Method for producing fluoro-diiodoalkanes and divinyl perfluoroalkanes

Abstract

To provide novel methods for producing fluoro-diiodoalkanes and divinyl perfluoroalkanes, characterized by simplicity, less production equipment limitations, and reduced energy consumption during manufacturing.SOLUTION: The present invention provides a method for producing "R1-CHICH2-Rf-CH2CHI-R1" (fluoro-diiodoalkanes) by reacting a perfluoroalkyl diiodide represented by the general formula (1) I-Rf-I (1) and an unsaturated compound represented by the general formula (2) H2C=CHR1 (2) in the presence of (i) an amine through light irradiation in an organic solvent, or a method for producing "R1CH=CH-Rf-CH=CHR1" (divinyl perfluoroalkane) by reacting the perfluoroalkyl diiodide and the unsaturated compound in the presence of (ii) a cyclic amidine through light irradiation in an organic solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel process for the preparation of fluorodiiodoalkanes and divinylperfluoroalkanes. [Background technology]

[0002] Fluorodiiodoalkanes are widely used as synthetic precursors for divinylperfluoroalkanes, which are useful for synthesizing fluorine-based functional polymer materials (e.g., Patent Document 1), and as synthetic precursors for diepoxyperfluoroalkanes, which are useful as raw materials for sealants for electrical and electronic applications (e.g., Patent Document 2).

[0003] As a method for producing fluorodiiodoalkanes, Patent Document 2 discloses a method of reacting perfluorodiiodide with an unsaturated alcohol in the presence of an azo-based thermal radical initiator at a high temperature of 50°C to 200°C and under a high pressure of up to 1 MPa gauge pressure. Patent Document 3 discloses a method of reacting perfluorodiiodide with ethylene at a high temperature of 180°C and under a high pressure of up to 5 MPa gauge pressure. Patent Document 4 discloses a method of reacting perfluorodiiodide with ethylene in the presence of a peroxide-based thermal radical initiator at 50°C and under a high pressure of up to 1.3 MPa gauge pressure.

[0004] All of these methods have the problem of high reaction pressures, which require specific equipment under the High Pressure Gas Safety Act, resulting in restrictions on manufacturing facilities. In addition, when a thermal radical initiator is used, a large amount of energy is required to heat the reaction system, and at high temperatures, there are problems such as the possibility of fluorodiiodoalkanes being thermally decomposed or side reactions such as telomerization in which fluorodiiodoalkanes undergo further radical addition. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2012-21054 A [Patent Document 2] JP 2009-67687 A [Patent Document 3] Special Publication No. 2015-500910 [Patent Document 4] Special Publication No. 2012-530800 Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above-mentioned background art, an object of the present invention is to provide a novel method for producing fluorodiiodoalkanes and divinylfluoroalkanes which is simple, requires fewer equipment restrictions, and consumes less energy in the production. [Means for solving the problem]

[0007] As a result of intensive research to solve the above-mentioned problems, the inventors have discovered that by reacting a perfluoroalkyl diiodide with an unsaturated compound in the presence of amines in an organic solvent by irradiating it with light, it is possible to produce fluorodiiodoalkanes and divinylperfluoroalkanes with little equipment constraints due to the low reaction pressure and with little energy consumption involved in the production due to the reaction temperature being room temperature or lower, thereby completing the present invention.

[0008] That is, the present invention relates to the following inventions. [1] The following general formula (1) I-Rf-I (1) (In the general formula (1), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms.) and a perfluoroalkyl diiodide represented by the formula: The following general formula (2) H2C=CHR 1 (2) (In general formula (2), R 1represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. In the presence of an amine, The reaction is carried out by irradiation with light in an organic solvent, and the reaction is carried out according to the following general formula (3): R 1 -CHICH2-Rf-CH2CHI-R 1 (3) In the general formula (3), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms; R 1 represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. A method for producing a fluorodiiodoalkane represented by the following formula: [2] The organic solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, 2-pentanone, 2-hexanone, cyclopentanone, cyclohexanone, dimethyl sulfoxide and acetonitrile. The method according to [1]. [3] The amines are represented by the following general formula (4): [ka] (In formula (4), R 2 , R 3 and R 4 each independently represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms which may contain a nitrogen atom, and each may be bonded to each other to form a ring, but R 2 , R 3 and R 4 are not all hydrogen atoms.) The manufacturing method according to item [1], wherein the compound is at least one selected from the group represented by the formula: [4] The method according to item [1], wherein the wavelength of the light to be irradiated is 250 nm to 450 nm. [5] The method according to any one of [1] to [4], wherein the amine is at least one selected from the group consisting of tertiary amines. [6] The method according to any one of items [1] to [4], wherein the perfluoroalkyl diiodide is 1,4-diiodooctafluorobutane or 1,6-diiodoperfluoro-n-hexane. [7] The unsaturated compound is ethylene or R 1 The method according to any one of items [1] to [4], wherein the hydrocarbon group is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms and containing a hydroxyl group therein. [8] The method according to any one of items [1] to [4], wherein the unsaturated compound is ethylene or allyl alcohol. [9] The method according to any one of items [1] to [4], wherein the organic solvent is acetone and the amine is triethylamine.

[10] The following general formula (1) I-Rf-I (1) (In the general formula (1), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms.) and a perfluoroalkyl diiodide represented by the formula: The following general formula (2) H2C=CHR 1 (2) (In general formula (2), R 1 represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. In the presence of cyclic amidines, an unsaturated compound represented by the following general formula (5) is reacted by light irradiation in an organic solvent: R 1 CH=CH-Rf-CH=CHR 1 (5) (In the general formula (5), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms; R 1 represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. A method for producing a divinylperfluoroalkane represented by the formula:

[11] The organic solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, 2-pentanone, 2-hexanone, cyclopentanone, cyclohexanone, dimethyl sulfoxide and acetonitrile. The method according to

[10] .

[12] The method according to item

[10] , wherein the cyclic amidines are 1,5-diazabicyclo[4.3.0]-5-nonene and / or 1,8-diazabicyclo[5.4.0]undec-7-ene.

[13] The method according to item

[10] , wherein the wavelength of the light to be irradiated is 250 nm to 450 nm.

[14] The method according to any one of items

[10] to

[13] , wherein the cyclic amidine is 1,8-diazabicyclo[5.4.0]undec-7-ene.

[15] The method according to any one of items

[10] to

[13] , wherein the perfluoroalkyl diiodide is 1,4-diiodooctafluorobutane or 1,6-diiodoperfluoro-n-hexane.

[16] The method according to any one of items

[10] to

[13] , wherein the unsaturated compound is ethylene.

[17] The method according to any one of items

[10] to

[13] , wherein the organic solvent is acetone and the cyclic amidine is 1,8-diazabicyclo[5.4.0]undec-7-ene. Effect of the Invention

[0009] The present invention provides a novel industrial process for producing fluorodiiodoalkanes and divinylperfluoroalkanes which is simple, requires fewer restrictions on production equipment, and consumes less energy in the production.

[0010] The present invention will be described in detail below.

[0011] The present invention relates to a compound represented by the following general formula (1): I-Rf-I (1) (In the general formula (1), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms.) and a perfluoroalkyl diiodide represented by the formula: The following general formula (2) H2C=CHR 1 (2) (In general formula (2), R 1 represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent.) is reacted with an unsaturated compound represented by the following general formula (3) by irradiation with light in an organic solvent in the presence of an amine to form a compound represented by the following general formula (3): R 1 -CHICH2-Rf-CH2CHI-R 1 (3) In the general formula (3), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms; R 1 represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent.

[0012] In the perfluorodiiodide represented by the above general formula (1), Rf is a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms, of which a linear perfluoroalkylene group having 4 to 8 carbon atoms is preferred, and a linear perfluoroalkylene group having 4 or 6 carbon atoms is particularly preferred.

[0013] The organic solvent used in this reaction is not particularly limited as long as it does not inhibit the reaction, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, 2-pentanone, 2-hexanone, cyclopentanone, cyclohexanone, dimethyl sulfoxide, and acetonitrile, among which acetone is preferably used. These can be used alone, or two or more types can be mixed and used.

[0014] The amines used in this reaction include those represented by the following general formula (4): [ka] (In formula (4), R 2 , R 3 and R 4 each independently represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms which may contain a nitrogen atom; R 2 , R 3 and R 4 Any two or all of the above may be bonded together to form a ring, such as 1-Azabicyclo[1.1.1]pentane (CAS: 34743-91-4). 2 , R 3 and R 4 are not all hydrogen atoms.

[0015] As the amines, primary amines, secondary amines, and tertiary amines can be used. As the primary amines, for example, normal propylamine, isopropylamine, methyl amine, normal butylamine, ethylenediamine, etc. Examples of the secondary amine include diethylamine, diisopropylamine, pyrrolidine, N,N'-dimethylethylenediamine, and proline. Examples of tertiary amines include triethylamine, diisopropylethylamine, N-methylmorpholine, N-ethylmorpholine, N-methylpiperidine, N-ethylpiperidine, N-methylpiperazine, N-ethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, pyridine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]undec-7-ene, phenanthroline, and N,N,N',N'-tetramethylethylenediamine. Among these, tertiary amines are preferred, and triethylamine is particularly preferred. These amines can be used alone or in combination of two or more.

[0016] The amount of the amine used in this reaction is preferably 0.01 mol to 4.0 mol, more preferably 0.01 mol to 2.0 mol, and particularly preferably 0.01 mol to 1.0 mol, per mol of the perfluoroalkyl diiodide used in the reaction. Furthermore, when the above-mentioned 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]undec-7-ene, phenanthroline, N,N,N',N'-tetramethylethylenediamine or the like among the amines is used for producing a fluorodiiodoalkane, the amount thereof is preferably 0.01 mol to 1.0 mol, more preferably 0.01 mol to 0.5 mol, and particularly preferably 0.01 mol to 0.3 mol, per mol of perfluoroalkyl diiodide.

[0017] The light source applicable to this reaction is not particularly limited as long as the wavelength of light emitted is 100 nm to 500 nm, preferably 250 nm to 450 nm. For example, ordinary external light (sunlight) or a commercially available light-emitting diode (LED) for chemical experiments can be used as long as it does not deviate from the purpose of the reaction. When using an LED as a light source, a white LED, UV LED, etc. can be used as appropriate as long as it can cover wavelengths of, for example, about 365 nm or about 405 nm. It is also preferable to control the light intensity during light irradiation, and when using an LED, it is sufficient to use one with an appropriate wattage (W). Furthermore, a photosensitizer can be used as appropriate to increase the intensity of light irradiation. Any photosensitizer can be used as long as it does not affect the reaction and has a sensitizing effect that can cover the required wavelengths.

[0018] The apparatus for carrying out this reaction preferably satisfies the following requirements: it is a container of a size appropriate for the amounts of various materials used in the production; it does not cause reactions other than the intended purpose, such as reactions with the various materials used in the production; if it has an external light source, it is made of a material that does not block light irradiation into the container; and if it is sealed, it is a pressure-resistant container appropriate for the pressure level during production.

[0019] The amount of the unsaturated compound used in the reaction of the present invention is preferably 0.1 mol to 50.0 mol, more preferably 1.0 mol to 40.0 mol, and particularly preferably 2.0 mol to 30.0 mol, per mol of the perfluoroalkyl diiodide used in the reaction.

[0020] The reaction temperature in the present invention is usually preferably in the range of -20°C to 40°C, more preferably in the range of 0°C to 30°C.

[0021] The post-treatment of the reaction of the present invention can be carried out by a known method. The reaction product can be directly or The product can be purified after washing with water. It can be isolated or purified by distillation under normal pressure or reduced pressure to obtain fluorodiiodoalkanes, which are the target compounds of the present invention. For example, after obtaining a crude product by simple distillation, it may be further purified by precision distillation as necessary.

[0022] In addition, the following general formula (1) I-Rf-I (1) (In the general formula (1), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms.) and a perfluoroalkyl diiodide represented by the formula: The following general formula (2) H2C=CHR 1 (2) (In general formula (2), R 1 represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. In the presence of cyclic amidines, an unsaturated compound represented by the following general formula (5) is reacted by light irradiation in an organic solvent: R 1 CH=CH-Rf-CH=CHR 1 (5) (In the general formula (5), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms; R 1 represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. This is a method for producing a divinylperfluoroalkane represented by the following formula:

[0023] The organic solvent used in this reaction is not particularly limited as long as it does not inhibit the reaction, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, 2-pentanone, 2-hexanone, cyclopentanone, cyclohexanone, dimethyl sulfoxide, and acetonitrile, among which acetone is preferably used. These can be used alone, or two or more types can be mixed and used.

[0024] Examples of cyclic amidines used in this reaction include 1,5-diazabicyclo[4.3.0]-5-nonene and 1,8-diazabicyclo[5.4.0]undec-7-ene. These can be used alone or in combination. Among these, 1,8-diazabicyclo[5.4.0]undec-7-ene is particularly preferred. The amount of cyclic amidines used in the reaction of the present invention is preferably more than 1 mol per mol of perfluoroalkyl diiodide used in the reaction, more preferably more than 2 mol. From a practical standpoint, it is advisable to use 2 mol to 10 mol, further 2 mol to 5 mol, and particularly preferably 2 mol to 3 mol of cyclic amidines. The reason for this is based on the finding that, while fluorodiiodoalkanes can be obtained by reacting a perfluoroalkyldiiodide with an unsaturated compound in the presence of amines by irradiation with light in an organic solvent, in the presence of a certain amount or more of cyclic amidines among the amines, deiodination of the fluorodiiodoalkanes proceeds to obtain divinylperfluoroalkanes.

[0025] The light source applicable to the reaction of the present invention is not particularly limited as long as the wavelength of light emitted is 100 nm to 500 nm, preferably 250 nm to 450 nm. For example, ordinary external light (sunlight) or a commercially available light-emitting diode (LED) for chemical experiments can be used as long as it does not deviate from the purpose. When using an LED as a light source, a white LED, UV LED, etc. can be used as appropriate as long as it can cover wavelengths of, for example, about 365 nm or about 405 nm. It is also preferable to control the light intensity during light irradiation, and when using an LED, it is sufficient to use one with an appropriate wattage (W). Furthermore, a photosensitizer can be used as appropriate to increase the intensity of light irradiation. Any photosensitizer can be used as long as it does not affect the reaction and has a sensitizing effect that can cover the required wavelengths.

[0026] The apparatus for carrying out this reaction preferably satisfies the following requirements: it is a container of a size appropriate for the amounts of various materials used in the production; it does not cause reactions other than the intended purpose, such as reactions with the various materials used in the production; if it has an external light source, it is made of a material that does not block light irradiation into the container; and if it is sealed, it is a pressure-resistant container appropriate for the pressure level during production.

[0027] The amount of the unsaturated compound used in the reaction of the present invention is preferably 0.1 to 50.0 mol, more preferably 1.0 to 40.0 mol, 2.0 to 30.0 mol, and particularly preferably 4.0 to 20.0 mol, per mol of the perfluoroalkyl diiodide used in the reaction.

[0028] The reaction temperature in the present invention is usually preferably in the range of -20°C to 40°C, more preferably in the range of 0°C to 30°C.

[0029] The post-treatment of the reaction of the present invention can be carried out by a known method. The reaction product can be directly or The divinylperfluoroalkanes can be isolated or purified by distillation under normal or reduced pressure, and the divinylperfluoroalkanes, which are the target compounds of the present invention, can be obtained. For example, after obtaining a crude product by simple distillation, the product may be further purified by precision distillation as necessary. EXAMPLES

[0030] Examples of the present invention are shown below, but the present invention is not limited to these examples.

[0031] The following instruments were used for the analysis: <nmr> 1 H-NMR (400MHz), 19 F-NMR (376MHz): Bruker AVANCE II 400

[0032] Example 1 0.52g (1.1mmol, Tosoh Finechem Co., Ltd.), 7.1g (0.12mol, Mitsui Chemicals Co., Ltd.), and 0.02g (0.2mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) of 1,4-diiodoperfluorobutane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 0.1g (4mmol, Air Water Inc.) of ethylene was bubbled into the tube under ice cooling, and then the tube was irradiated with 405nm UV light for 15 minutes using an LED light (Contec Co., Ltd.) at room temperature. Then, 0.02g (0.2mmol) of triethylamine was added, and 0.1g (4mmol) of ethylene was bubbled into the tube under ice cooling, and then the tube was irradiated with 405nm UV light for 15 minutes using an LED light. The same operation was repeated twice more. After that, 7.36g of a brown transparent liquid was obtained. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 7.8% by weight of 3,3,4,4,5,5,6,6-octafluoro-1,8-diiodooctane (98% yield). The yield was based on the starting material, 1,4-diiodoperfluorobutane (molar yield).

[0033] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.23 (m, 4H, CH2), 2.35 (m, 4H, CH2). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -115.62 (m, 4F, CF2), -124.04 (t, 4F, CF2).

[0034] Example 2 0.52g (0.94mmol, Tosoh Finechem Co., Ltd.), 7.1g (0.12mol, Mitsui Chemicals Co., Ltd.), and 0.02g (0.2mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) of 1,6-diiodoperfluorohexane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 0.1g (4mmol, Air Water Inc.) of ethylene was bubbled into the tube under ice cooling, and then the tube was irradiated with 405nm UV light for 15 minutes using an LED light (Contec Co., Ltd.) at room temperature. Then, 0.02g (0.2mmol) of triethylamine was added, and 0.1g (4mmol) of ethylene was bubbled into the tube under ice cooling, and then the tube was irradiated with 405nm UV light for 15 minutes using an LED light. The same operation was repeated twice more. After that, 7.27g of a brown transparent liquid was obtained. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 7.6% by weight of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,10-diiododecane (96% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0035] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.31 (m, 4H, CH2), 2.37 (m, 4H, CH2). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -115.52 (m, 4F, CF2), -122.39 (m, 4F, CF2), -124.08 (m, 4F, CF2).

[0036] Example 3 0.51g (1.1mmol, Tosoh Finechem Co., Ltd.), 7.1g (0.12mol, Mitsui Chemicals Co., Ltd.), 0.01g (0.08mmol, Fujifilm Wako Pure Chemical Co., Ltd.), and 0.14g (2.4mmol, Fujifilm Wako Pure Chemical Co., Ltd.) of allyl alcohol were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and the mixture was irradiated with 405nm UV light (Contec Co., Ltd.) at room temperature for 20 hours. After that, 8.34g of brown transparent liquid was obtained. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 6.1% by weight of 4,4,5,5,6,6,7,7-octafluoro-2,9-diiodo-1,10-decanediol (yield 80%). The yield was based on the starting material 1,4-diiodoperfluorobutane (molar yield).

[0037] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.14 (m, 2H, CH), 2.64 (m, 2H, CH), 3.22 (dd, 2H, CH), 3.39 (dd, 2H, CH), 3.79 (m, 2H, CH). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -114.28 (m, 4F, CF2), -124.16 (m, 4F, CF2).

[0038] Example 4 0.49g (0.88mmol, Tosoh Finechem Co., Ltd.), 7.8g (0.13mol, Mitsui Chemicals Co., Ltd.), 0.08g (0.8mmol, Fujifilm Wako Pure Chemical Co., Ltd.), and 0.13g (2.2mol, Fujifilm Wako Pure Chemical Co., Ltd.) of allyl alcohol were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and the mixture was irradiated with 405nm UV light (Contec Co., Ltd.) at room temperature for 16 hours. After that, 8.37g of brown transparent liquid was obtained. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 6.5% by weight of 4,4,5,5,6,6,7,7,8,8,9,9-dodecafluoro-2,11-diiodo-1,12-dodecanediol (91% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0039] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.17 (m, 2H, CH), 2.65 (m, 2H, CH), 3.22 (dd, 2H, CH) 3.39 (dd, 2H, CH), 3.79 (m, 2H, CH). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -114.15 (m, 4F, CF2), -122.25 (m, 4F, CF2), -124.32 (m, 4F, CF2).

[0040] Example 5 0.51g (0.92mmol, Tosoh Finechem Co., Ltd.), 8.1g (0.13mol, Mitsui Chemicals Co., Ltd.), and 0.03g (0.3mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 0.1g (4mmol, Air Water Inc.) of ethylene was bubbled into the tube under ice cooling, and then 405nm UV irradiation was performed for 30 minutes using an LED light (Contec Co., Ltd.) at room temperature. Then, 0.02g (0.2mmol) of diethylamine was added, and 0.1g (4mmol) of ethylene was bubbled into the tube under ice cooling, and then 405nm UV irradiation was performed for 30 minutes using an LED light. The same operation was repeated four more times. After that, 7.63g of a brown transparent liquid was obtained. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 5.7% by weight of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,10-diiododecane (70% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0041] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.31 (m, 4H, CH2), 2.37 (m, 4H, CH2). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -115.52 (m, 4F, CF2), -122.39 (m, 4F, CF2), -124.08 (m, 4F, CF2).

[0042] Example 6 0.50g (0.90mmol, Tosoh Finechem Co., Ltd.), 6.5g (0.12mol, Mitsui Chemicals Co., Ltd.), and 0.01g (0.1mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) of 1,6-diiodoperfluorohexane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 0.1g (4mmol, Air Water Inc.) of ethylene was bubbled into the tube under ice cooling, and then the tube was irradiated with 405nm UV light for 20 minutes using an LED light (Contec Co., Ltd.) at room temperature. Then, 0.01g (0.1mmol) of pyridine was added, and 0.1g (4mmol) of ethylene was bubbled into the tube under ice cooling, and then the tube was irradiated with 405nm UV light for 20 minutes using an LED light. The same operation was repeated twice more. After that, 6.17g of a brown transparent liquid was obtained. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 0.37% by weight of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,10-diiododecane (4% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0043] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.31 (m, 4H, CH2), 2.37 (m, 4H, CH2). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -115.52 (m, 4F, CF2), -122.39 (m, 4F, CF2), -124.08 (m, 4F, CF2).

[0044] Example 7 0.50g (0.90mmol, Tosoh Finechem Co., Ltd.), 6.5g (0.11mol, Mitsui Chemicals Co., Ltd.), and 0.02g (0.2mmol, Tokyo Chemical Industry Co., Ltd.) of 1,6-diiodoperfluorohexane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 0.1g (4mmol, Air Water Inc.) of ethylene was bubbled into the tube under ice cooling, and then the tube was irradiated with UV light at 405nm for 20 minutes using an LED light (Contec Co., Ltd.) at room temperature. Then, 0.01g (0.1mmol) of piperidine was added, and 0.1g (4mmol) of ethylene was bubbled into the tube under ice cooling, and then the tube was irradiated with UV light at 405nm for 20 minutes using an LED light. The same operation was repeated six more times. After that, 5.78g of a brown transparent liquid was obtained. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 7.4% by weight of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,10-diiododecane (77% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0045] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.31 (m, 4H, CH2), 2.37 (m, 4H, CH2). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -115.52 (m, 4F, CF2), -122.39 (m, 4F, CF2), -124.08 (m, 4F, CF2).

[0046] Example 8 0.51g (0.92mmol, Tosoh Finechem Co., Ltd.), 7.2g (0.13mol, Mitsui Chemicals Co., Ltd.), and 0.03g (0.2mmol, Fujifilm Wako Pure Chemical Co., Ltd.) of 1,6-diiodoperfluorohexane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 0.1g (4mmol, Air Water Inc.) of ethylene was bubbled into the tube under ice cooling, followed by 30 minutes of UV irradiation at 405nm using an LED light (Contec Co., Ltd.) at room temperature. After that, 0.1g (4mmol) of ethylene was bubbled into the tube under ice cooling, followed by 30 minutes of UV irradiation at 405nm using an LED light, obtaining 7.52g of a brown transparent liquid. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 6.2% by weight of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,10-diiododecane (83% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0047] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.31 (m, 4H, CH2), 2.37 (m, 4H, CH2). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -115.52 (m, 4F, CF2), -122.39 (m, 4F, CF2), -124.08 (m, 4F, CF2).

[0048] Example 9 0.50g (0.9mmol, Tosoh Finechem Co., Ltd.), 4.8g (0.11mol, Mitsui Chemicals Co., Ltd.), and 0.05g (0.5mmol, Fujifilm Wako Pure Chemical Co., Ltd.) of 1,6-diiodoperfluorohexane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 1.5g (0.02mol, Fujifilm Wako Pure Chemical Co., Ltd.) of 1-hexene was added at room temperature, and the mixture was irradiated with 405nm UV light using an LED light (Contec Co., Ltd.) for 2 hours at room temperature. Then, 0.04g (0.4mmol) of triethylamine was added, and the mixture was irradiated with 405nm UV light using an LED light (Contec Co., Ltd.) for 3 hours at room temperature, obtaining 6.59g of a brown transparent liquid. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 9.2% by weight of 7,7,8,8,9,9,10,10,11,11,12,12-dodecafluoro-1,18-diiodooctadecane (95% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0049] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 0.93 (t, 6H, CH3), 1.40 (m, 8H, CH2), 1.80 (m, 4H, CH2), 2.84 (m, 4H, CH2), 4.34 (ddd, 2H, CH). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -112.35 (ttd, 2F, CF), -115.07 (ttd, 2F, CF), -122.21 (m, 4F, CF2), -124.25 (m, 4F, CF2).

[0050] Example 10 0.50g (0.90mmol, Tosoh Finechem Co., Ltd.), 1.1g (0.02mol, Mitsui Chemicals Co., Ltd.), and 0.18g (2mmol, Fujifilm Wako Pure Chemical Industries Co., Ltd.) of 1,6-diiodoperfluorohexane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 2.2g (0.02mol, Tokyo Chemical Industry Co., Ltd.) of allyl bromide was added at room temperature, and the mixture was irradiated with 405nm UV light (Contec Co., Ltd.) at room temperature for 52 hours. After that, 3.57g of a brown transparent liquid was obtained. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 2.6% by weight of 4,4,5,5,6,6,7,7,8,8,9,9-dodecafluoro-1,12-dibromo-2,11-diiodododecane (13% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0051] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.84 (dd, 4H, CH3), 3.41 (dd, 4H, CH2), 4.37 (dddd, 2H, CH). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -114.08 (m, 4F, CF2), -122.35 (m, 4F, CF2), -123.72 (m, 4F, CF2).

[0052] Example 11 0.50g (0.90mmol, Tosoh Finechem Co., Ltd.), 1.0g (0.02mol, Mitsui Chemicals Co., Ltd.), and 0.18g (1.8mmol, Fujifilm Wako Pure Chemical Co., Ltd.) of 1,6-diiodoperfluorohexane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 1.3g (0.02mol, Fujifilm Wako Pure Chemical Co., Ltd.) of ethyl vinyl ether was added at room temperature, and the mixture was irradiated with 405nm UV light (Contec Co., Ltd.) for 4 hours at room temperature. Then, 0.5g (7mmol) of ethyl vinyl ether was added at room temperature, and the mixture was irradiated with 405nm UV light (Contec Co., Ltd.) for 3 hours at room temperature, obtaining 3.98g of a brown transparent liquid. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 10.0% by weight of 4,4,5,5,6,6,7,7,8,8,9,9-dodecafluoro-2,11-diiodo-1,12-diethoxydodecane (56% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0053] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 1.69 (m, 6H, CH3), 2.53 (m, 4H, CH2), 3.59 (m, 4H, CH2), 3.59 (t, 2H, CH). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -113.82 (dF, CF2), -121.48 (m, 4F, CF2), -124.24 (m, 4F, CF2).

[0054] Example 12 0.51g (0.92mmol, Tosoh Finechem Co., Ltd.), 5.8g (0.1mol, Mitsui Chemicals Co., Ltd.), 0.04g (0.4mmol, Fujifilm Wako Pure Chemical Co., Ltd.), and 2.69g (0.02mol, Fujifilm Wako Pure Chemical Co., Ltd.) of 5-bromo-1-pentene were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and the mixture was irradiated with 405nm UV light (Contec Co., Ltd.) at room temperature for 1 hour. After that, 0.05g (0.5mmol) of triethylamine was added at room temperature and irradiated with 405nm UV light (Contec Co., Ltd.) at room temperature for 1 hour twice, obtaining 8.71g of a brown transparent liquid. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 9.0% by weight of 6,6,7,7,8,8,9,9,10,10,11,11-dodecafluoro-1,16-dibromo-4,13-diiodohexadecane (yield 100%). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0055] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 1.94 (m, 4H, CH2), 2.16 (m, 4H, CH2), 2.79 (m, 4H, CH2), 3.45 (m, 4H, CH2Br), 4.30 (m, 2H, CHI). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -112.57 (ttd, 2F, CF), -114.75 (ttd, 2F, CF), -122.21 (m, 4F, CF2), -124.19 (m, 4F, CF2).

[0056] Example 13 0.51 g (1.1 mmol, Tosoh Finechem Co., Ltd.), 8.7 g (0.1 mol, Mitsui Chemicals, Inc.), and 0.02 g (0.1 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) of 1,8-diazabicyclo[5.4.0]undec-7-ene were added to a 40 mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 0.1 g (4 mmol, Air Water Inc.) of ethylene was bubbled through the tube under ice cooling. The tube was then exposed to 405 nm UV irradiation at room temperature for 30 minutes using an LED light (Contec Co., Ltd.). After that, 0.1g (4mmol) of ethylene was bubbled in while cooling with ice, then 0.02g (0.1mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene was added at room temperature, and the mixture was irradiated with 405nm UV light for 30 minutes using an LED light (Contec Co., Ltd.) and this operation was repeated four times. Next, 0.29g (1.9mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene was added at room temperature and stirred for 30 minutes to obtain 8.52g of a brown transparent liquid. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 2.9% by weight of 3,3,4,4,5,5,6,6-octafluoro-1,7-octadiene (82% yield). The yield was based on the starting material, 1,4-diiodoperfluorobutane (molar yield).

[0057] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 5.43 (m, 2H, CH), 5.54 (m, 2H, CH), 5.65 (m, 2H, CH). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -114.48 (m, 4F, CF2), -124.01 (m, 4F, CF2).

[0058] Example 14 0.52g (0.94mmol, Tosoh Finechem Co., Ltd.), 8.1g (0.1mol, Mitsui Chemicals Co., Ltd.), and 0.03g (0.2mmol, Fujifilm Wako Pure Chemical Co., Ltd.) of 1,6-diiodoperfluorohexane were added to a 40mL pressure-resistant tube (ACE GLASS Co., Ltd.), and 0.1g (4mmol, Air Water Inc.) of ethylene was bubbled into the tube under ice cooling, followed by 30 minutes of UV irradiation at 405nm using an LED light (Contec Co., Ltd.) at room temperature. After that, 0.1g (4mmol) of ethylene was bubbled into the tube under ice cooling, followed by 30 minutes of UV irradiation at 405nm using an LED light (Contec Co., Ltd.) at room temperature. Next, 0.29 g (1.9 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene was added at room temperature, and the mixture was stirred for 30 minutes to obtain 8.23 ​​g of a brown, transparent liquid. Benzotrifluoride as internal standard 19 F-NMR analysis revealed that the brown transparent liquid contained 3.7% by weight of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluoro-1,9-decadiene (91% yield). The yield was based on the starting material, 1,6-diiodoperfluorohexane (molar yield).

[0059] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 5.37 (m, 2H, CH), 5.44 (m, 2H, CH), 5.54 (m, 2H, CH). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -114.39 (m, 4F, CF2), -122.23 (m, 4F, CF2), -124.40 (m, 4F, CF2). [Industrial Applicability]

[0060] According to the present invention, fluoroiododiakanes and divinylperfluoroalkanes can be industrially produced simply and efficiently without requiring any specific facilities under the High Pressure Gas Safety Law and while reducing the energy consumption involved in the production.< / nmr>

Claims

1. The following general formula (1) I-Rf-I (1) (In general formula (1), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms.) and a perfluoroalkyl diiodide represented by the formula: The following general formula (2) H ２ C=CHR 1 (2) (In general formula (2), R １ represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. In the presence of an amine, The compound represented by the following general formula (3) is reacted by irradiation with light in an organic solvent. R １ -CHICH ２ -Rf-CH ２ CHI-R １ (3) (In the general formula (3), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms; R １ represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. A method for producing a fluorodiiodoalkane represented by the following formula:

2. The method according to claim 1, wherein the organic solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, 2-pentanone, 2-hexanone, cyclopentanone, cyclohexanone, dimethyl sulfoxide, and acetonitrile.

3. The amine is represented by the following general formula (4): 【Chemistry 3】 (In formula (4), R ２ , R ３ and R ４ each independently represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 8 carbon atoms which may contain a nitrogen atom, and each may be bonded to each other to form a ring, ２ , R ３ and R ４ are not all hydrogen atoms.) The method according to claim 1, wherein the compound is at least one selected from the group represented by the formula:

4. The method according to claim 1, wherein the wavelength of the light to be irradiated is from 250 nm to 450 nm.

5. The method according to any one of claims 1 to 4, wherein the amine is at least one selected from the group consisting of tertiary amines.

6. The method according to any one of claims 1 to 4, wherein the perfluoroalkyl diiodide is 1,4-diiodooctafluorobutane or 1,6-diiodoperfluoro-n-hexane.

7. The unsaturated compound is ethylene or R 1 The method according to any one of claims 1 to 4, wherein the alkyl group is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms and containing a hydroxyl group therein.

8. The process according to any one of claims 1 to 4, wherein the unsaturated compound is ethylene or allyl alcohol.

9. The process according to any one of claims 1 to 4, wherein the organic solvent is acetone and the amine is triethylamine.

10. The following general formula (1) I-Rf-I (1) (In general formula (1), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms.) and a perfluoroalkyl diiodide represented by the formula: The following general formula (2) H ２ C=CHR 1 (2) (In general formula (2), R １ represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. In the presence of cyclic amidines, an unsaturated compound represented by the following general formula (5) is reacted by light irradiation in an organic solvent: R １ CH=CH-Rf-CH=CHR １ (5) (In the general formula (5), Rf represents a perfluoroalkylene group having 1 to 2 carbon atoms, or a linear, branched, or cyclic perfluoroalkylene group having 3 to 8 carbon atoms; R １ represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms which may contain a substituent. A method for producing a divinylperfluoroalkane represented by the formula:

11. The method according to claim 10, wherein the organic solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diisobutyl ketone, 2-pentanone, 2-hexanone, cyclopentanone, cyclohexanone, dimethyl sulfoxide, and acetonitrile.

12. The method according to claim 10, wherein the cyclic amidines are 1,5-diazabicyclo[4.3.0]-5-nonene and / or 1,8-diazabicyclo[5.4.0]undec-7-ene.

13. The method according to claim 10, wherein the wavelength of the light to be irradiated is 250 nm to 450 nm.

14. The method according to any one of claims 10 to 13, wherein the cyclic amidine is 1,8-diazabicyclo[5.4.0]undec-7-ene.

15. The method according to any one of claims 10 to 13, wherein the perfluoroalkyl diiodide is 1,4-diiodooctafluorobutane or 1,6-diiodoperfluoro-n-hexane.

16. The process according to any one of claims 10 to 13, wherein the unsaturated compound is ethylene.

17. The method according to any one of claims 10 to 13, wherein the organic solvent is acetone and the cyclic amidine is 1,8-diazabicyclo[5.4.0]undec-7-ene.

Images