperature control system. The reaction medium was brought to 90-100° C. under stirring. Anhydrous reagent 0.5 mol of CF 2=CHF and 0.8 mol HI (composed of H 2 and I 2 Preparation) was introduced into the reaction medium. After 4 hours of reaction under stirring, a sample was taken out, washed and dried, and then analyzed by gas chromatography (area percentage). 2 = The conversion rate of CHF is 85%, and the conversion rate of CF 2 I-CH 2 The selectivity for F was 89%.

[0153] Example 2

[0154] A chromium oxyfluoride catalyst containing 15 wt% to 20 wt% of fluorine was introduced into a tubular reactor made of Inconel 600. The catalyst was heated at 0 2 The hexafluoropropylene gas stream and the H 2 and I 2 A gaseous stream of the prepared hydrogen iodide (HFP / HI molar ratio = 1 / 2) was passed over the catalyst at a temperature of 270° C. under 3 bar. At the reactor outlet, the gas was washed, then dried and condensed in a cold trap. A sample was taken and analyzed by gas chromatography (area percentage). The conversion of hexafluoropropylene was 95%, with respect to CF 3 -CHF-CF 2 The selectivity for I was 97%.

[0155] CF 3 -CF=CHF、CF 3 -CH=CHF、CF 3 -CF=CH 2 and CF 3 -CH=CH 2 As in the case of fluoroolefins, comparable (equal) conversion and selectivity values ​​were obtained.

[0156] Invention II

[0157] Summary of Invention II

[0158] The present invention relates to a process for producing iodofluoroalkane compounds, comprising the following step a): contacting an olefin with anhydrous iodine monofluoride (IF) to form a stream A comprising the iodofluoroalkane compound and optionally unreacted iodine monofluoride.

[0159] The present process makes it possible to obtain iodofluoroalkane compounds with improved selectivity while maintaining a high conversion of the starting olefin.

[0160] According to a preferred embodiment, the olefin is a fluoroolefin.

[0161] According to a preferred embodiment, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0162] According to a preferred embodiment, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0163] According to a preferred embodiment, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0164] The iodofluoroalkane compound is obtained by adding an iodine monofluoride (IF) molecule to the carbon-carbon double bond of the olefin.

[0165] According to a preferred embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom;

[0166] Or the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above;

[0167] Or the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0168] According to a preferred embodiment, the olefin is a fluoroolefin selected from the following: CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CF 2 =CF 2 , CH 3 -CF=CH 2 , CH 3 -CH=CHF、CH 2 F-CH=CH 2 , CH 3 -CF=CHF、CH 2 F-CF=CH 2 , CH 3 -CH=CF 2 , CH 2 F-CH=CHF, CHF 2 -CH=CH 2 , CH 3 -CF=CF 2 , CH 2 F-CF=CHF、CHF 2 -CF=CH 2 , CH 2 F-CH=CF 2 , CHF 2 -CH=CHF、CF 3 -CH=CH 2 , CH 2 F-CF=CF 2 , CHF 2 -CF=CHF、CF 3 -CF=CH 2 , CHF 2 -CH=CF 2 CF 3 -CH=CHF, CHF 2 -CF=CF 2 CF 3 -CF=CHF、CF 3 -CH=CF 2 CF 3 -CF=CF 2 ; preferably selected from CF 2 =CH 2 CF 2 =CHF, CF 2 =CF 2 CF 3 -CH=CH 2 CF 3-CF=CH 2 CF 3 -CH=CHF、CF 3 -CF=CHF、CF 3 -CF=CF 2 .

[0169] According to a preferred embodiment, the iodofluoroalkane compound is selected from CHFI-CH 2 F. CHF 2 -CH 2 I. CF 2 I-CH 2 F. CF 3 -CH 2 I. CHFI-CHF 2 CF 2 I-CHF 2 CF 3 -CHFI, CF 2 I-CF 3 , CH 3 -CFI-CH 2 F, CH 3 -CF 2 -CH 2 I. CH 3 -CHI-CHF 2 , CH 3 -CHF-CHFI, CH 2 F-CHI-CH 2 F, CH 2 F-CHF-CH 2 I. CH 3 -CFI-CHF 2 , CH 3 -CF 2 -CHFI, CH 2 F-CFI-CH 2 F, CH 2 F-CF 2 -CH 2 I. CH 3 -CHI-CF 3 , CH 3 -CHF-CF 2 I. CH 2 F-CHI-CHF 2 , CH 2 F-CHF-CHFI, CHF 2 -CHF-CH 2 I. CH 3 -CFI-CF 3 , CH 3 -CF2 -CF 2 I, CH 2 F - CFI - CHF 2 , CH 2 F - CF 2 -CHFI, CHF 2 -CF 2 -CH 2 I, CH 2 F - CHF - CF 2 I, CHF 2 -CHI - CHF 2 , CHF 2 -CHF - CHFI, CF 3 -CHI - CH 2 F, CF 3 -CHF - CH 2 I, CH 2 F - CF 2 -CF 2 I, CHF 2 -CFI - CHF 2 , CHF 2 -CF 2 -CHFI, CF 3 -CFI - CH 2 F, CF 3 -CF 2 -CH 2 I, CHF 2 -CHF - CF 2 I, CF 3 -CHI - CHF 2 , CF 3 -CHF - CHFI, CHF 2 -CF 2 -CF 2 I, CF 3 -CFI - CHF 2 , CF 3 -CF 2 -CHFI, CF 3 -CHI - CF 3 , CF 3 -CHF - CF 2 I, CF 3 -CFI - CF 3 , CF 3 -CF 2 -CF 2 I; preferably selected from CF 2 I - CH 2 F, CF 3 -CH 2 I, CF2 I-CHF 2 CF 3 -CHFI, CF 2 I-CF 3 CF 3 -CHI-CH 2 F. CF 3 -CHF-CH 2 I. CF 3 -CFI-CH 2 F. CF 3 -CF 2 -CH 2 I. CF 3 -CHI-CHF 2 CF 3 -CHF-CHFI, CF 3 -CFI-CHF 2 CF 3 -CF 2 -CHFI, CF 3 -CFI-CF 3 CF 3 -CF 2 -CF 2 I.

[0170] According to a preferred embodiment, step a) is:

[0171] -CF 2 =CH 2 Convert to CF 3 -CH 2 I;

[0172] -CF 2 =CHF to CF 3 -CHFI; or

[0173] -CF 2 =CF 2 Convert to CF 3 -CF 2 I; or

[0174] -CF 3 -CH=CH 2 Convert to CF 3 -CHI-CH 2 F; or

[0175] -CF 3 -CF=CH 2 Convert to CF 3 -CF 2 -CH 2 I; or

[0176] -CF 3 -CH=CHF is converted to CF 3 -CHI-CHF 2 ;or

[0177] -CF 3 -CF = CHF to CF 3 -CFI-CHF 2 ;or

[0178] -CF 3 -CF=CF 2 Convert to CF 3 -CFI-CF 3 .

[0179] According to a preferred embodiment, anhydrous iodine monofluoride is prepared by 2 ) and anhydrous iodine pentafluoride (IF 5 ) are prepared by mixing.

[0180] According to a preferred embodiment, the process comprises the following step b): purifying said stream A to form a stream B1 comprising at least 90% by weight of said iodofluoroalkane compound.

[0181] Detailed description of invention II

[0182] The present invention relates to a process for producing iodofluoroalkane compounds, comprising the following step a): contacting an olefin with anhydrous iodine monofluoride (IF) to form a stream A comprising the iodofluoroalkane compound and optionally unreacted iodine monofluoride.

[0183] Step a) of the process

[0184] The present process makes it possible to obtain iodofluoroalkane compounds with improved selectivity while maintaining a high conversion of the starting olefin.

[0185] The olefin may have the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C 1 -C 10 Alkyl group, C 3 -C 10 Cycloalkyl groups, C 2 -C 10 Alkenyl group, C 3 -C10 Cycloalkenyl groups and C 6 -C 10 Aryl group.

[0186] Carrying out step a) with anhydrous iodine monofluoride makes it possible to improve the selectivity and conversion rate of the reaction. The term "anhydrous" means here that the iodine monofluoride contains less than 500 ppm of water, advantageously less than 250 ppm, preferably less than 100 ppm of water, more preferentially less than 50 ppm of water, in particular less than 25 ppm of water, more particularly less than 10 ppm, preferably less than 5 ppm of water; preferably, the iodine monofluoride does not contain water.

[0187] According to a preferred embodiment, the olefin is a fluoroolefin. Preferably, the fluoroolefin is anhydrous. The term "anhydrous" means here that the fluoroolefin contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the fluoroolefin is free of water. The use of anhydrous fluoroolefins in the present process makes it possible to avoid the formation of impurities (reaction by-products, polymers derived from fluoroolefins, etc.).

[0188] According to a preferred embodiment, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0189] The term "alkyl" refers to a monovalent group derived from a linear or branched alkane comprising a specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane comprising a specified number of carbon atoms. The term "alkenyl" refers to a monovalent group comprising a specified number of carbon atoms and at least one carbon-carbon double bond. The term "cycloalkenyl" refers to a monovalent group derived from a cycloalkene comprising at least one carbon-carbon double bond in its cyclic portion and a specified number of carbon atoms. The term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon comprising a specified number of carbon atoms.

[0190] Preferably, the alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl groups are not substituted by functional groups other than fluorine. However, the groups may include several fluorine atoms on their carbon chains, for example, the groups may contain 1-10 fluorine atoms, preferably 1-5 fluorine atoms.

[0191] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0192] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0193] According to a preferred embodiment, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above including at least one fluorine atom.

[0194] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above including at least one fluorine atom.

[0195] According to another preferred embodiment, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0196] The fluoroolefin may have the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0197] The fluoroolefin may have the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F, and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0198] The fluoroolefin may have the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 are independently selected from H and F for each unit n, and n is an integer from 1 to 5; provided that the substituent R 1 , R 2, R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0199] In particular, the fluoroolefin is selected from CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CF 2 =CF 2 , CH 3 -CF=CH 2 , CH 3 -CH=CHF、CH 2 F-CH=CH 2 , CH 3 -CF=CHF、CH 2 F-CF=CH 2 , CH 3 -CH=CF 2 , CH 2 F-CH=CHF, CHF 2 -CH=CH 2 , CH 3 -CF=CF 2 , CH 2 F-CF=CHF、CHF 2 -CF=CH 2 , CH 2 F-CH=CF 2 , CHF 2 -CH=CHF、CF 3 -CH=CH 2 , CH 2 F-CF=CF 2 , CHF 2 -CF=CHF、CF 3 -CF=CH 2 , CHF 2 -CH=CF 2 CF 3 -CH=CHF, CHF 2 -CF=CF 2 CF 3 -CF=CHF、CF 3 -CH=CF 2 CF 3 -CF=CF 2 .

[0200] More particularly, the fluoroolefin is selected from CF2 =CH 2 CF 2 =CHF, CF 2 =CF 2 CF 3 -CH=CH 2 CF 3 -CF=CH 2 CF 3 -CH=CHF、CF 3 -CF=CHF、CF 3 -CF=CF 2 .

[0201] Preferably, iodine monofluoride is contacted with an olefin, preferably a fluoroolefin, in a stoichiometric amount or in excess thereof. For example, the IF / fluoroolefin molar ratio is 1-50, preferably 1.5-25, in particular 2-20.

[0202] Preferably, anhydrous iodine monofluoride is prepared from an anhydrous reagent. Preferably, anhydrous iodine monofluoride is prepared by mixing anhydrous iodine (I 2 ) and anhydrous iodine pentafluoride (IF 5 ) are prepared in situ by mixing with iodofluoroalkane compounds. In this case, the stream A may also include unreacted iodine and / or iodine pentafluoride in addition to the iodofluoroalkane compounds and optionally unreacted iodine monofluoride. For both iodine and iodine pentafluoride, the term "anhydrous" means herein that the water content in the compound under consideration is less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water. Preferably, iodine and iodine pentafluoride are free of water.

[0203] The mixing of anhydrous iodine and anhydrous iodine pentafluoride can be carried out in a liquid state. Thus, iodine is dissolved in iodine pentafluoride. Alternatively, iodine can be introduced into the iodine pentafluoride solution in a gaseous form.

[0204] Alternatively, anhydrous iodine monofluoride can be produced by reacting anhydrous iodine with anhydrous IF 7 Mix or mix anhydrous iodine with anhydrous fluorine gas F 2 Mix or mix anhydrous iodine with anhydrous IF 3 mix.

[0205] The iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0206] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0207] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3)(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0208] According to a preferred embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above including at least one fluorine atom.

[0209] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above including at least one fluorine atom.

[0210] According to another preferred embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0211] The iodofluoroalkane compound may have the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0212] The iodofluoroalkane compound may have the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0213] The iodofluoroalkane compound may have the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-]n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0214] According to a preferred embodiment, the iodofluoroalkane compound is selected from CHFI-CH 2 F. CHF 2 -CH 2 I. CF 2 I-CH 2 F. CF 3 -CH 2 I. CHFI-CHF 2 CF 2 I-CHF 2 CF 3 -CHFI, CF 2 I-CF 3 , CH 3 -CFI-CH 2 F, CH 3 -CF 2 -CH 2 I. CH 3 -CHI-CHF 2 , CH 3 -CHF-CHFI, CH 2 F-CHI-CH 2 F, CH 2 F-CHF-CH 2 I. CH 3 -CFI-CHF 2 , CH 3 -CF 2 -CHFI, CH 2 F-CFI-CH 2 F, CH 2 F-CF 2 -CH 2 I. CH 3 -CHI-CF 3 , CH 3 -CHF-CF 2 I. CH 2 F-CHI-CHF 2 , CH2 F-CHF-CHFI、CHF 2 -CHF-CH 2 I、CH 3 -CFI-CF 3 、CH 3 -CF 2 -CF 2 I、CH 2 F-CFI-CHF 2 、CH 2 F-CF 2 -CHFI、CHF 2 -CF 2 -CH 2 I、CH 2 F-CHF-CF 2 I、CHF 2 -CHI-CHF 2 、CHF 2 -CHF-CHFI、CF 3 -CHI-CH 2 F、CF 3 -CHF-CH 2 I、CH 2 F-CF 2 -CF 2 I、CHF 2 -CFI-CHF 2 、CHF 2 -CF 2 -CHFI、CF 3 -CFI-CH 2 F、CF 3 -CF 2 -CH 2 I、CHF 2 -CHF-CF 2 I、CF 3 -CHI-CHF 2 、CF 3 -CHF-CHFI、CHF 2 -CF 2 -CF 2 I、CF 3 -CFI-CHF 2 、CF 3 -CF 2 -CHFI、CF 3 -CHI-CF 3 、CF 3 -CHF-CF 2 I、CF 3 -CFI-CF 3 、CF3 -CF 2 -CF 2 I.

[0215] Preferably, the iodofluoroalkane compound is selected from CF 2 I-CH 2 F. CF 3 -CH 2 I. CF 2 I-CHF 2 CF 3 -CHFI, CF 2 I-CF 3 CF 3 -CHI-CH 2 F. CF 3 -CHF-CH 2 I. CF 3 -CFI-CH 2 F. CF 3 -CF 2 -CH 2 I. CF 3 -CHI-CHF 2 CF 3 -CHF-CHFI, CF 3 -CFI-CHF 2 CF 3 -CF 2 -CHFI, CF 3 -CFI-CF 3 CF 3 -CF 2 -CF 2 I.

[0216] According to a preferred embodiment, step a) is:

[0217] -CF 2 =CH 2 Convert to CF 3 -CH 2 I;

[0218] -CF 2 =CHF to CF 3 -CHFI; or

[0219] -CF 2 =CF 2 Convert to CF 3 -CF 2 I; or

[0220] -CF 3 -CH=CH 2 Convert to CF3 -CHI-CH 2 F; or

[0221] -CF 3 -CF=CH 2 Convert to CF 3 -CF 2 -CH 2 I; or

[0222] -CF 3 -CH=CHF is converted to CF 3 -CHI-CHF 2 ;or

[0223] -CF 3 -CF = CHF to CF 3 -CFI-CHF 2 ;or

[0224] -CF 3 -CF=CF 2 Convert to CF 3 -CFI-CF 3 .

[0225] Step a) can be carried out in the liquid phase or in the gas phase.Step a) can be carried out in the presence or absence of a catalyst.

[0226] Gas phase step a)

[0227] When step a) is carried out in the gas phase, step a) may be carried out in the presence of a catalyst. Preferably, the catalyst is selected from oxides, oxyhalides or halides of metals or metalloids of columns 4 to 15 of the periodic table or of metals selected from Li, Na, K, Cs, Mg and Ca.

[0228] Preferably, the catalyst is a chromium oxide, a chromium oxyfluoride or a chromium fluoride. The chromium oxyfluoride preferably has a fluorine content of 10% to 50% by weight, preferably 20% to 50% by weight, in particular 30% to 50% by weight. The fluorine content is measured ionically or by weight change of the catalyst or by any other quantitative method known to those skilled in the art. The chromium oxyfluoride or chromium fluoride catalyst preferably has a fluorine content of 15 to 100% by weight. 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2The specific surface area of ​​the catalyst is 0.01-10% by weight relative to the fluoroolefin. When the catalyst is chromium oxide, chromium oxyfluoride or chromium fluoride, it may further contain 0.5-10% by weight of a promoter relative to the total weight of the catalyst. The promoter is selected from Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb and Mg.

[0229] When the metal is selected from Li, Na, K, Cs, Mg and Ca, the anion bound to the metal is F - , Cl - ,I - or CO 3 2- Preferably, the catalyst is NaI or KI. The catalyst preferably has 20-1000 m 2 / g, especially 20-300m 2 / g specific surface area.

[0230] The catalyst may be deposited on a porous support. The porous support may be selected from activated carbon, graphite, alumina and alumina fluoride.

[0231] When the metal of the catalyst is selected from Li, Na, K, Cs, Mg and Ca, the catalyst content is 1 wt% to 30 wt% relative to the fluoroolefin.

[0232] When the catalyst is selected from oxides, oxyhalides or halides of metals or metalloids of columns 4 to 15 of the periodic table, it can be activated before being used in step a). For example, the catalyst can be activated in the presence of oxygen, air, hydrogen iodide or HF or a mixture thereof.

[0233] The catalyst may also deactivate over time. Thus, step a) may be carried out in the presence of oxygen or air or an oxygen-nitrogen mixture. If oxygen is used in step a), it is present in an amount of 0.005 mol% to 10 mol% relative to the molar amount of fluoroolefin.

[0234] The catalyst may also be regenerated after the process is carried out. The regeneration step may comprise contacting the catalyst with a stream of oxygen or air at a temperature of from 200°C to 700°C.

[0235] Alternatively, step a) can be carried out in the gas phase in the absence of a catalyst.

[0236] Step a) is carried out at a temperature ranging from 150°C to 700°C, preferably from 250°C to 600°C, in the gas phase, in the presence or absence of a catalyst.

[0237] Regardless of whether step a) is carried out in the gas phase in the presence or absence of a catalyst, the pressure in this step is from 0.1 bar to 30 bar, preferably from 1 bar to 20 bar, in particular from 1 bar to 15 bar.

[0238] Liquid phase step a)

[0239] Alternatively, step a) is carried out in liquid phase. The temperature at which step a) is carried out in liquid phase is 50°C to 280°C, preferably 50°C to 250°C.

[0240] Step a) can be carried out in the presence of solvent S1. Preferably, solvent S1 is anhydrous. The term "anhydrous" herein means that solvent S1 contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferably less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the solvent S1 is free of water. Solvent S1 has a boiling point of 0°C-250°C, preferably 20°C-250°C, in particular 20°C-200°C. The solvent S1 is selected from acetic acid, CCl 4 , chloroform, dichloromethane, sulfolane, tetramethylene sulfone, N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone, and mixtures thereof.

[0241] According to one embodiment, step a) is carried out in the presence of a catalyst selected from alkali metal or alkaline earth metal salts. Preferably, the catalyst is an alkali metal salt. Any alkali metal iodide may be used, but preferably sodium iodide or potassium iodide is used. The ratio between the catalyst and the olefin (preferably the fluoroolefin as described above) is 1-20, preferably 1-10. The catalyst preferably has 20-1000 m 2 / g, especially 20-300m 2 The catalyst may be deposited on a porous support. The porous support may be selected from activated carbon, graphite, alumina and alumina fluoride.

[0242] According to another embodiment, step a) is carried out in the presence of a Lewis acid catalyst, a catalyst comprising a metal halide, in particular antimony, tin, tantalum or titanium, or a transition metal halide such as molybdenum, niobium or iron. For example, the catalyst may be SbF 5 , SbF 3 、TiF 4 、SnF 4 、TaF 5 ,NbF 5 、TiF 4 , FeF3 or MoF 6 Preferably, the catalyst is liquid at the temperature at which step a) is carried out. Therefore, when using these catalysts to carry out step a), the presence of solvent S1 is optional.

[0243] According to another embodiment, the process may be carried out in the presence of a mixture of fluoroolefins as defined above resulting in the production of a mixture of iodofluoroalkane compounds in said stream A and in said stream B1 .

[0244] As described above, step a) makes it possible to obtain a stream A comprising the iodofluoroalkane compound and optionally unreacted iodine monofluoride. 2 ) and anhydrous iodine pentafluoride (IF 5 ) is mixed and prepared, the logistics A may also include unreacted iodine and / or iodine pentafluoride. Logistics A may also include other compounds such as impurities, reaction by-products (e.g., products obtained by adding one or more iodine or fluorine atoms to one or more carbon atoms of olefins) or even unreacted olefins.

[0245] Step b) of the process

[0246] The stream A is purified to form a stream B1 comprising at least 90% by weight of the iodofluoroalkane compound. Preferably, after purification, the content of the iodofluoroalkane compound in the stream B1 is greater than 92%, advantageously greater than 94%, preferably greater than 96%, more preferentially greater than 98%, in particular greater than 99%, more particularly greater than 99.5%. The stream A is preferably purified by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent or a combination thereof. The stream A may also be purified by contact with an adsorbent. The adsorbent may be a molecular sieve or zeolite having pore openings with an average diameter of 3-11 angstroms, advantageously 4-10 angstroms, preferably 5-10 angstroms. The purification of the stream A may successively comprise one or more purification techniques as described above, i.e. one (sub) or more (sub) distillations, or a combination of, for example, cold separation and distillation, etc.

[0247] The purification of the stream A also results in the formation of a stream B2 comprising, for example, iodine monofluoride, or, if the stream A comprises iodine and iodine pentafluoride, iodine and iodine pentafluoride, or, if the stream A comprises unreacted olefins, unreacted olefins. Depending on the composition of the stream B2, it may be purified before being subjected to step c) to remove impurities or reaction by-products formed during step a) and possibly present in the stream A before purification. Preferably, the stream B2 comprises unreacted iodine and iodine pentafluoride and optionally unreacted iodine monofluoride and olefins.

[0248] Step c) of the process

[0249] Step c) of the process comprises recycling stream B2 to step a). This recycling step improves the overall yield of the process (better conversion) and saves expensive reagents (and catalysts), while minimizing environmental impact. Without this recycling step, unreacted iodine monofluoride (or its precursor I 2 and IF 5 ) and / or olefins will have to be incinerated, increasing the carbon footprint of the process.

[0250] If stream B1 comprises unreacted olefins, said reagents can be removed from stream B1 and also recycled into step a).

[0251] The process can be carried out continuously or in a batch or semi-batch manner.

[0252] Preferably, in order to avoid corrosion problems, the reactor in which step a) is carried out is made of a material comprising a base layer made of material M1 and an inner layer made of material M2.

[0253] Advantageously, the material M2 comprises at least 40% by weight of nickel relative to the total weight of the material M2. Preferably, the material M2 comprises at least 45% by weight of nickel relative to the total weight of the material M2, more preferentially at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel.

[0254] Material M2 may also include a chromium content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % relative to the total weight of material M2.

[0255] Material M2 may also include a molybdenum content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % based on the total weight of material M2.

[0256] Preferably, the material M2 is or

[0257] According to a preferred embodiment, material M1 comprises at least 70 wt. % iron, advantageously at least 75 wt. %, preferably at least 80 wt. %, more preferentially at least 85 wt. %, in particular at least 90 wt. %, more particularly at least 95 wt. % iron, based on the total weight of material M1.

[0258] The material M1 may also include less than 2% by weight, advantageously less than 1.5% by weight, preferably less than 1% by weight, more preferentially less than 0.75% by weight, in particular less than 0.5% by weight, more particularly less than 0.2% by weight, and well less than 0.1% by weight of carbon, based on the total weight of the material M1. More particularly, the material M1 may include 0.01% by weight to 0.2% by weight of carbon, based on the total weight of the material M1.

[0259] Preferably, the base layer and the inner layer are attached to each other by hot or cold plating, hot or cold rolling, or welding.

[0260] Example

[0261] Example 1

[0262] CF 3 -CFI-CF 3 Synthesis

[0263] The equipment used consisted of a Hastelloy C276 autoclave with a capacity of 0.8 L on which a condenser and a pressure regulating valve were mounted. The autoclave was degassed and made inert with nitrogen, and the following ingredients were introduced successively: 150 g (0.59 mol) of anhydrous iodine, 65 g (0.29 mol) of anhydrous iodine pentafluoride and 6.5 g (0.03 mol) of antimony pentafluoride (SbF 5 The autoclave was then stirred for 45 minutes and immersed in an oil bath and the temperature was raised to 80° C., while the condenser temperature was maintained at about 17° C. When the temperature of the reaction medium reached 80° C., 12.5 g / h (0.083 mol / h) of hexafluoropropylene (C 3 F 6 ).

[0264] During the reaction, volatile products are continuously removed, washed and collected. After reacting for 6 hours, the autoclave is cooled to room temperature. Then it is degassed and the reaction product is washed, dried and analyzed by gas chromatography (area percentage).

[0265] CF 3 -CFI-CF 3 The yield of CF 3 -CFI-CF 3 The ratio of the mole number of fluorinated ether to the mole number of hexafluoropropylene initially introduced was 93.6%.

[0266] Example 2

[0267] CF 3 -CF 2 -CH 2 Synthesis of I

[0268] The following were introduced successively into the same reaction assembly as in Example 1: 200 g (0.79 mol) of anhydrous iodine, 85 g (0.38 mol) of anhydrous iodine pentafluoride and 22.0 g (0.1 mol) of antimony pentafluoride (SbF 5 ). The autoclave was then stirred for 60 minutes and immersed in an oil bath and the temperature was raised to 80° C., while the condenser temperature was kept at about 17° C. When the temperature of the reaction medium reached 80° C., 11.4 g / h (0.1 mol / h) of 2,3,3,3-tetrafluoropropene (HFO-1234yf) was continuously injected.

[0269] During the reaction, volatile products are continuously removed, washed and collected. After reacting for 10 hours, the autoclave is cooled to room temperature. Then it is degassed and the reaction product is washed, dried and analyzed by gas chromatography (area percentage).

[0270] CF 3 -CF 2 -CH 2 The yield of I was detected by CF 3 -CF 2 -CH 2 The molar number of I to the initial introduction of CF 3 -CF=CH 2 The molar ratio is 80.5%.

[0271] Invention III

[0272] Summary of Invention III

[0273] The present invention relates to a process for producing an iodofluoroalkane compound comprising the following step a): contacting a hydrofluoroalkane with anhydrous iodine to form a stream A comprising said iodofluoroalkane compound, hydrogen iodide (HI) and unreacted iodine. Step a) thus allows the hydrogen atoms of said hydrofluoroalkane to be replaced with iodine atoms to form said iodofluoroalkane. Preferably, the hydrofluoroalkane is composed of carbon, hydrogen and fluorine atoms.

[0274] According to a preferred embodiment, the process comprises the following step b): during step b), the stream A is separated to form a stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted iodine; hydrogen iodide is contained in stream B1, or stream B2, or both.

[0275] According to a preferred embodiment, the process comprises a step c) of recycling the stream B2 during step c) into step a).

[0276] According to a preferred embodiment, the hydrofluoroalkane has the formula (I) (R1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group and a C 3 -C 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is H or is a group as defined above including at least one hydrogen atom.

[0277] According to a preferred embodiment, the iodofluoroalkane has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by at least one fluorine atom and / or at least one iodine atom 1 -C 10 an alkyl group, and a C 3 -C 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is I or is a group as defined above comprising at least one iodine atom.

[0278] According to a preferred embodiment, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CH(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 5 Perfluoroalkyl groups and C 5 -C 10 Perfluorocycloalkyl groups.

[0279] According to a preferred embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CFI, where R 1 and R 2 independently selected from H, F, C1 -C 5 Perfluoroalkyl groups and C 5 -C 10 Perfluorocycloalkyl groups.

[0280] According to a preferred embodiment, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of is H.

[0281] According to a preferred embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of is 1.

[0282] According to a preferred embodiment, the hydrofluoroalkane compound is selected from CH 3 F, CH 2 F 2 , CHF 3、CH 2 F-CH 3 、CHF 2 -CH 3 、CH 2 F-CH 2 F、CF 3 -CH 3 、CHF 2 -CH 2 F、CF 3 -CH 2 F、CHF 2 -CHF 2 、CF 3 -CHF 2 、CH 2 F-CH 2 -CH 3 、CH 3 -CHF-CH 3 、CH 2 F-CH 2 -CH 2 F、CHF 2 -CH 2 -CH 3 、CH 2 F-CHF-CH 3 、CH 3 -CF 2 -CH 3 、CHF 2 -CH 2 -CH 2 F、CF 3 -CH 2 -CH 3 、CH 2 F-CHF-CH 2 F、CHF 2 -CHF-CH 3 、CH 2 F-CF 2 -CH 3 、CHF 2 -CH 2 -CHF 2 、CF 3 -CH 2 -CH 2 F、CHF 2 -CHF-CH 2 F、CF 3 -CHF-CH 3 、CH 2 F-CF 2 -CH 2 F、CHF 2 -CF2 -CH 3 、CF 3 -CH 2 -CHF 2 、CHF 2 -CHF-CHF 2 、CF 3 -CHF-CH 2 F、CHF 2 -CF 2 -CH 2 F、CF 3 -CF 2 -CH 3 、CF 3 -CH 2 -CF 3 、CF 3 -CHF-CHF 2 、CHF 2 -CF 2 -CHF 2 、CF 3 -CF 2 -CH 2 F、CF 3 -CHF-CF 3 、CF 3 -CF 2 -CHF 2 ; preferably selected from CH 2 F 2 、CHF 3 、CHF 2 -CH 3 、CF 3 -CH 3 、CF 3 -CH 2 F、CF 3 -CHF 2 、CH 2 F-CHF-CH 3 、CF 3 -CH 2 -CH 3 、CF 3 -CH 2 -CH 2 F、CF 3 -CHF-CH 3 、CF 3 -CH 2 -CHF 2 、CF 3 -CHF-CH 2 F、CF 3 -CH 2 -CF3 CF 3 -CHF-CHF 2 CF 3 -CHF-CF 3 .

[0283] According to a preferred embodiment, the iodofluoroalkane compound is selected from CH 2 FI, CHFI 2 , CHF 2 I. CF 2 I 2 CF 3 I. CHFI-CH 3 , CH 2 F-CH 2 I. CFI 2 -CH 3 , CH 2 F-CHI 2 、CHFI-CH 2 I. CF 2 I-CH 3 , CHF 2 -CH 2 I. CHF 2 -CHI 2 CF 2 I-CH 2 I. CHFI-CH 2 F. CFI 2 -CH 2 F, CHFI-CHFI, CF 3 -CH 2 I. CF 3 -CHI 2 CF 2 I-CH 2 F. CHF 2 -CHFI, CHF 2 -CFI 2 CF 2 I-CHFI、CF 3 -CHFI, CF 3 -CFI 2 CF 2 I-CHF 2 CF 2 I-CF 2 I. CF 3 -CF 2 I. CHFI-CH 2 -CH 3 , CH 2 F-CHI-CH 3 , CH 2F-CH 2 -CH 2 I、CFI 2 -CH 2 -CH 3 、CH 2 F-CI 2 -CH 3 、CH 2 F-CH 2 -CHI 2 、CHFI-CHI-CH 3 、CHFI-CH 2 -CH 2 I、CH 2 F-CHI-CH 2 I、CH 2 I-CHF-CH 3 、CH 3 -CFI-CH 3 、CHI 2 -CHF-CH 3 、CH 2 I-CFI-CH 3 、CH 2 I-CHF-CH 2 I、CHFI-CH 2 -CH 2 F、CH 2 F-CHI-CH 2 F、CFI 2 -CH 2 -CH 2 F、CH 2 F-CI 2 -CH 2 F、CHFI-CHI-CH 2 F、CHFI-CH 2 -CHFI、CF 2 I-CH 2 -CH 3 、CHF 2 -CHI-CH 3 、CHF 2 -CH 2 -CH 2 I、CHF 2 -CI 2 -CH 3 、CHF 2 -CH 2 -CHI 2 、CF 2 I-CHI-CH 3 、CF 2 I-CH 2-CH 2 I、CHF 2 -CHI-CH 2 I、CHFI-CHF-CH 3 、CH 2 F-CFI-CH 3 、CH 2 F-CHF-CH 2 I、CFI 2 -CHF-CH 3 、CH 2 F-CHF-CHI 2 、CHFI-CFI-CH 3 、CHFI-CHF-CH 2 I、CH 2 F-CFI-CH 2 I、CH 2 I-CF 2 -CH 3 、CHI 2 -CF 2 -CH 3 、CH 2 I-CF 2 -CH 2 I、CF 2 I-CH 2 -CH 2 F、CHF 2 -CHI-CH 2 F、CHF 2 -CH 2 -CHFI、CHF 2 -CI 2 -CH 2 F、CHF 2 -CH 2 -CFI 2 、CF 2 I-CHI-CH 2 F、CF 2 I-CH 2 -CHFI、CHF 2 -CHI-CHFI、CF 3 -CHI-CH 3 、CF 3 -CH 2 -CH 2 I、CF 3 -CI 2 -CH 3 、CF 3 -CH 2 -CHI 2 、CF 3 -CHI-CH2 I、CHFI-CHF-CH 2 F、CH 2 F-CFI-CH 2 F、CFI 2 -CHF-CH 2 F、CHFI-CFI-CH 2 F、CHFI-CHF-CHFI、CF 2 I-CHF-CH 3 、CHF 2 -CFI-CH 3 、CHF 2 -CHF-CH 2 I、CHF 2 -CHF-CHI 2 、CF 2 I-CFI-CH 3 、CF 2 I-CHF-CH 2 I、CHF 2 -CFI-CH 2 I、CHFI-CF 2 -CH 3 、CH 2 F-CF 2 -CH 2 I、CFI 2 -CF 2 -CH 3 、CH 2 F-CF 2 -CHI 2 、CHFI-CF 2 -CH 2 I、CF 2 I-CH 2 -CHF 2 、CHF 2 -CHI-CHF 2 、CHF 2 -CI 2 -CHF 2 、CF 2 I-CHI-CHF 2 、CF 2 I-CH 2 -CF 2 I、CF 3 -CHI-CH 2 F、CF 3 -CH 2 -CHFI、CF 3 -CI 2 -CH 2 F、CF3 -CH 2 -CFI 2 、CF 3 -CHI-CHFI、CF 2 I-CHF-CH 2 F、CHF 2 -CFI-CH 2 F、CHF 2 -CHF-CHFI、CHF 2 -CHF-CFI 2 、CF 2 I-CFI-CH 2 F、CF 2 I-CHF-CHFI、CHF 2 -CFI-CHFI、CF 3 -CFI-CH 3 、CF 3 -CHF-CH 2 I、CF 3 -CHF-CHI 2 、CF 3 -CFI-CH 2 I、CHFI-CF 2 -CH 2 F、CFI 2 -CF 2 -CH 2 F、CHFI-CF 2 -CHFI、CF 2 I-CF 2 -CH 3 、CHF 2 -CF 2 -CH 2 I、CHF 2 -CF 2 -CHI 2 、CF 2 I-CF 2 -CH 2 I、CF 3 -CHI-CHF 2 、CF 3 -CH 2 -CF 2 I、CF 3 -CI 2 -CHF 2 、CF 3 -CHI-CF 2 I、CF 2 I-CHF-CHF 2 、CHF 2 -CFI-CHF2 , CF 2 I - CFI - CHF 2 , CF 2 I - CHF - CF 2 I, CF 3 - CFI - CH 2 F, CF 3 - CHF - CHFI, CF 3 - CHF - CFI 2 , CF 3 - CFI - CHFI, CF 2 I - CF 2 - CH 2 F, CHF 2 - CF 2 - CHFI, CHF 2 - CF 2 - CFI 2 , CF 2 I - CF 2 - CHFI, CF 3 - CF 2 - CH 2 I, CF 3 - CF 2 - CHI 2 , CF 3 - CHI - CF 3 , CF 3 - CI 2 - CF 3 , CF 3 - CFI - CHF 2 , CF 3 - CHF - CF 2 I, CF 3 - CFI - CF 2 I, CF 2 I - CF 2 - CHF 2 , CF 2 I - CF 2 - CF 2 I, CF 3 - CF 2 - CHFI, CF 3 - CF 2 - CFI 2 , CF 3 - CFI - CF 3 , CF 3 - CF 2 - CF 2 I; Advantageously, the iodo - fluoroalkane compound is selected from CHF 2 I, CF 2 I2 、CF 3 I、CF 2 I-CH 3 、CHF 2 -CH 2 I、CHF 2 -CHI 2 、CF 2 I-CH 2 I、CF 3 -CH 2 I、CF 3 -CHI 2 、CF 3 -CHFI、CF 3 -CFI 2 、CF 3 -CF 2 I、CHFI-CHF-CH 3 、CH 2 F-CFI-CH 3 、CH 2 F-CHF-CH 2 I、CFI 2 -CHF-CH 3 、CH 2 F-CHF-CHI 2 、CHFI-CFI-CH 3 、CHFI-CHF-CH 2 I、CH 2 F-CFI-CH 2 I、CF 3 -CHI-CH 3 、CF 3 -CH 2 -CH 2 I、CF 3 -CI 2 -CH 3 、CF 3 -CH 2 -CHI 2 、CF 3 -CHI-CH 2 I、CF 3 -CHI-CH 2 F、CF 3 -CH 2 -CHFI、CF 3 -CI 2 -CH 2 F、CF 3 -CH 2 -CFI 2 、CF 3 -CHI-CHFI、CF3 -CFI-CH 3 、CF 3 -CHF-CH 2 I、CF 3 -CHF-CHI 2 、CF 3 -CFI-CH 2 I、CF 3 -CHI-CHF 2 、CF 3 -CH 2 -CF 2 I、CF 3 -CI 2 -CHF 2 、CF 3 -CHI-CF 2 I、CF 3 -CFI-CH 2 F、CF 3 -CHF-CHFI、CF 3 -CHF-CFI 2 、CF 3 -CFI-CHFI、CF 3 -CHI-CF 3 、CF 3 -CI 2 -CF 3 、CF 3 -CFI-CHF 2 、CF 3 -CHF-CF 2 I、CF 3 -CFI-CF 2 I、CF 3 -CFI-CF 3 ; Preferably, the iodo-fluoroalkane compound is selected from CH 2 FI, CHF 2 I, CF 3 I, CHFI-CH 3 、CF 2 I-CH 3 、CHFI-CH 2 F、CF 3 -CH 2 I、CF 2 I-CH 2 F、CF 3 -CHFI、CF 2 I-CHF 2 、CF 3 -CF 2 I、CHFI-CH 2 -CH3 、CH 3 -CFI-CH 3 、CHFI-CH 2 -CH 2 F、CF 2 I-CH 2 -CH 3 、CHFI-CHF-CH 3 、CH 2 I-CF 2 -CH 3 、CF 2 I-CH 2 -CH 2 F、CF 3 -CH 2 -CH 2 I、CHFI-CHF-CH 2 F、CF 2 I-CHF-CH 3 、CHFI-CF 2 -CH 3 、CF 2 I-CH 2 -CHF 2 、CF 3 -CH 2 -CHFI、CF 2 I-CHF-CH 2 F、CF 3 -CFI-CH 3 、CHFI-CF 2 -CH 2 F、CF 2 I-CF 2 -CH 3 、CF 3 -CH 2 -CF 2 I、CF 2 I-CHF-CHF 2 、CF 3 -CHF-CHFI、CF 2 I-CF 2 -CH 2 F、CF 3 -CF 2 -CH 2 I、CF 3 -CHI-CF 3 、CF 3 -CHF-CF 2 I、CF 2 I-CF 2 -CHF 2 、CF3 -CF 2 -CHFI, CF 3 -CFI-CF 3 CF 3 -CF 2 -CF 2 I; In particular, the iodofluoroalkane compound is selected from CHF 2 I. CF 3 I. CF 2 I-CH 3 CF 3 -CH 2 I. CF 3 -CHFI, CF 3 -CF 2 I. CHFI-CHF-CH 3 CF 3 -CH 2 -CH 2 I. CF 3 -CH 2 -CHFI, CF 3 -CFI-CH 3 CF 3 -CH 2 -CF 2 I. CF 3 -CHF-CHFI, CF 3 -CHI-CF 3 CF 3 -CHF-CF 2 I. CF 3 -CFI-CF 3 .

[0284] According to a preferred embodiment, step a) involves one of the following reactions:

[0285] -CH 2 F 2 Convert to CHF 2 I or CF 2 I 2 or a mixture of the two; preferably converted to CHF 2 I;

[0286] -CHF 3 Convert to CF 3 I;

[0287] -CHF 2 -CH 3 Convert to CF 2 I-CH 3 or CHF 2 -CH 2I or CHF 2 -CHI 2 or CF 2 I-CH 2 I or a mixture thereof; preferably converted to CF 2 I-CH 3 ;

[0288] -CF 3 -CH 3 Convert to CF 3 -CH 2 I or CF 3 -CHI 2 or a mixture of the two; preferably converted to CF 3 -CH 2 I;

[0289] -CF 3 -CH 2 F to CF 3 -CHFI or CF 3 -CFI 2 or a mixture of the two; preferably converted to CF 3 -CHFI;

[0290] -CF 3 -CHF 2 Convert to CF 3 -CF 2 I;

[0291] -CH 2 F-CHF-CH 3 Converted to CHFI-CHF-CH 3 or CH 2 F-CFI-CH 3 or CH 2 F-CHF-CH 2 I or CFI 2 -CHF-CH 3 or CH 2 F-CHF-CHI 2 or CHFI-CFI-CH 3 or CHFI-CHF-CH 2 I or CH 2 F-CFI-CH 2 I or a mixture thereof; preferably converted to CHFI-CHF-CH 3 ;

[0292] -CF 3 -CH 2 -CH 3 Convert to CF 3-CHI-CH 3 or CF 3 -CH 2 -CH 2 I or CF 3 -CI 2 -CH 3 or CF 3 -CH 2 -CHI 2 or CF 3 -CHI-CH 2 I or a mixture thereof; preferably converted to CF 3 -CH 2 -CH 2 I;

[0293] -CF 3 -CH 2 -CH 2 F to CF 3 -CHI-CH 2 F or CF 3 -CH 2 -CHFI or CF 3 -CI 2 -CH 2 F or CF 3 -CH 2 -CFI 2 or CF 3 -CHI-CHFI or a mixture thereof; preferably converted to CF 3 -CH 2 -CHFI;

[0294] -CF 3 -CHF-CH 3 Convert to CF 3 -CFI-CH 3 or CF 3 -CHF-CH 2 I or CF 3 -CHF-CHI 2 or CF 3 -CFI-CH 2 I or a mixture thereof; preferably converted to CF 3 -CFI-CH 3 ;

[0295] -CF 3 -CH 2 -CHF 2 Convert to CF 3 -CHI-CHF 2 or CF 3 -CH 2 -CF2 I or CF 3 -CI 2 -CHF 2 or CF 3 -CHI-CF 2 I or a mixture thereof; preferably converted to CF 3 -CH 2 -CF 2 I;

[0296] -CF 3 -CHF-CH 2 F to CF 3 -CFI-CH 2 F or CF 3 -CHF-CHFI or CF 3 -CHF-CFI 2 or CF 3 -CFI-CHFI or a mixture thereof; preferably converted to CF 3 -CHF-CHFI;

[0297] -CF 3 -CH 2 -CF 3 Convert to CF 3 -CHI-CF 3 or CF 3 -CI 2 -CF 3 or a mixture of the two; preferably converted to CF 3 -CHI-CF 3 ;

[0298] -CF 3 -CHF-CHF 2 Convert to CF 3 -CFI-CHF 2 or CF 3 -CHF-CF 2 I or CF 3 -CFI-CF 2 I or a mixture thereof; preferably converted to CF 3 -CHF-CF 2 I; or

[0299] -CF 3 -CHF-CF 3 Convert to CF 3 -CFI-CF 3 .

[0300] According to a preferred embodiment, step a) is carried out in the presence of a catalyst selected from: antimony halides, iron halides, titanium halides or tin halides; chromium or aluminum oxides, oxyhalides or halides; and alkali metal or alkaline earth metal salts, or mixtures thereof.

[0301] According to a preferred embodiment, step a) is carried out in the gas phase at a temperature between 250°C and 700°C.

[0302] According to a preferred embodiment, step a) is carried out in liquid phase in the presence of a polar aprotic solvent, preferably at a temperature ranging from 50°C to 300°C.

[0303] Detailed description of invention III

[0304] The present invention relates to a process for producing iodofluoroalkane compounds. In particular, the process involves contacting a hydrofluoroalkane with anhydrous iodine. Thus, step a) results in the formation of a stream A comprising the iodofluoroalkane compound, hydrogen iodide and unreacted iodine.

[0305] Preferably, the process further comprises the step of separating the compounds contained in stream A. The process may further comprise the step of recycling the starting reagents.

[0306] Therefore, preferably, the process comprises the following steps:

[0307] a) contacting a hydrofluoroalkane with anhydrous iodine to form a stream A comprising the iodofluoroalkane compound, hydrogen iodide (HI) and unreacted iodine;

[0308] b) separating the stream A to form a stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted iodine; hydrogen iodide is contained in the stream B1, the stream B2 or both.

[0309] c) recycling said stream B2 into step a).

[0310] Step a) of the process

[0311] Step a) of the present process requires contacting the hydrofluoroalkane with anhydrous iodine. The term "anhydrous" herein means that the iodine contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, particularly less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the iodine is free of water. The use of anhydrous iodine in the present process prevents the formation of impurities.

[0312] The hydrofluoroalkane preferably has the formula (I) (R 1 )(R 2 )CF(R 3 ), where R1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group and a C 3 -C 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is H or is a group as defined above including at least one hydrogen atom.

[0313] The term "alkyl" means a monovalent group derived from a linear or branched alkane including the specified number of carbon atoms. The term "cycloalkyl" means a monovalent group derived from a cycloalkane including the specified number of carbon atoms.

[0314] Preferably, the alkyl or cycloalkyl group is not substituted by functional groups other than fluorine. However, the group may include several fluorine atoms in its carbon chain, for example, the group may contain 1-5 fluorine atoms, preferably 1-3 fluorine atoms.

[0315] More preferably, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group and a C 3 -C 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is H or is a group as defined above including at least one hydrogen atom.

[0316] In particular, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by 1 to 5 fluorine atoms 1 -C 5 An alkyl group and a C 5 -C 10Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is H or is a group as defined above including at least one hydrogen atom.

[0317] Therefore, advantageously, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by at least one fluorine atom and / or at least one iodine atom 1 -C 10 an alkyl group, and a C 3 -C 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is I or is a group as defined above comprising at least one iodine atom.

[0318] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms and / or at least one iodine atom 1 -C 10 an alkyl group, and a C 3 -C 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is I or is a group as defined above comprising at least one iodine atom.

[0319] In particular, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms and / or at least one iodine atom 1 -C10 an alkyl group, and a C 3 -C 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is I or is a group as defined above comprising at least one iodine atom.

[0320] According to a preferred embodiment, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CH(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 10 Perfluoroalkyl groups and C 3 -C 10 Preferably, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CH(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 5 Perfluoroalkyl groups and C 5 -C 10 Perfluorocycloalkyl groups.

[0321] In this embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(R 3 )I, where R 1 and R 2 independently selected from H, F, C 1 -C 10 Perfluoroalkyl groups and C 3 -C 10 Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(R 3 )I, where R 1 and R 2 independently selected from H, F, C 1 -C 5 Perfluoroalkyl groups and C 5 -C 10 Perfluorocycloalkyl groups.

[0322] According to another preferred embodiment, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of is H. Preferably, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of is H.

[0323] In this embodiment, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of is I. Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of is 1.

[0324] According to another preferred embodiment, the hydrofluoroalkane is selected from CH 3 F, CH 2 F 2 , CHF 3 , CH 2 F-CH 3 , CHF 2 -CH 3 , CH 2 F-CH 2 F. CF 3 -CH 3 , CHF 2 -CH 2 F. CF 3 -CH 2 F. CHF 2 -CHF 2 CF 3 -CHF 2 , CH 2 F-CH 2 -CH 3 , CH 3-CHF-CH 3 、CH 2 F-CH 2 -CH 2 F、CHF 2 -CH 2 -CH 3 、CH 2 F-CHF-CH 3 、CH 3 -CF 2 -CH 3 、CHF 2 -CH 2 -CH 2 F、CF 3 -CH 2 -CH 3 、CH 2 F-CHF-CH 2 F、CHF 2 -CHF-CH 3 、CH 2 F-CF 2 -CH 3 、CHF 2 -CH 2 -CHF 2 、CF 3 -CH 2 -CH 2 F、CHF 2 -CHF-CH 2 F、CF 3 -CHF-CH 3 、CH 2 F-CF 2 -CH 2 F、CHF 2 -CF 2 -CH 3 、CF 3 -CH 2 -CHF 2 、CHF 2 -CHF-CHF 2 、CF 3 -CHF-CH 2 F、CHF 2 -CF 2 -CH 2 F、CF 3 -CF 2 -CH 3 、CF 3 -CH 2 -CF 3 、CF 3 -CHF-CHF2 , CHF 2 -CF 2 -CHF 2 CF 3 -CF 2 -CH 2 F. CF 3 -CHF-CF 3 CF 3 -CF 2 -CHF 2 ; preferably selected from CH 2 F 2 , CHF 3 , CHF 2 -CH 3 CF 3 -CH 3 CF 3 -CH 2 F. CF 3 -CHF 2 , CH 2 F-CHF-CH 3 CF 3 -CH 2 -CH 3 CF 3 -CH 2 -CH 2 F. CF 3 -CHF-CH 3 CF 3 -CH 2 -CHF 2 CF 3 -CHF-CH 2 F. CF 3 -CH 2 -CF 3 CF 3 -CHF-CHF 2 CF 3 -CHF-CF 3 .

[0325] In this preferred embodiment, the iodofluoroalkane compound is selected from CH 2 FI, CHFI 2 , CHF 2 I. CF 2 I 2 CF 3 I. CHFI-CH 3 , CH 2 F-CH 2 I. CFI 2 -CH 3 , CH2 F-CHI 2 、CHFI-CH 2 I、CF 2 I-CH 3 、CHF 2 -CH 2 I、CHF 2 -CHI 2 、CF 2 I-CH 2 I、CHFI-CH 2 F、CFI 2 -CH 2 F、CHFI-CHFI、CF 3 -CH 2 I、CF 3 -CHI 2 、CF 2 I-CH 2 F、CHF 2 -CHFI、CHF 2 -CFI 2 、CF 2 I-CHFI、CF 3 -CHFI、CF 3 -CFI 2 、CF 2 I-CHF 2 、CF 2 I-CF 2 I、CF 3 -CF 2 I、CHFI-CH 2 -CH 3 、CH 2 F-CHI-CH 3 、CH 2 F-CH 2 -CH 2 I、CFI 2 -CH 2 -CH 3 、CH 2 F-CI 2 -CH 3 、CH 2 F-CH 2 -CHI 2 、CHFI-CHI-CH 3 、CHFI-CH 2 -CH 2 I、CH 2 F-CHI-CH 2 I、CH 2 I-CHF-CH 3 、CH3 -CFI-CH 3 、CHI 2 -CHF-CH 3 、CH 2 I-CFI-CH 3 、CH 2 I-CHF-CH 2 I、CHFI-CH 2 -CH 2 F、CH 2 F-CHI-CH 2 F、CFI 2 -CH 2 -CH 2 F、CH 2 F-CI 2 -CH 2 F、CHFI-CHI-CH 2 F、CHFI-CH 2 -CHFI、CF 2 I-CH 2 -CH 3 、CHF 2 -CHI-CH 3 、CHF 2 -CH 2 -CH 2 I、CHF 2 -CI 2 -CH 3 、CHF 2 -CH 2 -CHI 2 、CF 2 I-CHI-CH 3 、CF 2 I-CH 2 -CH 2 I、CHF 2 -CHI-CH 2 I、CHFI-CHF-CH 3 、CH 2 F-CFI-CH 3 、CH 2 F-CHF-CH 2 I、CFI 2 -CHF-CH 3 、CH 2 F-CHF-CHI 2 、CHFI-CFI-CH 3 、CHFI-CHF-CH 2 I、CH 2 F-CFI-CH 2 I、CH2 I-CF 2 -CH 3 、CHI 2 -CF 2 -CH 3 、CH 2 I-CF 2 -CH 2 I、CF 2 I-CH 2 -CH 2 F、CHF 2 -CHI-CH 2 F、CHF 2 -CH 2 -CHFI、CHF 2 -CI 2 -CH 2 F、CHF 2 -CH 2 -CFI 2 、CF 2 I-CHI-CH 2 F、CF 2 I-CH 2 -CHFI、CHF 2 -CHI-CHFI、CF 3 -CHI-CH 3 、CF 3 -CH 2 -CH 2 I、CF 3 -CI 2 -CH 3 、CF 3 -CH 2 -CHI 2 、CF 3 -CHI-CH 2 I、CHFI-CHF-CH 2 F、CH 2 F-CFI-CH 2 F、CFI 2 -CHF-CH 2 F、CHFI-CFI-CH 2 F、CHFI-CHF-CHFI、CF 2 I-CHF-CH 3 、CHF 2 -CFI-CH 3 、CHF 2 -CHF-CH 2 I、CHF 2 -CHF-CHI 2 、CF 2I-CFI-CH 3 、CF 2 I-CHF-CH 2 I、CHF 2 -CFI-CH 2 I、CHFI-CF 2 -CH 3 、CH 2 F-CF 2 -CH 2 I、CFI 2 -CF 2 -CH 3 、CH 2 F-CF 2 -CHI 2 、CHFI-CF 2 -CH 2 I、CF 2 I-CH 2 -CHF 2 、CHF 2 -CHI-CHF 2 、CHF 2 -CI 2 -CHF 2 、CF 2 I-CHI-CHF 2 、CF 2 I-CH 2 -CF 2 I、CF 3 -CHI-CH 2 F、CF 3 -CH 2 -CHFI、CF 3 -CI 2 -CH 2 F、CF 3 -CH 2 -CFI 2 、CF 3 -CHI-CHFI、CF 2 I-CHF-CH 2 F、CHF 2 -CFI-CH 2 F、CHF 2 -CHF-CHFI、CHF 2 -CHF-CFI 2 、CF 2 I-CFI-CH 2 F、CF 2 I-CHF-CHFI、CHF 2 -CFI-CHFI、CF 3 -CFI-CH3 、CF 3 -CHF-CH 2 I、CF 3 -CHF-CHI 2 、CF 3 -CFI-CH 2 I、CHFI-CF 2 -CH 2 F、CFI 2 -CF 2 -CH 2 F、CHFI-CF 2 -CHFI、CF 2 I-CF 2 -CH 3 、CHF 2 -CF 2 -CH 2 I、CHF 2 -CF 2 -CHI 2 、CF 2 I-CF 2 -CH 2 I、CF 3 -CHI-CHF 2 、CF 3 -CH 2 -CF 2 I、CF 3 -CI 2 -CHF 2 、CF 3 -CHI-CF 2 I、CF 2 I-CHF-CHF 2 、CHF 2 -CFI-CHF 2 、CF 2 I-CFI-CHF 2 、CF 2 I-CHF-CF 2 I、CF 3 -CFI-CH 2 F、CF 3 -CHF-CHFI、CF 3 -CHF-CFI 2 、CF 3 -CFI-CHFI、CF 2 I-CF 2 -CH 2 F、CHF 2 -CF 2 -CHFI、CHF 2 -CF2 -CFI 2 、CF 2 I-CF 2 -CHFI、CF 3 -CF 2 -CH 2 I、CF 3 -CF 2 -CHI 2 、CF 3 -CHI-CF 3 、CF 3 -CI 2 -CF 3 、CF 3 -CFI-CHF 2 、CF 3 -CHF-CF 2 I、CF 3 -CFI-CF 2 I、CF 2 I-CF 2 -CHF 2 、CF 2 I-CF 2 -CF 2 I、CF 3 -CF 2 -CHFI、CF 3 -CF 2 -CFI 2 、CF 3 -CFI-CF 3 、CF 3 -CF 2 -CF 2 I; Advantageously, the iodo-fluoroalkane compound is selected from CHF 2 I、CF 2 I 2 、CF 3 I、CF 2 I-CH 3 、CHF 2 -CH 2 I、CHF 2 -CHI 2 、CF 2 I-CH 2 I、CF 3 -CH 2 I、CF 3 -CHI 2 、CF 3 -CHFI、CF 3 -CFI 2 、CF 3 -CF 2I、CHFI-CHF-CH 3 、CH 2 F-CFI-CH 3 、CH 2 F-CHF-CH 2 I、CFI 2 -CHF-CH 3 、CH 2 F-CHF-CHI 2 、CHFI-CFI-CH 3 、CHFI-CHF-CH 2 I、CH 2 F-CFI-CH 2 I、CF 3 -CHI-CH 3 、CF 3 -CH 2 -CH 2 I、CF 3 -CI 2 -CH 3 、CF 3 -CH 2 -CHI 2 、CF 3 -CHI-CH 2 I、CF 3 -CHI-CH 2 F、CF 3 -CH 2 -CHFI、CF 3 -CI 2 -CH 2 F、CF 3 -CH 2 -CFI 2 、CF 3 -CHI-CHFI、CF 3 -CFI-CH 3 、CF 3 -CHF-CH 2 I、CF 3 -CHF-CHI 2 、CF 3 -CFI-CH 2 I、CF 3 -CHI-CHF 2 、CF 3 -CH 2 -CF 2 I、CF 3 -CI 2 -CHF 2 、CF 3 -CHI-CF 2I, CF 3 -CFI-CH 2 F, CF 3 -CHF-CHFI, CF 3 -CHF-CFI 2 , CF 3 -CFI-CHFI, CF 3 -CHI-CF 3 , CF 3 -CI 2 -CF 3 , CF 3 -CFI-CHF 2 , CF 3 -CHF-CF 2 I, CF 3 -CFI-CF 2 I, CF 3 -CFI-CF 3 ; Preferably, the iodo-fluoroalkane compound is selected from CH 2 FI, CHF 2 I, CF 3 I, CHFI-CH 3 , CF 2 I-CH 3 , CHFI-CH 2 F, CF 3 -CH 2 I, CF 2 I-CH 2 F, CF 3 -CHFI, CF 2 I-CHF 2 , CF 3 -CF 2 I, CHFI-CH 2 -CH 3 , CH 3 -CFI-CH 3 , CHFI-CH 2 -CH 2 F, CF 2 I-CH 2 -CH 3 , CHFI-CHF-CH 3 , CH 2 I-CF 2 -CH 3 , CF 2 I-CH 2 -CH 2 F, CF 3 -CH 2 -CH 2 I, CHFI-CHF-CH2 F, CF 2 I-CHF-CH 3 , CHFI-CF 2 -CH 3 、CF 2 I-CH 2 -CHF 2 、CF 3 -CH 2 -CHFI, CF 2 I-CHF-CH 2 F, CF 3 -CFI-CH 3 、CHFI-CF 2 -CH 2 F, CF 2 I-CF 2 -CH 3 、CF 3 -CH 2 -CF 2 I, CF 2 I-CHF-CHF 2 、CF 3 -CHF-CHFI, CF 2 I-CF 2 -CH 2 F, CF 3 -CF 2 -CH 2 I, CF 3 -CHI-CF 3 、CF 3 -CHF-CF 2 I, CF 2 I-CF 2 -CHF 2 、CF 3 -CF 2 -CHFI, CF 3 -CFI-CF 3 、CF 3 -CF 2 -CF 2 I; In particular, the iodo-fluoroalkane compound is selected from CHF 2 I, CF 3 I, CF 2 I-CH 3 、CF 3 -CH 2 I, CF 3 -CHFI, CF 3 -CF 2 I, CHFI-CHF-CH 3 、CF 3-CH 2 -CH 2 I. CF 3 -CH 2 -CHFI, CF 3 -CFI-CH 3 CF 3 -CH 2 -CF 2 I. CF 3 -CHF-CHFI, CF 3 -CHI-CF 3 CF 3 -CHF-CF 2 I. CF 3 -CFI-CF 3 .

[0326] According to a particularly preferred embodiment, step a) of the process involves one of the following reactions:

[0327] -CH 2 F 2 Convert to CHF 2 I or CF 2 I 2 or a mixture of the two; preferably converted to CHF 2 I;

[0328] -CHF 3 Convert to CF 3 I;

[0329] -CHF 2 -CH 3 Convert to CF 2 I-CH 3 or CHF 2 -CH 2 I or CHF 2 -CHI 2 or CF 2 I-CH 2 I or a mixture thereof; preferably converted to CF 2 I-CH 3 ;

[0330] -CF 3 -CH 3 Convert to CF 3 -CH 2 I or CF 3 -CHI 2 or a mixture of the two; preferably converted to CF 3 -CH 2 I;

[0331] -CF3 -CH 2 F to CF 3 -CHFI or CF 3 -CFI 2 or a mixture of the two; preferably converted to CF 3 -CHFI;

[0332] -CF 3 -CHF 2 Convert to CF 3 -CF 2 I;

[0333] -CH 2 F-CHF-CH 3 Converted to CHFI-CHF-CH 3 or CH 2 F-CFI-CH 3 or CH 2 F-CHF-CH 2 I or CFI 2 -CHF-CH 3 or CH 2 F-CHF-CHI 2 or CHFI-CFI-CH 3 or CHFI-CHF-CH 2 I or CH 2 F-CFI-CH 2 I or a mixture thereof; preferably converted to CHFI-CHF-CH 3 ;

[0334] -CF 3 -CH 2 -CH 3 Convert to CF 3 -CHI-CH 3 or CF 3 -CH 2 -CH 2 I or CF 3 -CI 2 -CH 3 or CF 3 -CH 2 -CHI 2 or CF 3 -CHI-CH 2 I or a mixture thereof; preferably converted to CF 3 -CH 2 -CH 2 I;

[0335] -CF 3 -CH 2-CH 2 F to CF 3 -CHI-CH 2 F or CF 3 -CH 2 -CHFI or CF 3 -CI 2 -CH 2 F or CF 3 -CH 2 -CFI 2 or CF 3 -CHI-CHFI or a mixture thereof; preferably converted to CF 3 -CH 2 -CHFI;

[0336] -CF 3 -CHF-CH 3 Convert to CF 3 -CFI-CH 3 or CF 3 -CHF-CH 2 I or CF 3 -CHF-CHI 2 or CF 3 -CFI-CH 2 I or a mixture thereof; preferably converted to CF 3 -CFI-CH 3 ;

[0337] -CF 3 -CH 2 -CHF 2 Convert to CF 3 -CHI-CHF 2 or CF 3 -CH 2 -CF 2 I or CF 3 -CI 2 -CHF 2 or CF 3 -CHI-CF 2 I or a mixture thereof; preferably converted to CF 3 -CH 2 -CF 2 I;

[0338] -CF 3 -CHF-CH 2 F to CF 3 -CFI-CH 2 F or CF 3 -CHF-CHFI or CF 3 -CHF-CFI 2or CF 3 -CFI-CHFI or a mixture thereof; preferably converted to CF 3 -CHF-CHFI;

[0339] -CF 3 -CH 2 -CF 3 Convert to CF 3 -CHI-CF 3 or CF 3 -CI 2 -CF 3 or a mixture of the two; preferably converted to CF 3 -CHI-CF 3 ;

[0340] -CF 3 -CHF-CHF 2 Convert to CF 3 -CFI-CHF 2 or CF 3 -CHF-CF 2 I or CF 3 -CFI-CF 2 I or a mixture thereof; preferably converted to CF 3 -CHF-CF 2 I; or

[0341] -CF 3 -CHF-CF 3 Convert to CF 3 -CFI-CF 3 .

[0342] Preferably, step a) is carried out in the presence of anhydrous hydrofluoroalkane. The term "anhydrous" herein means that the hydrofluoroalkane contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the hydrofluoroalkane is free of water. The use of anhydrous iodine and anhydrous hydrofluoroalkane in the present process prevents the formation of impurities and improves the reaction selectivity.

[0343] Preferably, iodine (I 2 ) is contacted with the hydrofluoroalkane in a stoichiometric amount or in an excess amount. For example, 2 The molar ratio of hydrofluoroalkane to hydrofluoroalkane is 1-50, preferably 2-25, especially 5-20.

[0344] Alternatively, iodine may be deficient relative to the hydrofluoroalkane. In this case, the streams A and B2 comprise the unreacted hydrofluoroalkane instead of unreacted iodine. The compound recycled into step a) is therefore the hydrofluoroalkane.

[0345] Step a) can be carried out in the presence or absence of a catalyst.

[0346] According to one embodiment, the catalyst is selected from alkali metal or alkaline earth metal salts or mixtures thereof. The alkali metal or alkaline earth metal is preferably selected from Li, Na, K, Cs, Mg and Ca. The anion bound to the metal is F - , Cl - ,I - or CO 3 2- Preferably, the catalyst is NaI or KI. The catalyst preferably has 20-1000 m 2 / g, especially 20-300m 2 The specific surface area of ​​1000 g is 1000 g. The catalyst content is 1 wt% to 30 wt% relative to the hydrofluoroalkane. For liquid phase reaction, the above catalysts are preferred.

[0347] According to another specific embodiment, the catalyst can be selected from oxides, oxyhalides or halides of metals or metalloids in columns 4 to 15 of the periodic table. The catalyst can be an oxide, oxyhalide or halide of chromium or aluminum; in particular, the halide is a fluoride. More particularly, the catalyst can be a chromium fluoride, a chromium oxyfluoride or a chromium oxide. The chromium or aluminum oxyfluoride preferably has a fluorine content of 10% to 50% by weight, preferably 20% to 50% by weight, in particular 30% to 50% by weight. The fluorine content is measured in an ion metering manner or by a weight change of the catalyst or by any other quantitative method known to those skilled in the art. The chromium oxyfluoride or chromium fluoride catalyst preferably has a fluorine content of 15-100 m 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2 / g specific surface area. The specific surface area is measured using the standard 5-point method (BET method) on a Micromeritics Gemini 2360 machine. When the catalyst is chromium oxide, chromium oxyfluoride or chromium fluoride, it may also contain 0.5 wt %-10 wt % of a promoter relative to the total weight of the catalyst. The promoter is selected from Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb and Mg. The catalyst content is preferably 0.01 wt %-20 wt %, in particular 0.1 wt %-10 wt % relative to the hydrofluoroalkane. These catalysts are preferred for carrying out step a) in the gas phase.

[0348] According to another embodiment, the catalyst may be an antimony, iron, titanium or tin based catalyst, for example an antimony, iron, titanium or tin halide based catalyst. Thus the catalyst may be SbCl 5 , SbF 5 、FeCl 3 、TiCl 4 or SnCl 4 The catalyst content is preferably 0.01% to 50% by weight, in particular 0.1% to 30% by weight, relative to the hydrofluoroalkane. These catalysts can be used in the liquid phase or the gas phase.

[0349] Therefore, the preferred catalyst for carrying out step a) is selected from SbCl 5 , SbF 5 、FeCl 3 、TiCl 4 SnCl 4 、NaI、KI、Cr 2 O 3 、Al 2 O 3 , chromium oxyfluoride, aluminum oxyfluoride, chromium fluoride and aluminum fluoride.

[0350] The above-mentioned catalysts can be deposited on a porous carrier. The porous carrier can be selected from activated carbon, graphite, alumina and alumina fluoride. When it is loaded, the catalyst is present in a mass content of 1%-50% relative to the total weight of the catalyst and the carrier.

[0351] The catalyst may be activated before it is used in step a) of the process. Activation preferably involves treating the catalyst with HF, Cl 2 ,I 2 or 2 Or logistics processing of mixtures thereof.

[0352] The catalyst may also deactivate over time. Thus, step a) may be carried out in the presence of oxygen or air or an oxygen-nitrogen mixture. If oxygen is used in step a), it is present in an amount of 0.005 mol% to 10 mol% relative to the molar amount of hydrofluoroalkane.

[0353] The catalyst may also be regenerated after the process is carried out. The regeneration step may comprise contacting the catalyst with a stream of oxygen or air at a temperature of from 200°C to 700°C.

[0354] Step a) can be carried out in the liquid phase or in the gas phase.

[0355] When it is carried out in the gas phase, step a) is also carried out at a temperature of 250°C to 700°C, preferably 300°C to 600°C.

[0356] When it is carried out in the liquid phase, step a) is also carried out at a temperature ranging from 50°C to 300°C, preferably from 50°C to 280°C.

[0357] Furthermore, when it is carried out in the liquid phase, step a) is also carried out in the presence of a polar aprotic solvent S1. Preferably, the solvent S1 is anhydrous. The term "anhydrous" herein means that the solvent S1 contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the solvent S1 is free of water. The solvent S1 has a boiling point of 0°C-250°C, preferably 20°C-250°C, in particular 20°C-200°C. The solvent S1 is selected from acetic acid, CCl 4 , chloroform, dichloromethane, sulfolane, tetramethylene sulfone, N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone, and mixtures thereof.

[0358] Step b) of the process

[0359] The stream A is then separated to form a first stream B1 comprising the iodofluoroalkane compounds and a stream B2 comprising unreacted iodine. Both the stream B1 and the stream B2 may contain impurities, reaction by-products or even unreacted hydrofluoroalkanes. Both the stream B1 and the stream B2 may optionally contain hydrogen iodide. The stream B1 is preferably subjected to an additional purification step to obtain a stream B1 comprising the purified iodofluoroalkane compounds. The stream B2 may also be subjected to an additional purification step to separate any hydrogen iodide and unreacted iodine that may be present. Preferably, after the separation and possible purification steps, the content of the iodofluoroalkane compounds in the stream B1 is greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, in particular greater than 98%, more particularly greater than 99%.

[0360] Said stream A is preferably separated and / or purified by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent or a combination thereof.

[0361] The stream A can also be separated or purified by contacting it with an adsorbent. The adsorbent can be a molecular sieve or a zeolite having pore openings with an average diameter of 3-11 angstroms, advantageously 4-10 angstroms, preferably 5-10 angstroms.

[0362] Step c) of the process

[0363] Step c) of the process comprises recycling stream B2 to step a). This recycling step improves the overall yield of the process (better conversion) and saves expensive reagents (and catalysts) while minimizing environmental impact. Without this recycling step, unreacted iodine would have to be incinerated, thereby increasing the carbon footprint of the process.

[0364] If stream B1 comprises unreacted hydrofluoroalkane, said reagent can be removed from stream B1 and can also be recycled into step a).

[0365] The process can be carried out continuously or in a batch or semi-batch manner.

[0366] Preferably, in order to avoid corrosion problems, the reactor in which step a) is carried out is made of a material comprising a base layer made of material M1 and an inner layer made of material M2.

[0367] Advantageously, the material M2 comprises at least 40% by weight of nickel relative to the total weight of the material M2. Preferably, the material M2 comprises at least 45% by weight of nickel relative to the total weight of the material M2, more preferentially at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel.

[0368] Material M2 may also include a chromium content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % relative to the total weight of material M2.

[0369] Material M2 may also include a molybdenum content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % based on the total weight of material M2.

[0370] Preferably, the material M2 is or

[0371] According to a preferred embodiment, material M1 comprises at least 70 wt. % iron, advantageously at least 75 wt. %, preferably at least 80 wt. %, more preferentially at least 85 wt. %, in particular at least 90 wt. %, more particularly at least 95 wt. % iron, based on the total weight of material M1.

[0372] The material M1 may also include less than 2% by weight, advantageously less than 1.5% by weight, preferably less than 1% by weight, more preferentially less than 0.75% by weight, in particular less than 0.5% by weight, more particularly less than 0.2% by weight, and well less than 0.1% by weight of carbon, based on the total weight of the material M1. More particularly, the material M1 may include 0.01% by weight to 0.2% by weight of carbon, based on the total weight of the material M1.

[0373] Preferably, the base layer and the inner layer are attached to each other by hot or cold plating, hot or cold rolling, or welding.

[0374] Example

[0375] Example 1

[0376] The equipment used consisted of a Hastelloy C276 autoclave with a capacity of 500 ml, equipped with a stirrer, a heating device and a temperature regulation system. The autoclave was degassed and made inert with nitrogen, and the following anhydrous ingredients were introduced successively: 250 ml of sulfolane, 15.0 g (0.1 mol) of sodium iodide, 67.0 g (0.5 mol) of CF 3 -CH 2 -CHF 2 (HFC-245fa) and 200.0 g (0.79 mol) anhydrous I 2 The reaction medium is brought to 170-180° C. with stirring. After 6 hours of reaction with stirring, a sample is taken out, washed and dried and then analyzed by gas chromatography (area percentage). 3 -CH 2 -CHF 2 The conversion rate of CF 3 -CH 2 -CF 2 The selectivity for I was 92%. A small amount of CF 3 -CHI-CHF 2 CF 3 -CI 2 -CHF 2 and CF 3 -CHI-CF 2 I.

[0377] Example 2

[0378] A reactor consisting of an Inconel 600 tube with an inner diameter of 28 mm and a length of 640 mm placed vertically in a tube furnace was used. The catalytic bed consisted of a 40 mm layer of corundum in the lower part, followed by an 85 mm layer of a chromium oxyfluoride catalyst containing 15 wt % to 25 wt % of fluorine. The catalyst was heated to 0.5 °C. 2The CF was preactivated at 350°C in the presence of a gaseous stream. 3 -CHF-CH 2 F(HFC-245eb) gaseous stream and anhydrous I 2 Gas flow (CF 3 -CHF-CH 2 F / I 2 Molar ratio = 1 / 2) was passed over the catalyst at a temperature of 550° C. At the reactor outlet, the gas was washed, then dried and condensed in a cold trap. A sample was taken and analyzed by gas chromatography (area percentage). CF 3 -CHF-CH 2 The conversion rate of F(HFC-245eb) was 94%. 3 The selectivity of -CHF-CHFI was 98%. A small amount of CF 3 -CFI-CH 2 F. CF 3 -CHF-CFI 2 and CF 3 -CFI-CHFI.

[0379] For CF 3 -CHF-CH 3 Convert to CF 3 -CFI-CH 3 CF 3 -CH 2 -CH 2 F to CF 3 -CH 2 -CHFI and CF 3 -CHF-CHF 2 Convert to CF 3 -CHF-CF 2 I, comparable (equal) conversion and selectivity values ​​were obtained.

[0380] Invention IV

[0381] Summary of Invention IV

[0382] According to a first aspect, the present invention relates to a process for producing iodofluoroolefin compounds, comprising the following steps:

[0383] a) Formula (I) (R 1 )(R 2 )C=CH(R 3 ) of fluoroolefins and iodine (I 2 ) are contacted in a liquid phase to form a compound of formula (II) (R 1 )(R 2)C(I)-CH(I)(R 3 ) of a diiodofluoroalkane compound;

[0384] b) dehydroiodination of the diiodofluoroalkane compound of formula (II) obtained in step a) to form a compound of formula (III) (R 1 )(R 2 )C=C(I)(R 3 ) of the iodofluoroolefin stream B;

[0385] Substituent R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0386] According to a preferred embodiment, R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that R 1 , R 2 and R 3 Not H at the same time.

[0387] According to a preferred embodiment, R 1 , R 2 and R 3 are independently selected from H, F or Y1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0388] According to a preferred embodiment, the fluoroolefin is selected from CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CH 3 -CF=CH 2 , CH 3 -CH=CHF、CH 2 F-CH=CH 2 , CH 3 -CF=CHF、CH 2 F-CF=CH 2 , CH 3 -CH=CF 2 , CH 2 F-CH=CHF, CHF 2 -CH=CH 2 , CH 3 -CF=CF 2 , CH 2 F-CF=CHF、CHF 2 -CF=CH 2 , CH 2 F-CH=CF 2 , CHF 2 -CH=CHF、CF 3 -CH=CH 2 , CH 2 F-CF=CF 2 , CHF 2 -CF=CHF、CF 3 -CF=CH 2 , CHF 2 -CH=CF 2 CF 3 -CH=CHF, CHF 2 -CF=CF 2, CF 3 -CF=CHF, CF 3 -CH=CF 2 ; Advantageously, the fluoroolefin is selected from CF 2 =CH 2 , CF 2 =CHF, CF 3 -CH=CH 2 , CF 3 -CF=CH 2 , CF 3 -CH=CHF, CF 3 -CF=CHF;

[0389] And the diiodofluoroalkane compound is selected from CHFI-CH 2 I, CF 2 I-CH 2 I, CHFI-CHFI, CF 2 I-CHFI, CH 3 -CFI-CH 2 I, CH 3 -CHI-CHFI, CH 2 F-CHI-CH 2 I, CH 3 -CFI-CHFI, CH 2 F-CFI-CH 2 I, CH 3 -CHI-CF 2 I, CH 2 F-CHI-CHFI, CHF 2 -CHI-CH 2 I, CH 3 -CFI-CF 2 I, CH 2 F-CFI-CHFI, CHF 2 -CFI-CH 2 I, CH 2 F-CHI-CF 2 I, CHF 2 -CHI-CHFI, CF 3 -CHI-CH 2 I, CH 2 F-CFI-CF 2 I, CHF 2 -CFI-CHFI, CF 3 -CFI-CH 2 I, CHF 2 -CHI-CF 2 I, CF 3 -CHI-CHFI, CHF2 -CFI-CF 2 I, CF 3 -CFI-CHFI, CF 3 -CHI-CF 2 I; Advantageously, the diiodofluoroalkane compound is selected from CF 2 I-CH 2 I, CF 2 I-CHFI, CF 3 -CHI-CH 2 I, CF 3 -CFI-CH 2 I, CF 3 -CHI-CHFI, CF 3 -CFI-CHFI;

[0390] and the iodofluoroolefin is selected from CFI=CH 2 , CHF=CHI, CF 2 =CHI, CFI=CHF, CF 2 =CFI, CH 2 =CF-CH 2 I, CH 3 -CF=CHI, CH 2 =CH-CHFI, CH 3 -CI=CHF, CH 3 -CH=CFI, CHF=CH-CH 2 I, CH 2 F-CI=CH 2 , CH 2 F-CH=CHI, CH 2 =CF-CHFI, CH 3 -CF=CFI, CHF=CF-CH 2 I, CH 2 F-CF=CHI, CH 2 =CH-CF 2 I, CH 3 -CI=CF 2 , CHF=CH-CHFI, CH 2 F-CI=CHF, CH 2 F-CH=CFI, CF 2 =CH-CH 2 I, CHF 2 -CI=CH 2 , CHF 2 -CH=CHI, CH 2 =CF-CF 2 I, CHF=CF-CHFI, CH 2F-CF=CFI, CF 2 =CF-CH 2 I, CHF 2 -CF=CHI, CHF=CH-CF 2 I, CH 2 F-CI=CF 2 、CF 2 =CH-CHFI, CHF 2 -CI=CHF, CHF 2 -CH=CFI, CF 3 -CI=CH 2 、CF 3 -CH=CHI, CHF=CF-CF 2 I, CF 2 =CF-CHFI, CHF 2 -CF=CFI, CF 3 -CF=CHI, CF 2 =CH-CF 2 I, CHF 2 -CI=CF 2 、CF 3 -CI=CHF, CF 3 -CH=CFI, CF 2 =CF-CF 2 I, CF 3 -CF=CFI, CF 3 -CI=CF 2 ; Preferably, the iodo-fluoroolefin is selected from CHI=CHF, CF 2 =CHI, CFI=CHF, CF 2 =CFI, CH 3 -CF=CHI, CH 3 -CI=CHF, CH 2 F-CI=CH 2 、CH 2 =CF-CHFI, CH 2 F-CF=CHI, CH 3 -CI=CF 2 、CH 2 F-CI=CHF, CHF 2 -CI=CH 2 、CH 2 =CF-CF 2 I, CHF=CF-CHFI, CHF 2 -CF=CHI, CH 2 F-CI=CF 2 、CHF 2 -CI=CHF, CF3 -CI=CH 2 、CHF=CF-CF 2 I. CHF 2 -CF=CFI、CF 3 -CF=CHI、CHF 2 -CI=CF 2 CF 3 -CI=CHF、CF 2 =CF-CF 2 I. CF 3 -CF=CFI、CF 3 -CI=CF 2 In particular, the iodofluoroolefin is selected from CF 2 =CHI, CF 2 =CFI, CF 3 -CI=CH 2 CF 3 -CF=CHI、CF 3 -CI=CHF、CF 3 -CF = CFI.

[0391] According to a preferred embodiment, stream B also comprises HI and the process comprises a step of separation between said iodofluoroolefin and HI.

[0392] According to a preferred embodiment, the diiodofluoroalkane compound is dried and optionally purified before being used in step b).

[0393] According to a preferred embodiment, step a) is carried out in liquid phase in the presence of a solvent selected from aqueous potassium iodide, ethers, fluorinated ethers, alcohols, fluorinated alcohols, esters, aromatic solvents, fluorinated aromatic solvents, halogenated solvents and mixtures thereof.

[0394] According to a preferred embodiment, step b) is carried out using an alkaline aqueous mixture; advantageously, the mixture comprises a base chosen from alkali metal or alkaline earth metal hydroxides; preferably, the mixture has an alkali metal or alkaline earth metal hydroxide content of 20% to 80% by weight relative to the total weight of the mixture.

[0395] According to a preferred embodiment, step b) is carried out in the gas phase and the dehydroiodination catalyst is selected from oxides, oxyhalides or halides of metals or metalloids of columns 4 to 15 of the periodic table, preferably from oxides, oxyhalides or halides of aluminum, iron or chromium.

[0396] According to a second aspect, the present invention provides a process for producing the diiodofluoroalkane compound, which comprises the following steps a): making a compound of formula (I) (R 1 )(R 2)C=CH(R 3 ) of fluoroolefins and iodine (I 2 ) are contacted in a liquid phase to form a compound of formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ) of a diiodofluoroalkane compound; wherein R 1 , R 2 and R 3 As defined above

[0397] According to a preferred embodiment, the diiodofluoroalkane compound is selected from CHFI-CH 2 I. CF 2 I-CH 2 I. CHFI-CHFI, CF 2 I-CHFI, CH 3 -CFI-CH 2 I. CH 3 -CHI-CHFI, CH 2 F-CHI-CH 2 I. CH 3 -CFI-CHFI, CH 2 F-CFI-CH 2 I. CH 3 -CHI-CF 2 I. CH 2 F-CHI-CHFI, CHF 2 -CHI-CH 2 I. CH 3 -CFI-CF 2 I. CH 2 F-CFI-CHFI, CHF 2 -CFI-CH 2 I. CH 2 F-CHI-CF 2 I. CHF 2 -CHI-CHFI, CF 3 -CHI-CH 2 I. CH 2 F-CFI-CF 2 I. CHF 2 -CFI-CHFI, CF 3 -CFI-CH 2 I. CHF 2 -CHI-CF 2 I. CF 3 -CHI-CHFI, CHF 2 -CFI-CF 2 I. CF 3-CFI-CHFI, CF 3 -CHI-CF 2 I; Advantageously, the iodofluoroalkane compound is selected from CF 2 I-CH 2 I. CF 2 I-CHFI、CF 3 -CHI-CH 2 I. CF 3 -CFI-CH 2 I. CF 3 -CHI-CHFI, CF 3 -CFI-CHFI.

[0398] According to a preferred embodiment, the diiodofluoroalkane compound is separated and purified.

[0399] DETAILED DESCRIPTION OF THE INVENTION

[0400] According to a first aspect, the present invention relates to a process for producing an iodofluoroolefin compound. Preferably, the process comprises at least one of the following steps: 1 )(R 2 )C=CH(R 3 ) of fluoroolefins and iodine (I 2 ) are contacted in a liquid phase to form a compound of formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 Preferably, the process further comprises the following steps: dehydroiodination of the diiodofluoroalkane compound of formula (II) obtained in step a) to form a diiodofluoroalkane compound of formula (III) (R 1 )(R 2 )C=C(I)(R 3 ) of the iodofluoroolefin stream B. Substituent R 1 , R 2 and R 3 As defined below.

[0401] Therefore, the process comprises the following steps:

[0402] a) Formula (I) (R 1 )(R 2 )C=CH(R 3 ) of fluoroolefins and iodine (I 2 ) are contacted in a liquid phase to form a compound of formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ) of a diiodofluoroalkane compound;

[0403] b) dehydroiodination of the diiodofluoroalkane compound of formula (II) obtained in step a) to form a compound of formula (III) (R 1 )(R 2 )C=C(I)(R 3 ) of the iodofluoroolefin stream B;

[0404] Substituent R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0405] Step a) of the process

[0406] Step a) of the process requires reacting a fluoroolefin with iodine (I 2 ) in contact in the liquid phase.

[0407] The fluoroolefin preferably has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0408] The fluoroolefin preferably has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0409] The term "alkyl" refers to a monovalent group derived from a linear or branched alkane comprising a specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane comprising a specified number of carbon atoms. The term "alkenyl" refers to a monovalent group comprising a specified number of carbon atoms and at least one carbon-carbon double bond. The term "cycloalkenyl" refers to a monovalent group derived from a cycloalkene comprising at least one carbon-carbon double bond in its cyclic portion and a specified number of carbon atoms. The term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon comprising a specified number of carbon atoms.

[0410] Preferably, the alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl groups are not substituted by functional groups other than fluorine. However, the groups may include several fluorine atoms on their carbon chains, for example, the groups may contain 1-10 fluorine atoms, preferably 1-5 fluorine atoms.

[0411] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R2 and R 3 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0412] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0413] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0414] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0415] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0416] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0417] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R3 At least one of is F or is a perfluorinated group as defined above.

[0418] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0419] Alternatively, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0420] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, I, F or Y1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0421] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0422] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3, Y 1 , Y 2 or Y 3 At least one of them is F.

[0423] According to a preferred embodiment, the fluoroolefin is selected from CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CH 3 -CF=CH 2 , CH 3 -CH=CHF、CH 2 F-CH=CH 2 , CH 3 -CF=CHF、CH 2 F-CF=CH 2 , CH 3 -CH=CF 2 , CH 2 F-CH=CHF, CHF 2 -CH=CH 2 , CH 3 -CF=CF 2 , CH 2 F-CF=CHF、CHF 2 -CF=CH 2 , CH 2 F-CH=CF 2 , CHF 2 -CH=CHF、CF 3 -CH=CH 2 , CH 2 F-CF=CF 2 , CHF 2 -CF=CHF、CF 3 -CF=CH 2 , CHF 2 -CH=CF 2 CF 3 -CH=CHF, CHF 2 -CF=CF 2 CF 3 -CF=CHF、CF 3 -CH=CF 2 Advantageously, the fluoroolefin is selected from CF 2 =CH 2 CF 2 =CHF, CF 3 -CH=CH 2 CF 3 -CF=CH 2 CF3 -CH=CHF、CF 3 -CF = CHF.

[0424] The fluoroolefin may have a boiling point of less than 100°C at atmospheric pressure. Advantageously, the fluoroolefin has a boiling point of less than 75°C at atmospheric pressure. Preferably, the fluoroolefin has a boiling point of less than 50°C at atmospheric pressure. More preferentially, the fluoroolefin has a boiling point of less than 25°C at atmospheric pressure. In particular, the fluoroolefin has a boiling point of less than 10°C at atmospheric pressure.

[0425] According to a preferred embodiment, according to the present process, step a) can be carried out in the presence of a mixture of fluoroolefins so as to result in the co-production of iodofluoroolefins via the corresponding diiodofluoroalkane compounds.

[0426] Step a) allows the formation of 1 )(R 2 )C(I)-CH(I)(R 3 ) of a diiodofluoroalkane compound, wherein R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0427] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0428] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0429] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0430] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0431] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0432] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0433] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0434] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0435] Alternatively, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0436] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, I, F or Y 1-[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0437] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0438] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2, R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0439] In particular, the diiodofluoroalkane compound is selected from CHFI-CH 2 I. CF 2 I-CH 2 I. CHFI-CHFI, CF 2 I-CHFI, CH 3 -CFI-CH 2 I. CH 3 -CHI-CHFI, CH 2 F-CHI-CH 2 I. CH 3 -CFI-CHFI, CH 2 F-CFI-CH 2 I. CH 3 -CHI-CF 2 I. CH 2 F-CHI-CHFI, CHF 2 -CHI-CH 2 I. CH 3 -CFI-CF 2 I. CH 2 F-CFI-CHFI, CHF 2 -CFI-CH 2 I. CH 2 F-CHI-CF 2 I. CHF 2 -CHI-CHFI, CF 3 -CHI-CH 2 I. CH 2 F-CFI-CF 2 I. CHF 2 -CFI-CHFI, CF 3 -CFI-CH 2 I. CHF 2 -CHI-CF 2 I. CF 3 -CHI-CHFI, CHF 2 -CFI-CF 2 I. CF 3 -CFI-CHFI, CF 3 -CHI-CF 2 I. More particularly, the diiodofluoroalkane compound is selected from CF 2 I-CH 2 I. CF 2I-CHFI、CF 3 -CHI-CH 2 I. CF 3 -CFI-CH 2 I. CF 3 -CHI-CHFI, CF 3 -CFI-CHFI.

[0440] Preferably, step a) allows at least one of the following reactions:

[0441] -CHF=CH 2 Conversion to CHFI-CH 2 I; or

[0442] -CF 2 =CH 2 Convert to CF 2 I-CH 2 I; or

[0443] - converting CHF=CHF into CHFI-CHFI; or

[0444] -CF 2 =CHF to CF 2 I-CHFI; or

[0445] -CH 3 -CF=CH 2 Convert to CH 3 -CFI-CH 2 I; or

[0446] -CH 3 -CH=CHF is converted to CH 3 -CHI-CHFI; or

[0447] -CH 2 F-CH=CH 2 Convert to CH 2 F-CHI-CH 2 I; or

[0448] -CH 3 -CF = CHF to CH 3 -CFI-CHFI; or

[0449] -CH 2 F-CF=CH 2 Convert to CH 2 F-CFI-CH 2 I; or

[0450] -CH 3 -CH=CF 2Convert to CH 3 -CHI-CF 2 I; or

[0451] -CH 2 F-CH = CHF to CH 2 F-CHI-CHFI; or

[0452] -CHF 2 -CH=CH 2 Convert to CHF 2 -CHI-CH 2 I; or

[0453] -CH 3 -CF=CF 2 Convert to CH 3 -CFI-CF 2 I; or

[0454] -CH 2 F-CF = CHF to CH 2 F-CFI-CHFI; or

[0455] -CHF 2 -CF=CH 2 Convert to CHF 2 -CFI-CH 2 I; or

[0456] -CH 2 F-CH=CF 2 Convert to CH 2 F-CHI-CF 2 I; or

[0457] -CHF 2 -CH=CHF is converted to CHF 2 -CHI-CHFI; or

[0458] -CF 3 -CH=CH 2 Convert to CF 3 -CHI-CH 2 I; or

[0459] -CH 2 F-CF=CF 2 Convert to CH 2 F-CFI-CF 2 I; or

[0460] -CHF 2 -CF = CHF converted to CHF 2 -CFI-CHFI; or

[0461] -CF 3 -CF=CH 2 Convert to CF 3 -CFI-CH 2 I; or

[0462] -CHF 2 -CH=CF 2 Convert to CHF 2 -CHI-CF 2 I; or

[0463] -CF 3 -CH=CHF is converted to CF 3 -CHI-CHFI;

[0464] -CHF 2 -CF=CF 2 Convert to CHF 2 -CFI-CF 2 I; or

[0465] -CF 3 -CF = CHF to CF 3 -CFI-CHFI; or

[0466] -CF 3 -CH=CF 2 Convert to CF 3 -CHI-CF 2 I.

[0467] Preferably, step a) is carried out in the absence of a catalyst. Preferably, step a) is carried out in the presence of solvent S1. Preferably, solvent S1 is selected from potassium iodide aqueous solution, ether, fluorinated ether, alcohol, fluorinated alcohol, ester, aromatic solvent, fluorinated aromatic solvent, halogenated solvent and mixture thereof. Advantageously, solvent S1 is selected from potassium iodide aqueous solution, ethyl and methyl ether, hydrofluoroether, ethanol and methanol, ethyl lactate, toluene, xylene, p-chlorotrifluoromethylbenzene, hexafluorobenzene, tetrachloromethane, chloroform, methylene dichloride, 1-propane bromo and mixture thereof. The use of solvent in this process makes it possible to avoid the blocking problem relevant to the sublimation of iodine and the formation of limiting impurities (reaction byproducts, polymers derived from fluoroolefins, etc.), which makes it possible to achieve particularly favorable selectivity from an industrial point of view.

[0468] Preferably, iodine is contacted with the fluoroolefin as defined above in a stoichiometric amount or in excess. 2 The molar ratio of olefin to olefin is 0.1-50, preferably 0.5-25, especially 1-20.

[0469] Preferably, the content of oxygen dissolved in the solvent S1 is less than 3000 ppm, advantageously less than 2000 ppm, preferably less than 1000 ppm, more preferentially less than 500 ppm, in particular less than 250 ppm, more particularly less than 100 ppm, preferably less than 50 ppm, preferentially preferably less than 10 ppm. This avoids degradation (deterioration) of the starting materials and the desired product. The solvent S1 preferably has a boiling point of 0°C-250°C, preferably 20°C-250°C, in particular 20°C-200°C.

[0470] The temperature at which step a) is carried out is 20-280° C., preferably 30-250° C. Step a) may be carried out at a pressure of 0.1-15 bar, preferably 1-10 bar abs.

[0471] The diiodofluoroalkane compound may be dried before use in step b). This allows removal of any traces of water that may be present. Drying may be carried out by contact with an adsorbent, an absorbent, a 3-5 angstrom molecular sieve or a zeolite.

[0472] The diiodofluoroalkane compound may be purified before being used in step b). The purification may be carried out before or after the drying step. This allows the removal of certain impurities that may be difficult to separate from the iodofluoroalkene compound obtained in step b). This step also makes it possible to improve the selectivity of step b). The purification may be carried out by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent, or by contact with an adsorbent, or a combination thereof. Advantageously, the purification of the diiodofluoroalkane compound involves the production of a stream A in which the content of diiodofluoroalkane compound is greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, in particular greater than 98%, more particularly greater than 99%. This stream A is then used in step b).

[0473] When step a) is carried out using a mixture of fluoroolefins, it provides, if purification is carried out, a mixture of diiodofluoroalkane compounds or a specific diiodofluoroalkane compound, depending on the conditions used to carry out the purification.

[0474] The dried diiodofluoroalkane compound can be purified as described above or used as such in step b). The dried diiodofluoroalkane compound is used directly in step b) without purification after the drying step, for example when step a) is carried out with high conversion and selectivity, for example greater than 90%, preferably greater than 95%. The absence of purification between step a) and step b) can be advantageous from the point of view of the overall productivity of the process, since the purification step can incur significant costs.

[0475] The diiodofluoroalkane compound used in step b) is preferably anhydrous, i.e. the stream containing the diiodofluoroalkane compound used in step b) is anhydrous. The term "anhydrous" herein means that the water mass content in the stream containing the diiodofluoroalkane compound and used in step b) is less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, particularly less than 25 ppm water, more particularly less than 10 ppm, more preferably less than 5 ppm water; preferably, the diiodofluoroalkane compound or the stream containing it used in step b) does not contain water.

[0476] Step b) of the process

[0477] Step b) of the present process is to dehydroiodinate the diiodofluoroalkane compound of formula (II) obtained in step a) to form a compound of formula (III) (R 1 )(R 2 )C=C(I)(R 3 ) of the stream B of the iodofluoroolefin.

[0478] The iodofluoroolefin obtained in step b) has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0479] The iodofluoroolefin preferably has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1, R 2 and R 3 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0480] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0481] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3are independently selected from H, F, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0482] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0483] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C optionally substituted by 1 to 5 fluorine atoms1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0484] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0485] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0486] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0487] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 or R 3 At least one of is F or is a perfluorinated group as defined above.

[0488] Alternatively, the iodofluoroolefin has the formula (III) (R1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0489] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0490] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0491] Preferably, the iodofluoroolefin has the formula (III) (R 1 )(R 2 )C=C(I)(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0492] In particular, the iodofluoroolefin is selected from CFI=CH 2 、CHF=CHI、CF 2 =CHI, CFI =CHF, CF 2 =CFI, CH 2 =CF-CH 2 I. CH 3 -CF=CHI、CH 2 =CH-CHFI, CH 3 -CI=CHF、CH 3 -CH=CFI、CHF=CH-CH 2 I. CH 2 F-CI=CH 2 , CH 2 F-CH=CHI、CH 2 =CF-CHFI, CH 3 -CF=CFI、CHF=CF-CH 2 I. CH 2F-CF=CHI、CH 2 =CH-CF 2 I、CH 3 -CI=CF 2 、CHF=CH-CHFI、CH 2 F-CI=CHF、CH 2 F-CH=CFI、CF 2 =CH-CH 2 I、CHF 2 -CI=CH 2 、CHF 2 -CH=CHI、CH 2 =CF-CF 2 I、CHF=CF-CHFI、CH 2 F-CF=CFI、CF 2 =CF-CH 2 I、CHF 2 -CF=CHI、CHF=CH-CF 2 I、CH 2 F-CI=CF 2 、CF 2 =CH-CHFI、CHF 2 -CI=CHF、CHF 2 -CH=CFI、CF 3 -CI=CH 2 、CF 3 -CH=CHI、CHF=CF-CF 2 I、CF 2 =CF-CHFI、CHF 2 -CF=CFI、CF 3 -CF=CHI、CF 2 =CH-CF 2 I、CHF 2 -CI=CF 2 、CF 3 -CI=CHF、CF 3 -CH=CFI、CF 2 =CF-CF 2 I、CF 3 -CF=CFI、CF 3 -CI=CF 2 ; Preferably, the iodo-fluoroolefin is selected from CHI=CHF, CF 2 =CHI、CFI=CHF、CF 2 =CFI、CH 3 -CF=CHI、CH 3 -CI=CHF、CH 2 F-CI=CH2 , CH 2 =CF-CHFI, CH 2 F-CF=CHI、CH 3 -CI=CF 2 , CH 2 F-CI=CHF、CHF 2 -CI=CH 2 , CH 2 =CF-CF 2 I. CHF=CF-CHFI, CHF 2 -CF=CHI、CH 2 F-CI=CF 2 , CHF 2 -CI=CHF、CF 3 -CI=CH 2 、CHF=CF-CF 2 I. CHF 2 -CF=CFI、CF 3 -CF=CHI、CHF 2 -CI=CF 2 CF 3 -CI=CHF、CF 2 =CF-CF 2 I. CF 3 -CF=CFI、CF 3 -CI=CF 2 In particular, the iodofluoroolefin is selected from CF 2 =CHI, CF 2 =CFI, CF 3 -CI=CH 2 CF 3 -CF=CHI、CF 3 -CI=CHF、CF 3 -CF = CFI.

[0493] Preferably, step b) allows at least one of the following reactions:

[0494] -CHFI-CH 2 I is converted to CHI=CHF;

[0495] -CF 2 I-CH 2 I to CF 2 =CHI;

[0496] -Convert CHFI-CHFI into CFI=CHF;

[0497] -CF 2 I-CHFI to CF2 =CFI;

[0498] -CH 3 -CFI-CH 2 I to CH 3 -CF = CHI;

[0499] -CH 3 -CHI-CHFI is converted to CH 3 -CI = CHF;

[0500] -CH 2 F-CHI-CH 2 I to CH 2 F-CI=CH 2 ;

[0501] -CH 3 -CFI-CHFI is converted to CH 2 =CF-CHFI;

[0502] -CH 2 F-CFI-CH 2 I to CH 2 F-CF = CHI;

[0503] -CH 3 -CHI-CF 2 I to CH 3 -CI=CF 2 ;

[0504] -CH 2 F-CHI-CHFI is converted to CH 2 F-CI = CHF;

[0505] -CHF 2 -CHI-CH 2 I to CHF 2 -CI=CH 2 ;

[0506] -CH 3 -CFI-CF 2 I to CH 2 =CF-CF 2 I;

[0507] -CH 2 F-CFI-CHFI is converted to CHF = CF-CHFI;

[0508] -CHF 2 -CFI-CH 2 I to CHF 2-CF = CHI;

[0509] -CH 2 F-CHI-CF 2 I to CH 2 F-CI=CF 2 ;

[0510] -CHF 2 -CHI-CHFI is converted to CHF 2 -CI = CHF;

[0511] -CF 3 -CHI-CH 2 I to CF 3 -CI=CH 2 ;

[0512] -CH 2 F-CFI-CF 2 I is converted to CHF = CF-CF 2 I;

[0513] -CHF 2 -CFI-CHFI to CHF 2 -CF = CFI;

[0514] -CF 3 -CFI-CH 2 I to CF 3 -CF = CHI;

[0515] -CHF 2 -CHI-CF 2 I to CHF 2 -CI=CF 2 ;

[0516] -CF 3 -CHI-CHFI to CF 3 -CI = CHF;

[0517] -CHF 2 -CFI-CF 2 I to CF 2 =CF-CF 2 I;

[0518] -CF 3 -CFI-CHFI conversion to CF 3 -CF = CFI;

[0519] -CF 3 -CHI-CF 2 I to CF 3-CI=CF 2 .

[0520] Gas phase step b)

[0521] Step b) can be carried out in the gas phase.

[0522] Step b) can be carried out in the gas phase and in the presence or absence of a catalyst.

[0523] Preferably, the dehydroiodination catalyst is selected from oxides, oxyhalides or halides of metals or metalloids from columns 4 to 15 of the periodic table or of metals selected from Li, Na, K, Cs, Mg, Ca, Al and Sb.

[0524] In particular, the dehydroiodination catalyst is selected from aluminum, iron or chromium oxides, oxyhalides or halides. Preferably, the catalyst is chromium oxide, chromium oxyfluoride or chromium fluoride. The chromium oxyfluoride preferably has a fluorine content of 10% to 50% by weight, preferably 20% to 50% by weight, in particular 30% to 50% by weight. The fluorine content is measured in an ion metering manner or by a weight change of the catalyst or by any other quantitative method known to those skilled in the art. The chromium oxyfluoride or chromium fluoride catalyst preferably has a fluorine content of 15-100% by weight. 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2 The specific surface area is measured on a Micromeritics Gemini 2360 machine using a standard 5-point method (BET method). When the catalyst is a chromium oxide, a chromium oxyfluoride or a chromium fluoride, it may further comprise a promoter in an amount of 0.5 wt % to 10 wt % relative to the total weight of the catalyst. The promoter is selected from Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb and Mg.

[0525] When the catalyst is selected from oxides, oxyhalides or halides of metals or metalloids of columns 4 to 15 of the periodic table, it may be activated before it is used in step b). For example, the catalyst may be activated in the presence of oxygen, air, hydrogen iodide or HF or a mixture thereof. The catalyst may also be regenerated after carrying out the process. The regeneration step may comprise contacting the catalyst with a stream of oxygen or air at a temperature of 200° C. to 700° C. The catalyst may also be deactivated over time. Thus, step b) may be carried out in the presence of oxygen or air or an oxygen-nitrogen mixture. If oxygen is used in step b), it is present in an amount of 0.005 mol% to 10 mol% relative to the molar amount of fluoroolefin.

[0526] When the metal is selected from Li, Na, K, Cs, Mg, Ca, Al and Sb, the anion bound to the metal is F- , Cl - ,I - or CO 3 2- Preferably, the catalyst is NaI, KI, SbF 5 , AlF 3 or SbCl 5 The catalyst preferably has a mass of 20-1000 m 2 / g, especially 20-300m 2 When the metal of the catalyst is selected from Li, Na, K, Cs, Mg, Ca, Al and Sb, the catalyst content is 1 wt% to 30 wt% relative to the fluoroolefin.

[0527] The catalyst may be deposited on a porous support. The porous support may be selected from activated carbon, graphite, alumina and alumina fluoride.

[0528] According to a preferred embodiment, step b) is carried out in the gas phase, in the presence or absence of a catalyst, at a pressure ranging from 1 bar absolute to 20 bar absolute, preferably from 3 to 15 bar absolute.

[0529] According to a preferred embodiment, step b) is carried out at a temperature ranging from 150°C to 700°C, preferably from 250°C to 600°C, in the gas phase, in the presence or absence of a catalyst.

[0530] According to a preferred embodiment, stream B also comprises HI. The process thus comprises a step of separation between the iodofluoroolefin and HI.

[0531] Step b) in a non-aqueous liquid phase

[0532] Step b) can be carried out in a non-aqueous liquid phase in the presence or absence of a catalyst. Preferably, step b) is carried out in a non-aqueous liquid phase and in the presence of a solvent S2. Preferably, solvent S2 is anhydrous. The term "anhydrous" herein means that solvent S2 contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferably less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the solvent S2 is free of water. Solvent S2 has a boiling point of 0°C-250°C, preferably 20°C-250°C, in particular 20°C-200°C. The solvent S2 is selected from acetic acid, CCl 4, chloroform, dichloromethane, sulfolane, tetramethylene sulfone, N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone, and mixtures thereof.

[0533] Preferably, step b) is carried out in a non-aqueous liquid phase in the presence of a catalyst selected from alkali metal or alkaline earth metal salts. Preferably, the catalyst is an alkali metal salt. Any alkali metal iodide may be used, but preferably sodium iodide or potassium iodide is used. The ratio between the catalyst and the fluoroolefin is 1-20, preferably 1-10. The catalyst preferably has 20-1000 m 2 / g, especially 20-300m 2 The catalyst may be deposited on a porous support. The porous support may be selected from activated carbon, graphite, alumina and alumina fluoride.

[0534] The temperature at which step b) is carried out in the non-aqueous liquid phase is between 50°C and 280°C, preferably between 50°C and 250°C.

[0535] According to a preferred embodiment, stream B also comprises HI. The process thus comprises a step of separation between the iodofluoroolefin and HI.

[0536] Aqueous phase step b)

[0537] Step b) can be carried out using an alkaline aqueous mixture. The alkaline aqueous mixture is a liquid (e.g., solution, dispersion, emulsion, or suspension) having a pH of at least 7, advantageously at least 8, preferably at least 10. A pH of at least 10 is conducive to dehydroiodination reaction. The alkaline aqueous mixture includes a base selected from alkali metal or alkaline earth metal hydroxides, oxides, carbonates, or phosphates. Preferably, the base is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, or a mixture thereof. In particular, the base is selected from alkali metal or alkaline earth metal hydroxides and mixtures thereof. More particularly, the base is selected from sodium hydroxide, potassium hydroxide, or calcium hydroxide and mixtures thereof.

[0538] Advantageously, the alkaline aqueous mixture has a content of said base, whatever the base, ranging from 20% to 80% by weight relative to the total weight of the mixture, preferably ranging from 30% to 75% by weight relative to the mixture.

[0539] In this embodiment, step b) is carried out at a temperature of 25-250°C, advantageously 25-150°C, preferably 25-100°C.

[0540] In this embodiment, in addition to the alkaline aqueous mixture, step b) can also be carried out in the presence of a non-aqueous, non-alcoholic solvent. A phase transfer catalyst can also be used. The non-aqueous and non-alcoholic solvent is selected from acetonitrile, propionitrile, butyronitrile, methylglutaronitrile, adiponitrile, benzonitrile, ethylene carbonate, propylene carbonate, methyl ethyl ketone, methyl isoamyl ketone, diisobutyl ketone, anisole, 2-methyltetrahydrofuran, tetrahydrofuran, dioxane, diglyme, triglyme, tetraglyme, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, cyclopentane, dimethyl sulfoxide, perfluoro-N-methylmorpholine, perfluorotetrahydrofuran, and mixtures thereof. Preferably, the non-aqueous and non-alcoholic solvent is selected from acetonitrile, adiponitrile, 2-methyltetrahydrofuran, tetrahydrofuran, dioxane, diglyme and tetraglyme.

[0541] The phase transfer catalyst is a substance that promotes the transfer of ionic compounds from the aqueous phase to the organic phase. The phase transfer catalyst is preferably selected from crown ethers, onium salts, cryptands, polyalkylene glycol ethers and mixtures thereof. The amount of the phase transfer catalyst is 0.001-10 mol% relative to the amount of the base in the liquid phase, advantageously 0.01-5 mol% relative to the amount of the base in the liquid phase, preferably 0.05-5 mol% relative to the amount of the base in the liquid phase.

[0542] Crown ethers are cyclic molecules in which ether groups are linked via dimethylene groups; the compounds form molecular structures capable of capturing alkali metal ions. Crown ethers include 18-crown-6 used in combination with an alkaline aqueous mixture containing KOH, 15-crown-5 used in combination with an alkaline aqueous mixture containing NaOH, and 12-crown-4 used in combination with an alkaline aqueous mixture containing LiOH. Onium salts include those having the formula R a R b R c R d P (+) X - or R a R b R c R d N (+) X-quaternary phosphonium salts and quaternary ammonium salts, wherein R a , R b , R c and R d Independently selected from C 1 -C 40 Alkyl, C 6 -C 40 Aryl or C 6 -C 40 Aralkyl group and X is selected from F, Cl, Br, I, OH, CO 3 , HCO 3 、SO4 , HSO 4 , H 2 PO 4 , HPO 4 and PO 4 For example, onium salts include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, and triphenylmethylphosphonium chloride. Polyalkylene glycol ethers include those of formula R f O(R e O) t R g A compound wherein R e is an alkylene group containing two or more carbon atoms and each R f and R g are independently H, alkyl, aryl or aralkyl and t is an integer greater than 2. Polyalkylene glycol ethers include, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol, dipropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, tetramethylene glycol, and monoalkyl ethers thereof, dialkyl ethers thereof, and polyalkylene glycols such as polyethylene glycol dimethyl ether and polyethylene glycol dibutyl ether. Among the cryptands, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-(8.8.8)hexacosane (Cryptand TM 222 and Kryptofix TM 222).

[0543] According to a preferred embodiment, depending on the base used, an iodide salt is formed. The salt may be, for example, KI, CaI 2 or NaI.

[0544] According to a preferred embodiment, step b) is carried out at a pressure of 1 bar absolute to 20 bar absolute, preferably 3 to 15 bar absolute.

[0545] Step c) of the process

[0546] Preferably, the process comprises the following step c): purifying the stream B obtained in step b) to form a stream B1 comprising the iodofluoroolefin and a stream B2 comprising impurities, by-products or unreacted starting materials. Preferably, after the purification step, the content of the iodofluoroolefin in the stream B1 is greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, in particular greater than 98%, more particularly greater than 99%. The stream B is preferably purified by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent or a combination thereof. The stream B may also be separated or purified by contact with an adsorbent. The adsorbent may be a molecular sieve or zeolite having pore openings with an average diameter of 3 angstroms to 11 angstroms, advantageously 4 angstroms to 10 angstroms, preferably 5 angstroms to 10 angstroms.

[0547] The process can be carried out continuously or in a batch or semi-batch manner. Steps a) and b) can be carried out in two different reactors or in a single reactor. When several reactors are used, they are arranged in series.

[0548] Preferably, in order to avoid corrosion problems, the reactor in which steps a) and b) are carried out is made of a material comprising a base layer made of material M1 and an inner layer made of material M2.

[0549] Advantageously, the material M2 comprises at least 40% by weight of nickel relative to the total weight of the material M2. Preferably, the material M2 comprises at least 45% by weight of nickel relative to the total weight of the material M2, more preferentially at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel.

[0550] Material M2 may also include a chromium content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % relative to the total weight of material M2.

[0551] Material M2 may also include a molybdenum content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % based on the total weight of material M2.

[0552] Preferably, the material M2 is or

[0553] According to a preferred embodiment, material M1 comprises at least 70 wt. % iron, advantageously at least 75 wt. %, preferably at least 80 wt. %, more preferentially at least 85 wt. %, in particular at least 90 wt. %, more particularly at least 95 wt. % iron, based on the total weight of material M1.

[0554] The material M1 may also include less than 2% by weight, advantageously less than 1.5% by weight, preferably less than 1% by weight, more preferentially less than 0.75% by weight, in particular less than 0.5% by weight, more particularly less than 0.2% by weight, and well less than 0.1% by weight of carbon, based on the total weight of the material M1. More particularly, the material M1 may include 0.01% by weight to 0.2% by weight of carbon, based on the total weight of the material M1.

[0555] Preferably, the base layer and the inner layer are attached to each other by hot or cold plating, hot or cold rolling, or welding.

[0556] Example

[0557] Example 1

[0558] Step a): The equipment used consisted of a 2.0 L Hastelloy C276 autoclave equipped with a pressure indicator, a temperature probe, an explosion-proof membrane and a magnetic bar stirring system. The following were introduced successively into the autoclave: 140.0 g (0.55 mol) of iodine, 750.0 g of anhydrous ethanol and 60.0 g (0.52 mol) of CF 3 -CF=CH 2 (HFO-1234yf). The reactor was heated at 85°C for 11 hours and then cooled to room temperature. After degassing and then flushing with helium, the reaction mixture was collected after opening the autoclave. The organic phase was washed, dried, and then analyzed by gas chromatography (area percentage). The analysis confirmed the formation of the diiodofluoroalkane compound CF 3 -CFI-CH 2 I (95.3% conversion and 96.1% selectivity).

[0559] Step b): A reactor consisting of an Inconel 600 tube with an internal diameter of 28 mm and a length of 640 mm, placed vertically in a tube furnace, is used. The catalytic bed consists of a 40 mm layer of corundum in the lower part, followed by an 85 mm layer of a chromium oxyfluoride catalyst containing 15% to 20% by weight of preactivated fluorine. A gas stream consisting of the washed and dried organic phase obtained from step a) and a nitrogen stream (volume ratio 1 / 2) is passed over the catalyst at a temperature of 300°C. At the reactor outlet, the gas is washed, then dried and condensed in a cold trap. A sample is taken out and analyzed by gas chromatography (area percentage). CF 3-CF = CHI yield, measured by the CF 3 The ratio of the number of moles of -CF=CHI to the number of moles of HFO-1234yf initially introduced was expressed as 83.8%.

[0560] Example 2

[0561] Example 1 was repeated, wherein the diiodofluoroalkane compound was intermediately purified by distillation to completely remove excess iodine and impurities. CF after the two reaction steps 3 The yield of -CF=CHI was about 78.7%.

[0562] Invention V

[0563] Invention V Overview

[0564] According to a first aspect, the present invention relates to a process for producing iodofluoroalkane compounds, comprising the following steps:

[0565] a) reacting olefin with iodine (I 2 ) in a liquid phase to form a diiodoalkane compound;

[0566] b) fluorinating the diiodoalkane compound with hydrogen fluoride to form a stream B comprising iodofluoroalkane compounds.

[0567] According to a preferred embodiment, the diiodoalkane compound is dried before being used in step b).

[0568] According to a preferred embodiment, the diiodoalkane compound is purified before being used in step b).

[0569] According to a preferred embodiment, the stream B further comprises unreacted hydrogen fluoride, and the stream B is separated to form a stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted hydrogen fluoride.

[0570] According to a preferred embodiment, stream B2 is recycled into step b).

[0571] According to a preferred embodiment, the olefin is a fluoroolefin.

[0572] According to a preferred embodiment, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0573] According to a preferred embodiment, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0574] According to a preferred embodiment, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0575] According to a preferred embodiment, the diiodoalkane compound obtained in step a) has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0576] According to a preferred embodiment, the diiodoalkane compound obtained in step a) has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0577] According to a preferred embodiment, the diiodoalkane compound obtained in step a) has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0578] According to a preferred embodiment, the iodofluoroalkane compound obtained in step b) has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0579] According to a preferred embodiment, the iodofluoroalkane compound obtained in step b) has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0580] According to a preferred embodiment, the iodofluoroalkane compound obtained in step b) has the formula (II) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1-[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0581] According to a preferred embodiment, the fluoroolefin is selected from CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CF 2 =CF 2 , CH 3 -CF=CH 2 , CH 3 -CH=CHF、CH 2 F-CH=CH 2 , CH 3 -CF=CHF、CH 2 F-CF=CH 2 , CH 3 -CH=CF 2 , CH 2 F-CH=CHF, CHF 2 -CH=CH 2 , CH 3 -CF=CF 2 , CH 2 F-CF=CHF、CHF 2 -CF=CH 2 , CH 2 F-CH=CF 2 , CHF 2 -CH=CHF、CF 3 -CH=CH 2 , CH 2 F-CF=CF 2 , CHF 2 -CF=CHF、CF 3 -CF=CH 2 , CHF 2 -CH=CF 2 CF 3-CH=CHF, CHF 2 -CF=CF 2 CF 3 -CF=CHF、CF 3 -CH=CF 2 CF 3 -CF=CF 2 ; preferably selected from CF 2 =CH 2 CF 2 =CHF, CF 2 =CF 2 CF 3 -CH=CH 2 CF 3 -CF=CH 2 CF 3 -CH=CHF、CF 3 -CF=CHF、CF 3 -CF=CF 2 .

[0582] According to a preferred embodiment, the diiodoalkane compound is selected from CHFI-CH 2 I. CF 2 I-CH 2 I. CHFI-CHFI, CF 2 I-CHFI、CF 2 I-CF 2 I. CH 3 -CFI-CH 2 I. CH 3 -CHI-CHFI, CH 2 F-CHI-CH 2 I. CH 3 -CFI-CHFI, CH 2 F-CFI-CH 2 I. CH 3 -CHI-CF 2 I. CH 2 F-CHI-CHFI, CHF 2 -CHI-CH 2 I. CH 3 -CFI-CF 2 I. CH 2 F-CFI-CHFI, CHF 2 -CFI-CH 2 I. CH 2 F-CHI-CF 2 I. CHF 2 -CHI-CHFI, CF 3 -CHI-CH2 I. CH 2 F-CFI-CF 2 I. CHF 2 -CFI-CHFI, CF 3 -CFI-CH 2 I. CHF 2 -CHI-CF 2 I. CF 3 -CHI-CHFI, CHF 2 -CFI-CF 2 I. CF 3 -CFI-CHFI, CF 3 -CHI-CF 2 I. CF 3 -CFI-CF 2 I; preferably selected from CF 2 I-CH 2 I. CF 2 I-CHFI、CF 2 I-CF 2 I. CF 3 -CHI-CH 2 I. CF 3 -CFI-CH 2 I. CF 3 -CHI-CHFI, CF 3 -CFI-CHFI, CF 3 -CFI-CF 2 I.

[0583] According to a preferred embodiment, the iodofluoroalkane compound is selected from CHF 2 -CH 2 I. CHFI-CH 2 F. CF 3 -CH 2 I. CF 2 I-CH 2 F. CHF 2 -CHFI, CF 3 -CHFI, CF 2 I-CHF 2 CF 3 -CF 2 I. CH 3 -CF 2 -CH 2 I. CH 3 -CFI-CH 2 F, CH 3 -CHF-CHFI, CH 3 -CHI-CHF 2 , CH2 F-CHF-CH 2 I、CH 2 F-CHI-CH 2 F、CH 3 -CF 2 -CHFI、CH 3 -CFI-CHF 2 、CH 2 F-CF 2 -CH 2 I、CH 2 F-CFI-CH 2 F、CH 3 -CHF-CF 2 I、CH 3 -CHI-CF 3 、CH 2 F-CHF-CHFI、CH 2 F-CHI-CHF 2 、CHF 2 -CHF-CH 2 I、CH 3 -CF 2 -CF 2 I、CH 3 -CFI-CF 3 、CH 2 F-CF 2 -CHFI、CH 2 F-CFI-CHF 2 、CHF 2 -CF 2 -CH 2 I、CH 2 F-CHF-CF 2 I、CHF 2 -CHF-CHFI、CHF 2 -CHI-CHF 2 、CF 3 -CHF-CH 2 I、CF 3 -CHI-CH 2 F、CH 2 F-CF 2 -CF 2 I、CHF 2 -CF 2 -CHFI、CHF 2 -CFI-CHF 2 、CF 3 -CF 2 -CH 2 I、CF 3 -CFI-CH2 F, CHF 2 -CHF-CF 2 I, CF 3 -CHF-CHFI, CF 3 -CHI-CHF 2 , CHF 2 -CF 2 -CF 2 I, CF 3 -CF 2 -CHFI, CF 3 -CFI-CHF 2 , CF 3 -CHF-CF 2 I, CF 3 -CHI-CF 3 , CF 3 -CF 2 -CF 2 I, CF 3 -CFI-CF 3 ; Advantageously, the iodo-fluoroalkane compound is selected from CHF 2 -CH 2 I, CF 2 I-CH 2 F, CF 3 -CH 2 I, CHF 2 -CHFI, CF 2 I-CHF 2 , CF 3 -CHFI, CF 3 -CF 2 I, CH 3 -CF 2 -CH 2 I, CH 3 -CHI-CHF 2 , CH 2 F-CHI-CH 2 F, CH 3 -CF 2 -CHFI, CH 2 F-CF 2 -CH 2 I, CH 3 -CHI-CF 3 , CH 2 F-CHI-CHF 2 , CHF 2 -CHI-CH 2 F, CH 3 -CFI-CF 3 , CH 2 F-CF2 -CHFI, CHF 2 -CF 2 -CH 2 I. CH 2 F-CHI-CF 3 , CHF 2 -CHI-CHF 2 CF 3 -CHI-CH 2 F, CH 2 F-CFI-CF 3 , CHF 2 -CF 2 -CHFI, CF 3 -CFI-CH 2 F. CF 3 -CF 2 -CH 2 I. CHF 2 -CHI-CF 3 CF 3 -CHI-CHF 2 , CHF 2 -CFI-CF 3 CF 3 -CFI-CHF 2 CF 3 -CF 2 -CHFI, CF 3 -CHI-CF 3 CF 3 -CFI-CF 3 Preferably, the iodofluoroalkane compound is selected from CF 3 -CH 2 I. CF 3 -CHFI, CF 3 -CF 2 I. CF 3 -CHI-CH 2 F. CF 3 -CF 2 -CH 2 I. CF 3 -CHI-CHF 2 CF 3 -CF 2 -CHFI, CF 3 -CFI-CF 3 .

[0584] According to a preferred embodiment, the process comprises:

[0585] - In step a) CF 2 =CH2 Convert to CF 2 I-CH 2 I and in step b) CF 2 I-CH 2 I fluorinated to CF 3 -CH 2 I; or

[0586] - In step a) CF 2 =CHF to CF 2 I-CHFI and in step b) CF 2 Fluorination of I-CHFI to CF 3 -CHFI; or

[0587] - In step a) CF 2 =CF 2 Convert to CF 2 I-CF 2 I and in step b) CF 2 I-CF 2 I fluorinated to CF 3 -CF 2 I; or

[0588] - In step a) CF 3 -CH=CH 2 Convert to CF 3 -CHI-CH 2 I and in step b) CF 3 -CHI-CH 2 I Fluorinated CF 3 -CHI-CH 2 F; or

[0589] - In step a) CF 3 -CF=CH 2 Convert to CF 3 -CFI-CH 2 I and in step b) CF 3 -CFI-CH 2 I fluorinated to CF 3 -CF 2 -CH 2 I; or

[0590] - In step a) CF 3 -CH=CHF is converted to CF 3 -CHI-CHFI and in step b) CF 3 -CHI-CHFI fluorination to CF 3 -CHI-CHF 2 ;or

[0591] - In step a) CF 3 -CF = CHF to CF 3 -CFI-CHFI and in step b) CF 3 -CFI-CHFI fluorination to CF 3 -CF 2 -CHFI; or

[0592] - In step a) CF 3 -CF=CF 2 Convert to CF 3 -CFI-CF 2 I and in step b) CF 3 -CFI-CF 2 I fluorinated to CF 3 -CFI-CF 3 .

[0593] According to a preferred embodiment, step b) is carried out in the gas phase at a temperature of 150°C to 700°C, preferably 250°C to 600°C.

[0594] According to a preferred embodiment, step b) is carried out in the presence of a catalyst selected from oxides, oxyhalides or halides of metals or metalloids of columns 4 to 15 of the periodic table.

[0595] According to a preferred embodiment, step b) is carried out in the presence of a catalyst in the liquid phase at a temperature ranging from -50°C to 250°C.

[0596] According to a preferred embodiment, step b) is carried out in the absence of a catalyst in the liquid phase at a temperature ranging from 20°C to 300°C.

[0597] According to a preferred embodiment, step a) is carried out in liquid phase in the presence of a solvent S1 selected from aqueous potassium iodide, ethers, fluorinated ethers, alcohols, fluorinated alcohols, esters, aromatic solvents, fluorinated aromatic solvents, halogenated solvents and mixtures thereof.

[0598] DETAILED DESCRIPTION OF THE INVENTION

[0599] According to a first aspect, the present invention relates to a process for producing iodofluoroalkane compounds. Preferably, the process comprises reacting an olefin with iodine (I 2 Preferably, the process further comprises the step of fluorinating the diiodoalkane compound obtained in step a) with hydrogen fluoride to form a stream B comprising iodofluoroalkane compounds.

[0600] Step a) of the process

[0601] Step a) of the process requires contacting the olefin with iodine in the liquid phase.

[0602] For example, the olefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C 1 -C 10 Alkyl group, C 3 -C 10 Cycloalkyl groups, C 2 -C 10 Alkenyl group, C 3 -C 10 Cycloalkenyl groups and C 6 -C 10 Aryl group.

[0603] Preferably, the olefin is a fluoroolefin.

[0604] In particular, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0605] The olefin is a fluoroolefin, preferably having the formula (I) (R1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0606] The term "alkyl" refers to a monovalent group derived from a linear or branched alkane comprising a specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane comprising a specified number of carbon atoms. The term "alkenyl" refers to a monovalent group comprising a specified number of carbon atoms and at least one carbon-carbon double bond. The term "cycloalkenyl" refers to a monovalent group derived from a cycloalkene comprising at least one carbon-carbon double bond in its cyclic portion and a specified number of carbon atoms. The term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon comprising a specified number of carbon atoms.

[0607] Preferably, the alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl groups are not substituted by functional groups other than fluorine. However, the groups may include several fluorine atoms on their carbon chains, for example, the groups may contain 1-10 fluorine atoms, preferably 1-5 fluorine atoms.

[0608] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0609] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0610] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0611] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0612] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0613] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 independently selected from H, F, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0614] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1-C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0615] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 independently selected from H, F, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0616] Alternatively, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0617] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0618] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F, and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3, R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0619] Preferably, the olefin is of formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 are independently selected from H and F for each unit n, and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0620] Preferably, the olefin is a fluoroolefin selected from the following: CHF=CH 2 CF 2 =CH 2 ,CHF=CHF,CF 2 =CHF, CF 2 =CF 2 , CH 3 -CF=CH 2 , CH 3 -CH=CHF、CH 2 F-CH=CH 2 , CH 3 -CF=CHF、CH 2 F-CF=CH 2 , CH 3 -CH=CF 2 , CH 2 F-CH=CHF, CHF 2 -CH=CH 2 , CH 3 -CF=CF 2 , CH 2 F-CF=CHF、CHF 2-CF=CH 2 , CH 2 F-CH=CF 2 , CHF 2 -CH=CHF、CF 3 -CH=CH 2 , CH 2 F-CF=CF 2 , CHF 2 -CF=CHF、CF 3 -CF=CH 2 , CHF 2 -CH=CF 2 CF 3 -CH=CHF, CHF 2 -CF=CF 2 CF 3 -CF=CHF、CF 3 -CH=CF 2 CF 3 -CF=CF 2 ; especially selected from CF 2 =CH 2 CF 2 =CHF, CF 2 =CF 2 CF 3 -CH=CH 2 CF 3 -CF=CH 2 CF 3 -CH=CHF、CF 3 -CF=CHF、CF 3 -CF=CF 2 .

[0621] The olefin, in particular the fluoroolefin as defined above, may have a boiling point below 100° C. at atmospheric pressure. Advantageously, the olefin, in particular the fluoroolefin as defined above, has a boiling point below 75° C. at atmospheric pressure. Preferably, the olefin, in particular the fluoroolefin as defined above, has a boiling point below 50° C. at atmospheric pressure. More preferentially, the olefin, in particular the fluoroolefin as defined above, has a boiling point below 25° C. at atmospheric pressure. In particular, the olefin, in particular the fluoroolefin as defined above, has a boiling point below 10° C. at atmospheric pressure.

[0622] According to a preferred embodiment, according to the present process, step a) can be carried out in the presence of an olefin or a mixture of fluoroolefins as defined above, so as to result in the co-production of an iodofluoroalkane compound via the corresponding diiodoalkane compound.

[0623] Step a) allows the formation of a diiodoalkane compound. Preferably, the diiodoalkane compound obtained in step a) has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ).

[0624] The diiodoalkane compound obtained in step a) may have the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C 1 -C 10 Alkyl group, C 3 -C 10 Cycloalkyl groups, C 2 -C 10 Alkenyl group, C 3 -C 10 Cycloalkenyl groups and C 6 -C 10 Aryl group.

[0625] Advantageously, the diiodoalkane compound obtained in step a) has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0626] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0627] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0628] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0629] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0630] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0631] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0632] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0633] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0634] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0635] Alternatively, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y1 , Y 2 or Y 3 At least one of them is F.

[0636] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0637] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0638] Preferably, the diiodoalkane compound has the formula (II) (R 1 )(R 2 )C(I)-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0639] In particular, the diiodoalkane compound is selected from CHFI-CH 2 I. CF 2 I-CH 2 I. CHFI-CHFI, CF 2 I-CHFI、CF 2 I-CF 2 I. CH 3 -CFI-CH 2 I. CH 3 -CHI-CHFI, CH 2 F-CHI-CH 2 I. CH 3 -CFI-CHFI, CH 2 F-CFI-CH 2 I. CH 3 -CHI-CF 2 I. CH 2 F-CHI-CHFI, CHF 2 -CHI-CH 2 I. CH 3 -CFI-CF 2 I. CH 2 F-CFI-CHFI, CHF 2 -CFI-CH 2 I. CH 2 F-CHI-CF 2 I. CHF2 -CHI-CHFI, CF 3 -CHI-CH 2 I. CH 2 F-CFI-CF 2 I. CHF 2 -CFI-CHFI, CF 3 -CFI-CH 2 I. CHF 2 -CHI-CF 2 I. CF 3 -CHI-CHFI, CHF 2 -CFI-CF 2 I. CF 3 -CFI-CHFI, CF 3 -CHI-CF 2 I. CF 3 -CFI-CF 2 I; more particularly selected from CF 2 I-CH 2 I. CF 2 I-CHFI、CF 2 I-CF 2 I. CF 3 -CHI-CH 2 I. CF 3 -CFI-CH 2 I. CF 3 -CHI-CHFI, CF 3 -CFI-CHFI, CF 3 -CFI-CF 2 I.

[0640] More particularly, step a) of the process involves:

[0641] -CF 2 =CH 2 Convert to CF 2 I-CH 2 I; or

[0642] -CF 2 =CHF to CF 2 I-CHFI; or

[0643] -CF 2 =CF 2 Convert to CF 2 I-CF 2 I; or

[0644] -CF 3 -CH=CH 2 Convert to CF3 -CHI-CH 2 I; or

[0645] -CF 3 -CF=CH 2 Convert to CF 3 -CFI-CH 2 I; or

[0646] -CF 3 -CH=CHF is converted to CF 3 -CHI-CHFI; or

[0647] -CF 3 -CF = CHF to CF 3 -CFI-CHFI; or

[0648] -CF 3 -CF=CF 2 Convert to CF 3 -CFI-CF 2 I.

[0649] As mentioned above, step a) may be performed using, for example, a 2 =CH 2 CF 2 =CHF, CF 2 =CF 2 CF 3 -CH=CH 2 CF 3 -CF=CH 2 CF 3 -CH=CHF、CF 3 -CF=CHF、CF 3 -CF=CF 2 A mixture of olefins is carried out to obtain a mixture comprising, for example, CF 2 I-CH 2 I. CF 2 I-CHFI、CF 2 I-CF 2 I. CF 3 -CHI-CH 2 I. CF 3 -CFI-CH 2 I. CF 3 -CHI-CHFI, CF 3 -CFI-CHFI, CF 3 -CFI-CF 2 Stream A is a mixture of diiodoalkane compounds I.

[0650] Preferably, step a) can be carried out in liquid phase. Preferably, step a) is carried out in the absence of catalyst. Preferably, step a) is carried out in the presence of solvent S1. Preferably, solvent S1 is selected from potassium iodide aqueous solution, ether, fluorinated ether, alcohol, fluorinated alcohol, ester, aromatic solvent, fluorinated aromatic solvent, halogenated solvent and mixture thereof. Advantageously, solvent S1 is selected from potassium iodide aqueous solution, ethyl and methyl ether, hydrofluoroether, ethanol and methanol, ethyl lactate, toluene, xylene, p-chlorotrifluoromethylbenzene, hexafluorobenzene, tetrachloromethane, chloroform, methylene dichloride, 1-propane bromo and mixture thereof. The use of solvent in this process makes it possible to avoid the blocking problem relevant to the sublimation of iodine and the formation of limiting impurities (reaction byproducts, polymers derived from olefins, etc.), which makes it possible to realize particularly favorable selectivity from an industrial perspective.

[0651] Preferably, iodine is contacted with the olefin, in particular with the fluoroolefin as defined above, in stoichiometric amounts or in excess. 2 The molar ratio of olefin to olefin is 0.1-50, preferably 0.5-25, especially 1-20.

[0652] Preferably, the content of oxygen dissolved in the solvent S1 is less than 3000 ppm, advantageously less than 2000 ppm, preferably less than 1000 ppm, more preferentially less than 500 ppm, in particular less than 250 ppm, more particularly less than 100 ppm, preferably less than 50 ppm, preferentially preferably less than 10 ppm. This avoids degradation (deterioration) of the starting materials and the desired product. The solvent S1 preferably has a boiling point of 0°C-250°C, preferably 20°C-250°C, in particular 20°C-200°C.

[0653] The temperature at which step a) is carried out is 20-280° C., preferably 30-250° C. Step a) may be carried out at a pressure of 0.1-15 bar, preferably 1-10 bar abs.

[0654] The diiodoalkane compound may be dried before being used in step b). This allows the removal of any traces of water that may be present. Drying may be carried out by contact with an adsorbent, an absorbent, a 3-5 angstrom molecular sieve or a zeolite. The dried diiodoalkane compound may be purified or used as is in step b).

[0655] The diiodoalkane compound may be purified before being used in step b). The purification may be carried out before or after the drying step. This allows the removal of certain impurities that may be difficult to separate from the iodofluoroalkane compound. This step also makes it possible to improve the selectivity of step b). The purification may be carried out by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent, or by contact with an adsorbent, or a combination thereof. Advantageously, the purification of the diiodoalkane compound involves the production of a stream A in which the content of diiodoalkane compound is greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, in particular greater than 98%, more particularly greater than 99%. This stream A is then used in step b).

[0656] When step a) is carried out using a mixture of olefins, it provides, if purification is carried out, a mixture of diiodoalkane compounds or a specific diiodoalkane compound, depending on the conditions used to carry out the purification.

[0657] Alternatively, the dried diiodoalkane compound can be used directly in step b) without purification after the drying step. This can be done when step a) is carried out with high conversion and selectivity, for example greater than 90%, preferably greater than 95%. The absence of purification between step a) and step b) is advantageous from the point of view of the overall productivity of the process, since the purification step can incur significant costs.

[0658] The diiodoalkane compound used in step b) is preferably anhydrous, that is, the stream containing the diiodoalkane compound used in step b) is anhydrous. The term "anhydrous" herein means that the water mass content in the stream containing the diiodoalkane compound and used in step b) is less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, especially less than 25 ppm water, more particularly less than 10 ppm, more preferably less than 5 ppm water; preferably, the diiodoalkane compound or the stream containing it used to carry out step b) does not contain water.

[0659] Step b) of the process

[0660] Step b) of the present process is a step of fluorinating the diiodoalkane compound with hydrogen fluoride to form a stream B comprising an iodofluoroalkane compound. The diiodoalkane compound is as defined above in step a) of the process. Advantageously, the iodofluoroalkane compound obtained in step b) has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2, R 3 and R 4 are independently selected from H, F, Cl, I, C 1 -C 10 Alkyl group, C 3 -C 10 Cycloalkyl groups, C 2 -C 10 Alkenyl group, C 3 -C 10 Cycloalkenyl groups and C 6 -C 10 Aryl group.

[0661] Therefore, the iodofluoroalkane compound preferably has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, Cl, I, C optionally substituted by at least one fluorine atom 1 -C 10 An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0662] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, C optionally substituted by at least one fluorine atom 1 -C 10An alkyl group, a C 3 -C 10 A cycloalkyl group, a C 2 -C 10 an alkenyl group, a C 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising at least one fluorine atom.

[0663] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0664] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R4 are independently selected from H, F, C optionally substituted by 1 to 10 fluorine atoms 1 -C 10 An alkyl group, a C 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 10 fluorine atoms 2 -C 10 Alkenyl group, C optionally substituted by 1-10 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 10 fluorine atoms.

[0665] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, I, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0666] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F, C optionally substituted by 1 to 5 fluorine atoms 1 -C 10 An alkyl group, optionally substituted by 1 to 5 fluorine atoms, 3 -C 10 Cycloalkyl group, C optionally substituted by 1 to 5 fluorine atoms 2 -C 10 Alkenyl group, optionally substituted by 1-5 fluorine atoms 3 -C 10 A cycloalkenyl group, and a C 6 -C 10 aryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a group as defined above comprising 1 to 5 fluorine atoms.

[0667] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0668] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, C 1 -C 10 Perfluoroalkyl group, C 3 -C 10 Perfluorocycloalkyl group, C 2 -C 10 Perfluoroalkenyl group, C 3 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0669] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, I, C 1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0670] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 independently selected from H, F, C1 -C 5 Perfluoroalkyl group, C 5 -C 10 Perfluorocycloalkyl group, C 2 -C 5 Perfluoroalkenyl group, C 5 -C 10 Perfluorocycloalkenyl group, C 6 -C 10 a perfluoroaryl group; provided that the substituent R 1 , R 2 , R 3 or R 4 At least one of is F or is a perfluorinated group as defined above.

[0671] Alternatively, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0672] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, I, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 5; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0673] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0674] Preferably, the iodofluoroalkane compound has the formula (III) (R 1 )(R 2 )CF-C(I)(R 3 )(R 4 ), where R 1 , R 2 , R 3 and R 4 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently from each other and for each n unit independently selected from H and F; and n is an integer from 1 to 5; provided that the substituent R1 , R 2 , R 3 , R 4 , Y 1 , Y 2 or Y 3 At least one of them is F.

[0675] Preferably, the iodofluoroalkane compound is selected from CHF 2 -CH 2 I. CHFI-CH 2 F. CF 3 -CH 2 I. CF 2 I-CH 2 F. CHF 2 -CHFI, CF 3 -CHFI, CF 2 I-CHF 2 CF 3 -CF 2 I. CH 3 -CF 2 -CH 2 I. CH 3 -CFI-CH 2 F, CH 3 -CHF-CHFI, CH 3 -CHI-CHF 2 , CH 2 F-CHF-CH 2 I. CH 2 F-CHI-CH 2 F, CH 3 -CF 2 -CHFI, CH 3 -CFI-CHF 2 , CH 2 F-CF 2 -CH 2 I. CH 2 F-CFI-CH 2 F, CH 3 -CHF-CF 2 I. CH 3 -CHI-CF 3 , CH 2 F-CHF-CHFI, CH 2 F-CHI-CHF 2 , CHF 2 -CHF-CH 2 I. CH 3 -CF 2 -CF 2 I. CH3 -CFI-CF 3 、CH 2 F-CF 2 -CHFI、CH 2 F-CFI-CHF 2 、CHF 2 -CF 2 -CH 2 I、CH 2 F-CHF-CF 2 I、CHF 2 -CHF-CHFI、CHF 2 -CHI-CHF 2 、CF 3 -CHF-CH 2 I、CF 3 -CHI-CH 2 F、CH 2 F-CF 2 -CF 2 I、CHF 2 -CF 2 -CHFI、CHF 2 -CFI-CHF 2 、CF 3 -CF 2 -CH 2 I、CF 3 -CFI-CH 2 F、CHF 2 -CHF-CF 2 I、CF 3 -CHF-CHFI、CF 3 -CHI-CHF 2 、CHF 2 -CF 2 -CF 2 I、CF 3 -CF 2 -CHFI、CF 3 -CFI-CHF 2 、CF 3 -CHF-CF 2 I、CF 3 -CHI-CF 3 、CF 3 -CF 2 -CF 2 I、CF 3 -CFI-CF 3 ; Advantageously, the iodo-fluoroalkane compound is selected from CHF 2 -CH 2 I、CF 2 I-CH2 F、CF 3 -CH 2 I、CHF 2 -CHFI、CF 2 I-CHF 2 、CF 3 -CHFI、CF 3 -CF 2 I、CH 3 -CF 2 -CH 2 I、CH 3 -CHI-CHF 2 、CH 2 F-CHI-CH 2 F、CH 3 -CF 2 -CHFI、CH 2 F-CF 2 -CH 2 I、CH 3 -CHI-CF 3 、CH 2 F-CHI-CHF 2 、CHF 2 -CHI-CH 2 F、CH 3 -CFI-CF 3 、CH 2 F-CF 2 -CHFI、CHF 2 -CF 2 -CH 2 I、CH 2 F-CHI-CF 3 、CHF 2 -CHI-CHF 2 、CF 3 -CHI-CH 2 F、CH 2 F-CFI-CF 3 、CHF 2 -CF 2 -CHFI、CF 3 -CFI-CH 2 F、CF 3 -CF 2 -CH 2 I、CHF 2 -CHI-CF 3 、CF 3 -CHI-CHF 2 、CHF 2 -CFI-CF 3 、CF 3-CFI-CHF 2 CF 3 -CF 2 -CHFI, CF 3 -CHI-CF 3 CF 3 -CFI-CF 3 Preferably, the iodofluoroalkane compound is selected from CF 3 -CH 2 I. CF 3 -CHFI, CF 3 -CF 2 I. CF 3 -CHI-CH 2 F. CF 3 -CF 2 -CH 2 I. CF 3 -CHI-CHF 2 CF 3 -CF 2 -CHFI, CF 3 -CFI-CF 3 .

[0676] Therefore, step b) of the process involves:

[0677] -CF 2 I-CH 2 I fluorinated to CF 3 -CH 2 I; or

[0678] -CF 2 Fluorination of I-CHFI to CF 3 -CHFI; or

[0679] -CF 2 I-CF 2 I fluorinated to CF 3 -CF 2 I; or

[0680] -CF 3 -CHI-CH 2 I fluorinated to CF 3 -CHI-CH 2 F; or

[0681] -CF 3 -CFI-CH 2 I fluorinated to CF 3 -CF 2 -CH 2 I; or

[0682] -CF3 -CHI-CHFI fluorination to CF 3 -CHI-CHF 2 ;or

[0683] -CF 3 -CFI-CHFI fluorination to CF 3 -CF 2 -CHFI; or

[0684] -CF 3 -CFI-CF 2 I fluorinated to CF 3 -CFI-CF 3 .

[0685] When step a) is carried out using a mixture of olefins, step b) is preferably carried out using a mixture of diiodoalkane compounds to form a mixture of iodofluoroalkane compounds.

[0686] The fluorination in step b) involves a reaction between the diiodoalkane compound and hydrofluoric acid. This allows the iodine atoms to be replaced by fluorine atoms.

[0687] Preferably, hydrofluoric acid (HF) is anhydrous. The term "anhydrous" herein means that the hydrofluoric acid contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the hydrofluoric acid is free of water. The use of anhydrous hydrofluoric acid in the present process avoids the formation of impurities. The use of anhydrous hydrofluoric acid makes it possible to achieve a selectivity that is particularly advantageous from an industrial point of view. Preferably, the hydrofluoric acid is anhydrous and in gaseous form.

[0688] Preferably, hydrofluoric acid is contacted with the diiodoalkane compound in a stoichiometric amount or in a slight excess thereof. For example, the HF / diiodoalkane compound molar ratio is 1-10, preferably 1-5. Excessive amounts of hydrofluoric acid promote the overfluorination of the diiodoalkane compound. Thus, in the presence of a molar ratio of greater than 15, a large or even dominant amount of the compound of formula (IV) (R 1 )(R 2 )CF-C(F)(R 3 )(R 4 The substituent R in the compound of formula (IV) 1 , R 2 , R 3 and R 4 As defined above for the iodofluoroalkane compound of formula (III).

[0689] Step b) can be carried out in the liquid phase or in the gas phase. Step b) can be carried out in the presence or absence of a catalyst.

[0690] Gas phase step b)

[0691] In the gas phase, step b) is carried out at a temperature ranging from 150°C to 700°C, preferably from 250°C to 600°C.

[0692] Regardless of whether step b) is carried out in the gas phase in the presence or absence of a catalyst, the pressure in this step is from 0.1 bar to 30 bar, preferably from 1 bar to 20 bar, in particular from 1 bar to 15 bar.

[0693] When step b) is carried out in the gas phase, step b) can be carried out in the presence of a catalyst. Preferably, the catalyst is selected from oxides, oxyhalides or halides of metals or metalloids of columns 4 to 15 of the periodic table. Preferably, the catalyst is chromium oxide, chromium oxyfluoride or chromium fluoride. The chromium oxyfluoride preferably has a fluorine content of 10% to 50% by weight, preferably 20% to 50% by weight, in particular 30% to 50% by weight. The fluorine content is measured in an ion metering manner or by a weight change of the catalyst or by any other quantitative method known to those skilled in the art. The chromium oxyfluoride or chromium fluoride catalyst preferably has a fluorine content of 15-100 m 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2 The specific surface area is measured on a Micromeritics Gemini 2360 machine using a standard 5-point method (BET method). When the catalyst is a chromium oxide, a chromium oxyfluoride or a chromium fluoride, it may also contain 0.5 wt % to 10 wt % of a promoter relative to the total weight of the catalyst. The promoter is selected from Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb and Mg. As a catalyst, AlF 3 、SbCl 5 and SbF 5 The catalyst may be deposited on a porous support. The porous support may be selected from activated carbon, graphite, alumina and alumina fluoride.

[0694] The catalyst may be activated before it is used in step b). For example, the catalyst may be activated in the presence of oxygen, air, HF or a mixture thereof.

[0695] The catalyst may also deactivate over time. Thus, step b) may be carried out in the presence of oxygen or air or an oxygen-nitrogen mixture. If oxygen is used in step b), it is present in an amount of 0.005 mol% to 10 mol% relative to the molar amount of diiodoalkane.

[0696] The catalyst may also be regenerated after the process is carried out. The regeneration step may comprise contacting the catalyst with a stream of oxygen or air at a temperature of from 200°C to 700°C.

[0697] Alternatively, step b) can be carried out in the gas phase in the absence of a catalyst.

[0698] Liquid phase step b)

[0699] In the liquid phase, step b) can be carried out in the presence or absence of a solvent.

[0700] Step b) can be carried out in the presence of solvent S2 in the liquid phase. Preferably, solvent S2 is anhydrous. The term "anhydrous" herein means that solvent S2 contains less than 500 ppm water, advantageously less than 250 ppm, preferably less than 100 ppm water, more preferentially less than 50 ppm water, in particular less than 25 ppm water, more particularly less than 10 ppm, preferably less than 5 ppm water; preferably, the solvent S2 is free of water. Solvent S2 has a boiling point of 0°C-250°C, preferably 20°C-250°C, in particular 20°C-200°C. The solvent S2 is selected from 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,3,3-pentafluorobutane, 1,1,2-trichloro-2,2-difluoroethane, 1,1,2-trichloro-2-fluoroethane, 1,1,2-trichloro-1,2,2-trifluoroethane, nitromethane, nitrobenzene, cyclopentane, tetramethylene sulfone, N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone, and mixtures thereof.

[0701] Step b) can be carried out in the liquid phase in the absence of a solvent. In this case, the temperature and pressure conditions are such that the diiodoalkane compound and / or hydrofluoric acid are in liquid form. In addition, if a catalyst is present, the temperature and pressure conditions can be adjusted to keep the catalyst in liquid form.

[0702] Preferably, step b) is carried out in the liquid phase in the presence of a catalyst (regardless of the presence or absence of a solvent). The catalyst may be based on one or more metals selected from the metals of columns 1 to 15 of the Periodic Table of Elements and mixtures thereof. Lewis acids may be used; catalysts based on metal halides, in particular on antimony, tin, tantalum or titanium halides, transition metal halides such as iron, niobium, molybdenum or cesium halides; transition metal oxides, halides of group IVb metals, halides of group Vb metals, fluorinated chromium halides, fluorinated chromium oxides or mixtures of the two. Metal chlorides and fluorides may be advantageously used. Examples of such catalysts include: SbCl 5 、SbCl3 、TiCl 4 SnCl 4 、TaCl 5 、NbCl 5 、TiCl 4 、FeCl 3 、MoCl 6 、CsCl、KCl、MgCl 2 and their corresponding fluorinated derivatives. Pentavalent metal halides are suitable for use.

[0703] Preferably, the stream B formed in step b) is taken off in gaseous form. This is particularly advantageous when step b) is carried out in the liquid phase. The reaction product is thus taken off from the reactor in gaseous form and at the same time all or part of the reaction mixture (solvent, starting materials) is kept in liquid form.

[0704] Step c) of the process

[0705] As mentioned above, stream B comprises iodofluoroalkane compounds. Preferably, stream B also comprises unreacted hydrogen fluoride. Stream B also comprises hydrogen iodide obtained by replacing iodine atoms with fluorine atoms. In particular, stream B is separated to form stream B1 comprising the iodofluoroalkane compounds and stream B2 comprising unreacted hydrogen fluoride and hydrogen iodide (process step c)).

[0706] Logistics B may also include a compound of formula (IV) as described above and / or unreacted diiodoalkane compounds. After separation, the compound of formula (IV) may be contained in logistics B1 or in logistics B2 or in both. In this case, logistics B1 and B2 may be purified to remove the compound of formula (IV). Unreacted diiodoalkane compounds are preferably contained in logistics B2.

[0707] The streams B, B1 and B2 are preferably separated and / or purified by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent or a combination thereof. The streams B, B1 and B2 may also be separated or purified by contact with an adsorbent. The adsorbent may be a molecular sieve or zeolite having pore openings with an average diameter of 3-11 angstroms, advantageously 4-10 angstroms, preferably 5-10 angstroms.

[0708] Preferably, stream B2 is recycled to step b); preferably, stream B2 without compound (IV) is recycled to step b). This recycling step improves the overall yield of the process (better conversion) and saves expensive reagents (and catalysts), while minimizing the environmental impact. Without this recycling step, unreacted hydrofluoric acid would have to be incinerated, thereby increasing the carbon footprint of the process.

[0709] The process can be carried out continuously or in a batch or semi-batch manner. The process can be carried out in at least two reactors connected in series or in a single reactor comprising at least two reaction zones.

[0710] Thus, as described above in this patent application, the present process involves:

[0711] - In step a) CF 2 =CH 2 Convert to CF 2 I-CH 2 I and in step b) CF 2 I-CH 2 I fluorinated to CF 3 -CH 2 I; or

[0712] - In step a) CF 2 =CHF to CF 2 I-CHFI and in step b) CF 2 Fluorination of I-CHFI to CF 3 -CHFI; or

[0713] - In step a) CF 2 =CF 2 Convert to CF 2 I-CF 2 I and in step b) CF 2 I-CF 2 I fluorinated to CF 3 -CF 2 I; or

[0714] - In step a) CF 3 -CH=CH 2 Convert to CF 3 -CHI-CH 2 I and in step b) CF 3 -CHI-CH 2 I fluorinated to CF 3 -CHI-CH 2 F; or

[0715] - In step a) CF 3 -CF=CH 2 Convert to CF 3 -CFI-CH 2 I and in step b) CF 3 -CFI-CH 2 I fluorinated to CF 3 -CF 2 -CH2 I; or

[0716] - In step a) CF 3 -CH=CHF is converted to CF 3 -CHI-CHFI and in step b) CF 3 -CHI-CHFI fluorination to CF 3 -CHI-CHF 2 ;or

[0717] - In step a) CF 3 -CF = CHF to CF 3 -CFI-CHFI and in step b) CF 3 -CFI-CHFI fluorination to CF 3 -CF 2 -CHFI; or

[0718] - In step a) CF 3 -CF=CF 2 Convert to CF 3 -CFI-CF 2 I and in step b) CF 3 -CFI-CF 2 I fluorinated to CF 3 -CFI-CF 3 .

[0719] Preferably, in order to avoid corrosion problems, the reactor in which step a) and step b) are carried out is made of a material comprising a base layer made of material M1 and an inner layer made of material M2.

[0720] Advantageously, the material M2 comprises at least 40% by weight of nickel relative to the total weight of the material M2. Preferably, the material M2 comprises at least 45% by weight of nickel relative to the total weight of the material M2, more preferentially at least 50% by weight of nickel, in particular at least 55% by weight of nickel, more particularly at least 60% by weight of nickel, preferably at least 65% by weight of nickel, more preferably at least 70% by weight of nickel.

[0721] Material M2 may also include a chromium content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % relative to the total weight of material M2.

[0722] Material M2 may also include a molybdenum content of less than 35 weight %, advantageously less than 30 weight %, preferably less than 20 weight %, more preferentially less than 15 weight %, in particular less than 10 weight %, more particularly less than 5 weight % based on the total weight of material M2.

[0723] Preferably, the material M2 is or

[0724] According to a preferred embodiment, material M1 comprises at least 70 wt. % iron, advantageously at least 75 wt. %, preferably at least 80 wt. %, more preferentially at least 85 wt. %, in particular at least 90 wt. %, more particularly at least 95 wt. % iron, based on the total weight of material M1.

[0725] The material M1 may also include less than 2% by weight, advantageously less than 1.5% by weight, preferably less than 1% by weight, more preferentially less than 0.75% by weight, in particular less than 0.5% by weight, more particularly less than 0.2% by weight, and well less than 0.1% by weight of carbon, based on the total weight of the material M1. More particularly, the material M1 may include 0.01% by weight to 0.2% by weight of carbon, based on the total weight of the material M1.

[0726] Preferably, the base layer and the inner layer are attached to each other by hot or cold plating, hot or cold rolling, or welding.

[0727] Example

[0728] Example 1-CF 3 -CFI-CF 3 Synthesis

[0729] Step a): The equipment used consisted of a 1.0 L Hastelloy C276 autoclave equipped with a pressure indicator, a temperature probe, a burst-proof membrane and a magnetic bar stirring system.

[0730] The following were successively introduced into the autoclave: 127.0 g (0.5 mol) of iodine, 83.0 g (0.5 mol) of potassium iodide, 180.0 g of water and 60.0 g (0.4 mol) of hexafluoropropylene (C 3 F 6 ). The reactor was heated to 100°C: the pressure gradually increased, then decreased and stabilized after 8 hours of reaction. The reaction system was then cooled to room temperature.

[0731] After degassing and then flushing with helium, the reaction mixture was collected after opening the autoclave.The organic phase was separated using a separatory funnel, washed and dried, and then analyzed by gas chromatography (area percent).

[0732] CF 3 -CFI-CF 2The yield of I, expressed as the detected CF 3 -CFI-CF 2 The ratio of the number of moles of I to the number of moles of hexafluoropropylene initially introduced was expressed as 81.3%. The test was repeated twice, varying the temperature between 80° C. and 100° C. Comparable (equal) yield values ​​were obtained.

[0733] Step b): The equipment used consisted of a Hastelloy C276 autoclave having a capacity of 0.8 L on which a condenser and a pressure regulating valve were installed.

[0734] The autoclave was immersed in liquid nitrogen and the following ingredients were introduced successively: 60 g (3.0 mol) of hydrofluoric acid, all three washed and dried reaction mixtures from step a) and 13.3 g (0.07 mol) of titanium tetrachloride (TiCl 4 ). The temperature of the autoclave was then raised to room temperature (25°C). The autoclave was then immersed in an oil bath and the temperature was raised to 80°C while the temperature of the condenser was maintained at about 17°C.

[0735] During the reaction, volatile products are continuously removed, washed and collected in a water scrubber. After reacting for 4 hours, the autoclave is cooled to room temperature. Then it is degassed and the reaction product is washed, dried and analyzed by gas chromatography.

[0736] CF 3 -CFI-CF 3 The yield of CF 3 -CFI-CF 3 The ratio of the mole number of fluorinated propylene to the mole number of hexafluoropropylene initially introduced was 76.8%.

[0737] Example 2-CF 3 -CF 2 Synthesis of -CHFI

[0738] Step a): The equipment used consisted of a 2.0 L Hastelloy C276 autoclave equipped with a pressure indicator, a temperature probe, a burst-proof membrane and a magnetic bar stirring system.

[0739] The following were introduced successively into the autoclave: 102.0 g (0.4 mol) of iodine, 600.0 g of anhydrous ethanol and 53.0 g (0.4 mol) of (Z)-CF 3 -CF=CHF(HFO-1225ye(Z)) The reactor was heated at 70°C for 8 hours and then cooled to room temperature.

[0740] After degassing and then flushing with helium, the reaction mixture was collected after opening the autoclave. The organic phase was washed, dried and then analyzed by gas chromatography (area percent).

[0741] CF 3 -CFI-CHFI yield, as measured by the detected CF 3 The ratio of the number of moles of -CFI-CHFI to the number of moles of HFO-1225ye(Z) initially introduced was expressed as 67.4%.

[0742] Step b): The equipment used consisted of a 0.5 L Hastelloy C276 autoclave equipped with a pressure indicator, a temperature probe, an explosion-proof membrane and a magnetic bar stirring system.

[0743] The autoclave was immersed in liquid nitrogen and the following ingredients were introduced successively: 20 g (1.0 mol) of hydrofluoric acid, 96.2 g (0.25 mol) of CF 3 -CFI-CHFI and 100.0 g of tetramethylene sulfone (sulfolane). The temperature of the autoclave was then raised to room temperature (25°C) and then gradually heated to 100°C.

[0744] After 4 hours of reaction, the autoclave was cooled to room temperature. It was then degassed and the reaction product was washed, dried and analyzed by gas chromatography.

[0745] CF 3 -CF 2 -CHFI yield, as detected by CF 3 -CF 2 The molar number of CHFI to the initial CF 3 The molar ratio of -CFI to CHFI was 98.6%.

Claims

1. A process for producing an iodofluoroalkane compound, comprising the following step a): contacting a hydrofluoroalkane with anhydrous iodine to form a stream A comprising the iodofluoroalkane compound, hydrogen iodide (HI) and unreacted iodine.

2. A process as claimed in the preceding claim, wherein the process comprises the following step b): during step b), the stream A is separated to form a stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted iodine; hydrogen iodide is contained in stream B1, or stream B2 or both.

3. A process as claimed in the preceding claim, wherein the process comprises a step c) of recycling the stream B2 during step c) into step a).

4. A process as claimed in any one of the preceding claims wherein the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, C1-C 10 an alkyl group and a C3-C 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is H or is a group as defined above including at least one hydrogen atom.

5. A process as claimed in any one of the preceding claims wherein the iodofluoroalkane has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I, C1-C1 optionally substituted by at least one fluorine atom and / or at least one iodine atom 10 an alkyl group, and a C3-C4-alkyl group optionally substituted by at least one fluorine atom and / or at least one iodine atom 10 Cycloalkyl group; provided that the substituent R 1 , R 2 or R 3 At least one of is I or is a group as defined above comprising at least one iodine atom.

6. A process as claimed in any one of claims 1 to 4, wherein the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CH(R 3 ), where R 1 , R 2 and R 3 independently selected from H, F, C1-C5 perfluoroalkyl groups and C5-C 10 Perfluorocycloalkyl groups.

7. A process as claimed in any preceding claim, wherein the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CFI, where R 1 and R 2 independently selected from H, F, C1-C5 perfluoroalkyl groups and C5-C 10 Perfluorocycloalkyl groups.

8. A process as claimed in any one of claims 1 to 4, wherein the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of is H.

9. A process as claimed in any preceding claim wherein the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 , R 2 and R 3 are independently selected from H, F, I or Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 , Y 2 and Y 3 independently of one another and for each unit n are independently selected from H, I and F; and n is an integer from 1 to 10; provided that the substituent R 1 , R 2 , R 3 , Y 1 , Y 2 or Y 3 At least one of is 1.

10. A process as claimed in any one of the preceding claims 1 to 4, wherein the hydrofluoroalkane compound is selected from the group consisting of CH3F, CH2F2, CHF3, CH2F-CH3, CHF2-CH3, CH2F-CH2F, CF3-CH3, CHF2-CH2F, CF3-CH2F, CHF2-CHF2, CF3-CHF2, CH2F-CH2-CH3, CH3-CHF-CH3, CH2F-CH2-CH2F , CHF2-CH2-CH3, CH2F-CHF-CH3, CH3-CF2-CH3, CHF2-CH2-CH2F, CF3-CH2-CH3, CH2F-CHF-CH2F, CHF 2-CHF-CH3, CH2F-CF2-CH3, CHF2-CH2-CHF2, CF3-CH2-CH2F, CHF2-CHF-CH2F, CF3-CHF-CH3, CH2F-C F2-CH2F, CHF2-CF2-CH3, CF3-CH2-CHF2, CHF2-CHF-CHF2, CF3-CHF-CH2F, CHF2-CF2-CH2F, CF3-CF2 -CH3, CF3-CH2-CF3, CF3-CHF-CHF2, CHF2-CF2-CHF2, CF3-CF2-CH2F, CF3-CHF-CF3, CF3-CF2-CHF2; Preferably it is selected from CH2F2, CHF3, CHF2-CH3, CF3-CH3, CF3-CH2F, CF3-CHF2, CH2F-CHF-CH3, CF3-CH2-CH3, CF3-CH2-CH2F, CF3-CHF-CH3, CF3-CH2-CHF2, CF3-CHF-CH2F, CF3-CHF-CH3, CF3-CH2-CHF2, CF3-CHF-CH2F, CF3-CH2-CF3, CF3-CHF-CHF2, CF3-CHF-CF3.

11. A process as claimed in any preceding claim, wherein the iodofluoroalkane compound is selected from the group consisting of CH2FI, CHFI2, CHF2I, CF2I2, CF3I, CHFI-CH3, CH2F-CH2I, CFI2-CH3, CH2F-CHI2, CHFI-CH2I, CF2I-CH3, CHF2-CH2I, CHF2-CHI2, CF2I-CH2I, CHFI-CH2F, CFI2-CH2F, CHFI-CHFI, CF3-CH2I, CF3-CHI2, CF2I-CH2F, CHF2-CHFI, CHF2-CFI2, CF2I-CHFI, CF3-CHFI, CF3-CF I2, CF2I-CHF2, CF2I-CF2I, CF3-CF2I, CHFI-CH2-CH3, CH2F-CHI-CH3, CH2F-CH2-CH2I, CFI2-CH2-CH3, CH2F-CI2-CH3, CH2F-CH2-CHI2, CHFI-CHI-CH3 , CHFI-CH2-CH2I, CH2F-CHI-CH2I, CH2I-CHF-CH3, CH3-CFI-CH3, CHI2-CHF-CH3, CH2I-CFI-CH3, CH2I-CHF-CH2I, CHFI-CH2-CH2F, CH2F-CHI-CH2F, CFI 2-CH2-CH2F, CH2F-CI2-CH2F, CHFI-CHI-CH2F, CHFI-CH2-CHFI, CF2I-CH2-CH3, CHF2-CHI-CH3, CHF2-CH2-CH2I, CHF2-CI2-CH3, CHF2-CH2-CHI2, CF2I -CHI-CH3, CF2I-CH2-CH2I, CHF2-CHI-CH2I, CHFI-CHF-CH3, CH2F-CFI-CH3, CH2F-CHF-CH2I, CFI2-CHF-CH3, CH2F-CHF-CHI2, CHFI-CFI-CH3, CHFI-CHF -CH2I, CH2F-CFI-CH2I, CH2I-CF2-CH3, CHI2-CF2-CH3, CH2I-CF2-CH2I, CF2I-CH2-CH2F, CHF2-CHI-CH2F, CHF2-CH2-CHFI, CHF2-CI2-CH2F, CHF2-CH2 -CFI2, CF2I-CHI-CH2F, CF2I-CH2-CHFI, CHF2-CHI-CHFI, CF3-CHI-CH3, CF3-CH2-CH2I, CF3-CI2-CH3, CF3-CH2-CHI2, CF3-CHI-CH2I, CHFI-CHF-CH2F,CH2F-CFI-CH2F、CFI2-CHF-CH2F、CHFI-CFI-CH2F、CHFI-CHF-CHFI、CF2I-CHF-CH3、CHF2-CFI-CH3、CHF2-CHF-CH2I、CHF2-CHF-CHI2、CF2I-CFI-CH3、CF2I-CHF-CH2I、CHF2-CFI-CH2I、CHFI-CF2-CH3、CH2F-CF2-CH2I、CFI2-CF2-CH3、CH2F-CF2-CHI2、CHFI-CF2-CH2I、CF2I-CH2-CHF2、CHF2-CHI-CHF2、CHF2-CI2-CHF2、CF2I-CHI-CHF2、CF2I-CH2-CF2I、CF3-CHI-CH2F、CF3-CH2-CHFI、CF3-CI2-CH2F、CF3-CH2-CFI2、CF3-CHI-CHFI、CF2I-CHF-CH2F、CHF2-CFI-CH2F、CHF2-CHF-CHFI、CHF2-CHF-CFI2、CF2I-CFI-CH2F、CF2I-CHF-CHFI、CHF2-CFI-CHFI、CF3-CFI-CH3、CF3-CHF-CH2I、CF3-CHF-CHI2、CF3-CFI-CH2I、CHFI-CF2-CH2F、CFI2-CF2-CH2F、CHFI-CF2-CHFI、CF2I-CF2-CH3、CHF2-CF2-CH2I、CHF2-CF2-CHI2、CF2I-CF2-CH2I、CF3-CHI-CHF2、CF3-CH2-CF2I、CF3-CI2-CHF2、CF3-CHI-CF2I、CF2I-CHF-CHF2、CHF2-CFI-CHF2、CF2I-CFI-CHF2、CF2I-CHF-CF2I、CF3-CFI-CH2F、CF3-CHF-CHFI、CF3-CHF-CFI2、CF3-CFI-CHFI、CF2I-CF2-CH2F、CHF2-CF2-CHFI、CHF2-CF2-CFI2、CF2I-CF2-CHFI、CF3-CF2-CH2I、CF3-CF2-CHI2、CF3-CHI-CF3、CF3-CI2-CF3、CF3-CFI-CHF2、CF3-CHF-CF2I、CF3-CFI-CF2I、CF2I-CF2-CHF2、CF2I-CF2-CF2I、CF3-CF2-CHFI、CF3-CF2-CFI2、CF3-CFI-CF3、CF3-CF2-CF2I; Advantageously, the iodofluoroalkane compound is selected from CHF2I, CF2I2, CF3I, CF2I-CH3, CHF2-CH2I, CHF2-CHI2, CF2I-CH2I, CF3-CH2I, CF3-CHI2, CF3-CHFI, CF3-CFI2, CF3-CF2I, CHFI-CHF-CH3, CH2F-CFI-CH3, CH2F-CHF-CH2I, CFI2-CHF-CH3, CH2F-CHF-CHI2, CHFI-CFI-CH3, CHFI-CHF-CH2I, CH2F-CFI-CH2I, CF3-CHI-CH3 , CF3-CH2-CH2I, CF3-CI2-CH3, CF3-CH2-CHI2, CF3-CHI-CH2I, CF3-CHI-CH2F, CF3-CH2-CHFI, CF3-CI2-CH2F, CF3-CH2-CFI2, CF3-CHI-CHFI, CF3-CFI -CH3, CF3-CHF-CH2I, CF3-CHF-CHI2, CF3-CFI-CH2I, CF3-CHI-CHF2, CF3-CH2-CF2I, CF3-CI2-CHF2, CF3-CHI-CF2I, CF3-CFI-CH2F, CF3-CHF-CHFI, CF3 -CHF-CFI2, CF3-CFI-CHFI, CF3-CHI-CF3, CF3-CI2-CF3, CF3-CFI-CHF2, CF3-CHF-CF2I, CF3-CFI-CF2I, CF3-CFI-CF3; preferably, the iodofluoroalkane compound is selected from CH2FI, CHF2I, CF3I, CHFI-CH3, CF2I-CH3, CHFI-CH2F, CF3-CH2I, CF2I-CH2F, CF3-CHFI, CF2I-CHF2, CF3-CF2I, CHFI-CH2-CH3, CH3-CFI-CH3, CHFI-CH2-CH2F, CF2I -CH2-CH3, CHFI-CHF-CH3, CH2I-CF2-CH3, CF2I-CH2-CH2F, CF3-CH2-CH2I, CHFI-CHF-CH2F, CF2I-CHF-CH3, CHFI-CF2-CH3, CF2I-CH2-CHF2, CF3-CH2- CHFI, CF2I-CHF-CH2F, CF3-CFI-CH3, CHFI-CF2-CH2F, CF2I-CF2-CH3, CF3-CH2-CF2I, CF2I-CHF-CHF2, CF3-CHF-CHFI, CF2I-CF2-CH2F, CF3-CF2-CH2I,CF3-CHI-CF3, CF3-CHF-CF2I, CF2I-CF2-CHF2, CF3-CF2-CHFI, CF3-CFI-CF3, CF3-CF2-CF2I; in particular, the iodofluoroalkane compound is selected from CHF2I, CF3I, CF2I-CH3, CF3-CH2I, CF3-CHFI, CF3-CF2I, CHFI-CHF-CH3, CF3-CH2-CH2I, CF3-CH2-CHFI, CF3-CFI-CH3, CF3-CH2-CF2I, CF3-CHF-CHFI, CF3-CHI-CF3, CF3-CHF-CF2I, CF3-CFI-CF3.

12. A process as claimed in any one of the preceding claims 1 to 4, wherein step a) involves one of the following reactions: - converting CH2F2 into CHF2I or CF2I2 or a mixture of the two; preferably into CHF2I; -Convert CHF3 into CF3I; - converting CHF2-CH3 into CF2I-CH3 or CHF2-CH2I or CHF2-CHI2 or CF2I-CH2I or a mixture thereof; preferably into CF2I-CH3; - converting CF3-CH3 into CF3-CH2I or CF3-CHI2 or a mixture of the two; preferably into CF3-CH2I; - converting CF3-CH2F into CF3-CHFI or CF3-CFI2 or a mixture of the two; preferably into CF3-CHFI; -Convert CF3-CHF2 into CF3-CF2I; - converting CH2F-CHF-CH3 into CHFI-CHF-CH3 or CH2F-CFI-CH3 or CH2F-CHF-CH2I or CFI2-CHF-CH3 or CH2F-CHF-CHI2 or CHFI-CFI-CH3 or CHFI-CHF-CH2I or CH2F-CFI-CH2I or a mixture thereof; preferably into CHFI-CHF-CH3; - converting CF3-CH2-CH3 into CF3-CHI-CH3 or CF3-CH2-CH2I or CF3-CI2-CH3 or CF3-CH2-CHI2 or CF3-CHI-CH2I or a mixture thereof; preferably into CF3-CH2-CH2I; - converting CF3-CH2-CH2F into CF3-CHI-CH2F or CF3-CH2-CHFI or CF3-CI2-CH2F or CF3-CH2-CFI2 or CF3-CHI-CHFI or a mixture thereof; preferably into CF3-CH2-CHFI; - converting CF3-CHF-CH3 into CF3-CFI-CH3 or CF3-CHF-CH2I or CF3-CHF-CHI2 or CF3-CFI-CH2I or a mixture thereof; preferably into CF3-CFI-CH3; - converting CF3-CH2-CHF2 into CF3-CHI-CHF2 or CF3-CH2-CF2I or CF3-CI2-CHF2 or CF3-CHI-CF2I or a mixture thereof; preferably into CF3-CH2-CF2I; - converting CF3-CHF-CH2F into CF3-CFI-CH2F or CF3-CHF-CHFI or CF3-CHF-CFI2 or CF3-CFI-CHFI or a mixture thereof; preferably into CF3-CHF-CHFI; -Converting CF3-CH2-CF3 into CF3-CHI-CF3 or CF3-CI2-CF3 or a mixture of the two; preferably into CF3-CHI-CF3; - converting CF3-CHF-CHF2 into CF3-CFI-CHF2 or CF3-CHF-CF2I or CF3-CFI-CF2I or a mixture thereof; preferably into CF3-CHF-CF2I; or -Convert CF3-CHF-CF3 to CF3-CFI-CF3.

13. A process as claimed in any one of the preceding claims, wherein step a) is carried out in the presence of a catalyst selected from the group consisting of: antimony halides, iron halides, titanium halides or tin halides; oxides, oxyhalides or halides of chromium or aluminium; and alkali metal or alkaline earth metal salts, or mixtures thereof.

14. A process as claimed in any one of the preceding claims, wherein step a) is carried out in the gas phase at a temperature of from 250°C to 700°C.

15. A process as claimed in any one of the preceding claims 1 to 13, wherein step a) is carried out in liquid phase in the presence of a polar aprotic solvent, preferably at a temperature of 50°C to 300°C.