Method for producing fluoroiodoalkanes using a trifluoroiodomethane solution composition

Abstract

To provide a novel method of producing fluoroiodoalkane that is more convenient and has less restriction on a production apparatus using a trifluoroiodomethane solution composition as a raw material.SOLUTION: A trifluoroiodomethane solution composition comprises trifluoroiodomethane and an organic solvent, where the organic solvent is at least one solvent selected from the group consisting of dimethyl formamide, diethyl formamide, dimethyl acetoamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrolidone, and acetonitrile, and 10.0-90.0 wt.% of trifluoroiodomethane are contained in the trifluoroiodomethane solution composition. Also provided are a method of producing the same, and a method of producing fluoroiodoalkane using the trifluoroiodomethane solution composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel method for producing fluoroiodoalkanes using a trifluoroiodomethane solution composition. [Background technology]

[0002] Fluoriodoalkanes are widely used for purposes such as non-flammability of liquid compositions like solvents, detergents, and refrigerants, or for the synthesis of pharmaceutical and agrochemical intermediates (for example, Patent Document 1). Patent Document 2 discloses a method for producing fluoroiodoalkanes by iodinating fluorine-containing alkyl-substituted ethyl halides obtained by reducing fluorine-containing alkyl-substituted vinyl halides. However, this reaction requires multiple steps, resulting in poor production efficiency. Furthermore, the reduction step requires the reaction to be carried out under high pressure of 2 MPa gauge pressure, necessitating specific equipment under the High Pressure Gas Safety Act, thus creating constraints on the manufacturing equipment.

[0003] Non-patent document 1 discloses a method for reacting trifluoroiodomethane with an unsaturated hydrocarbon. However, this method requires a large excess of expensive trifluoroiodomethane, and since the reaction temperature is 200°C, the reaction system is expected to be under high pressure. This results in poor production efficiency in order to ensure sufficient porosity, making it unsuitable for mass production. Non-patent document 2 discloses a method for reacting trifluoroiodomethane with an unsaturated hydrocarbon by photoreaction. However, this method suffers from poor reaction efficiency, long reaction times, and reduced selectivity due to the overreaction of the resulting fluoroiodoalkane. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2022-113658 [Patent Document 2] Japanese Patent Publication No. 2010-1272 [Non-patent literature]

[0005] [Non-Patent Document 1] Journal of the Chemical Society C: Organic, 1970, Vol. 3, pp. 414-421 [Non-Patent Document 2] Journal of the Chemical Society (Resumed), 1949, pp. 2856-2861 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In view of the above-mentioned background art, the object of the present invention is to provide a novel method for producing fluoroiodoalkanes that is simpler and less restricted in terms of manufacturing equipment, using a trifluoroiodomethane solution composition as a raw material. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that by preparing a trifluoroiodomethane solution composition consisting of trifluoroiodomethane and an organic solvent in a pressure vessel, and reacting the trifluoroiodomethane solution composition with an unsaturated hydrocarbon in the presence of a radical initiator in a pressure vessel, fluoroiodoalkanes can be produced at a gauge pressure of 0.4 to less than 1.0 MPa, which does not require specific equipment under the High Pressure Gas Safety Act, thus completing the present invention.

[0008] In other words, the present invention is characterized by using a trifluoroiodomethane solution composition obtained by charging an organic solvent into a pressure vessel under reduced pressure in the range of absolute pressure from 0.1 kPa to 5.0 kPa, introducing trifluoroiodomethane to a gauge pressure of 0.4 MPa, and then releasing it to atmospheric pressure, to react with an unsaturated hydrocarbon in the pressure vessel in the presence of a radical initiator, as described in the following general formula (1): CF3-CH2CHX-I (1) (In formula (1), X represents a hydrogen atom or a methyl group.) This invention provides a method for producing fluoroiodoalkanes represented by [formula]. [Effects of the Invention]

[0009] The present invention provides a simple and convenient industrial method for producing fluoroiodoalkanes with fewer constraints on manufacturing equipment.

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

[0011] <Trifluoroiodomethane solution composition> The present invention relates to a trifluoroiodomethane solution composition comprising trifluoroiodomethane and an organic solvent, The organic solvent is at least one selected from the group consisting of dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and acetonitrile. The aforementioned trifluoroiodomethane solution composition contains trifluoroiodomethane in an amount of 10.0% to 90.0% by weight. This relates to a trifluoroiodomethane solution composition.

[0012] The organic solvents used in the trifluoroiodomethane solution composition of the present invention are preferably dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and acetonitrile, with dimethylformamide and diethylformamide being more preferred, and dimethylformamide being particularly preferred. These can be used individually, or two or more can be used in combination.

[0013] In the trifluoroiodomethane solution composition of the present invention, the content of trifluoroiodomethane is usually preferably 10.0 parts by weight to 90.0 parts by weight, more preferably 70.0 parts by weight to 90.0 parts by weight. When the content falls within this range, the effect of the present invention, which is an industrially simple process for producing fluoroiodoalkanes with few restrictions on production equipment, can be achieved.

[0014] <Method for producing trifluoroiodomethane solution composition> The present invention relates to a method for producing a trifluoroiodomethane solution composition, which comprises charging an organic solvent into a pressure-resistant vessel, reducing the pressure to 0.1 kPa to 5.0 kPa in absolute pressure, then introducing trifluoroiodomethane up to 0.4 MPa in gauge pressure, and bringing the system to atmospheric pressure by releasing to the atmosphere, the organic solvent is at least one selected from the group consisting of dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone and acetonitrile, The trifluoroiodomethane solution composition contains 10.0% by weight to 90.0% by weight of trifluoroiodomethane, relating to the method for producing the trifluoroiodomethane solution composition.

[0015] As the pressure-resistant vessel used in the method for producing the trifluoroiodomethane solution composition of the present invention, it is desirable to satisfy the requirements that the vessel has a scale corresponding to the amount of various materials used for production, the vessel is made of a material that does not cause reactions other than the intended purpose such as reactions with various materials used for production, and the vessel is a pressure-resistant vessel corresponding to the pressure level under production conditions.

[0016] An organic solvent is charged into this pressure-resistant vessel, and the pressure is preferably reduced to 0.1 kPa to 10.0 kPa in absolute pressure, more preferably 0.1 kPa to 5.0 kPa, particularly preferably 0.1 kPa to 3.0 kPa. After the pressure reduction, it is preferable to introduce trifluoroiodomethane up to a gauge pressure of 0.4 MPa. After the introduction of trifluoroiodomethane, the pressure-resistant vessel is preferably opened to the atmosphere to bring the system to atmospheric pressure.

[0017] Here, absolute pressure is an absolute representation with absolute vacuum set to 0, indicating the actual pressure being applied. Gauge pressure is a relative pressure representation with atmospheric pressure set to 0, indicating the pressure relative to the ambient pressure. The relationship between the two is as follows: (Gauge pressure) + (Atmospheric pressure) = (Absolute pressure)

[0018] The organic solvents used in the method for producing the trifluoroiodomethane solution composition of the present invention are preferably dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and acetonitrile, more preferably dimethylformamide and diethylformamide, and particularly preferably dimethylformamide. These can be used individually, or two or more can be used in combination.

[0019] The trifluoroiodomethane used in the method for producing the trifluoroiodomethane solution composition of the present invention is preferably contained in the composition in an amount of 10.0 to 90.0 parts by weight, and more preferably in an amount of 70.0 to 90.0 parts by weight. Within this content range, the effect of the present invention, which is a simple industrial method for producing fluoroiodoalkanes with fewer constraints on manufacturing equipment, can be achieved.

[0020] <Method for producing fluoroiodoalkanes> The present invention relates to a method for producing fluoroiodoalkanes represented by the following general formula (1), wherein the reaction pressure is in the range of 0.4 MPa to less than 1.0 MPa in gauge pressure in a pressure vessel, in the presence of a trifluoroiodomethane solution composition comprising trifluoroiodomethane and an organic solvent and a radical initiator, and the reaction pressure is in the range of 0.4 MPa to less than 1.0 MPa. The organic solvent is at least one selected from the group consisting of dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and acetonitrile. The trifluoroiodomethane solution composition contains 10.0% to 90.0% by weight of trifluoroiodomethane. Method for producing fluoroiodoalkanes CF3-CH2CHX-I (1) (In formula (1), X represents a hydrogen atom or a methyl group.) It relates to.

[0021] The pressure vessel used in the method for producing fluoroiodoalkanes of the present invention is desirable to satisfy the following requirements: it should be a vessel of a scale appropriate to the amount of various materials used in production; it should be made of a material that does not cause reactions other than those intended, such as reactions with the various materials used in production; and it should be a pressure vessel appropriate to the pressure level under production.

[0022] A trifluoroiodomethane solution composition consisting of trifluoroiodomethane and an organic solvent, along with a radical initiator, is charged into this pressure vessel, and the mixture is reacted with an unsaturated hydrocarbon at a reaction pressure of 0.4 MPa or more and less than 1.0 MPa, more preferably 0.7 MPa or more and less than 1.0 MPa, and particularly preferably 0.9 MPa or more and less than 1.0 MPa in gauge pressure.

[0023] In the method for producing fluoroiodoalkanes of the present invention, the content of trifluoroiodomethane in the trifluoroiodomethane solution composition is preferably 40.0% to 90.0% by weight, more preferably 60.0% to 90.0% by weight, and particularly preferably 80.0% to 90.0% by weight.

[0024] The radical initiators for the reaction of the present invention are 2,2'-azobis(isobutyronitrile), dimethyl-2,2'-azobis(2-methylpropinate), 2,2'-azobis(2,4'-dimethylvaleronitrile), (2-ethylhexanoyl)t-butyl peroxide, t-butyl pivalate peroxide, t-hexyl pivalate peroxide, lauroyl peroxide, succinic acid peroxide, 1,1,3,3-tetramethylbutylperoxy ethylhexanoate, and 2,5-dimethyl-2,5-di(2 -Ethylhexanoylperoxy)hexane, di(3,5,5-trimethylhexanoyl)peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, disec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxynedecanoate, di2-ethylhexyl peroxydicarbonate, t-hexyl peroxynedecanoate, and t-butyl peroxynedecanoate are preferred, with 2,2'-azobis(isobutyronitrile) being particularly preferred. These can be used individually, or two or more can be used in combination.

[0025] The amount of radical initiator used in the present invention is preferably 0.01 mol to 0.10 mol, more preferably 0.01 mol to 0.05 mol, and especially preferably 0.01 mol to 0.03 mol per 1 mol of trifluoroiodomethane in the reaction.

[0026] The unsaturated hydrocarbon used in the present invention is preferably ethylene, propylene, or a mixture of both.

[0027] The amount of unsaturated hydrocarbon used in this invention is preferably 1.0 mol to 2.0 mol, more preferably 1.0 mol to 1.5 mol, and especially preferably 1.0 mol to 1.2 mol, per 1 mol of trifluoroiodomethane in the reaction.

[0028] The preparation temperature for the trifluoroiodomethane solution composition of the present invention is usually preferably in the range of -60°C to 40°C, and more preferably in the range of -10°C to 10°C.

[0029] The reaction temperature in this invention is usually preferably in the range of 40°C to 100°C, and more preferably in the range of 50°C to 70°C.

[0030] The reaction time in this invention is usually preferably in the range of 6 to 30 hours, and more preferably in the range of 10 to 24 hours.

[0031] The post-reaction treatment of the present invention can be carried out by known methods, and the reaction product can be purified directly or after washing with water. It can be isolated or purified by distillation under atmospheric pressure or reduced pressure to obtain the fluoroiodoalkane, which is the target compound of the present invention. For example, after obtaining a crude product by simple distillation, it may be further purified by precision distillation as needed. [Examples]

[0032] Examples of the present invention are shown below, but the present invention is not limited to these examples.

[0033] The following equipment was used for the analysis. <nmr> 1 H-NMR (400 MHz), 19 F-NMR (376MHz): Bruker AVANCE II 400

[0034] Example 1 42 g of dimethylformamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 0.6 mol) was added to a 300 mL stainless steel pressure vessel at room temperature under a nitrogen atmosphere. After reducing the pressure to 3.0 kPa absolute pressure, 173 g of trifluoroiodomethane (manufactured by Tosoh Finechem Co., Ltd., 0.9 mol) was added at 5-30°C. Subsequently, the mixture was cooled to 0-10°C and opened to the atmosphere to obtain 213 g of the trifluoroiodomethane solution composition. Benzotrifluoride is used as the internal standard. 19 1F-NMR analysis revealed that the solution composition contained 80% by weight of trifluoroiodomethane.

[0035] The analysis results were as follows: 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ(ppm): -12.1(s, 3F, CF3).

[0036] Example 2 213 g (0.9 mol as trifluoroiodomethane) of a trifluoroiodomethane solution composition prepared in the same manner as in Example 1, and 3 g (0.02 mol) of 2,2'-azobis(isobutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 300 mL stainless steel pressure vessel in an ambient atmosphere, and stirring was started. Subsequently, the temperature was raised to 65°C, and while maintaining an internal temperature of 65-70°C, 29 g (1.0 mol) of ethylene (manufactured by Air Water Inc.) was added intermittently over 17 hours at a gauge pressure of 0.80-0.98 MPa. After cooling to room temperature, the mixture was opened to the atmosphere, yielding 233 g of a brown, transparent liquid. Benzotrifluoride is used as the internal standard. 19 From F-NMR analysis, the brown transparent liquid contained 84% by weight of 1,1,1-trifluoro-3-iodopropane (yield 98%). The yield was based on the starting material trifluoroiodomethane (molar yield). Further, the obtained brown transparent liquid was washed with pure water, and the resulting yellow transparent liquid was subjected to simple distillation at 50 to 100°C under an absolute pressure of 40 kPa, to obtain 173 g of 1,1,1-trifluoro-3-iodopropane (colorless transparent liquid) (isolated yield 84%).

[0037] The analysis results were as follows. 1 H-NMR (solvent: deuterochloroform, internal standard: chloroform) δ(ppm): 2.46 (qt, 2H, CH₂), 2.95 (t, 2H, CH₂). 19 F-NMR (solvent: deuterochloroform, internal standard: benzotrifluoride) δ(ppm): -67.6 (s, 3F, CF₃).

[0038] Comparative Example 1 In a 300 mL stainless steel pressure vessel, 259 g of the trifluoroiodomethane solution composition (1.1 mol as trifluoroiodomethane) prepared in the same manner as in Example 1 in an inert atmosphere, and 5 g of 1,1-azobis(cyclohexane-1-carbonitrile) (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 0.02 mol) were added, and stirring was started. Subsequently, after the temperature was raised to 89°C, while maintaining the internal temperature at 89 to 93°C, 34 g of ethylene (manufactured by Air Water Inc., 1.2 mol) was added intermittently over 15 hours within the gauge pressure range of 1.4 to 1.6 MPa. After cooling to room temperature, the vessel was opened to the atmosphere to obtain 289 g of a brown transparent liquid. Using benzotrifluoride as the internal standard 19 From F-NMR analysis, the brown transparent liquid contained 80% by weight of 1,1,1-trifluoro-3-iodopropane (yield 98%). The yield was based on the starting material trifluoroiodomethane (molar yield).

[0039] The analysis results were as follows. 1 ¹H-NMR (solvent: deuterated chloroform, internal standard: chloroform) δ (ppm): 2.46 (qt, 2H, CH2), 2.95 (t, 2H, CH2). 19 F-NMR (solvent: deuterated chloroform, internal standard: benzotrifluoride) δ (ppm): -67.6 (s, 3F, CF3).

[0040] Comparative Example 2 In a 300 mL stainless steel pressure vessel, 119 g of a trifluoroiodomethane solution composition (0.06 mol as trifluoroiodomethane) prepared by the method of Example 1 with a trifluoroiodomethane content of 9.5 parts by weight was added in an ambient atmosphere, and 0.2 g of 2,2'-azobis(isobutyronitrile, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 0.001 mol) was added, and stirring was started. Subsequently, the temperature was raised to 65°C, and while maintaining an internal temperature of 65-70°C, ethylene (manufactured by Air Water Inc., 0.08 mol) was added intermittently over 11 hours at a gauge pressure in the range of 0.80-0.98 MPa. After cooling to room temperature, the mixture was opened to the atmosphere, and 110 g of a brown transparent liquid was obtained. Benzotrifluoride is used as the internal standard. 19 1F-NMR analysis revealed that the brown, transparent liquid contained only trace amounts of 1,1,1-trifluoro-3-iodopropane. [Industrial applicability]

[0041] This invention makes it possible to industrially produce fluoroiodoalkanes in a simple manner and with high yield without requiring specific equipment under the High Pressure Gas Safety Act.< / nmr>

Claims

1. A trifluoroiodomethane solution composition comprising trifluoroiodomethane and an organic solvent, The organic solvent is at least one selected from the group consisting of dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and acetonitrile. The aforementioned trifluoroiodomethane solution composition contains 70.0% to 90.0% by weight of trifluoroiodomethane. A trifluoroiodomethane solution composition.

2. The trifluoroiodomethane solution composition according to claim 1, wherein the organic solvent is dimethylformamide.

3. A method for producing a trifluoroiodomethane solution composition, comprising charging an organic solvent into a pressure vessel, reducing the absolute pressure to 0.1 kPa to 5.0 kPa, introducing trifluoroiodomethane to a gauge pressure of 0.4 MPa, and then releasing to atmospheric pressure, wherein the mixture is brought to atmospheric pressure. The organic solvent is at least one selected from the group consisting of dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and acetonitrile. A method for producing a trifluoroiodomethane solution composition, wherein the trifluoroiodomethane solution composition contains 70.0% to 90.0% by weight of trifluoroiodomethane.

4. A method for producing a trifluoroiodomethane solution composition according to claim 3, wherein the organic solvent is dimethylformamide.

5. A method for producing a fluoroiodoalkane represented by the following general formula (1), comprising reacting an unsaturated hydrocarbon with trifluoroiodomethane in a pressure vessel in the presence of a trifluoroiodomethane solution composition consisting of trifluoroiodomethane and an organic solvent, and a radical initiator, at a gauge pressure of 0.4 MPa or more and less than 1.0 MPa, The organic solvent is at least one selected from the group consisting of dimethylformamide, diethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, and acetonitrile. The trifluoroiodomethane solution composition contains 10.0% to 90.0% by weight of trifluoroiodomethane. A method for producing fluoroiodoalkanes. CF ３ -CH ２ CHX-I (1) (In formula (1), X represents a hydrogen atom or a methyl group.)

6. A method for producing fluoroiodoalkanes according to claim 5, wherein the trifluoroiodomethane solution composition contains 40.0% to 90.0% by weight of trifluoroiodomethane.

7. The radical initiators are 2,2'-azobis(isobutyronitrile), dimethyl 2,2'-azobis(2-methylpropinate), 2,2'-azobis(2,4'-dimethylvaleronitrile), (2-ethylhexanoyl) t-butyl peroxide, t-butyl pivalate peroxide, t-hexyl pivalate peroxide, lauroyl peroxide, succinic acid peroxide, 1,1,3,3-tetramethylbutyl peroxide of 2-ethylhexanoate, and 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxide). A method for producing a fluoroiodoalkane according to claim 5, wherein the at least one is selected from the group consisting of oxy)hexane, di(3,5,5-trimethylhexanoyl)peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, disec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, di-2-ethylhexyl peroxydicarbonate, t-hexyl peroxyneodecanoate, and t-butyl peroxyneodecanoate.

8. A method for producing a fluoroiodoalkane according to claim 5, wherein the unsaturated hydrocarbon is ethylene and / or propylene.

9. A method for producing a fluoroiodoalkane according to claim 5 or claim 6, wherein the initiator is 2,2'-azobis(isobutyronitrile) and the unsaturated hydrocarbon is ethylene.

10. A method for producing fluoroiodoalkane according to claim 5 or claim 6, wherein the reaction temperature is 40°C to 70°C.