Fluorine-containing compounds and methods for producing the same

Abstract

The present invention provides a novel fluorine-containing compound that can be used as a raw material for functional materials, and also provides a manufacturing method that can efficiently produce such a fluorine-containing compound. [Solution] As a new fluorine-containing compound, for example, a fluorine-containing compound represented by the following structural formula (I) can be mentioned. [Formula 1] TIFF2026165630000029.tif24166[In the formula, R1 represents an organic group such as R2-OC(=O)-(wherein R2 represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group), R represents a single bond or a divalent organic group, Rf represents a perfluoroalkyl group or polyfluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group or a perfluoroethyl group, X represents a single bond or a divalent organic group, and the tilde represents the trans or cis isomer.]

Description

[Technical Field]

[0001] The present invention relates to a fluorine-containing compound and a method for producing the same. More specifically, the present invention relates to a compound containing a fluorine-containing alkoxy group in its molecule and a method for producing the same. [Background technology]

[0002] Fluorine-containing compounds are used in various functional materials. In particular, materials having perfluoroalkyl groups or polyfluoroalkyl groups at their termini are useful as water repellents and surfactants. There are few reported examples of compounds in which such perfluoroalkyl groups or polyfluoroalkyl groups are ether-bonded via oxygen atoms. Furthermore, while compounds with functional groups are advantageous for deriving various functional materials, there are also few reported examples of such compounds.

[0003] Metathesis is a known catalytic reaction primarily used for rearranging bonds between two olefins. In recent years, there have been reports of using metathesis in the production of fluorine-containing compounds (see Non-Patent Documents 1-3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2011-522798 [Non-patent literature]

[0005] [Non-Patent Document 1] Chem. Commun., 2001, 1692-1693 [Non-Patent Document 2] Nature 2017, 542, 80-86 [Non-Patent Document 3] Chem. Sci., 2024, 15, 8472-8477 [Overview of the project] PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] The main object of the present invention is to provide a novel fluorine-containing compound which has a perfluoroalkyl group or polyfluoroalkyl group ether-bonded via an oxygen atom and can be used as a raw material for functional materials, and to provide a production method capable of efficiently producing such a fluorine-containing compound. MEANS FOR SOLVING THE PROBLEMS

[0007] As a result of extensive and intensive studies, the present inventors have found that the above problems can be solved by performing a metathesis reaction using a symmetric fluorine-containing compound and a similarly symmetric olefin-containing compound, and have completed the present invention. Examples of the present invention include the following embodiments.

[0008] [1] A fluorine-containing compound represented by the following structural formula (I):

[0009] [Chemical Formula]

[0010] In the formula, R1 represents an organic group, R represents a single bond or a divalent organic group, Rf represents a perfluoroalkyl group or polyfluoroalkyl group having 1 to 4 carbon atoms, X represents a single bond or a divalent organic group, and the wavy line represents a trans isomer or a cis isomer, respectively. [2] The fluorine-containing compound according to the above [1], wherein R1 is R2-O-C(=O)- (wherein R2 represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group), a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted heterocyclic group containing a nitrogen atom bonded to the adjacent X as a ring-constituting atom (hereinafter referred to as "X-adjacent heterocyclic group"). [3] The fluorine-containing compound described in [1] above, wherein Rf is a trifluoromethyl group or a perfluoroethyl group.

[0011] [4] A method for producing a fluorine-containing compound as described in [1] above, comprising the step of carrying out a metathesis reaction using a fluorine-containing compound represented by the following structural formula (II) as a raw material.

[0012] [ka]

[0013] (In the formula, R, Rf, and the dashed line are as defined above.) [5] A method for producing the fluorine-containing compound described in [4] above, comprising the step of carrying out a metathesis reaction using the fluorine-containing compound (II) described in [4] above and an olefin-containing compound represented by the following structural formula (III) or (III') as raw materials.

[0014] [ka]

[0015] (In the formula, R1' represents an organic group, or two R1' groups in structural formula (III) combine with adjacent Y groups to form a 6-10 membered ring. Y represents a single bond or a divalent organic group. The wavy line indicates the trans or cis isomer.) [6] A method for producing a fluorine-containing compound according to [4] or [5] above, wherein Rf is a trifluoromethyl group or a perfluoroethyl group. [7] A method for producing a fluorine-containing compound as described in [5] above, wherein R1' is R2-OC(=O)-(wherein R2 represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group), a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted heterocyclic group containing a nitrogen atom bonded to an adjacent Y as a ring constituent atom (hereinafter referred to as "Y adjacent heterocyclic group").

[0016] [8]Fluorine-containing compounds represented by the following structural formula (II):

[0017] [ka]

[0018] In the formula, R, Rf, and the dashed line are equivalent to those defined above. [9] The fluorine-containing compound according to [8] above, wherein Rf is a trifluoromethyl group or a perfluoroethyl group. [Effects of the Invention]

[0019] Depending on the embodiment of the present invention, a novel fluorine-containing compound (I) can be produced efficiently. Specifically, for example, using 1 mole of fluorine-containing compound (II) as a raw material, 2 moles of the target novel fluorine-containing compound (I) can be produced by a metathesis reaction. [Modes for carrying out the invention]

[0020] The present invention will be described in detail below. 1. Fluorine-containing compound (I) according to the present invention The fluorine-containing compound (I) according to the present invention (hereinafter referred to as "compound (1)") has the following structure.

[0021] [ka]

[0022] In the formula, R1 represents an organic group, R represents a single-bonded or divalent organic group, Rf represents a perfluoroalkyl group or polyfluoroalkyl group having 1 to 4 carbon atoms, X represents a single-bonded or divalent organic group, and the dashed line represents the trans or cis isomer. Examples of "organic groups" related to R1 include, for example, R2-OC(=O)-(wherein R2 represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group), a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and an X-adjacent heterocyclic group.

[0023] Here, the C1-C8 alkyl group can be a linear or branched C1-C8 alkyl group, such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, or octyl group. Preferably, for example, a linear or branched C1-C4 alkyl group can be used. More preferably, for example, a methyl group or an ethyl group can be used.

[0024] Examples of substituents on the phenyl group and the benzyl group include substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms (preferably linear or branched substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, halogenomethyl group, halogenoethyl group)), alkoxy groups having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, propyloxy group), halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), and nitro groups.

[0025] Examples of alkenyl groups include alkenyl groups having 2 to 10 carbon atoms, specifically, ethenyl, 2-propenyl, 1,3-butadienyl, hexenyl, octenyl, and decenyl groups.

[0026] Examples of substituents on the alkenyl group include alkoxy groups having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, propyloxy group) and halogenoalkoxy groups having 1 to 4 carbon atoms (e.g., monofluoromethoxy, difluoromethoxy, trifluoromethoxy group, perfluoroethoxy group, perfluoropropyloxy group).

[0027] Examples of alkynyl groups include alkynyl groups having 2 to 4 carbon atoms, specifically, ethynyl groups, 2-propynyl groups, and butynyl groups.

[0028] Examples of substituents on the alkynyl group include alkoxy groups having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, propyloxy group) and halogenoalkoxy groups having 1 to 4 carbon atoms (e.g., monofluoromethoxy, difluoromethoxy, trifluoromethoxy group, perfluoroethoxy group, perfluoropropyloxy group).

[0029] Examples of X-adjacent heterocyclic groups or Y-adjacent heterocyclic groups include 5 to 18 saturated or unsaturated heterocyclic groups that contain a nitrogen atom bonded to the adjacent X or Y as a ring element. Specifically, examples include pyrrolidine group, pyrrole group, imidazoline group, pyrazoline group, imidazole group, pyrazole group, oxazoline group, thiazine group, piperidine group, piperazine group, morpholine group, indole group, isoindole group, benzimidazole group, benzotriazole group, indoline group, and isoindoline group.

[0030] Examples of substituents on the X-adjacent heterocyclic group or the Y-adjacent heterocyclic group include C1-C8 alkyl groups (preferably linear or branched C1-C4 alkyl groups), C1-C4 alkoxy groups (e.g., methoxy group, ethoxy group, propyloxy group), oxo groups, halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), and nitro groups.

[0031] Examples of "divalent organic groups" include alkylene groups. Specifically, examples include methylene groups, ethylene groups, and propylene groups.

[0032] Specifically, examples of the "perfluoroalkyl group or polyfluoroalkyl group having 1 to 4 carbon atoms" related to Rf include, for example, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, trifluoromethoxymethyl group, perfluoroethoxymethyl group, trifluoromethoxyethyl group, and perfluoroethoxyethyl group. Among these, trifluoromethyl group and perfluoroethyl group are preferred.

[0033] 2. Method for producing compound (I) of the present invention Compound (I) of the present invention can be produced, for example, by carrying out a metathesis reaction using a fluorine-containing compound represented by the following symmetrical structural formula (II) (hereinafter referred to as "Compound (II) of the present invention") as a raw material. More specifically, it can be produced, for example, by carrying out a metathesis reaction using Compound (II) of the present invention and an olefin-containing compound represented by the following structural formula (III) or (III') (hereinafter referred to as "olefin-containing compound (III)") as raw materials.

[0034] [ka]

[0035] In the formula, R, Rf, and the dashed line are equivalent to those defined above.

[0036] [ka]

[0037] In the formula, R1' represents an organic group, or two R1' groups in structural formula (III) combine with adjacent Y groups to form a 6-10 membered ring. Y represents a single bond or a divalent organic group. The wavy line indicates a trans or cis isomer.

[0038] The raw materials for the present invention, compound (II) and olefin-containing compound (III), may be either trans or cis isomers, but a mixture of the trans and cis isomers may also be used as raw materials. In that case, the compound (I) produced will be a mixture of the trans and cis isomers. The compound (I) obtained as a cis-trans mixture can be separated into the trans and cis isomers by conventional methods, such as column chromatography or liquid-liquid extraction, if necessary.

[0039] Specific examples of compound (II) of the present invention, which is a raw material for producing compound (I) of the present invention, include, but are not limited to, the following compounds.

[0040] [ka]

[0041] In the other raw material, the olefin-containing compound (III), preferred specific examples of R1' include R2-OC(=O)-(wherein R2 represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group), a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and an adjacent Y heterocyclic group. Among these, R2 is more preferably a methyl group, an ethyl group, a phenyl group, or a benzyl group. Furthermore, as R1', preferred examples include a phenyl group substituted with one or two substituents selected from the group consisting of a nitro group, a halogenomethyl group, a halogen atom, and an alkoxy group, a substituted or unsubstituted indoline, a substituted or unsubstituted isoindoline, imidazoline, and oxazoline.

[0042] Specific examples of olefin-containing compounds (III) include aromatic rings substituted with cycloalkenes having 6 to 10 carbon atoms and alkenes having 2 to 6 carbon atoms.

[0043] In the present invention, the catalyst used in the metathesis reaction is not particularly limited as long as it is a Grubbs catalyst commonly used in metathesis reactions, but examples include the following compounds.

[0044] [ka]

[0045] More specifically, compound (I) of the present invention can be produced by, for example, the following procedure and reaction conditions.

[0046] Compound (I) of the present invention can be produced by dissolving two raw materials (compound (II) of the present invention and olefin-containing compound (III)) in a suitable solvent, adding a Grubbs catalyst, and stirring at a suitable temperature for a suitable time. The solvent used here is not particularly limited as long as it can dissolve the raw materials, and examples include toluene, benzene, and dichloromethane. The reaction temperature is, for example, in the range of 10°C to 60°C, preferably in the range of 15°C to 30°C, and the reaction time is, for example, in the range of 3 hours to 24 hours, preferably in the range of 6 hours to 12 hours. [Examples]

[0047] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the examples described below.

[0048] [Example 1] Synthesis of Benzyl 6-(trifluoromethoxy)hex-4-enoate

[0049] [ka]

[0050] In a glove box, 54.0 mg (0.2 mmol, purity: 83%) of 1,4-bis(trifluoromethoxy)but-2-ene and 35.3 mg (0.1 mmol) of Dibenzyl oct-4-enedioate were placed in a test tube that had been oven-dried with a stirring bar. Next, 6.3 mg (0.01 mmol) of the ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 0.5 mL of degassed anhydrous toluene and stirred at room temperature for 6 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:ethyl acetate = 97:3), and the target compound Benzyl 6-(trifluoromethoxy)hex-4-enoate was isolated and recovered as a pale yellow clear liquid at a concentration of 35.9 mg (0.125 mmol, 62%).

[0051] The ruthenium catalyst Ru6 has the following structure.

[0052] [ka]

[0053] 1 H NMR (300 MHz, CDCl3) δ: 7.36 (s, 6H), 5.87-5.79 (m, 1H), 5.64-5.55 (m, 1H), 5.12 (s, 2H), 4.37 (d, J = 6.3 Hz, 2H), 2.51-2.42 (m, 4H) ppm 19 F NMR (282 MHz, CDCl3) δ: -60.6 (s, 3F) ppm HRMS (ESI) m / z: [M+Na] + calcd for C 14 H 15 F3O3Na, 311.0871; found, 331.0867

[0054] [Example 2] Synthesis of Methyl 5-(trifluoromethoxy)pent-3-enoate

[0055] [ka]

[0056] In a glove box, 54.0 mg (0.2 mmol, purity: 83%) of 1,4-bis(trifluoromethoxy)but-2-ene and 17.2 mg (0.1 mmol) of Dimethyl trans-3-hexenedioate were placed in a test tube that had been oven-dried with a stirring bar. Next, 6.3 mg (0.01 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 0.5 mL of degassed anhydrous toluene and stirred at room temperature for 6 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:ethyl acetate = 97:3), and 19.8 mg (0.10 mmol, 50%) of the target compound Methyl 5-(trifluoromethoxy)pent-3-enoate was isolated and recovered as a colorless, transparent liquid.

[0057] 1 H NMR (300 MHz, CDCl3) δ: 6.01-5.91 (m, 1H), 5.76-5.67 (m, 1H), 4.45 (d, J = 6.2 Hz, 2H), 3.71 (s, 3H), 3.15 (d, J = 6.9 Hz, 2H) ppm 19 F NMR (282 MHz, CDCl3) δ: -60.8 (s, 3F) ppm

[0058] [Example 3] Synthesis of Benzyl 6-(perfluoroethoxy)hex-4-enoate

[0059] [ka]

[0060] In a glove box, 64.8 mg (0.2 mmol) of 1,4-bis(perfluoroethoxy)but-2-ene and 35.3 mg (0.1 mmol) of Dibenzyl oct-4-enedioate were placed in an oven-dried test tube together with a stirring bar. Then, 3.1 mg (0.005 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 0.5 mL of degassed anhydrous toluene, and the resulting solution was stirred at room temperature for 6 hours. The reaction solution was quenched with water-containing toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:ethyl acetate = 97:3), and 55.3 mg (0.163 mmol, 82%) of the target compound Benzyl 6-(perfluoroethoxy)hex-4-enoate was isolated and recovered as a pale yellow transparent liquid.

[0061] 1 H NMR (300 MHz, CDCl3) δ: 7.36 (s, 5H), 5.88-5.79 (m, 1H), 5.65-5.55 (m, 1H), 5.12 (s, 2H), 4.43 (d, J = 6.0 Hz, 2H), 2.50-2.42 (m, 4H) ppm 19 F NMR (282 MHz, CDCl3) δ: -86.5 (s, 3F), -90.6 (s, 2F) ppm HRMS (ESI) m / z: [M+Na] + calcd for C 15 H 15 F5O3Na, 361.0839; found, 361.0842

[0062] [Example 4] Synthesis of Methyl 5-(perfluoroethoxy)pent-3-enoate

[0063] [Chemical Formula]

[0064] In a glove box, 64.8 mg (0.2 mmol) of 1,4-bis(perfluoroethoxy)but-2-ene and 17.2 mg (0.1 mmol) of Dimethyl trans-3-Hexenedioate were placed in a test tube that had been oven-dried with a stirring bar. Next, 3.1 mg (0.005 mmol) of the ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 0.5 mL of degassed anhydrous toluene and stirred at room temperature for 6 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:ethyl acetate = 97:3), and the target compound Methyl 5-(perfluoroethoxy)pent-3-enoate was isolated and recovered as a colorless, clear liquid at a concentration of 30.6 mg (0.123 mmol, 62%).

[0065] 1 H NMR (300 MHz, CDCl3) δ: 6.02-5.92 (m, 1H), 5.78-5.67 (m, 1H), 4.51 (d, J = 6.0 Hz, 2H), 3.71 (s, 3H), 3.15 (d, J = 6.6 Hz, 2H) ppm 19 F NMR (282 MHz, CDCl3) δ: -86.5 (s, 3F), -90.8 (s, 2F) ppm

[0066] [Example 5] Synthesis of 4-(trifluoromethoxy)but-2-en-1-yl acetate

[0067] [ka]

[0068] In a glove box, 140.0 mg (0.4 mmol, purity: 64%) of 1,4-bis(trifluoromethoxy)but-2-ene and 20.6 mg (0.2 mmol, purity: 97%) of allyl acetate were placed in a test tube that had been oven-dried with a stirring bar. Next, 12.5 mg (0.02 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 1.0 mL of degassed anhydrous toluene and stirred at room temperature for 6 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:diethyl ether = 98:2), and 20.7 mg (0.104 mmol, 52%) of the target compound 4-(trifluoromethoxy)but-2-en-1-yl acetate was isolated and recovered as a colorless, transparent liquid.

[0069] 1 H NMR (300 MHz, CDCl3) δ: 5.98-5.81 (m, 2H), 4.61 (d, J = 4.4 Hz, 2H), 4.48 (d, J = 4.5 Hz, 2H), 2.10 (s, 3H) ppm 19 F NMR (282 MHz, CDCl3) δ: -61.0 (s, 3F) ppm HRMS (ESI) m / z: [MH] - calcd for C7H8F3O3, 197.0426; found, 197.0426

[0070] [Example 6] Synthesis of Benzyl 4-(trifluoromethoxy)but-2-enoate

[0071] [ka]

[0072] In a glove box, 96.4 mg (0.4 mmol, purity: 93%) of 1,4-bis(trifluoromethoxy)but-2-ene and 32.4 mg (0.2 mmol) of Benzyl acrylate were placed in an oven-dried test tube with a stirring bar. Next, 12.5 mg (0.02 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 1.0 mL of degassed anhydrous toluene and stirred at room temperature for 6 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:diethyl ether = 96:4), and the target compound, Benzyl 4-(trifluoromethoxy)but-2-enoate, was isolated and recovered as a colorless, clear liquid at a concentration of 31.7 mg (0.122 mmol, 61%).

[0073] 1 H NMR (700 MHz, CDCl3) δ: 7.38 (d, J = 4.4 Hz, 4H), 7.36-7.33 (m, 1H), 6.94 (dt, J1= 15.6 Hz, J2= 4.4 Hz, 1H), 6.19 (dt, J1= 15.6 Hz, J2= 2.0 Hz, 1H), 5.21 (s, 2H), 4.63 (q, J = 2.3 Hz, 2H) ppm 19 F NMR (659 MHz, CDCl3) δ: -61.6 (s, 3F) ppm LCMS (ESI) m / z: [M+Na] + calcd for C7H9F3O3Na, 283.06; found, 283.10

[0074] [Example 7] Synthesis of 2-(6-(trifluoromethoxy)hex-4-en-1-yl)isoindoline-1,3-dione

[0075] [ka]

[0076] In a glove box, 140.0 mg (0.4 mmol, purity: 64%) of 1,4-bis(trifluoromethoxy)but-2-ene and 43.1 mg (0.2 mmol) of 2-(pent-4-en-1-yl)isoindoline-1,3-dione were placed in a test tube that had been oven-dried with a stirring bar. Next, 12.5 mg (0.02 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 1.0 mL of degassed anhydrous toluene and stirred at room temperature for 6 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:diethyl ether = 9:1), and the target compound 2-(6-(trifluoromethoxy)hex-4-en-1-yl)isoindoline-1,3-dione was isolated and recovered as a white solid at a concentration of 57.0 mg (0.182 mmol, 91%).

[0077] 1 H NMR (300 MHz, CDCl3) δ: 7.87-7.84 (m, 2H), 7.74-7.71 (m, 2H), 5.89-5.79 (m, 1H), 5.66-5.57 (m, 1H), 4.37 (d, J = 6.0 Hz, 2H), 3.71 (t, J = 7.1 Hz, 2H), 2.19-2.12 (m, 2H), 1.86-1.76 (m, 2H) ppm 19 F NMR (282 MHz, CDCl3) δ: -60.6 (s, 3F) ppm HRMS (ESI) m / z: [M+Na] + calcd for C 15 H 14 F3NO3Na, 336.0823; found, 336.0826

[0078] [Example 8] Synthesis of 1-nitro-4-(3-(trifluoromethoxy)prop-1-en-1-yl)benzene

[0079] [ka]

[0080] In a glove box, 140.0 mg (0.4 mmol, purity: 64%) of 1,4-bis(trifluoromethoxy)but-2-ene and 30.4 mg (0.2 mmol) of 1-nitro-4-vinylbenzene were placed in a test tube that had been oven-dried with a stirring bar. Next, 12.5 mg (0.02 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 1.0 mL of degassed anhydrous toluene and stirred at room temperature for 6 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:diethyl ether = 95:5), and the target compound 1-nitro-4-(3-(trifluoromethoxy)prop-1-en-1-yl)benzene was isolated and recovered as a yellow liquid at a concentration of 24.9 mg (0.101 mmol, 50%).

[0081] 1 H NMR (300 MHz, CDCl3) δ: 8.22 (d, J = 8.8 Hz, 2H), 7.55 (d, J = 8.6 Hz, 2H), 6.78 (d, J = 16.0 Hz, 1H), 6.47-6.38 (m, 1H), 4.68 (dd, J1= 5.8 Hz, J2= 1.4 Hz, 2H) ppm 19 F NMR (282 MHz, CDCl3) δ: -60.9 (s, 3F) ppm HRMS (ESI) m / z: [MH] - calcd for C 10 H7F3NO3, 246.0378; found, 246.0377

[0082] [Example 9] Synthesis of 1,12-bis(trifluoromethoxy)dodeca-2,10-diene

[0083] [ka]

[0084] In a glove box, 140.0 mg (0.4 mmol, purity: 64%) of 1,4-bis(trifluoromethoxy)but-2-ene and 23.2 mg (0.2 mmol, purity: 95%) of cyclooctene were placed in a test tube that had been oven-dried with a stirring bar. Next, 12.5 mg (0.02 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 1.0 mL of degassed anhydrous toluene and stirred at room temperature for 18 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane), and the target compound 1,12-bis(trifluoromethoxy)dodeca-2,10-diene was isolated and recovered as a colorless, transparent liquid at a concentration of 59.3 mg (0.177 mmol, 89%).

[0085] 1 H NMR (700 MHz, CDCl3) δ: 5.84-5.80 (m, 2H), 5.59-5.54 (m, 2H), 4.40 (dd, J1= 6.6 Hz, J2= 1.0 Hz, 4H), 2.07 (q, J = 7.2 Hz, 4H), 1.40-1.37 (m, 4H), 1.31-1.28 (m, 4H) ppm 19 F NMR (659 MHz, CDCl3) δ: -60.5 (s, 3F) ppm LCMS (ESI) m / z: [M+H] + calcd for C 14 H 21 F6O2, 335.14; found, 335.15.

[0086] [Example 10] Synthesis of 1,2-dimethoxy-4-(3-(trifluoromethoxy)prop-1-en-1-yl)benzene

[0087] [ka]

[0088] In a glove box, 140.0 mg (0.4 mmol, purity: 64%) of 1,4-bis(trifluoromethoxy)but-2-ene and 35.7 mg (0.2 mmol) of 4-(1-Propenyl)-1,2-dimethoxybenzene were placed in a test tube that had been oven-dried with a stirring bar. Next, 12.5 mg (0.02 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 1.0 mL of degassed anhydrous toluene and stirred at room temperature for 18 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was purified by silica gel column chromatography (hexane:diethyl ether = 9:1), and 10.4 mg (0.04 mmol, 20%) of the target compound 1,2-dimethoxy-4-(3-(trifluoromethoxy)prop-1-en-1-yl)benzene was isolated and recovered as a colorless, transparent liquid.

[0089] 1 H NMR (700 MHz, CDCl3) δ: 6.96-6.94 (m, 2H), 6.84 (d, J = 8.8 Hz, 1H), 6.13 (dt, J1= 15.9 Hz, J2= 6.6 Hz, 1H), 4.62 (dd, J1= 6.8 Hz, J2= 1.2 Hz, 2H), 3.90 (d, J = 10.4 Hz, 6H) ppm 19 F NMR (659 MHz, CDCl3) δ: -60.5 (s, 3F) ppm LCMS (ESI) m / z: [M+H] + calcd for C12 H 14 F3O3, 263.09; found, 263.05.

[0090] [Example 11] Synthesis of 1-(3-(trifluoromethoxy)prop-1-en-1-yl)-4-(trifluoromethyl)benzene

[0091] [ka]

[0092] In a glove box, 140.0 mg (0.4 mmol, purity: 64%) of 1,4-bis(trifluoromethoxy)but-2-ene and 35.2 mg (0.2 mmol, purity: 98%) of 1-(trifluoromethyl)-4-vinylbenzene were placed in a test tube that had been oven-dried with a stirring bar. Next, 12.5 mg (0.02 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 1.0 mL of degassed anhydrous toluene and stirred at room temperature for 18 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was collected by silica gel column chromatography (hexane) to obtain 27.0 mg of the target compound 1-(3-(trifluoromethoxy)prop-1-en-1-yl)-4-(trifluoromethyl)benzene as a mixture with the dimer. 19 The yield was estimated from the mixture using 1F NMR and was found to be 35%.

[0093] 1 H NMR (700 MHz, CDCl3) δ: 7.60 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 6.73 (d, J = 16.0 Hz, 1H), 6.35 (dt, J1= 15.9 Hz, J2= 6.1 Hz, 1H), 4.66 (dd, J1= 6.0 Hz, J2= 1.2 Hz, 2H) ppm 19 F NMR (659 MHz, CDCl3) δ: -60.8 (s, 3F), -63.1 (s, 3F) ppm

[0094] The dimer has the following structure.

[0095] [ka]

[0096] [Example 12] Synthesis of 1-bromo-4-(3-(trifluoromethoxy)prop-1-en-1-yl)benzene

[0097] [ka]

[0098] In a glove box, 96.4 mg (0.4 mmol, purity: 93%) of 1,4-bis(trifluoromethoxy)but-2-ene and 38.5 mg (0.2 mmol, purity: 95%) of 1-bromo-4-vinylbenzene were placed in a test tube that had been oven-dried with a stirring bar. Next, 12.5 mg (0.02 mmol) of ruthenium catalyst Ru6 was weighed out and added to the mixture. This mixture was dissolved in 1.0 mL of degassed anhydrous toluene and stirred at room temperature for 6 hours. The reaction mixture was quenched with aqueous toluene and concentrated. The concentrate was collected by silica gel column chromatography (hexane) to recover 36.3 mg of the target compound, 1-bromo-4-(3-(trifluoromethoxy)prop-1-en-1-yl)benzene, as a mixture with the dimer. 19 The yield was estimated from the mixture using 1F NMR and was found to be 15%.

[0099] 1H NMR (500 MHz, CDCl3) δ: 7.50-7.46 (m, 2H), 7.38-7.35 (m, 2H), 6.64 (d, J = 15.9 Hz, 1H), 6.25 (dt, J1= 15.8 Hz, J2= 6.2 Hz, 1H), 4.61 (dd, J1= 6.3 Hz, J2= 1.4 Hz, 2H) ppm 19 F NMR (659 MHz, CDCl3) δ: -60.5 (s, 3F) ppm

[0100] The dimer has the following structure.

[0101] [ka] [Industrial applicability]

[0102] Compound (I) of the present invention can be used as a raw material for various functional materials and is useful as an industrial material. Furthermore, the manufacturing method according to the present invention can efficiently produce Compound (I), and is therefore useful for the production of Compound (I).

Claims

1. Fluorine-containing compounds represented by the following structural formula (I): 【Chemistry 1】 In the formula, R1 represents an organic group, R represents a single-bonded or divalent organic group, Rf represents a perfluoroalkyl group or polyfluoroalkyl group having 1 to 4 carbon atoms, X represents a single-bonded or divalent organic group, and the dashed line represents the trans or cis isomer.

2. The fluorine-containing compound according to claim 1, wherein R1 is R2-O-C(=O)-(wherein R2 represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group), a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted heterocyclic group containing a nitrogen atom bonded to an adjacent X as a ring constituent atom.

3. The fluorine-containing compound according to claim 1, wherein Rf is a trifluoromethyl group or a perfluoroethyl group.

4. A method for producing a fluorine-containing compound according to claim 1, comprising the step of carrying out a metathesis reaction using a fluorine-containing compound represented by the following structural formula (II) as a raw material. 【Chemistry 2】 (In the formula, R represents a single bond or a divalent organic group, Rf represents a perfluoroalkyl group or polyfluoroalkyl group having 1 to 4 carbon atoms, and the dashed line represents the trans or cis isomer.)

5. A method for producing a fluorine-containing compound according to claim 4, comprising the step of carrying out a metathesis reaction using the fluorine-containing compound (II) described in claim 4 and an olefin-containing compound represented by the following structural formula (III) or (III') as raw materials. 【Transformation 3】 (In the formula, R1' represents an organic group, or two R1' groups in structural formula (III) combine with adjacent Y groups to form a 6- to 10-membered ring. Y represents a single bond or a divalent organic group. The wavy line indicates a trans or cis isomer.)

6. A method for producing a fluorine-containing compound according to claim 4 or 5, wherein Rf is a trifluoromethyl group or a perfluoroethyl group.

7. A method for producing a fluorine-containing compound according to claim 5, wherein R1' is R2-O-C(=O)-(wherein R2 represents an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group), a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted heterocyclic group containing a nitrogen atom bonded to an adjacent Y as a ring constituent atom.

8. Fluorine-containing compounds represented by the following structural formula (II): 【Chemistry 4】 In the formula, R represents a single bond or a divalent organic group, Rf represents a perfluoroalkyl group or polyfluoroalkyl group having 1 to 4 carbon atoms, and the dashed line represents the trans or cis isomer.

9. The fluorine-containing compound according to claim 8, wherein Rf is a trifluoromethyl group or a perfluoroethyl group.

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