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 the 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] Iodofluoro compounds also have applications in the refrigeration sector or in air conditioning equipment. From WO 2006 / 112 881 a composition comprising CF3I and HFC-152A is known which is intended for use in refrigerant compositions, refrigeration systems, compositions based on swelling agents, aerogel propellants and the like.

[0005] Furthermore, patent application FR 2794456 discloses a process for preparing trifluoroiodomethane or pentafluoroiodoethane. Furthermore, patent application 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] Overview 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 to 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 to limit corrosion of the equipment.

[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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 independently for each unit n are 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 )(R2 )CH-C(I)(R 3 )(R 4 ), where R 1 、R 2 、R 3 and R 4 independently selected from H, F, I, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or 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 independently for each unit n are 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.

[0023] According to a preferred embodiment, the fluoroolefin is selected from the group consisting of CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CF2=CF2, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF2-C H=CHF、CF3-CH=CH2、CH2F-CF=CF2、CHF2-CF=CHF、CF3-CF=CH2、CHF2-CH=CF2、CF3-CH=CHF、CHF2-CF=CF2、CF3-CF=CHF、CF3- CH=CF2, CF3-CF=CF2; preferably selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2.

[0024] According to a preferred embodiment, the iodofluoroalkane compound is selected from CH2F-CH2I, CHFI-CH3, CHF2-CH2I, CF2I-CH3, CH2F-CHFI, CHF2-CHFI, CF2I-CH2F, CHF2-CF2I, CH3-CHF-CH2I, CH3-CFI-CH3, CH3-CH2-CHFI, CH3-CHI-CH2F, CH2F-CH2-CH2I, CH3-CHF-CHFI, CH3-CFI-CH2F, CH2F-CHF-CH2I , CH3-CH2-CF2I, CH3-CHI-CHF2, CH2F-CH2-CHFI, CH2F-CHI-CH2F, CHF2-CH2-CH2I, CH3-CHF-CF2I, CH3-CFI-CHF2, CH2F-CH F-CHFI, CH2F-CFI-CH2F, CHF2-CHF-CH2I, CH2F-CH2-CF2I, CH2F-CHI-CHF2, CHF2-CH2-CHFI, CF3-CH2-CH2I, CF3-CHI-CH3, CH2F-CHF-CF2I, CH2F-CFI-CHF2, CHF2-CHF-CHFI, CF3-CHF-CH2I, CF3-CFI-CH3, CHF2-CH2-CF2I, CHF2-CHI-CHF2, CF3-CH2 -CHFI, CF3-CHI-CH2F, CHF2-CHF-CF2I, CHF2-CFI-CHF2, CF3-CHF-CHFI, CF3-CFI-CH2F, CF3-CH2-CF2I, CF3-CHI-CHF2, CF3 -CHF-CF2I, CF3-CFI-CHF2; preferably selected from CHF2-CH2I, CF2I-CH3, CHF2-CHFI, CF2I-CH2F, CHF2-CF2I, CF3-CH2-CH2I, CF3-CHI-CH3, CF3-CHF-CH2I, CF3-CFI-CH3, CF3-CH2-CHFI, CF3-CHI-CH2F, CF3-CHF-CHFI, CF3-CFI-CH2F, CF3-CHF-CF2I, CF3-CFI-CHF2.

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

[0026] - converting CF2=CH2 into CF2I-CH3; or

[0027] - converting CF2=CHF into CF2I-CH2F; or

[0028] - converting CF2=CF2 into CHF2-CF2I; or

[0029] - converting CF3-CH=CH2 into CF3-CH2-CH2I; or

[0030] - converting CF3-CF=CH2 into CF3-CFI-CH3; or

[0031] - converting CF3-CH=CHF into CF3-CH2-CHFI; or

[0032] - converting CF3-CF=CHF into CF3-CHF-CHFI; or

[0033] -Convert CF3-CF=CF2 into CF3-CHF-CF2I.

[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 group consisting of 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 to 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including at least one fluorine atom.

[0049] The term "alkyl" refers to a monovalent group derived from a linear or branched alkane containing the specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane containing the specified number of carbon atoms. The term "alkenyl" refers to a monovalent group derived from a cycloalkene containing the 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 containing at least one carbon-carbon double bond in its cyclic portion and the specified number of carbon atoms. The term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon containing the 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 include 1 to 10 fluorine atoms, preferably 1 to 5 fluorine atoms.

[0051] Preferably, the fluoroolefin has the formula (I) (R1 )(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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 1 to 5 fluorine atoms.

[0053] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ), where R1 、R 2 、R 3 and R 4 independently selected from H, F, I, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 independently for each unit n are 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 independently for each unit n are 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 independently for each unit n are 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 independently of one another and independently for each unit n are 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.

[0059] In particular, the fluoroolefin is selected from the group consisting of CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CF2=CF2, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CF=CHF, CF3-CF=CH2, CHF2-CH=CF2, CHF2-CF=CHF, CF3-CF=CH2, CHF2-CH=CF2, CF3-CH=CHF, CHF2-CH=CF2, CF3-CF=CF2.

[0060] More particularly, the fluoroolefin is selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2.

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

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

[0065] Preferably, hydrogen iodide is prepared by contacting hydrogen (H2) with iodine (I2). In particular, hydrogen iodide is prepared by contacting anhydrous hydrogen with anhydrous iodine. The term "anhydrous" refers to the same definition as mentioned above for hydrogen iodide.

[0066] Alternatively, the 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 the 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 1 to 10 fluorine atoms.

[0070] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CH-C(I)(R 3 )(R4 ), where R 1 、R 2 、R 3 and R 4 are independently selected from H, F, I, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 independently for each unit n are 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 of one another 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 、R3 、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 of one another 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 of one another 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 the group consisting of CH2F-CH2I, CHFI-CH3, CHF2-CH2I, CF2I-CH3, CH2F-CHFI, CHF2-CHFI, CF2I-CH2F, CHF2-CF2I, CH3-CHF-CH2I, CH3-CFI-CH3, CH3-CH2-CHFI, CH3-CHI-CH2F, CH2F-CH2-CH2I, CH3-CHF-CHFI, CH3-CFI-CH2F, CH2F-CHF-CH2I, CH3-CH2-CF2I, CH3-CHI-CHF2, CH2F-CH2-CHFI, CH2F-CHI-CH2F, CHF2-CH2-CH2I, CH3-CHF-CF2I, CH3-CHF-CHF2, CH2F-CHF-CHFI, CH2F-CFI -CH2F, CHF2-CHF-CH2I, CH2F-CH2-CF2I, CH2F-CHI-CHF2, CHF2-CH2-CHFI, CF3-CH2-CH2I, CF3 -CHI-CH3, CH2F-CHF-CF2I, CH2F-CFI-CHF2, CHF2-CHF-CHFI, CF3-CHF-CH2I, CF3-CFI-CH3, CHF 2-CH2-CF2I, CHF2-CHI-CHF2, CF3-CH2-CHFI, CF3-CHI-CH2F, CHF2-CHF-CF2I, CHF2-CFI-CHF2 , CF3-CHF-CHFI, CF3-CFI-CH2F, CF3-CH2-CF2I, CF3-CHI-CHF2, CF3-CHF-CF2I, CF3-CFI-CHF2.

[0078] More particularly, the iodofluoroalkane is selected from the group consisting of CHF2-CH2I, CF2I-CH3, CHF2-CHFI, CF2I-CH2F, CHF2-CF2I, CF3-CH2-CH2I, CF3-CHI-CH3, CF3-CHF-CH2I, CF3-CFI-CH3, CF3-CH2-CHFI, CF3-CHI-CH2F, CF3-CHF-CHFI, CF3-CFI-CH2F, CF3-CHF-CF2I, CF3-CFI-CHF2.

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

[0080] - converting CF2=CH2 into CF2I-CH3; or

[0081] - converting CF2=CHF into CF2I-CH2F; or

[0082] - converting CF2=CF2 into CHF2-CF2I; or

[0083] - converting CF3-CH=CH2 into CF3-CH2-CH2I; or

[0084] - converting CF3-CF=CH2 into CF3-CFI-CH3; or

[0085] - converting CF3-CH=CHF into CF3-CH2-CHFI; or

[0086] - converting CF3-CF=CHF into CF3-CHF-CHFI; or

[0087] -Convert CF3-CF=CF2 into CF3-CHF-CF2I.

[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 from columns 4 to 12 of the periodic table or 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 m 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2 The 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, wherein 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 CO3 2- Preferably, the catalyst is NaI or KI. The catalyst preferably has a 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. Therefore, 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 has been 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 water, 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.

[0102] The solvent S1 has a boiling point of 0° C. to 250° C., preferably 20° C. to 250° C., and particularly 20° C. to 200° C. The solvent S1 is selected from acetic acid, CCl4, 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 sodium iodide or potassium iodide is preferably used. The ratio between the catalyst and the fluoroolefin is 1-20, preferably 1-10. The catalyst preferably has a mass of 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 catalyst metal is selected from Li, Na, K, Cs, Mg, Ca, Al, and Sb, the catalyst content is 1% to 30% by weight 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 CF2=CH2, stream A may include CHF2-CH2I in addition to CF2I-CH3. When the fluoroolefin is CF2=CHF, stream A may include CF3-CHFI in addition to CF2I-CH2F. When the fluoroolefin is CF3-CH=CH2, stream A may include CF3-CHI-CH3 in addition to CF3-CH2-CH2I. When the fluoroolefin is CF3-CF=CH2, stream A may include CF3-CHF-CH2I in addition to CF3-CFI-CH3. When the fluoroolefin is CF3-CH=CHF, stream A may include CF3-CHI-CH2F in addition to CF3-CH2-CHFI. When the fluoroolefin is CF3-CF=CHF, stream A may include CF3-CHF-CH2F in addition to CF3-CH2-CHFI. When the fluoroolefin is CF3-CF=CHF, stream A may include CF3-CFI-CH2F in addition to CF3-CHF-CHFI. When the fluoroolefin is CF3-CF=CF2, stream A may also include CF3-CFI-CHF2 in addition to CF3-CHF-CF2I.

[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] Stream A is then separated to form a first stream B1 comprising the iodofluoroalkane compound and a stream B2 comprising unreacted hydrogen iodide. Both stream B1 and stream B2 may contain impurities, reaction by-products, or even unreacted fluoroolefins. In this case, stream B1 is subjected to a further purification step to obtain stream B1 comprising the purified iodofluoroalkane compound. Preferably, after the separation and possible purification steps, the content of the iodofluoroalkane compound in stream B1 is greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, particularly greater than 98%, and even 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 present 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, 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 relative to the total weight of the material M2.

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

[0119] 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 % relative to the total weight of material M2.

[0120] Preferably, the material M2 is or

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

[0122] The material M1 may also contain 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 preferably less than 0.1% by weight of carbon relative to the total weight of the material M1. More particularly, the material M1 may contain 0.01% 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 abutted against 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 steps of:

[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 to 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 items, 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including at least one fluorine atom.

[0132] 5. The 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro group as defined above.

[0133] 6. The process as described in any one of items 1 to 4 above, 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 independently for each unit n are 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 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 5 or as defined 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 R 1 、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 the group consisting of CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CF2=CF2, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CF=CHF, CF3-CF=CH2, CHF2-CH=CF2, CF3-CH=CHF, CHF2-CF=CF2, CF3-CF=CHF, C F3-CH=CF2, CF3-CF=CF2; preferably selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2.

[0136] 9. A process as described in the preceding item, characterized in that the iodofluoroalkane compound is selected from the group consisting of CH2F-CH2I, CHFI-CH3, CHF2-CH2I, CF2I-CH3, CH2F-CHFI, CHF2-CHFI, CF2I-CH2F, CHF2-CF2I, CH3-CHF-CH2I, CH3-CFI-CH3, CH3-CH2-CHFI, CH3-CHI-CH2F, CH2F-CH2-CH2I, CH3-CHF-CHFI, CH3-CFI-CH2F, CH2F-CHF -CH2I, CH3-CH2-CF2I, CH3-CHI-CHF2, CH2F-CH2-CHFI, CH2F-CHI-CH2F, CHF2-CH2-CH2I, CH3-CHF-CF2I, CH3-CFI-CHF2, CH2 F-CHF-CHFI, CH2F-CFI-CH2F, CHF2-CHF-CH2I, CH2F-CH2-CF2I, CH2F-CHI-CHF2, CHF2-CH2-CHFI, CF3-CH2-CH2I, CF3-CHI-C H3, CH2F-CHF-CF2I, CH2F-CFI-CHF2, CHF2-CHF-CHFI, CF3-CHF-CH2I, CF3-CFI-CH3, CHF2-CH2-CF2I, CHF2-CHI-CHF2, CF3-C H2-CHFI, CF3-CHI-CH2F, CHF2-CHF-CF2I, CHF2-CFI-CHF2, CF3-CHF-CHFI, CF3-CFI-CH2F, CF3-CH2-CF2I, CF3-CHI-CHF2, CF 3-CHF-CF2I, CF3-CFI-CHF2; preferably selected from CHF2-CH2I, CF2I-CH3, CHF2-CHFI, CF2I-CH2F, CHF2-CF2I, CF3-CH2-CH2I, CF3-CHI-CH3, CF3-CHF-CH2I, CF3-CFI-CH3, CF3-CH2-CHFI, CF3-CHI-CH2F, CF3-CHF-CHFI, CF3-CFI-CH2F, CF3-CHF-CF2I, CF3-CFI-CHF2.

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

[0138] - converting CF2=CH2 into CF2I-CH3; or

[0139] - converting CF2=CHF into CF2I-CH2F; or

[0140] - converting CF2=CF2 into CHF2-CF2I; or

[0141] - converting CF3-CH=CH2 into CF3-CH2-CH2I; or

[0142] - converting CF3-CF=CH2 into CF3-CFI-CH3; or

[0143] - converting CF3-CH=CHF into CF3-CH2-CHFI; or

[0144] - converting CF3-CF=CHF into CF3-CHF-CHFI; or

[0145] -Convert CF3-CF=CF2 into CF3-CHF-CF2I.

[0146] 11. Process as claimed in any one of the preceding items, characterised 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 group consisting of 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 claimed in any one of the preceding items, characterised 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. 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. The anhydrous reagents 0.5 mol of CF2=CHF and 0.8 mol of HI (prepared from H2 and I2) were introduced into the reaction medium. After 4 hours of reaction under stirring, a sample was removed, washed, dried, and then analyzed by gas chromatography (area percentage). The conversion of CF2=CHF was 85%, and the selectivity for CF2I-CH2F was 89%.

[0153] Example 2

[0154] The chromium oxyfluoride catalyst that comprises 15 % by weight -20 % by weight of fluorine is introduced in the tubular reactor made of Inconel600.With catalyst at O2 gas stream in the presence of 300 ℃ temperature pre-activation.Make the gaseous stream of hexafluoropropylene and by H2 and I2 gaseous stream (HFP / HI molar ratio=1 / 2) of hydrogen iodide prepared at 270 ℃ temperature under 3 bar, pass through above this catalyst.At the reactor outlet, with gas washing, then dry and condense in cold trap.Take out sample and it is analyzed by gas chromatography (area percentage).The conversion of hexafluoropropylene is 95%, to CF3-CHF-CF2I selectivity is 97%.

[0155] Comparable (equal) conversion and selectivity values ​​were obtained in the case of CF3-CF=CHF, CF3-CH=CHF, CF3-CF=CH2 and CF3-CH=CH2 as fluoroolefins.

[0156] Invention II

[0157] Overview 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 )(R4 ) of a fluoroolefin, wherein R 1 、R 2 、R 3 and R 4 are independently selected from H, F, Cl, I, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 independently for each unit n are 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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;

[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, C1-C5 perfluoroalkyl groups, C5-C 10Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or 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 of one another 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=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CF2=CF2, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF 2-CH=CHF、CF3-CH=CH2、CH2F-CF=CF2、CHF2-CF=CHF、CF3-CF=CH2、CHF2-CH=CF2、CF3-CH=CHF、CHF2-CF=CF2、CF3-CF=CHF、CF 3-CH=CF2, CF3-CF=CF2; preferably selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2.

[0169] According to a preferred embodiment, the iodofluoroalkane compound is selected from the group consisting of CHFI-CH2F, CHF2-CH2I, CF2I-CH2F, CF3-CH2I, CHFI-CHF2, CF2I-CHF2, CF3-CHFI, CF2I-CF3, CH3-CFI-CH2F, CH3-CF2-CH2I, CH3-CHI-CHF2, CH3-CHF-CHFI, CH2F-CHI-CH2F, CH2F-CHF-CH2I, CH3-CFI-CHF2, CH3-CF2-CHF I. CH2F-CFI-CH2F, CH2F-CF2-CH2I, CH3-CHI-CF3, CH3-CHF-CF2I, CH2F-CHI-CHF2, CH2F-CHF-CHFI, CHF2-CHF-CH2I, CH3-C FI-CF3, CH3-CF2-CF2I, CH2F-CFI-CHF2, CH2F-CF2-CHFI, CHF2-CF2-CH2I, CH2F-CHF-CF2I, CHF2-CHI-CHF2, CHF2-CHF-CHF I. CF3-CHI-CH2F, CF3-CHF-CH2I, CH2F-CF2-CF2I, CHF2-CFI-CHF2, CHF2-CF2-CHFI, CF3-CFI-CH2F, CF3-CF2-CH2I, CHF2- CHF-CF2I, CF3-CHI-CHF2, CF3-CHF-CHFI, CHF2-CF2-CF2I, CF3-CFI-CHF2, CF3-CF2-CHFI, CF3-CHI-CF3, CF3-CHF-CF2I, CF 3-CFI-CF3, CF3-CF2-CF2I; preferably selected from CF2I-CH2F, CF3-CH2I, CF2I-CHF2, CF3-CHFI, CF2I-CF3, CF3-CHI-CH2F, CF3-CHF-CH2I, C F3-CFI-CH2F, CF3-CF2-CH2I, CF3-CHI-CHF2, CF3-CHF-CHFI, CF3-CFI-CHF2, CF3-CF2-CHFI, CF3-CFI-CF3, CF3-CF2-CF2I.

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

[0171] -Convert CF2=CH2 into CF3-CH2I;

[0172] - converting CF2=CHF into CF3-CHFI; or

[0173] - converting CF2=CF2 into CF3-CF2I; or

[0174] - converting CF3-CH=CH2 into CF3-CHI-CH2F; or

[0175] - converting CF3-CF=CH2 into CF3-CF2-CH2I; or

[0176] - converting CF3-CH=CHF into CF3-CHI-CHF2; or

[0177] - converting CF3-CF=CHF into CF3-CFI-CHF2; or

[0178] -Convert CF3-CF=CF2 into CF3-CFI-CF3.

[0179] According to a preferred embodiment, anhydrous iodine monofluoride is prepared by mixing anhydrous iodine (I2) with anhydrous iodine pentafluoride (IF5).

[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 independently selected from H, F, Cl, I, Cl-C 10 Alkyl groups, C3-C 10 Cycloalkyl groups, C2-C 10 Alkenyl groups, C3-C 10 Cycloalkenyl groups and C6-C 10 Aryl group.

[0186] Carrying out step a) with anhydrous iodine monofluoride makes it possible to increase the selectivity and conversion of the reaction. The term "anhydrous" herein means 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" herein means that the fluoroolefin contains less than 500 ppm water, advantageously less than 250 ppm water, preferably less than 100 ppm water, more preferably less than 50 ppm water, particularly less than 25 ppm water, more particularly less than 10 ppm water, and preferably less than 5 ppm water; preferably, the fluoroolefin is free of water. The use of anhydrous fluoroolefins in the present process avoids the formation of impurities (reaction by-products, polymers derived from the fluoroolefin, 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including at least one fluorine atom.

[0189] The term "alkyl" refers to a monovalent group derived from a linear or branched alkane containing the specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane containing the specified number of carbon atoms. The term "alkenyl" refers to a monovalent group derived from a cycloalkene containing the 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 containing at least one carbon-carbon double bond in its cyclic portion and the specified number of carbon atoms. The term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon containing the 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 include 1 to 10 fluorine atoms, preferably 1 to 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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 4 are independently selected from H, F, I, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or is a perfluoro 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 4 independently selected from H, F, I, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4At least one of is F or is a perfluoro 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 independently for each unit n are 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 Y 1 、Y 2 and Y 3 independently of one another and independently for each unit n are 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 )(R2 )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 independently for each unit n are 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 independently of one another and independently for each unit n are 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.

[0199] In particular, the fluoroolefin is selected from the group consisting of CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CF2=CF2, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CF=CHF, CF3-CF=CH2, CHF2-CH=CF2, CHF2-CF=CHF, CF3-CF=CH2, CHF2-CH=CF2, CF3-CH=CHF, CHF2-CH=CF2, CF3-CF=CF2.

[0200] More particularly, the fluoroolefin is selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2.

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

[0202] Preferably, anhydrous iodine monofluoride is prepared by anhydrous reagent.Preferably, anhydrous iodine monofluoride is by by anhydrous iodine (I 2 ) with anhydrous iodine pentafluoride (IF 5 ) mix and original position preparation.In the case, described logistics A also can comprise unreacted iodine and / or iodine pentafluoride except described iodine fluoroalkane compound and optional unreacted iodine monofluoride.For both iodine and iodine pentafluoride, term " anhydrous () " refers to that the water content in the compound of consideration is less than 500ppm water, advantageously less than 250ppm, preferably less than 100ppm water, more preferentially less than 50ppm water, particularly less than 25ppm water, more particularly less than 10ppm, preferably less than 5ppm water.Preferentially preferably, iodine and iodine pentafluoride are water-free.

[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 mixing anhydrous iodine with anhydrous IF7, or mixing anhydrous iodine with anhydrous fluorine gas F2, or mixing anhydrous iodine with anhydrous IF3.

[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 R 4 are independently selected from H, F, Cl, I, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 1 to 10 fluorine atoms.

[0207] Preferably, the iodofluoroalkane compound has the formula (II) (R 1 )(R2 )CF-C(I)(R 3 )(R 4 ), where R 1 、R 2 、R 3 and R 4 are independently selected from H, F, I, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or is a perfluoro 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)(R 3 )(R 4 ), where R 1 、R 2 、R 3 and R 4independently selected from H, F, I, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or is a perfluoro 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 independently for each unit n are 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 、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 3independently of one another and independently for each unit n are 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 of one another 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 of one another 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 、R4 、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 the group consisting of CHFI-CH2F, CHF2-CH2I, CF2I-CH2F, CF3-CH2I, CHFI-CHF2, CF2I-CHF2, CF3-CHFI, CF2I-CF3, CH3-CFI-CH2F, CH3-CF2-CH2I, CH3-CHI-CHF2, CH3-CHF-CHFI, CH2F-CHI-CH2F, CH2F-CHF-CH2I, CH3-CFI-CHF2, CH3-CF2-CHFI, CH2F-CFI-CH2F, CH2F-CF2-CH2I, CH3-CHI-CF3, CH3-CHF-CF2I, CH2F-CHI-CHF2, CH2F-CHF-CH2I, CH3-CFI-CF3, CH3-CHF-CF2I, CH2F-CHI-CHF2, CH2F-CHF-CHFI, CHF2-CHF-CH2I, CH3-CFI-CF3, CH3- CF2-CF2I, CH2F-CFI-CHF2, CH2F-CF2-CHFI, CHF2-CF2-CH2I, CH2F-CHF-CF2I, CHF2-CHI-CHF2, CHF2-CHF-CHFI, CF3-CHI-CH2F, CF3-CHF-CH2I, CH2F-CF2-CF2I, CHF2-CFI-CHF2, CHF2-CF2-CH FI, CF3-CFI-CH2F, CF3-CF2-CH2I, CHF2-CHF-CF2I, CF3-CHI-CHF2, CF3-CHF-CHFI, CHF2-CF2-C F2I, CF3-CFI-CHF2, CF3-CF2-CHFI, CF3-CHI-CF3, CF3-CHF-CF2I, CF3-CFI-CF3, CF3-CF2-CF2I.

[0215] Preferably, the iodofluoroalkane compound is selected from CF2I-CH2F, CF3-CH2I, CF2I-CHF2, CF3-CHFI, CF2I-CF3, CF3-CHI-CH2F, CF3-CHF-CH2I, CF3-CFI-CH2F, CF3-CF2-CH2I, CF3-CHI-CHF2, CF3-CHF-CHFI, CF3-CFI-CHF2, CF3-CF2-CHFI, CF3-CFI-CF3, CF3-CF2-CF2I.

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

[0217] -Convert CF2=CH2 into CF3-CH2I;

[0218] - converting CF2=CHF into CF3-CHFI; or

[0219] - converting CF2=CF2 into CF3-CF2I; or

[0220] - converting CF3-CH=CH2 into CF3-CHI-CH2F; or

[0221] - converting CF3-CF=CH2 into CF3-CF2-CH2I; or

[0222] - converting CF3-CH=CHF into CF3-CHI-CHF2; or

[0223] - converting CF3-CF=CHF into CF3-CFI-CHF2; or

[0224] -Convert CF3-CF=CF2 into CF3-CFI-CF3.

[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 from columns 4 to 15 of the periodic table or metals selected from Li, Na, K, Cs, Mg and Ca.

[0228] Preferably, the catalyst is a 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 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 m 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2The specific surface area is 0.01 to 10% by weight of the catalyst relative to the fluoroolefin. When the catalyst is a chromium oxide, chromium oxyfluoride, or chromium fluoride, it may further contain a promoter in an amount of 0.5 to 10% by weight relative to the total weight of the catalyst. The promoter is selected from the group consisting of 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 CO3 2- Preferably, the catalyst is NaI or KI. The catalyst preferably has a mass fraction of 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 the oxides, oxyhalides or halides of metals or metalloids of columns 4 to 15 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.

[0233] The catalyst may also deactivate over time. Therefore, 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 has been 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, with or without 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 for carrying out step a) 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 a solvent S1. Preferably, the solvent S1 is anhydrous. The term "anhydrous" herein means that the solvent S1 contains less than 500 ppm of water, advantageously less than 250 ppm, preferably less than 100 ppm of water, more preferably 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 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, CCl4, 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 can 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 a molecular weight of 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 SbF5, SbF3, TiF4, SnF4, TaF5, NbF5, TiF4, FeF3 or MoF6. Preferably, the catalyst is liquid at the temperature at which step a) is carried out. Therefore, when these catalysts are used 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. When iodine monofluoride is prepared by mixing anhydrous iodine (I2) and anhydrous iodine pentafluoride (IF5), the stream A may also comprise unreacted iodine and / or iodine pentafluoride. Stream A may also comprise 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 an olefin) or even unreacted olefin.

[0245] Step b) of the process

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

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

[0248] Step c) of the process

[0249] The step c) of this process comprises that logistics B2 is recycled to step a).This recycling step improves the overall yield of the process (better conversion) and saves expensive reagents (and catalysts), and minimizes environmental impact simultaneously.Under the situation that does not have this recycling step, unreacted iodine monofluoride (or its precursor I2 and IF5) and / or olefins will have to be incinerated, thereby increased the carbon emission of this 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, 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 relative to the total weight of the material M2.

[0254] Material M2 may also include a chromium content of less than 35% by weight, advantageously less than 30% by weight, preferably less than 20% by weight, more preferentially less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by 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, the material M1 comprises at least 70% by weight of iron, advantageously at least 75% by weight, preferably at least 80% by weight, more preferentially at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, based on the total weight of the material M1.

[0258] The material M1 may also contain 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 preferably less than 0.1% by weight of carbon, based on the total weight of the material M1. More particularly, the material M1 may contain 0.01% 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 abutted against each other by hot or cold plating, hot or cold rolling, or welding.

[0260] Example

[0261] Example 1

[0262] Synthesis of CF3-CFI-CF3

[0263] The equipment used consisted of a Hastelloy C276 autoclave with a capacity of 0.8 L, on which was mounted a condenser and a pressure regulating valve. The autoclave was degassed and rendered 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 (SbF5). 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 approximately 17°C. When the temperature of the reaction medium reached 80°C, 12.5 g / h (0.083 mol / h) of hexafluoropropylene (C3F6) were continuously injected.

[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] The yield of CF3-CFI-CF3, expressed as the ratio of the number of moles of CF3-CFI-CF3 detected to the number of moles of hexafluoropropylene initially introduced, was 93.6%.

[0266] Example 2

[0267] Synthesis of CF3-CF2-CH2I

[0268] The following were successively introduced 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 (SbF5). 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 maintained at approximately 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-tetrafluoropropylene (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] The yield of CF3-CF2-CH2I, expressed as the ratio of the number of moles of CF3-CF2-CH2I detected to the number of moles of CF3-CF=CH2 initially introduced, was 80.5%.

[0271] Invention III

[0272] Overview of Invention III

[0273] The present invention relates to a process for producing iodofluoroalkane compounds, 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. Step a) thus allows the hydrogen atoms of the hydrofluoroalkane to be replaced by iodine atoms to form the 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, stream B2 or both.

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

[0276] 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, C1-C10 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.

[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, 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.

[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, C1-C5 perfluoroalkyl groups and C5-C 10 Perfluorocycloalkyl group.

[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-C5 perfluoroalkyl groups and C5-C 10 Perfluorocycloalkyl group.

[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 independently for each unit n are 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 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 independently for each unit n are 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 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-CH3, CHF2-CH2-CH2F, CF3-CH2-CH3, CH2F-CHF-CH3, CH3-CF2-CH3, CHF2-CH2-CH2F, CF3-CH2-CH3, CH2F-CHF-CH2F, CHF2-CHF-CH3, CH2F-CF2-CH3, CHF2-CH2-CHF2, CF3-CH2-CH2F, CHF2-CHF-CH2F, CF3-CHF-CH3, CH2F-CF2-CH2F, CHF2-CF2-CH3, CF3-CH2-CHF2, CHF2-CHF-CHF2, CF3-CHF-CH2F, CHF2-CF2-CH2F, CF3-CF2-CH3, C F3-CH2-CF3, CF3-CHF-CHF2, CHF2-CF2-CHF2, CF3-CF2-CH2F, CF3-CHF-CF3, CF3-CF2-CHF2; preferably 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-CH2-CF3, CF3-CHF-CHF2, CF3-CHF-CF3.

[0283] According to a preferred embodiment, 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-CFI2, CF2 I-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, CFI2-CH 2-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-CH I-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-C H2I, 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. ,

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

[0285] - converting CH2F2 into CHF2I or CF2I2 or a mixture of the two; preferably into CHF2I;

[0286] -Convert CHF3 into CF3I;

[0287] - converting CHF2-CH3 into CF2I-CH3 or CHF2-CH2I or CHF2-CHI2 or CF2I-CH2I or a mixture thereof; preferably into CF2I-CH3;

[0288] - converting CF3-CH3 into CF3-CH2I or CF3-CHI2 or a mixture of the two; preferably into CF3-CH2I;

[0289] - converting CF3-CH2F into CF3-CHFI or CF3-CFI2 or a mixture of the two; preferably into CF3-CHFI;

[0290] -Convert CF3-CHF2 into CF3-CF2I;

[0291] - 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;

[0292] - 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;

[0293] - 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;

[0294] - 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;

[0295] - 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;

[0296] - 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;

[0297] - converting CF3-CH2-CF3 into CF3-CHI-CF3 or CF3-CI2-CF3 or a mixture of the two; preferably into CF3-CHI-CF3;

[0298] - 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

[0299] -Convert CF3-CHF-CF3 into CF3-CFI-CF3.

[0300] According to a preferred embodiment, step a) is carried out in the presence of a catalyst selected from: antimony, iron, titanium or tin halides; chromium or aluminium 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 between 50°C and 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 stream B1, stream B2 or both.

[0309] c) Recirculating the 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 water, preferably less than 100 ppm water, more preferably less than 50 ppm water, particularly less than 25 ppm water, more particularly less than 10 ppm water, and 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 R 1 、R 2 and R 3 are independently selected from H, F, C1-C 10 an alkyl group and a C3-C10 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" refers to a monovalent group derived from a linear or branched alkane having the specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane having 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, C1-C2 optionally substituted by 1-10 fluorine atoms 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.

[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, a C1-C5 alkyl group optionally substituted by 1 to 5 fluorine atoms, and a C5-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.

[0317] Therefore, advantageously, the iodofluoroalkane compound has the formula (II) (R 1 )(R 2 )CF(R 3 ), where R 1 、R2 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.

[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, C1-C1 optionally substituted with 1 to 10 fluorine atoms and / or at least one iodine atom 10 an alkyl group, and a C3-C4 optionally substituted by 1 to 10 fluorine atoms 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.

[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, C1-C2 optionally substituted with 1 to 5 fluorine atoms and / or at least one iodine atom 10 an alkyl group, and a C3-C4 optionally substituted by 1 to 5 fluorine atoms 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.

[0320] According to a preferred embodiment, the hydrofluoroalkane has the formula (I) (R 1 )(R 2 )CH(R 3 ), where R 1 、R2 and R 3 independently selected from H, F, Cl-C 10 Perfluoroalkyl groups and C3-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, C1-C5 perfluoroalkyl groups and C5-C 10 Perfluorocycloalkyl group.

[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, Cl-C 10 Perfluoroalkyl groups and C3-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, C1-C5 perfluoroalkyl groups and C5-C 10 Perfluorocycloalkyl group.

[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 independently for each unit n are 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 3At 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 independently for each unit n are 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 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 Y 1 、Y 2 and Y 3 independently of one another and independently for each unit n are 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 Y1 、Y 2 and Y 3 independently of one another and independently for each unit n are 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 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-CH3, CH2F-CF2-CH3, CHF2-CH2-CH2F, CF3-CH2-CH3, CH2F-CHF-CH2F, CHF2-CHF-CH3, CH2F-CF2-CH3, CHF2-CH2-CHF2, CF3-CH2-CH2F, CHF2-CHF-CH2F, CF3-CHF-CH3, CH2F-CF2-CH2F, C HF2-CF2-CH3, CF3-CH2-CHF2, CHF2-CHF-CHF2, CF3-CHF-CH2F, CHF2-CF2-CH2F, CF3-CF2-CH3, C F3-CH2-CF3, CF3-CHF-CHF2, CHF2-CF2-CHF2, CF3-CF2-CH2F, CF3-CHF-CF3, CF3-CF2-CHF2; preferably 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-CH2-CF3, CF3-CHF-CHF2, CF3-CHF-CF3.

[0325] In this preferred embodiment, 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-CFI2, CF2I-CH F2, 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-C H2I, CH2F-CHI-CH2I, CH2I-CHF-CH3, CH3-CFI-CH3, CHI2-CHF-CH3, CH2I-CFI-CH3, CH2I-CHF-CH2I, CHFI-CH2-CH2F, CH2F-CHI-CH2F, CFI2-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, CF2 I-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-C FI-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-CH I-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 iodo-fluoroalkane 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 iodo-fluoroalkane 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. ,

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

[0327] - converting CH2F2 into CHF2I or CF2I2 or a mixture of the two; preferably into CHF2I;

[0328] -Convert CHF3 into CF3I;

[0329] - converting CHF2-CH3 into CF2I-CH3 or CHF2-CH2I or CHF2-CHI2 or CF2I-CH2I or a mixture thereof; preferably into CF2I-CH3;

[0330] - converting CF3-CH3 into CF3-CH2I or CF3-CHI2 or a mixture of the two; preferably into CF3-CH2I;

[0331] - converting CF3-CH2F into CF3-CHFI or CF3-CFI2 or a mixture of the two; preferably into CF3-CHFI;

[0332] -Convert CF3-CHF2 into CF3-CF2I;

[0333] - 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;

[0334] - 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;

[0335] - 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;

[0336] - 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;

[0337] - 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;

[0338] - 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;

[0339] - converting CF3-CH2-CF3 into CF3-CHI-CF3 or CF3-CI2-CF3 or a mixture of the two; preferably into CF3-CHI-CF3;

[0340] - 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

[0341] -Convert CF3-CHF-CF3 into CF3-CFI-CF3.

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

[0343] Preferably, iodine (I2) is contacted with the hydrofluoroalkane in a stoichiometric amount or in excess thereof, for example, the I2 / hydrofluoroalkane molar ratio is 1-50, preferably 2-25, in particular 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 to 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 CO3 2- Preferably, the catalyst is NaI or KI. The catalyst preferably has a mass fraction of 20-1000 m 2 / g, especially 20-300m 2 The catalyst content is 1 wt% to 30 wt% relative to the hydrofluoroalkane. For liquid phase reactions, the above catalysts are preferred.

[0347] According to another embodiment, the catalyst may be selected from oxides, oxyhalides or halides of metals or metalloids from columns 4 to 15 of the periodic table. The catalyst may be an oxide, oxyhalide or halide of chromium or aluminum; in particular, the halide is a fluoride. More particularly, the catalyst may 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 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 15-100 m 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2The specific surface area is 200 nm / g. The specific surface area is measured using the standard five-point method (BET method) on a Micromeritics Gemini 2360 machine. When the catalyst is a chromium oxide, chromium oxyfluoride, or chromium fluoride, it may further contain 0.5% to 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. The catalyst content is preferably 0.01% to 20% by weight, in particular 0.1% to 10% by weight, 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, a catalyst based on an antimony, iron, titanium, or tin halide. Thus, the catalyst may be SbCl5, SbF5, FeCl3, TiCl4, or SnCl4. 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 or gas phase.

[0349] Therefore, preferred catalysts for carrying out step a) are selected from the group consisting of SbCl5, SbF5, FeCl3, TiCl4, SnCl4, NaI, KI, Cr2O3, Al2O3, chromium oxyfluorides, aluminum oxyfluorides, chromium fluorides and aluminum fluorides.

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

[0351] The catalyst may be activated before it is used in step a) of the process. Activation preferably involves treating the catalyst with a stream of HF, Cl2, I2 or O2 or a mixture thereof.

[0352] The catalyst may also deactivate over time. Therefore, step a) may be carried out in the presence of oxygen, 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 the hydrofluoroalkane.

[0353] The catalyst may also be regenerated after the process has been 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 of 50°C to 300°C, preferably 50°C to 280°C.

[0357] Furthermore, when carried out in the liquid phase, step a) is also carried out in the presence of a polar aprotic solvent S1. Preferably, solvent S1 is anhydrous. The term "anhydrous" means that solvent S1 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, said solvent S1 is free of water. Solvent S1 has a boiling point of 0°C to 250°C, preferably 20°C to 250°C, in particular 20°C to 200°C. The solvent S1 is selected from acetic acid, CCl4, 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] Stream A is then separated to form a first stream B1 comprising the iodofluoroalkane compounds and a stream B2 comprising unreacted iodine. Both stream B1 and stream B2 may contain impurities, reaction byproducts, or even unreacted hydrofluoroalkanes. Both stream B1 and stream B2 may optionally contain hydrogen iodide. Stream B1 is preferably subjected to an additional purification step to obtain stream B1 comprising the purified iodofluoroalkane compounds. 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 iodofluoroalkane compounds in stream B1 is greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, particularly greater than 98%, and even 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 this process comprises recycling logistics B2 to step a).This recycling step improves the overall yield of the process (better conversion efficiency) 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 this process.

[0364] If stream B1 comprises unreacted hydrofluoroalkane, said reagent can be removed from stream B1 and can also be recycled to 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, 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 relative to the total weight of the material M2.

[0368] Material M2 may also include a chromium content of less than 35% by weight, advantageously less than 30% by weight, preferably less than 20% by weight, more preferentially less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by 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, the material M1 comprises at least 70% by weight of iron, advantageously at least 75% by weight, preferably at least 80% by weight, more preferentially at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, based on the total weight of the material M1.

[0372] The material M1 may also contain 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 preferably less than 0.1% by weight of carbon, based on the total weight of the material M1. More particularly, the material M1 may contain 0.01% 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 abutted against 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 500 ml Hastelloy C276 autoclave equipped with a stirrer, a heating device, and a temperature control system. The autoclave was degassed and rendered inert with nitrogen, and the following anhydrous ingredients were introduced in succession: 250 ml of sulfolane, 15.0 g (0.1 mol) of sodium iodide, 67.0 g (0.5 mol) of CF3-CH2-CHF2 (HFC-245fa), and 200.0 g (0.79 mol) of anhydrous I2. The reaction medium was brought to 170-180° C. with stirring. After 6 hours of reaction with stirring, a sample was removed, washed, dried, and then analyzed by gas chromatography (area percentage). The conversion of CF3-CH2-CHF2 was 88%, with a selectivity for CF3-CH2-CF2I of 92%. Small amounts of CF3-CHI-CHF2, CF3-CI2-CHF2, and CF3-CHI-CF2I were observed.

[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 at the bottom, followed by an 85 mm layer of a chromium oxyfluoride catalyst containing 15 to 25 weight percent fluorine. The catalyst was preactivated at 350° C. in the presence of a gaseous stream of O . A gaseous stream of CF 3 -CHF-CH 2 F (HFC-245eb) and a gaseous stream of anhydrous I 2 (CF 3 -CHF-CH 2 F / I 2 molar ratio = 1 / 2) were passed over the catalyst at 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). The conversion of CF 3 -CHF-CH 2 F (HFC-245eb) was 94%, and the selectivity to CF 3 -CHF-CHFI was 98%. Small amounts of CF3-CFI-CH2F, CF3-CHF-CFI2 and CF3-CFI-CHFI were observed.

[0379] Comparable (equal) conversion and selectivity values ​​were obtained for the conversion of CF3-CHF-CH3 to CF3-CFI-CH3, the conversion of CF3-CH2-CH2F to CF3-CH2-CHFI, and the conversion of CF3-CHF-CHF2 to CF3-CHF-CF2I.

[0380] Invention IV

[0381] Overview 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 ) is contacted with iodine (I2) in a liquid phase to form a fluoroolefin of formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ) diiodofluoroalkane compounds;

[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 2and R 3 are independently selected from H, F, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including at least one fluorine atom.

[0386] According to a preferred embodiment, R 1 、R 2 and R 3 independently selected from H, F, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 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 Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 、Y 2 and Y 3 independently of one another and independently for each unit n are 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 the group consisting of CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF 2. CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CF=CHF, CF3-CF=CH2, CHF2-CH=CF2, CF3-CH=CHF, CHF2-CF=CF2, CF3-CF=CHF, CF3-CH=CF2; advantageously, the fluoroolefin is selected from CF2=CH2, CF2=CHF, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF;

[0389] and the diiodofluoroalkane compound is selected from CHFI-CH2I, CF2I-CH2I, CHFI-CHFI, CF2I-CHFI, CH3-CFI-CH2I, CH3-CHI-CHFI, CH2F-CHI-CH2I, CH3-CFI-CHFI, CH2F-CFI-CH2I, CH3-CHI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CFI-CHFI, CHF2-CFI-CH2I, CH2F-CHI-CF2I, CHF Advantageously, the diiodofluoroalkane compound is selected from CF2I-CH2I, CF2I-CHFI, CF3-CHI-CH2I, CF3-CFI-CH2I, CHF2-CFI-CHFI, CF3-CFI-CH2I, CHF2-CHI-CF2I, CF3-CHI-CHFI, CHF2-CFI-CF2I, CF3-CFI-CHFI, CF3-CHI-CF2I; advantageously, the diiodofluoroalkane compound is selected from CF2I-CH2I, CF2I-CHFI, CF3-CHI-CH2I, CF3-CFI-CH2I, CF3-CHI-CHFI, CF3-CFI-CHFI;

[0390] and the iodofluoroolefin is selected from the group consisting of CFI=CH2, CHF=CHI, CF2=CHI, CFI=CHF, CF2=CFI, CH2=CF-CH2I, CH3-CF=CHI, CH2=CH-CHFI, CH3-CI=CHF, CH3-CH=CFI, CHF=CH-CH2I, CH2F-CI=CH2, CH2F-CH=CHI, CH2=CF-CHFI, CH3-CF=CFI, CHF=CF-CH2I, CH2F-CF=CHI, CH2=CH-CF2I, CH3-CI=CF2, CHF=CH-CHFI, CH2F-CI =CHF, CH2F-CH=CFI, CF2=CH-CH2I, CHF2-CI=CH2, CHF2-CH=CHI, CH2=CF-CF2I, CHF=CF-CHFI, CH2F-CF=CFI, CF2=CF-CH2I, CHF2-CF=CHI, CH F=CH-CF2I, CH2F-CI=CF2, CF2=CH-CHFI, CHF2-CI=CHF, CHF2-CH=CFI, CF3-CI=CH2, CF3-CH=CHI, CHF=CF-CF2I, CF2=CF-CHFI, CHF2-CF=CFI, CF3-CF=CHI, CF2=CH-CF2I, CHF2-CI=CF2, CF3-CI=CHF, CF3-CH=CFI, CF2=CF-CF2I, CF3-CF=CFI, CF3-CI=CF2; preferably, the iodofluoroolefin is selected from CHI=CHF, CF2=CHI, CFI=CHF, CF2=CFI, CH3-CF=CHI, CH3-CI=CHF, CH2F-CI=CH2, CH2=CF-CHFI, CH2F-CF=CHI, CH3-CI=CF2, CH2F-CI=CHF, CHF2-CI=CH2, CH2 =CF-CF2I, CHF=CF-CHFI, CHF2-CF=CHI, CH2F-CI=CF2, CHF2-CI=CHF, CF3-CI=CH2, CHF=CF-CF2I, CHF2-CF=CFI, CF3-CF=CHI, CHF2-CI=CF2, CF3-CI=CHF, CF2=CF-CF2I, CF3-CF=CFI, CF3-CI=CF2; in particular, the iodofluoroolefin is selected from CF2=CHI, CF2=CFI, CF3-CI=CH2, CF3-CF=CHI, CF3-CI=CHF, CF3-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, said mixture comprises a base chosen from alkali metal or alkaline earth metal hydroxides; preferably, said mixture has an alkali metal or alkaline earth metal hydroxide content of 20% to 80% by weight relative to the total weight of said 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): 1 )(R 2 )C=CH(R 3 ) is contacted with iodine (I2) in a liquid phase to form a fluoroolefin 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-CH2I, CF2I-CH2I, CHFI-CHFI, CF2I-CHFI, CH3-CFI-CH2I, CH3-CHI-CHFI, CH2F-CHI-CH2I, CH3-CFI-CHFI, CH2F-CFI-CH2I, CH3-CHI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CFI-CHFI, CHF2-CFI-CH2I, CH2F-CHI-CF2 I, CHF2-CHI-CHFI, CF3-CHI-CH2I, CH2F-CFI-CF2I, CHF2-CFI-CHFI, CF3-CFI-CH2I, CHF2-CHI-CF2I, CF3-CHI-CHFI, CHF2-CFI-CF2I, CF3-CFI-CHFI, CF3-CHI-CF2I; advantageously, the iodofluoroalkane compound is selected from CF2I-CH2I, CF2I-CHFI, CF3-CHI-CH2I, CF3-CFI-CH2I, CF3-CHI-CHFI, CF3-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 ) is contacted with iodine (I2) in a liquid phase to form a fluoroolefin of formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ). Preferably, the process further comprises the following steps: dehydroiodination of the diiodine fluoroalkane compound of formula (II) obtained in step a) to form a diiodine fluoroalkane 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 ) is contacted with iodine (I2) in a liquid phase to form a fluoroolefin of formula (II) (R 1 )(R 2 )C(I)-CH(I)(R 3 ) diiodofluoroalkane compounds;

[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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including at least one fluorine atom.

[0405] Step a) of the process

[0406] Step a) of the process requires contacting the fluoroolefin with iodine (I2) 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including at least one fluorine atom.

[0409] The term "alkyl" refers to a monovalent group derived from a linear or branched alkane containing the specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane containing the specified number of carbon atoms. The term "alkenyl" refers to a monovalent group derived from a cycloalkene containing the 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 containing at least one carbon-carbon double bond in its cyclic portion and the specified number of carbon atoms. The term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon containing the 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 include 1 to 10 fluorine atoms, preferably 1 to 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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, C1-C2 optionally substituted by 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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 3 are independently selected from H, F, I, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, C1-C2 optionally substituted by 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro group as defined above.

[0416] Preferably, the fluoroolefin has the formula (I) (R 1 )(R 2 )C=CH(R3 ), where R 1 、R 2 and R 3 independently selected from H, F, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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 independently for each unit n are 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 Y 1 -[-C(Y 2 )(Y 3 )-] n -, where Y 1 、Y 2 and Y 3 independently of one another and independently for each unit n are 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 3independently of one another and independently for each unit n are 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 independently for each unit n are 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 the group consisting of CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CF=CHF, CF3-CF=CH2, CHF2-CH=CF2, CF3-CH=CHF, CHF2-CH=CF2. Advantageously, the fluoroolefin is selected from CF2=CH2, CF2=CHF, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-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 preferably, 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-C 10 aryl group; provided that the substituent R1 、R 2 or R 3 At least one of is F or is a group as defined above including 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, C1-C2 optionally substituted by 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 1 to 5 fluorine atoms.

[0430] Preferably, the diiodofluoroalkane compound has the formula (II) (R 1 )(R2 )C(I)-CH(I)(R 3 ), where R 1 、R 2 and R 3 are independently selected from H, F, C1-C2 optionally substituted by 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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 、Y2 and Y 3 independently of one another and independently for each unit n are 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 independently for each unit n are 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 independently for each unit n are 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 independently for each unit n are 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-CH2I, CF2I-CH2I, CHFI-CHFI, CF2I-CHFI, CH3-CFI-CH2I, CH3-CHI-CHFI, CH2F-CHI-CH2I, CH3-CFI-CHFI, CH2F-CFI-CH2I, CH3-CHI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CFI-CHFI, CHF2-CFI-CH2I, CH2F-CHI-CF2I, CHF2-CHI-CHFI, CF3-CHI-CH2I, CH2F-CFI-CF2I, CHF2-CFI-CHFI, CF3-CFI-CH2I, CHF2-CHI-CF2I, CF3-CHI-CHFI, CHF2-CFI-CF2I, CF3-CHI-CHFI, CHF2-CFI-CF2I, CF3-CFI-CHFI, CF3-CHI-CF2I. More particularly, the diiodofluoroalkane compound is selected from CF2I-CH2I, CF2I-CHFI, CF3-CHI-CH2I, CF3-CFI-CH2I, CF3-CHI-CHFI, and CF3-CFI-CHFI.

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

[0441] - converting CHF=CH2 into CHFI-CH2I; or

[0442] - converting CF2=CH2 into CF2I-CH2I; or

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

[0444] - converting CF2=CHF into CF2I-CHFI; or

[0445] - converting CH3-CF=CH2 into CH3-CFI-CH2I; or

[0446] - converting CH3-CH=CHF into CH3-CHI-CHFI; or

[0447] - converting CH2F-CH=CH2 into CH2F-CHI-CH2I; or

[0448] - converting CH3-CF=CHF into CH3-CFI-CHFI; or

[0449] - converting CH2F-CF=CH2 into CH2F-CFI-CH2I; or

[0450] - converting CH3-CH=CF2 into CH3-CHI-CF2I; or

[0451] - converting CH2F-CH=CHF into CH2F-CHI-CHFI; or

[0452] - converting CHF2-CH=CH2 into CHF2-CHI-CH2I; or

[0453] - converting CH3-CF=CF2 into CH3-CFI-CF2I; or

[0454] - converting CH2F-CF=CHF into CH2F-CFI-CHFI; or

[0455] - converting CHF2-CF=CH2 into CHF2-CFI-CH2I; or

[0456] - converting CH2F-CH=CF2 into CH2F-CHI-CF2I; or

[0457] - converting CHF2-CH=CHF into CHF2-CHI-CHFI; or

[0458] - converting CF3-CH=CH2 into CF3-CHI-CH2I; or

[0459] - converting CH2F-CF=CF2 into CH2F-CFI-CF2I; or

[0460] - converting CHF2-CF=CHF into CHF2-CFI-CHFI; or

[0461] - converting CF3-CF=CH2 into CF3-CFI-CH2I; or

[0462] - converting CHF2-CH=CF2 into CHF2-CHI-CF2I; or

[0463] -Convert CF3-CH=CHF into CF3-CHI-CHFI;

[0464] - converting CHF2-CF=CF2 into CHF2-CFI-CF2I; or

[0465] - converting CF3-CF=CHF into CF3-CFI-CHFI; or

[0466] -Convert CF3-CH=CF2 into CF3-CHI-CF2I.

[0467] Preferably, step a) is carried out in the absence of catalyzer.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, dimethylbenzene, p-chlorotrifluoromethylbenzene, hexafluorobenzene, tetrachloromethane, chloroform, methylene dichloride, 1-propane bromo and mixture thereof.The use of solvent makes and can avoid the obstruction problem relevant with the sublimation of iodine and the formation of restriction impurity (reaction byproduct, derived from the polymer of fluoroolefin, etc.) in this technology, and this makes and can realize particularly favorable selectivity from industrial viewpoint.

[0468] Preferably, iodine is contacted with the fluoroolefin as defined above in a stoichiometric amount or in excess thereof, for example, in an I2 / olefin molar ratio of 0.1-50, preferably 0.5-25, in particular 1-20.

[0469] Preferably, the content of oxygen dissolved in solvent S1 is less than 3000 ppm, advantageously less than 2000 ppm, preferably less than 1000 ppm, more preferably less than 500 ppm, in particular less than 250 ppm, more particularly less than 100 ppm, preferably less than 50 ppm, and preferably less than 10 ppm. This avoids degradation (deterioration) of the starting materials and the desired product. 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 from 20° C. to 280° C., preferably from 30° C. to 250° C. Step a) may be carried out at a pressure of from 0.1 bar to 15 bar, preferably from 1 bar abs. to 10 bar abs.

[0471] The diiodofluoroalkane compound may be dried before use 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.

[0472] The diiodofluoroalkane compound may be purified before use in step b). Purification can be performed before or after the drying step. This allows for the removal of certain impurities that may be difficult to separate from the iodofluoroalkene compound obtained in step b). This step also allows for improved selectivity in step b). Purification can be performed by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent, or contact with an adsorbent, or a combination thereof. Advantageously, purification of the diiodofluoroalkane compound involves producing a stream A having a diiodofluoroalkane compound content greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, particularly greater than 98%, and even 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 is in step b). The dried diiodofluoroalkane compound can be used directly in step b) without purification after the drying step, for example when step a) is carried out at a high conversion and selectivity, for example, greater than 90%, preferably greater than 95%. The absence of purification between steps a) and b) can be advantageous from the perspective of the overall productivity of the process, as 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 content by mass in the stream containing the diiodofluoroalkane compound and used in step b) is less than 500 ppm water, advantageously less than 250 ppm water, 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, 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 diiodofluoroalkane 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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 3 are independently selected from H, F, C1-C2 optionally substituted by 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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 3are independently selected from H, F, I, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, C1-C2 optionally substituted by 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R2 or R 3 At least one of is F or a perfluoro 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 or R 3 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1、R 2 or R 3 At least one of is F or a perfluoro group as defined above.

[0488] Alternatively, 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 independently for each unit n are 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 independently for each unit n are 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 、R2 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 independently for each unit n are 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 independently for each unit n are 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 the group consisting of CFI=CH2, CHF=CHI, CF2=CHI, CFI=CHF, CF2=CFI, CH2=CF-CH2I, CH3-CF=CHI, CH2=CH-CHFI, CH3-CI=CHF, CH3-CH=CFI, CHF=CH-CH2I, CH2F-CI=CH2, CH2F-CH=CHI, CH2=CF-CHFI, CH3-CF=CFI, CHF=CF-CH2I, CH2F-CF=CHI, CH2=CH-CF2I, CH3-CI=CF2, CHF=CH-CHFI, CH2F- C HF=CH-CF2I、CH2F-CI=CF2、CF2=CH-CHFI、CHF2-CI=CHF、CHF2-CH=CFI、CF3-CI=CH2、CF3-CH=CHI、CHF=CF-CF2I、CF2=CF-CHFI、CHF2-CF=CFI , CF3-CF=CHI, CF2=CH-CF2I, CHF2-CI=CF2, CF3-CI=CHF, CF3-CH=CFI, CF2=CF-CF2I, CF3-CF=CFI, CF3-CI=CF2; Preferably, the iodofluoroolefin is selected from CHI=CHF, CF2=CHI, CFI=CHF, CF2=CFI, CH3-CF=CHI, CH3-CI=CHF, CH2F-CI=CH2, CH2=CF-CHFI, CH2F-CF=CHI, CH3-CI=CF2, CH2F-CI=CHF, CHF2-CI=CH2, CH2 =CF-CF2I, CHF=CF-CHFI, CHF2-CF=CHI, CH2F-CI=CF2, CHF2-CI=CHF, CF3-CI=CH2, CHF=CF-CF2I, CHF2-CF=CFI, CF3-CF=CHI, CHF2-CI=CF2, CF3-CI=CHF, CF2=CF-CF2I, CF3-CF=CFI, CF3-CI=CF2; in particular, the iodofluoroolefin is selected from CF2=CHI, CF2=CFI, CF3-CI=CH2, CF3-CF=CHI, CF3-CI=CHF, CF3-CF=CFI.

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

[0494] -Convert CHFI-CH2I into CHI=CHF;

[0495] -Convert CF2I-CH2I into CF2=CHI;

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

[0497] -Convert CF2I-CHFI into CF2=CFI;

[0498] -Convert CH3-CFI-CH2I into CH3-CF=CHI;

[0499] -Convert CH3-CHI-CHFI into CH3-CI=CHF;

[0500] -Convert CH2F-CHI-CH2I into CH2F-CI=CH2;

[0501] -Convert CH3-CFI-CHFI into CH2=CF-CHFI;

[0502] -Convert CH2F-CFI-CH2I into CH2F-CF=CHI;

[0503] -Convert CH3-CHI-CF2I into CH3-CI=CF2;

[0504] -Convert CH2F-CHI-CHFI into CH2F-CI=CHF;

[0505] -Convert CHF2-CHI-CH2I into CHF2-CI=CH2;

[0506] -Convert CH3-CFI-CF2I into CH2=CF-CF2I;

[0507] -Convert CH2F-CFI-CHFI into CHF=CF-CHFI;

[0508] -Convert CHF2-CFI-CH2I into CHF2-CF=CHI;

[0509] -Convert CH2F-CHI-CF2I into CH2F-CI=CF2;

[0510] -Convert CHF2-CHI-CHFI into CHF2-CI=CHF;

[0511] -Convert CF3-CHI-CH2I into CF3-CI=CH2;

[0512] -Convert CH2F-CFI-CF2I into CHF=CF-CF2I;

[0513] -Convert CHF2-CFI-CHFI into CHF2-CF=CFI;

[0514] -Convert CF3-CFI-CH2I into CF3-CF=CHI;

[0515] -Convert CHF2-CHI-CF2I into CHF2-CI=CF2;

[0516] -Convert CF3-CHI-CHFI into CF3-CI=CHF;

[0517] -Convert CHF2-CFI-CF2I into CF2=CF-CF2I;

[0518] -Convert CF3-CFI-CHFI into CF3-CF=CFI;

[0519] -Convert CF3-CHI-CF2I to CF3-CI=CF2.

[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 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 ionometric manner 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 m 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2The specific surface area is measured on a Micromeritics Gemini 2360 using a standard five-point method (BET method). When the catalyst is a chromium oxide, chromium oxyfluoride, or chromium fluoride, it may further contain 0.5% to 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.

[0525] When the catalyst is selected from oxides, oxyhalides, or halides of metals or metalloids from columns 4 to 15 of the Periodic Table, it may be activated prior to use 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 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 deactivate over time. Thus, step b) may be carried out in the presence of oxygen, air, or an oxygen-nitrogen mixture. If oxygen is used in step b), it may be 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 CO3 2- Preferably, the catalyst is NaI, KI, SbF5, AlF3 or SbCl5. 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, with or without 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 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 to 250°C, preferably 20°C to 250°C, in particular 20°C to 200°C. The solvent S2 is selected from acetic acid, CCl4, 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 sodium iodide or potassium iodide is preferably used. The ratio between the catalyst and the fluoroolefin is 1-20, preferably 1-10. The catalyst preferably has a mass of 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 comprises an alkali selected from alkali metal or alkaline earth metal hydroxides, oxides, carbonates, or phosphates. Preferably, the alkali 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 alkali is selected from alkali metal or alkaline earth metal hydroxides and mixtures thereof. More particularly, the alkali 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, sulfolane, 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] A 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 base in the liquid phase, advantageously 0.01-5 mol% relative to the amount of base in the liquid phase, and preferably 0.05-5 mol% relative to the amount of base in the liquid phase.

[0542] Crown ethers are cyclic molecules in which ether groups are linked via dimethylene groups; these 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 C1-C 40 Alkyl, C6-C 40 Aryl or C6-C 40 Aralkyl groups and X is selected from F, Cl, Br, I, OH, CO3, HCO3, SO4, HSO4, H2PO4, HPO4 and PO4. 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 can be mentioned. 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, CaI2 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 includes the following step c): purifying stream B obtained in step b) to form stream B1 comprising the iodofluoroolefin and stream B2 comprising impurities, by-products, or unreacted starting materials. Preferably, after the purification step, the iodofluoroolefin content in stream B1 is greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, particularly greater than 98%, and more particularly greater than 99%. Stream B is preferably purified by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent, or a combination thereof. Stream B can also be separated or purified by contact with an adsorbent. The adsorbent can be a molecular sieve or zeolite having pore openings with an average diameter of 3 to 11 angstroms, advantageously 4 to 10 angstroms, and preferably 5 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, 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 relative to the total weight of the material M2.

[0550] Material M2 may also include a chromium content of less than 35% by weight, advantageously less than 30% by weight, preferably less than 20% by weight, more preferentially less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by 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, the material M1 comprises at least 70% by weight of iron, advantageously at least 75% by weight, preferably at least 80% by weight, more preferentially at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, based on the total weight of the material M1.

[0554] The material M1 may also contain 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 preferably less than 0.1% by weight of carbon, based on the total weight of the material M1. More particularly, the material M1 may contain 0.01% 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 abutted against each other by hot or cold plating, hot or cold rolling, or welding.

[0556] Example

[0557] Example 1

[0558] Step a): The equipment used consists of a 2.0 L Hastelloy C276 autoclave equipped with a pressure indicator, a temperature probe, a bursting disk, and a magnetic stirring system. The following are 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 CF3-CF=CH2(HFO-1234yf). The reactor is heated at 85°C for 11 hours and then cooled to room temperature. After degassing and then flushing with helium, the reaction mixture is collected after opening the autoclave. The organic phase is washed, dried, and then analyzed by gas chromatography (area percentage). This analysis confirms the formation of the diiodofluoroalkane compound CF3-CFI-CH2I (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 is composed of a 40 mm layer of corundum in the lower portion, 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). The yield of CF3-CF=CHI, expressed as the ratio of the number of moles of CF3-CF=CHI detected to the number of moles of HFO-1234yf initially introduced, is 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. The yield of CF3-CF=CHI after two reaction steps was about 78.7%.

[0562] Invention V

[0563] Overview of Invention V

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

[0565] a) contacting an olefin with iodine (I2) in a liquid phase to form a diiodoalkane compound;

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

[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 to 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 R4 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 independently for each unit n are 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 independently for each unit n are 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 independently for each unit n are 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 、Y2 or Y 3 At least one of them is F.

[0581] According to a preferred embodiment, the fluoroolefin is selected from the group consisting of CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CF2=CF2, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF2-C H=CHF、CF3-CH=CH2、CH2F-CF=CF2、CHF2-CF=CHF、CF3-CF=CH2、CHF2-CH=CF2、CF3-CH=CHF、CHF2-CF=CF2、CF3-CF=CHF、CF3- CH=CF2, CF3-CF=CF2; preferably selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2.

[0582] According to a preferred embodiment, the diiodoalkane compound is selected from the group consisting of CHFI-CH2I, CF2I-CH2I, CHFI-CHFI, CF2I-CHFI, CF2I-CF2I, CH3-CFI-CH2I, CH3-CHI-CHFI, CH2F-CHI-CH2I, CH3-CFI-CHFI, CH2F-CFI-CH2I, CH3-CHI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CFI-CHFI, CHF2-CFI-CH2I, CH2F-CHI-CF2I, CHF2-C HI-CHFI, CF3-CHI-CH2I, CH2F-CFI-CF2I, CHF2-CFI-CHFI, CF3-CFI-CH2I, CHF2-CHI-CF2I, CF3-CHI-CHFI, CHF2-CFI-CF2I, CF3-CFI-CHFI, CF3-C HI-CF2I, CF3-CFI-CF2I; preferably selected from CF2I-CH2I, CF2I-CHFI, CF2I-CF2I, CF3-CHI-CH2I, CF3-CFI-CH2I, CF3-CHI-CHFI, CF3-CFI-CHFI, CF3-CFI-CF2I.

[0583] According to a preferred embodiment, the iodofluoroalkane compound is selected from the group consisting of CHF2-CH2I, CHFI-CH2F, CF3-CH2I, CF2I-CH2F, CHF2-CHFI, CF3-CHFI, CF2I-CHF2, CF3-CF2I, CH3-CF2-CH2I, CH3-CFI-CH2F, CH3-CHF-CHFI, CH3-CHI-CHF2, CH2F-CHF-CH2I, CH2F-CHI-CH2F, CH3-CF2-CHFI, CH3-CFI-CHF2, CH2F-CF2-CH2I, CH2F-CFI-CH2F, CH3-CHF-CF2I, CH3-CHI-CF3, CH2F-CHF-CHFI, CH2F-CHI-CHF2, CHF2-CHF-CH2I, CH3-CF2-CF2I, CH3 -CFI-CF3, CH2F-CF2-CHFI, CH2F-CFI-CHF2, CHF2-CF2-CH2I, CH2F-CHF-CF2I, CHF2-CHF-CHFI, CHF2-CHI-CHF2, CF3-CHF-CH2I, CF3-CHI-CH2F, CH2F-CF2-CF2I, CHF2-CF2-CHFI, CHF2-CFI-CH F2, CF3-CF2-CH2I, CF3-CFI-CH2F, CHF2-CHF-CF2I, CF3-CHF-CHFI, CF3-CHI-CHF2, CHF2-CF2-C F2I, CF3-CF2-CHFI, CF3-CFI-CHF2, CF3-CHF-CF2I, CF3-CHI-CF3, CF3-CF2-CF2I, CF3-CFI-CF3;Advantageously, the iodofluoroalkane compound is selected from the group consisting of CHF2-CH2I, CF2I-CH2F, CF3-CH2I, CHF2-CHFI, CF2I-CHF2, CF3-CHFI, CF3-CF2I, CH3-CF2-CH2I, CH3-CHI-CHF2, CH2F-CHI-CH2F, CH3-CF2-CHFI, CH2F-CF2-CH2I, CH3-CHI-CF3, CH2F-CHI-CHF2, CHF2-CHI-CH2F, CH3-CFI-CF3, CH2F-CF2-CHFI, CHF2-CF2-CH2I, CH2F-CHI-CF3, CHF2-CHI-CHF2, 3-CHI-CH2F, CH2F-CFI-CF3, CHF2-CF2-CHFI, CF3-CFI-CH2F, CF3-CF2-CH2I, CHF2-CHI-CF3, CF3-CHI-CHF2, CHF2-CFI-CF3, CF3-CFI-CHF2, CF3-CF2-CHFI, CF3-CHI-CF3, CF3-CFI-CF3; preferably, the iodofluoroalkane compound is selected from CF3-CH2I, CF3-CHFI, CF3-CF2I, CF3-CHI-CH2F, CF3-CF2-CH2I, CF3-CHI-CHF2, CF3-CF2-CHFI, CF3-CFI-CF3. ;

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

[0585] - in step a) converting CF2=CH2 into CF2I-CH2I and in step b) fluorinating CF2I-CH2I to CF3-CH2I; or

[0586] - in step a) converting CF2=CHF into CF2I-CHFI and in step b) fluorinating CF2I-CHFI to CF3-CHFI; or

[0587] - in step a) converting CF2=CF2 into CF2I-CF2I and in step b) fluorinating CF2I-CF2I to CF3-CF2I; or

[0588] - in step a) converting CF3-CH=CH2 into CF3-CHI-CH2I and in step b) fluorinating CF3-CHI-CH2I to CF3-CHI-CH2F; or

[0589] - in step a) converting CF3-CF=CH2 into CF3-CFI-CH2I and in step b) fluorinating CF3-CFI-CH2I to CF3-CF2-CH2I; or

[0590] - in step a) converting CF3-CH=CHF into CF3-CHI-CHFI and in step b) fluorinating CF3-CHI-CHFI to CF3-CHI-CHF2; or

[0591] - in step a) converting CF3-CF=CHF into CF3-CFI-CHFI and in step b) fluorinating CF3-CFI-CHFI to CF3-CF2-CHFI; or

[0592] - In step a) CF3-CF=CF2 is converted into CF3-CFI-CF2I and in step b) CF3-CFI-CF2I is fluorinated to CF3-CFI-CF3.

[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 from 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 liquid phase at a temperature between 20°C and 300°C in the absence of a catalyst.

[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 Invention V

[0599] According to a first aspect, the present invention relates to a process for producing an iodofluoroalkane compound. Preferably, the process comprises the step of contacting an olefin with iodine (I2) in a liquid phase to form a diiodoalkane compound. 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 the iodofluoroalkane compound.

[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 independently selected from H, F, Cl, I, Cl-C 10 Alkyl groups, C3-C 10 Cycloalkyl groups, C2-C 10 Alkenyl groups, C3-C 10 Cycloalkenyl groups and C6-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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including at least one fluorine atom.

[0605] The olefin is a fluoroolefin, preferably having the formula (I) (R 1 )(R 2 )C=C(R 3 )(R 4 ) of a fluoroolefin, wherein R 1 、R 2 、R 3 and R4 are independently selected from H, F, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including at least one fluorine atom.

[0606] The term "alkyl" refers to a monovalent group derived from a linear or branched alkane containing the specified number of carbon atoms. The term "cycloalkyl" refers to a monovalent group derived from a cycloalkane containing the specified number of carbon atoms. The term "alkenyl" refers to a monovalent group derived from a cycloalkene containing the 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 containing at least one carbon-carbon double bond in its cyclic portion and the specified number of carbon atoms. The term "aryl" refers to a monovalent group derived from an aromatic hydrocarbon containing the 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 include 1 to 10 fluorine atoms, preferably 1 to 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-C 10 aryl group; provided that the substituent R1 、R 2 、R 3 or R 4 At least one of is F or is a group as defined above including 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, C1-C2 optionally substituted by 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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 、R 3 and R 4 are independently selected from H, F, I, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-C 10 aryl group; provided that the substituent R 1 、R 2 、R 3 or R 4At least one of is F or is a group as defined above including 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, C1-C2 optionally substituted by 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 R1 、R 2 、R 3 and R 4 independently selected from H, F, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4At least one of is F or a perfluoro 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 Y 3 independently of one another and independently for each unit n are 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 independently for each unit n are 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 independently for each unit n are 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 independently of one another and independently for each unit n are 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.

[0620] Preferably, the olefin is a fluoroolefin selected from the following: CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CF2=CF2, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=CF2, CHF2-C H=CHF、CF3-CH=CH2、CH2F-CF=CF2、CHF2-CF=CHF、CF3-CF=CH2、CHF2-CH=CF2、CF3-CH=CHF、CHF2-CF=CF2、CF3-CF=CHF、CF3- CH=CF2, CF3-CF=CF2; in particular, selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2.

[0621] The olefin, in particular the fluoroolefin as defined above, may have a boiling point of less than 100° C. at atmospheric pressure. Advantageously, the olefin, in particular the fluoroolefin as defined above, has a boiling point of less than 75° C. at atmospheric pressure. Preferably, the olefin, in particular the fluoroolefin as defined above, has a boiling point of less than 50° C. at atmospheric pressure. More preferentially, the olefin, in particular the fluoroolefin as defined above, has a boiling point of less than 25° C. at atmospheric pressure. In particular, the olefin, in particular the fluoroolefin as defined above, has a boiling point of less than 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 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 R1 、R 2 、R 3 and R 4 independently selected from H, F, Cl, I, Cl-C 10 Alkyl groups, C3-C 10 Cycloalkyl groups, C2-C 10 Alkenyl groups, C3-C 10 Cycloalkenyl groups and C6-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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10a cycloalkenyl group, and a C6-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 including 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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, C1-C2 optionally substituted by 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-C 10aryl 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 including 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, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, C1-C2 optionally substituted by 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 、R3 and R 4 independently selected from H, F, I, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 independently for each unit n are 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 、R4 、Y 1 、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 independently for each unit n are 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 of one another 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 of one another 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-CH2I, CF2I-CH2I, CHFI-CHFI, CF2I-CHFI, CF2I-CF2I, CH3-CFI-CH2I, CH3-CHI-CHFI, CH2F-CHI-CH2I, CH3-CFI-CHFI, CH2F-CFI-CH2I, CH3-CHI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CHI-CHFI, CHF2-CHI-CH2I, CH3-CFI-CF2I, CH2F-CFI-CHFI, CHF2-CFI-CH2I, CH2F-CHI-CF2I, CHF2-CHI-C HFI, CF3-CHI-CH2I, CH2F-CFI-CF2I, CHF2-CFI-CHFI, CF3-CFI-CH2I, CHF2-CHI-CF2I, CF3-CHI-CHFI, CHF2-CFI-CF2I, CF3-CFI-CHFI, CF3-CHI -CF2I, CF3-CFI-CF2I; more particularly selected from CF2I-CH2I, CF2I-CHFI, CF2I-CF2I, CF3-CHI-CH2I, CF3-CFI-CH2I, CF3-CHI-CHFI, CF3-CFI-CHFI, CF3-CFI-CF2I.

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

[0641] - converting CF2=CH2 into CF2I-CH2I; or

[0642] - converting CF2=CHF into CF2I-CHFI; or

[0643] - converting CF2=CF2 into CF2I-CF2I; or

[0644] - converting CF3-CH=CH2 into CF3-CHI-CH2I; or

[0645] - converting CF3-CF=CH2 into CF3-CFI-CH2I; or

[0646] - converting CF3-CH=CHF into CF3-CHI-CHFI; or

[0647] - converting CF3-CF=CHF into CF3-CFI-CHFI; or

[0648] -Convert CF3-CF=CF2 into CF3-CFI-CF2I.

[0649] As described above, step a) can be carried out using a mixture of alkenes, for example, selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2, to obtain a stream A comprising a mixture of diiodoalkane compounds, for example, selected from CF2I-CH2I, CF2I-CHFI, CF2I-CF2I, CF3-CHI-CH2I, CF3-CFI-CH2I, CF3-CHI-CHFI, CF3-CFI-CHFI, CF3-CFI-CF2I.

[0650] Preferably, step a) can be carried out in liquid phase.Preferably, step a) is carried out in the absence of catalyzer.Preferably, step a) is carried out in the presence of solvent S1.Preferably, solvent S1 is selected from aqueous potassium iodide, ether, fluorinated ether, alcohol, fluorinated alcohol, ester, aromatic solvent, fluorinated aromatic solvent, halogenated solvent and mixture thereof.Advantageously, solvent S1 is selected from aqueous potassium iodide, ethyl and methyl ether, hydrofluoroether, ethanol and methanol, ethyl lactate, toluene, dimethylbenzene, p-chlorotrifluoromethylbenzene, hexafluorobenzene, tetrachloromethane, chloroform, methylene dichloride, 1-propane bromo and mixture thereof.The use of solvent makes and can avoid the obstruction problem relevant with the sublimation of iodine and the formation of restriction impurity (byproduct of reaction, derived from the polymer of olefin, etc.) in this technology, and this makes and can realize particularly favorable selectivity from industrial point of view.

[0651] Preferably, iodine is contacted with the olefin, in particular with the fluoroolefin as defined above, in a stoichiometric amount or in excess thereof, for example, in an I2 / olefin molar ratio of 0.1-50, preferably 0.5-25, in particular 1-20.

[0652] Preferably, the content of oxygen dissolved in solvent S1 is less than 3000 ppm, advantageously less than 2000 ppm, preferably less than 1000 ppm, more preferably less than 500 ppm, in particular less than 250 ppm, more particularly less than 100 ppm, preferably less than 50 ppm, and preferably less than 10 ppm. This avoids degradation (deterioration) of the starting materials and the desired product. 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 from 20° C. to 280° C., preferably from 30° C. to 250° C. Step a) may be carried out at a pressure of from 0.1 bar to 15 bar, preferably from 1 bar abs. to 10 bar abs.

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

[0655] The diiodoalkane compound may be purified before use in step b). Purification may be performed before or after the drying step. This allows for the removal of certain impurities that may be difficult to separate from the iodofluoroalkane compound. This step also allows for improved selectivity in step b). Purification may be performed by distillation, azeotropic distillation, distillation under pressure, extractive distillation, cold separation, absorption in a solvent, or contact with an adsorbent, or a combination thereof. Advantageously, purification of the diiodoalkane compound involves producing a stream A having a diiodoalkane compound content greater than 90%, advantageously greater than 92%, preferably greater than 94%, more preferentially greater than 96%, particularly greater than 98%, and even 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) after the drying step without purification. 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 steps a) and b) is advantageous from the perspective of the overall productivity of the process, as purification steps 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 content by mass in the stream containing the diiodoalkane compound and used in step b) is less than 500 ppm water, advantageously less than 250 ppm water, 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, more preferably less than 5 ppm water; preferably, the diiodoalkane compound or the stream containing it used in 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 independently selected from H, F, Cl, I, Cl-C 10 Alkyl groups, C3-C 10 Cycloalkyl groups, C2-C 10 Alkenyl groups, C3-C 10 Cycloalkenyl groups and C6-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 4are independently selected from H, F, Cl, I, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C4-alkenyl group optionally substituted with at least one fluorine atom 10 a cycloalkenyl group, and a C6-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 including 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, C1-C1 optionally substituted with 1-10 fluorine atoms 10an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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 R 4 are independently selected from H, F, C1-C2 optionally substituted by 1-10 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C4 optionally substituted by 1-10 fluorine atoms 10 Cycloalkenyl group, and C6-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 including 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, C1-C1 optionally substituted with 1-5 fluorine atoms 10 an alkyl group, a C3-C 10Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 1 to 5 fluorine atoms.

[0666] 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, C1-C2 optionally substituted by 1-5 fluorine atoms 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 Alkenyl group, C3-C 10 Cycloalkenyl group, and C6-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 including 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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, Cl-C 10 Perfluoroalkyl groups, C3-C 10 Perfluorocycloalkyl groups, C2-C 10 Perfluoroalkenyl group, C3-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 R1 、R 2 、R 3 and R 4 independently selected from H, F, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl group, C2-C5 perfluoroalkenyl group, C5-C 10 Perfluorocycloalkenyl group, C6-C 10 perfluoroaryl group; provided that the substituent R 1 、R 2 、R 3 or R 4 At least one of is F or a perfluoro 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 independently for each unit n are 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 Y 1 、Y2 and Y 3 independently of one another and independently for each unit n are 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 of one another 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 of one another 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 、R2 、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 the group consisting of CHF2-CH2I, CHFI-CH2F, CF3-CH2I, CF2I-CH2F, CHF2-CHFI, CF3-CHFI, CF2I-CHF2, CF3-CF2I, CH3-CF2-CH2I, CH3-CFI-CH2F, CH3-CHF-CHFI, CH3-CHI-CHF2, CH2F-CHF-CH2I, CH2F-CHI-CH2F, CH3-CF2-CHFI, CH3-CFI-CHF2, CH2F-CF2-CH2I, CH2F-CFI-CH2F, CH3-CHF-CF2I, CH3-CHI-CF3, CH2F-CHF-CHFI, CH2F-CHI-CHF2, CHF2-CHF-CH2I, CH3-CF2-CF2I, CH3-CFI -CF3, CH2F-CF2-CHFI, CH2F-CFI-CHF2, CHF2-CF2-CH2I, CH2F-CHF-CF2I, CHF2-CHF-CHFI, CHF 2-CHI-CHF2, CF3-CHF-CH2I, CF3-CHI-CH2F, CH2F-CF2-CF2I, CHF2-CF2-CHFI, CHF2-CFI-CHF2 , CF3-CF2-CH2I, CF3-CFI-CH2F, CHF2-CHF-CF2I, CF3-CHF-CHFI, CF3-CHI-CHF2, CHF2-CF2-CF 2I, CF3-CF2-CHFI, CF3-CFI-CHF2, CF3-CHF-CF2I, CF3-CHI-CF3, CF3-CF2-CF2I, CF3-CFI-CF3;Advantageously, the iodofluoroalkane compound is selected from the group consisting of CHF2-CH2I, CF2I-CH2F, CF3-CH2I, CHF2-CHFI, CF2I-CHF2, CF3-CHFI, CF3-CF2I, CH3-CF2-CH2I, CH3-CHI-CHF2, CH2F-CHI-CH2F, CH3-CF2-CHFI, CH2F-CF2-CH2I, CH3-CHI-CF3, CH2F-CHI-CHF2, CHF2-CHI-CH2F, CH3-CFI-CF3, CH2F-CF2-CHFI, CHF2-CF2-CH2I, CH2F-CHI-CF3, CHF2-CHI-CHF2, 3-CHI-CH2F, CH2F-CFI-CF3, CHF2-CF2-CHFI, CF3-CFI-CH2F, CF3-CF2-CH2I, CHF2-CHI-CF3, CF3-CHI-CHF2, CHF2-CFI-CF3, CF3-CFI-CHF2, CF3-CF2-CHFI, CF3-CHI-CF3, CF3-CFI-CF3; preferably, the iodofluoroalkane compound is selected from CF3-CH2I, CF3-CHFI, CF3-CF2I, CF3-CHI-CH2F, CF3-CF2-CH2I, CF3-CHI-CHF2, CF3-CF2-CHFI, CF3-CFI-CF3. ;

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

[0677] - Fluorination of CF2I-CH2I to CF3-CH2I; or

[0678] - Fluorination of CF2I-CHFI to CF3-CHFI; or

[0679] - Fluorination of CF2I-CF2I to CF3-CF2I; or

[0680] - Fluorination of CF3-CHI-CH2I to CF3-CHI-CH2F; or

[0681] - Fluorination of CF3-CFI-CH2I to CF3-CF2-CH2I; or

[0682] - Fluorination of CF3-CHI-CHFI to CF3-CHI-CHF2; or

[0683] - Fluorination of CF3-CFI-CHFI to CF3-CF2-CHFI; or

[0684] -Fluorination of CF3-CFI-CF2I to CF3-CFI-CF3.

[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 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 hydrofluoric acid is free of water. The use of anhydrous hydrofluoric acid in this 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 greater than 15, a large amount or even a predominant amount of the compound of formula (IV) (R 1 )(R 2 )CF-C(F)(R 3 )(R 4 ) compounds. 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 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 between 150°C and 700°C, preferably between 250°C and 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 the oxides, oxyhalides or halides of metals or metalloids from 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 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 m 2 The chromium oxide catalyst preferably has a specific surface area of ​​100-300 m 2 The specific surface area is 1.5-2.5 wt % of the catalyst. The specific surface area is measured using a 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 further comprise a promoter in an amount of 0.5-10 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. Other catalysts that may be mentioned include 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, aluminum oxide, and aluminum oxide 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. Therefore, 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 has been 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 liquid phase in the presence of 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 water, 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 water, preferably less than 5 ppm water; preferably, solvent S2 is free of water. Solvent S2 has a boiling point of 0°C to 250°C, preferably 20°C to 250°C, in particular 20°C to 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 and mixtures thereof. Lewis acids may be used; catalysts based on metal halides, in particular 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 thereof. Metal chlorides and fluorides may advantageously be used. Examples of such catalysts include: SbCl5, SbCl3, TiCl4, SnCl4, TaCl5, NbCl5, TiCl4, FeCl3, MoCl6, CsCl, KCl, MgCl2 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 removed from the reactor in gaseous form while all or part of the reaction mixture (solvent, starting materials) remains in liquid form.

[0704] Step c) of the process

[0705] As described 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 logistics B2 or 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 can also be separated or purified by contact with an adsorbent. The adsorbent can be a molecular sieve or zeolite having pore openings with an average diameter of 3 to 11 angstroms, advantageously 4 to 10 angstroms, and preferably 5 to 10 angstroms.

[0708] Stream B2 is preferably recycled to step b); preferably, stream B2 free of 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) converting CF2=CH2 into CF2I-CH2I and in step b) fluorinating CF2I-CH2I to CF3-CH2I; or

[0712] - in step a) converting CF2=CHF into CF2I-CHFI and in step b) fluorinating CF2I-CHFI to CF3-CHFI; or

[0713] - in step a) converting CF2=CF2 into CF2I-CF2I and in step b) fluorinating CF2I-CF2I to CF3-CF2I; or

[0714] - in step a) converting CF3-CH=CH2 into CF3-CHI-CH2I and in step b) fluorinating CF3-CHI-CH2I to CF3-CHI-CH2F; or

[0715] - in step a) converting CF3-CF=CH2 into CF3-CFI-CH2I and in step b) fluorinating CF3-CFI-CH2I to CF3-CF2-CH2I; or

[0716] - in step a) converting CF3-CH=CHF into CF3-CHI-CHFI and in step b) fluorinating CF3-CHI-CHFI to CF3-CHI-CHF2; or

[0717] - in step a) converting CF3-CF=CHF into CF3-CFI-CHFI and in step b) fluorinating CF3-CFI-CHFI to CF3-CF2-CHFI; or

[0718] - In step a) CF3-CF=CF2 is converted into CF3-CFI-CF2I and in step b) CF3-CFI-CF2I is fluorinated to CF3-CFI-CF3.

[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, 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 relative to the total weight of the material M2.

[0721] Material M2 may also include a chromium content of less than 35% by weight, advantageously less than 30% by weight, preferably less than 20% by weight, more preferentially less than 15% by weight, in particular less than 10% by weight, more particularly less than 5% by 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, the material M1 comprises at least 70% by weight of iron, advantageously at least 75% by weight, preferably at least 80% by weight, more preferentially at least 85% by weight, in particular at least 90% by weight, more particularly at least 95% by weight, based on the total weight of the material M1.

[0725] The material M1 may also contain 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 preferably less than 0.1% by weight of carbon, based on the total weight of the material M1. More particularly, the material M1 may contain 0.01% 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 abutted against each other by hot or cold plating, hot or cold rolling, or welding.

[0727] Example

[0728] Example 1 - Synthesis of CF3-CFI-CF3

[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 introduced successively 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 (C3F6). 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 percentage).

[0732] The yield of CF3-CFI-CF2I, expressed as the ratio of the number of moles of CF3-CFI-CF2I detected to the number of moles of hexafluoropropylene initially introduced, was 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 in succession: 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). 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 approximately 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] The yield of CF3-CFI-CF3, expressed as the ratio of the number of moles of CF3-CFI-CF3 detected to the number of moles of hexafluoropropylene initially introduced, was 76.8%.

[0737] Example 2 - Synthesis of CF3-CF2-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)-CF3-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 subsequent 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).

[0741] The yield of CF3-CFI-CHFI, expressed as the ratio of the number of moles of CF3-CFI-CHFI detected to the number of moles of HFO-1225ye(Z) initially introduced, was 67.4%.

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

[0743] The autoclave was immersed in liquid nitrogen and the following ingredients were introduced in succession: 20 g (1.0 mol) of hydrofluoric acid, 96.2 g (0.25 mol) of CF3-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, then degassed and the reaction product was washed, dried and analyzed by gas chromatography.

[0745] The yield of CF3-CF2-CHFI, expressed as the ratio of the number of moles of CF3-CF2-CHFI detected to the number of moles of CF3-CF2-CHFI initially introduced, was 98.6%.

Claims

1. A process for producing an iodofluoroalkane compound, 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.

2. A process as claimed in claim 1, wherein the olefin is a fluoroolefin.

3. A process as claimed in any one of the preceding claims, wherein 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C 10 A cycloalkenyl group, and a C6-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.

4. A process as claimed in any one of the preceding claims, wherein 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl groups, C2-C5 perfluoroalkenyl groups, C5-C 10 Perfluorocycloalkenyl groups, 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.

5. A process as claimed in any one of the preceding claims, wherein 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.

6. A process as claimed in any one of the preceding claims, wherein the iodofluoroalkane compound is obtained by adding an iodine monofluoride (IF) molecule to the carbon-carbon double bond of the olefin.

7. A process as claimed in any one of the preceding claims wherein 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, C1-C 10 an alkyl group, a C3-C 10 Cycloalkyl group, C2-C 10 an alkenyl group, a C3-C 10 A cycloalkenyl group, and a C6-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 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, C1-C5 perfluoroalkyl groups, C5-C 10 Perfluorocycloalkyl groups, C2-C5 perfluoroalkenyl groups, C5-C 10 Perfluorocycloalkenyl groups, 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; 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.

8. A process as claimed in any one of the preceding claims, wherein the olefin is a fluoroolefin selected from the group consisting of CHF=CH2, CF2=CH2, CHF=CHF, CF2=CHF, CF2=CF2, CH3-CF=CH2, CH3-CH=CHF, CH2F-CH=CH2, CH3-CF=CHF, CH2F-CF=CH2, CH3-CH=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CH=CHF, CHF2-CH=CH2, CH3-CF=CF2, CH2F-CF=CHF, CHF2-CF=CH2, CH2F-CH=C F2, CHF2-CH=CHF, CF3-CH=CH2, CH2F-CF=CF2, CHF2-CF=CHF, CF3-CF=CH2, CHF2-CH=CF2, CF3-CH=CHF, CHF2-CF=CF2, CF3-CF=CHF , CF3-CH=CF2, CF3-CF=CF2; preferably selected from CF2=CH2, CF2=CHF, CF2=CF2, CF3-CH=CH2, CF3-CF=CH2, CF3-CH=CHF, CF3-CF=CHF, CF3-CF=CF2.

9. A process as claimed in any one of the preceding claims, wherein the iodofluoroalkane compound is selected from the group consisting of CHFI-CH2F, CHF2-CH2I, CF2I-CH2F, CF3-CH2I, CHFI-CHF2, CF2I-CHF2, CF3-CHFI, CF2I-CF3, CH3-CFI-CH2F, CH3-CF2-CH2I, CH3-CHI-CHF2, CH3-CHF-CHFI, CH2F-CHI-CH2F, CH2F-CHF-CH2I, CH3-CFI-CHF2, CH3 -CF2-CHFI, CH2F-CFI-CH2F, CH2F-CF2-CH2I, CH3-CHI-CF3, CH3-CHF-CF2I, CH2F-CHI-CHF2, CH2F-CHF-CHFI, CHF2-CHF-CH2 I. CH3-CFI-CF3, CH3-CF2-CF2I, CH2F-CFI-CHF2, CH2F-CF2-CHFI, CHF2-CF2-CH2I, CH2F-CHF-CF2I, CHF2-CHI-CHF2, CHF2-C HF-CHFI, CF3-CHI-CH2F, CF3-CHF-CH2I, CH2F-CF2-CF2I, CHF2-CFI-CHF2, CHF2-CF2-CHFI, CF3-CFI-CH2F, CF3-CF2-CH2I, C HF2-CHF-CF2I, CF3-CHI-CHF2, CF3-CHF-CHFI, CHF2-CF2-CF2I, CF3-CFI-CHF2, CF3-CF2-CHFI, CF3-CHI-CF3, CF3-CHF-CF2I , CF3-CFI-CF3, CF3-CF2-CF2I; preferably selected from CF2I-CH2F, CF3-CH2I, CF2I-CHF2, CF3-CHFI, CF2I-CF3, CF3-CHI-CH2F, CF3-CHF-CH2I , CF3-CFI-CH2F, CF3-CF2-CH2I, CF3-CHI-CHF2, CF3-CHF-CHFI, CF3-CFI-CHF2, CF3-CF2-CHFI, CF3-CFI-CF3, CF3-CF2-CF2I.

10. A process as claimed in any one of the preceding claims, wherein Step a) consists in: -Convert CF2=CH2 into CF3-CH2I; - converting CF2=CHF into CF3-CHFI; or -Converting CF2=CF2 into CF3-CF2I; or - converting CF3-CH=CH2 into CF3-CHI-CH2F; or - converting CF3-CF=CH2 into CF3-CF2-CH2I; or - converting CF3-CH=CHF into CF3-CHI-CHF2; or - converting CF3-CF=CHF into CF3-CFI-CHF2; or -Convert CF3-CF=CF2 into CF3-CFI-CF3.

11. A process as claimed in any one of the preceding claims, wherein anhydrous iodine monofluoride is prepared by mixing anhydrous iodine (I2) with anhydrous iodine pentafluoride (IF5).

12. A process as claimed in any one of the preceding claims, comprising the step b) of purifying said stream A to form a stream B1 comprising at least 90% by weight of said iodofluoroalkane compound.