Fluorine-containing compound

Abstract

To provide a production method for a fluorine-containing compound using easily obtainable compounds under comparatively mild reaction conditions, a fluorine-containing compound suitably usable in the method, and a fluorine-containing compound obtained by the production method.SOLUTION: A method for producing a fluorine-containing compound, comprises reacting a compound having a partial structure represented by the following formula (a) with a Grignard reagent in the presence of a transition metal compound. Formula (a): -C(-Ra)(-Rb)-CH2-L, wherein Ra represents a fluorine atom or a fluoroalkyl group; Rb represents a hydrogen atom or a fluoroalkyl group; and L represents a sulfonate group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a fluorine-containing compound and to the fluorine-containing compound. [Background technology]

[0002] Fluorine compounds are used in a variety of fields, including agricultural chemicals, pharmaceuticals, and functional materials, and there is a demand for simpler methods to synthesize a variety of structures.

[0003] Various studies have been conducted on methods for synthesizing compounds having a structure in which an alkyl group is bonded to a fluoroalkyl group. For example, Patent Document 1 discloses a method for producing a fluorine-containing compound by adding a perfluoroalkyl bromide to an olefin compound by a radical reaction.

[0004] In the examples of Patent Document 2, an electrophilic agent R f -CF2CH2CH2-I(R f is a perfluoroalkyl group) with a Grignard reagent.

[0005] Furthermore, Non-Patent Document 1 discloses a compound represented by the following formula as an electrophilic perfluoroalkylating agent.

[0006] [ka] However, R f nC m F 2m+1 , Tf is SO2CF3, and R is H or F. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2018-43940 A [Patent Document 2] International Publication No. 2018 / 228975 [Non-patent literature]

[0008] [Non-Patent Document 1] Teruo Umemoto, “Electrophilic Perfluoroalkylating Agents”, Chem. Rev. 1996, 96, 1757-1777 Summary of the Invention [Problem to be solved by the invention]

[0009] The method of Patent Document 1 is unsuitable for synthesizing compounds having carbon-carbon double bonds because olefins are reacted, and the types of electrophiles are limited. Furthermore, the product may undergo further radical reactions to telomerize, resulting in the generation of various by-products. The electrophilic agent of Patent Document 2 was not easily available. Furthermore, the electrophilic perfluoroalkylating agent of Non-Patent Document 1 requires multiple steps for synthesis, resulting in low yields and being expensive as an electrophile.

[0010] The present invention aims to provide a method for producing a fluorine-containing compound using easily available compounds under relatively mild reaction conditions, a fluorine-containing compound that is suitably used in the production method, and a fluorine-containing compound obtainable by the production method. [Means for solving the problem]

[0011] To achieve the above object, the present invention relates to the following [1] to

[15] . [1] A compound having a partial structure represented by the following formula (a): with a Grignard reagent in the presence of a transition metal compound, A method for producing a fluorine-containing compound. -C(-R a )(-R b )-CH2-L formula (a) However, in the formula, R a is a fluorine atom or a fluoroalkyl group, R b is a hydrogen atom or a fluoroalkyl group, L is a sulfonate group. [2] The method for producing a fluorine-containing compound according to [1], wherein the compound having the partial structure represented by formula (a) is a compound represented by the following formula (A1) or formula (A2): G 1 -C(-R a )(-R b )-CH2-L Formula (A1) L-CH2-{C(-R a )(-R b )-G 2 -} n C(-R a )(-R b )-CH2-L Formula (A2) However, in the formula, R a is a fluorine atom or a fluoroalkyl group, and R a If there are multiple R a may be the same or different, R b is a hydrogen atom or a fluoroalkyl group, and R b If there are multiple R b may be the same or different, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, a hydrogen atom, an alkyl group, or a fluoroalkyl group, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, an alkylene group, or a fluoroalkylene group, L represents a sulfonate group, and in formula (A2), a plurality of Ls may be the same or different. n is 0 or 1. [3] In equation (A1), G 1 The method for producing a fluorine-containing compound according to [2], wherein is a monovalent group having a (poly)oxyfluoroalkylene chain or a perfluoroalkyl group. [4] In formula (A2), n is 0, or n is 1 and G 2 The method for producing a fluorine-containing compound according to [2], wherein is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, or a perfluoroalkylene group. [5] The method for producing a fluorine-containing compound according to any one of [1] to [4], wherein the Grignard reagent is represented by the following formula (B): R-MgX formula (B) In the formula, R is a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, and X is a halogen atom. [6] The method for producing a fluorine-containing compound according to [5], wherein the Grignard reagent is represented by the following formula (B1): R 1 -CH2-MgX Formula (B1) In the formula, R 1 is a hydrogen atom or a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, and X is a halogen atom. [7] The method for producing a fluorine-containing compound according to any one of [1] to [6], wherein L is a triflate group. [8] The method for producing a fluorine-containing compound according to any one of [1] to [7], wherein the transition metal compound contains copper. [9] A fluorine-containing compound represented by the following formula (A1) or formula (A2): G 1 -C(-R a )(-R b )-CH2-L Formula (A1) L-CH2-{C(-R a )(-R b )-G 2 -} n C(-R a )(-R b )-CH2-L Formula (A2) However, in the formula, R a is a fluorine atom or a fluoroalkyl group, and R a If there are multiple R amay be the same or different, R b is a hydrogen atom or a fluoroalkyl group, and R b If there are multiple R b may be the same or different, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, a hydrogen atom, an alkyl group, or a fluoroalkyl group, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, an alkylene group, or a fluoroalkylene group, L represents a sulfonate group, and in formula (A2), a plurality of Ls may be the same or different. n is 0 or 1.

[10] In equation (A1), G 1 The fluorine-containing compound according to [9], wherein is a monovalent group having a (poly)oxyfluoroalkylene chain or a perfluoroalkyl group.

[11] In formula (A2), n is 0, or n is 1 and G 2 The fluorine-containing compound according to [9], wherein is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, or a perfluoroalkylene group.

[12] The fluorine-containing compound according to any one of [9] to

[11] , wherein L is a triflate group.

[13] A fluorine-containing compound represented by the following formula (C1) or formula (C2): G 1 -C(-R a )(-R b )-CH2-R formula (C1) R-CH2-{C(-R a )(-R b )-G 2 -} n C(-R a )(-R b )-CH2-R Formula (C2) However, in the formula, R a is a fluorine atom or a fluoroalkyl group, and Ra If there are multiple R a may be the same or different, R b is a hydrogen atom or a fluoroalkyl group, and R b If there are multiple R b may be the same or different, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, a hydrogen atom, an alkyl group, or a fluoroalkyl group, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, an alkylene group, or a fluoroalkylene group, R is a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, n is 0 or 1.

[14] In equation (C1), G 1 The fluorine-containing compound according to

[13] , wherein is a monovalent group having a (poly)oxyfluoroalkylene chain or a perfluoroalkyl group.

[15] In formula (C2), n is 0, or n is 1 and G 2 The fluorine-containing compound according to

[13] , wherein is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, or a perfluoroalkylene group. [Effects of the Invention]

[0012] The present invention can provide a method for producing a fluorine-containing compound using easily available compounds under relatively mild reaction conditions, a fluorine-containing compound that is suitably used in the production method, and a fluorine-containing compound obtainable by the production method. DETAILED DESCRIPTION OF THE INVENTION

[0013] In this specification, the partial structure represented by formula (a) will be referred to as partial structure (a). Also, the compound represented by formula (A1) will be referred to as compound (A1). Compounds represented by other formulas will be referred to in the same manner. "(Poly)oxyfluoroalkylene" is a general term for oxyfluoroalkylene and polyoxyfluoroalkylene. A perfluoroalkyl group refers to an alkyl group in which all hydrogen atoms have been substituted with fluorine atoms. A fluoroalkyl group is a general term that includes partial fluoroalkyl groups and perfluoroalkyl groups. A partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms have been substituted with fluorine atoms and which also has one or more hydrogen atoms. That is, a fluoroalkyl group is an alkyl group that contains one or more fluorine atoms. The symbol "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0014] [Method of producing fluorine-containing compounds] The method for producing a fluorine-containing compound of the present invention (hereinafter also referred to as "the production method") comprises reacting a compound having a partial structure represented by the following formula (a) (hereinafter also referred to as compound (A)) with a Grignard reagent in the presence of a transition metal compound: -C(-R a )(-R b )-CH2-L formula (a) However, in the formula, R a is a fluorine atom or a fluoroalkyl group, R b is a hydrogen atom or a fluoroalkyl group, L is a sulfonate group.

[0015] When the Grignard reagent is represented by the following formula (B), the above reaction is represented by the following scheme (1). R-MgX formula (B) In the formula, R is a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, and X is a halogen atom.

[0016] Scheme (1) -C(-R a )(-R b)-CH2-L + R-MgX → -C(-R a )(-R b )-CH2-R However, each symbol in the scheme (1) is as described above.

[0017] In this production method, the reaction of the above scheme (1) can be carried out under relatively mild reaction conditions by using a sulfonate group as the leaving group L of the partial structure (a) that reacts with a Grignard reagent. Each component of this production method will be described in detail below.

[0018] L in partial structure (a) is a sulfonate group (-O-SO2-R 2 ) and is eliminated by reaction with Grignard reagents. 2 is an organic group. Specific examples of the sulfonate group include a tosylate group (OTs), a mesylate group (OMs), a triflate group (OTf), and a nonaflate group (ONf). Among these, a triflate group is preferred in terms of the reaction yield of Scheme (1).

[0019] R a and R b In the formula, the fluoroalkyl group may be a straight-chain or branched alkyl group. The fluoroalkyl group preferably has 1 to 18 carbon atoms, and from the viewpoint of ease of synthesis of compound (A), the fluoroalkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 6 carbon atoms. Specific examples of the fluoroalkyl group include CF3-, CHF2-, CH2F-, CF3CF2-, CF3CF2CF2-, CF3CF(CF3)-, CF3CF2CF(-CF2CF3)-, etc. Note that R a and R b The fluoroalkyl groups may be the same or different. R a From the viewpoint of ease of synthesis of compound (A), is preferably a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, and even more preferably a fluorine atom. Also, R bFrom the viewpoint of ease of synthesis of compound (A), is preferably a hydrogen atom or a fluoroalkyl group having 1 to 6 carbon atoms, more preferably a fluoroalkyl group having 1 to 6 carbon atoms, and even more preferably a perfluoroalkyl group having 1 to 6 carbon atoms.

[0020] The compound having the partial structure (a) is a compound having one or more partial structures (a). The number of partial structures (a) in the compound (A) is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 or 2, from the viewpoint of reaction yield.

[0021] The structure of the compound (A) may be appropriately selected depending on the intended use of the fluorine-containing compound obtained by the present production method. An example of the compound (A) having n5 partial structures (a) is a compound represented by the following formula (An5). G(-C(-R a )(-R b )-CH2-L) n5 Formula (An5) However, in the formula G is a hydrogen atom (where n5=1) or an n5-valent organic group; n5 is an integer equal to or greater than 1, R a , R b , L is as described above, and R a , R b Or if there are multiple Ls, the R a , R b Alternatively, each L may be the same or different from the others.

[0022] The organic group in G is a group containing one or more carbon atoms. The organic group may have a substituent, and may be a hydrocarbon group that may have a heteroatom or a bond other than a hydrocarbon group in the carbon chain or at the end bonded to the partial structure (a). The hydrocarbon group may be a linear or branched alkyl group, a cycloalkyl group, an aryl group, or a combination thereof. The hydrocarbon group may have a double or triple bond in the carbon chain. Examples of the combination include an alkyl group and an aryl group bonded directly, via a heteroatom, or via a bond other than a hydrocarbon group. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. The heteroatoms may form part of a ring structure, and among the heteroatoms, nitrogen, sulfur, and silicon atoms may form branching points that bond to three or more carbon atoms. Examples of bonds other than hydrocarbon groups include amide bonds, urea bonds, and urethane bonds. Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxy group, an amino group, a nitro group, and a sulfo group. From the viewpoint of the stability of the compound in the present production method, a halogen atom is preferred, and a fluorine atom is more preferred.

[0023] When the organic group has a ring structure such as a cycloalkyl group or an aryl group, examples of the ring structure include a 3- to 8-membered aliphatic ring, a 6- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings, and the ring structure shown in the following formula is preferred. The ring structure may have, as a substituent, a halogen atom, an alkyl group which may have an ether bond, a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, an oxo group, or the like.

[0024] [ka]

[0025] Of the compounds (A), specific examples of suitable compounds containing a ring structure include the following.

[0026] [ka] However, R a , R b and L are as described above.

[0027] In order to increase the yield of the present production method, the compound (A) is preferably a compound represented by the following formula (A1) or formula (A2). G 1 -C(-R a )(-R b )-CH2-L Formula (A1) L-CH2-{C(-R a )(-R b )-G 2 -} n C(-R a )(-R b )-CH2-L Formula (A2) However, in the formula, R a , R b , L is as described above, and R a , R b Or if there are multiple Ls, the R a , R b or L may be the same or different from each other, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, a hydrogen atom, an alkyl group, or a fluoroalkyl group, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, an alkylene group, or a fluoroalkylene group, n is 0 or 1.

[0028] G 1 The number of carbon atoms in the alkyl group or fluoroalkyl group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 6, from the viewpoint of increasing the yield of the present production method.

[0029] G 1 In the formula (A1), the monovalent group having a (poly)oxyfluoroalkylene chain is C(-R a )(-R b) or has an -O- between carbon atoms in a carbon chain having two or more carbon atoms, or a fluoroalkyl group containing both of these. 1 is preferably a structure represented by the following formula (G1-1). R f0 O-[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-(R f7 ) m7 - Formula (G1-1) however, R f0 is a fluoroalkyl group having 1 to 20 carbon atoms, R f1 is a fluoroalkylene group having one carbon atom, R f2 is a fluoroalkylene group having 2 carbon atoms, R f3 is a fluoroalkylene group having 3 carbon atoms, R f4 is a fluoroalkylene group having 4 carbon atoms, R f5 is a fluoroalkylene group having 5 carbon atoms, R f6 is a fluoroalkylene group having 6 carbon atoms, R f7 is a fluoroalkylene group having 1 to 6 carbon atoms, m1, m2, m3, m4, m5, and m6 each independently represent an integer of 0 or 1 or more; m7 is an integer of 0 or 1; and m1+m2+m3+m4+m5+m6+m7 is an integer of 0-200. In addition, (R f1 O)~(R f6 O) can be bonded in any order. In formula (G1-1), m1 to m6 are each represented by (R f1 O)~(Rf6 O), not the arrangement. For example, (R f5 O) m5 is (R f5 O) is m5, and (R f5 O) m5 It does not represent the block arrangement structure of (R f1 O)~(R f6 The order of the units does not represent the bonding order of the units. When m7 is 0, G 1 C(-R a )(-R b ) is bonded to -O-. When m7 is 1, G 1 C(-R a )(-R b ) is bonded to the carbon atom (R f7 (the terminal carbon atom of

[0030] G 1 Specific examples of the alkyl group include CH3-, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-, CH3CH2CH2CH2CH2-, CH3CH2CH2CH2CH2-, CH3CH2CH2CH2CH2-, CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2-O-[(CF2-O) m1 (CF2CF2-O) m2 ]-, CF3CF2CF2-O-CF2CF2-O-[(CF2-O) m1 (CF2CF2-O) m2 ]-, CF3-O(-CF2CF2-O-CF2CF2CF2CF2-O) m8 -CF2CF2-O-CF2CF2-, F(-CF2CF2CF2-O) m3 -CF2-, CF3-CF(-CF3)-CF2-O-, CF3-CF(-CF2CF3)-CF2-O-, CF3CF2CF2-O-(CF(-CF3)-CF2-O-) m9 - etc. (where m8 and m9 are integers from 1 to 100).

[0031] In this production method, in terms of yield and the like, it is preferable to use a compound having G 1 is preferably a monovalent group having a (poly)oxyfluoroalkylene chain or a perfluoroalkyl group.

[0032] G 2 The alkylene group or fluoroalkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, even more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, from the viewpoint of increasing the yield of the present production method.

[0033] G 2 In the formula (A2), the divalent group having a (poly)oxyfluoroalkylene chain is C(-R a )(-R b ) each have independently -O- at the two ends bonded to G, or have -O- between carbon atoms in a carbon chain having two or more carbon atoms, or a fluoroalkylene group which is a combination thereof. 2 is preferably a structure represented by the following formula (G2-1). -(O) m0 -[(R f1 O) m1 (R f2 O) m2 (R f3 O) m3 (R f4 O) m4 (R f5 O) m5 (R f6 O) m6 ]-(R f7 ) m7 - Formula (G2-1) where m0 is an integer of 0 or 1, and R f1 , R f2 , R f3 , R f4 , R f5 , R f6 , R f7 , m1, m2, m3, m4, m5, m6, and m7 are the G 1 It is the same as in the formula (G2-1). f1 O)~(R f6The bonding order of the groups (O) is arbitrary, as explained in the formula (G1-1) above. When m7 is 0, G 2 C(-R a )(-R b ) is bound to one end -O-. When m7 is 1, G 2 C(-R a )(-R b ) is bonded to the carbon atom (R f7 (The terminal carbon atom of the ) Also, when m0 is 1, G 2 C(-R a )(-R b ) is bound to -O-. When m0 is 0, G 2 C(-R a )(-R b ) is bonded to the carbon atom (R f1 ~R f7 (carbon atom at either end of the group, m0 or m7). Note that m0 and m7 each independently represent 0 or 1.

[0034] G 2 Specific examples of the alkyl group include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CF2-, -CF2CF2-, -CF2CF2CF2-, -CF2CF2CF2CF2-, -CF2CF2CF2CF2CF2-, -CF2CF2CF2CF2CF2CF2-, -O-[(CF2-O) m1 (CF2CF2-O) m2 ]-, -CF(-CF3)-CF2-O-, -CF(-CF2CF3)-CF2-O-, -O-CF(-CF2CF3)-CF2-O-CF2- and the like.

[0035] In addition, in formula (A2), when n is 0, compound (A) is L-CH2-C(-R a )(-R b )-CH2-L. In addition, in formula (A2), n is 1 and G 2 is a single bond, compound (A) is L-CH2-C(-R a )(-R b )-C(-Ra )(-R b )-CH2-L.

[0036] In this production method, in terms of yield and the like, it is preferable that n is 0 or n is 1 and G 2 is preferably a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, or a perfluoroalkylene group.

[0037] Specific examples of suitable compounds (A) include the following:

[0038] [ka] Here, n1, n2, n3, and n4 are integers from 1 to 100.

[0039] Compound (A) can be produced, for example, by a method in which a compound represented by the following formula (A1-2) or formula (A2-2) is reacted with trifluoromethanesulfonic anhydride, tosyl chloride, mesyl chloride, or the like in the presence of an organic amine compound such as triethylamine or pyridine to form a sulfonate. G 1 -C(-R a )(-R b )-CH2-OH formula (A1-2) HO-CH2-{C(-R a )(-R b )-G 2 -} n C(-R a )(-R b )-CH2-OH formula (A2-2) However, R in the formula a , R b , G 1 , G 2 and n are as described above.

[0040] The Grignard reagent may be any one that can react with the partial structure (a). In this production method, the Grignard reagent is preferably a compound represented by the following formula (B) in order to prevent side reactions. R-MgX formula (B) In the formula, R is a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, and X is a halogen atom.

[0041] R can be appropriately selected from those having the desired structure to be introduced into the compound (A). The hydrocarbon group for R has a basic skeleton that is a linear alkyl group, a branched alkyl group, a cycloalkyl group, an aryl group, or a group formed by a combination thereof, and may have a heteroatom, a substituent, or a double bond or a triple bond. Examples of heteroatoms include nitrogen (N), oxygen (O), sulfur (S), and silicon (Si) atoms, and from the viewpoint of compound stability, N, O, or S is preferred. Furthermore, a fluorine atom is preferred as the substituent. From the viewpoint of improving the yield in the present production method, the number of carbon atoms in R is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.

[0042] From the viewpoint of reactivity, the halogen atom for X is preferably a chlorine atom, a bromine atom, or an iodine atom, and among these, a chlorine atom or a bromine atom is more preferred.

[0043] Examples of such Grignard reagents include primary alkyl Grignard reagents in which the carbon atom bonded to magnesium is a primary carbon atom, such as methyl magnesium chloride, ethyl magnesium chloride, and allyl magnesium chloride; secondary alkyl Grignard reagents such as isopropyl magnesium chloride; tertiary alkyl Grignard reagents such as tert-butyl magnesium chloride; aryl Grignard reagents such as phenyl magnesium chloride; and vinyl magnesium chloride.

[0044] In this production method, the Grignard reagent is preferably a Grignard reagent represented by the following formula (B1), since the target product can be obtained in high yield. R 1 -CH2-MgX Formula (B1) In the formula, R 1 is a hydrogen atom or a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, and X is a halogen atom. 1 is preferably a residue obtained by removing -CH2 from R.

[0045] Since the carbon atom to which magnesium is bonded is a primary carbon atom, this production method can be carried out under relatively mild reaction conditions.

[0046] Specific examples of suitable compounds of formula (B1) include the following:

[0047] [ka]

[0048] The Grignard reagent can be produced, for example, by reacting the following formula (B2) with metallic magnesium. Alternatively, a commercially available product having the desired structure may be used. RX formula (B2) Here, R and X are as described above.

[0049] In the reaction of scheme (1), the amount of Grignard reagent used is preferably 1 to 30 equivalents, more preferably 3 to 20 equivalents, and even more preferably 5 to 15 equivalents, relative to the total number of leaving groups L contained in compound (A), from the viewpoint of improving the yield of the target compound.

[0050] The transition metal compound can be appropriately selected from known catalysts used in Grignard reactions. The transition metal compound is preferably a compound containing an element from Groups 3 to 12 of the periodic table as a transition metal, and more preferably a compound containing an element from Groups 8 to 11 of the periodic table. The element from Groups 8 to 11 preferably contains one or more elements selected from copper, nickel, palladium, cobalt, and iron, and more preferably contains copper.

[0051] When the transition metal compound contains copper, the copper may be any of zero-, monovalent, divalent, and trivalent compounds. However, from the viewpoint of catalytic activity, monovalent or divalent copper salts or complex salts are preferred. Furthermore, from the viewpoint of ease of availability, copper chloride is more preferred. As copper chloride, either CuCl or CuCl2 can be suitably used. Incidentally, copper chloride may be anhydrous or hydrated, but from the viewpoint of catalytic activity, copper chloride anhydride is more preferred. The amount of the transition metal compound used is, for example, 0.1 to 50 mol %, preferably 1 to 30 mol %, and more preferably 2 to 20 mol %, based on the total number of leaving groups L possessed by compound (A).

[0052] In the reaction of this production method, a ligand may be used in combination with the transition metal compound serving as a catalyst, if necessary. The use of a ligand improves the yield of the target product. On the other hand, in this production method, a sufficient yield can be obtained even without using a ligand, so the use of the ligand is not necessary. Examples of the ligand include 1,3-butadiene, phenylpropyne, tetramethylethylenediamine (TMEDA), etc. When a ligand is used, the amount used is preferably 0.01 to 2.0 equivalents, more preferably 0.1 to 1.2 equivalents, relative to the total number of leaving groups L possessed by compound (A), from the viewpoint of improving the yield of the target product.

[0053] The reaction in this production method is usually carried out in a solvent. The solvent can be appropriately selected from solvents that can dissolve compound (A) and the Grignard reagent. The solvent may be a single solvent or a mixed solvent of two or more solvents. For example, when compound (A) is a compound having a relatively low fluorine atom content (the ratio of fluorine atoms to the molecular weight of the compound molecule), the solvent is not particularly limited as long as it is inert to the reaction. Among the solvents inert to the reaction, ether solvents such as diethyl ether, tetrahydrofuran, and dioxane are preferred, and tetrahydrofuran is more preferred. When the compound (A) is a compound with a relatively high fluorine atom content, a mixed solvent of the above-mentioned ether solvent and a fluorine-containing solvent is preferred. Examples of fluorine-based solvents include hydrofluorocarbons (1H,4H-perfluorobutane, 1H-perfluorohexane, 1,1,1,3,3-pentafluorobutane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 2H,3H-perfluoropentane, etc.), hydrochlorofluorocarbons (3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb), etc.), hydrofluoroethers (CF3CH2OCF2CF2H(AE-3000)), (perfluorobutoxy)methane, (perfluorobutoxy)ethane, etc.), hydrochlorofluorocarbons (e.g., 1H,4H-perfluorobutane, 1H-perfluorohexane ... Examples of suitable fluoroolefins include (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(Z) form), (E)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(E) form), (Z)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(Z) form), (E)-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd(E) form), etc.), and fluorine-containing aromatic compounds such as perfluorobenzene, m-bis(trifluoromethyl)benzene (SR-solvent), and p-bis(trifluoromethyl)benzene.

[0054] This production method can be carried out, for example, by preparing a solution containing compound (A), adding a transition metal compound and, if necessary, a ligand, and then adding a separately prepared Grignard reagent solution. The reaction temperature of the compound (A) with the Grignard reagent may be appropriately adjusted depending on the combination of the compound (A) with the Grignard reagent, for example, −20° C. to 66° C. (the boiling point of tetrahydrofuran), preferably −20° C. to 40° C.

[0055] According to this production method, a fluorine-containing compound represented by the following formula (C1) or formula (C2) can be obtained. G 1 -C(-R a )(-R b )-CH2-R formula (C1) R-CH2-{C(-R a )(-R b )-G 2 -} n C(-R a )(-R b )-CH2-R Formula (C2) In the formula, R a , R b , G 1 , G 2 , R and n are as defined above, and R a , R b Or if there are multiple Rs, a , R b Alternatively, each R may be the same or different from the others.

[0056] Compound (C1) and compound (C2) can be used for various purposes. They can also be used as intermediates for various compounds. When used as intermediates, for example, when compound (C1) or compound (C2) has a vinyl group, the vinyl group may be hydrosilylated. Compound (C1) and compound (C2) may be used as a composition containing other compounds. The other compounds are not particularly limited, but examples include fluorine-containing compounds represented by the following formula (D1) or formula (D2). When compound (C1) and compound (C2) are used as intermediates, they may be used as a composition containing other compounds, or other compounds may be included in the final product. For example, when compound (C1) or compound (C2) has a vinyl group, a composition containing compound (D1) or compound (D2) may be further hydrosilylated, or compound (C1) or compound (C2) may be hydrosilylated and then compound (D1) or compound (D2) may be included. G 1 -C(=CF2)-CH2-R Formula (D1) R-CH2-{C(=CF2)-G 2 -} n C(=CF2)-CH2-R formula (D2) However, in the formula, G 1 , G 2 , R and n are as described above, and when there are multiple R, the Rs may be the same or different from one another. [Example]

[0057] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Examples 1, 3 to 10, and 12 to 13 are examples, and Examples 2 and 11 are comparative examples.

[0058] [Synthesis Example: Synthesis of Compound (A1-1)] 2,3,3,4,4,5,5,6,6,7,7,7-Dodecafluoro-2-(trifluoromethyl)-1-heptanol (12 g), dichloromethane (100 mL), and triethylamine (6.0 mL) were added and cooled to 0°C. Trifluoromethanesulfonic anhydride (5.6 mL) was added and stirred at room temperature. After washing with water, the mixture was dried over sodium sulfate. After filtration, the solvent was removed by distillation, and the mixture was subjected to flash column chromatography using silica gel to obtain 7.3 g of the following compound (A1-1). The NMR measurement results of the compound (A1-1) are shown below. 1 H-NMR(400MHz,Chloroform-d)δ 4.41(d,J=12.3Hz,2H). 19 F-NMR(376MHz,Chloroform-d)δ -70~-80(m),-120~125(m),-185(m).

[0059] [ka] OTf is triflate: -OS(=O)2(-CF3).

[0060] [Example 1: Production of fluorine-containing compound (1)] The compound (A1-1) (500 mg), CuCl (21.8 mg), and 1,3-butadiene THF solution (2.0 M, 0.45 mL) were added and cooled to 10°C. Then, n-butylmagnesium chloride THF solution (0.88 M, 9.2 mL) was added dropwise and stirred at room temperature. After cooling to 0°C, 1 M hydrochloric acid was added, and the mixture was extracted with AE-3000. After adding sodium sulfate and drying, the mixture was filtered and concentrated, and then purified by flash column chromatography using silica gel to obtain 190.6 mg of the following fluorine-containing compound (1). Note that THF is tetrahydrofuran. The NMR measurement results of the fluorine-containing compound (1) are shown below. 1 H-NMR(400MHz,Chloroform-d)δ 2.5~1.8(m,2H),1.6~1.1(m,6H),1.0~0.8(m,3H). 19 F-NMR(376MHz,Chloroform-d)δ -70~-80(m),-120~125(m),-165(m).

[0061] [ka]

[0062] [Examples 2 to 9: Methods for producing fluorine-containing compound (1)] Fluorine-containing compound (1) was produced in the same manner as in Example 1 above, except that the amounts of n-butylmagnesium chloride, 1,3-butadiene, and CuCl2 added were changed as shown in Table 1 below.

[0063] [Example 10: Method for producing fluorine-containing compound (1)] Fluorine-containing compound (1) was produced in the same manner as in Example 1 above, except that CuCl was used instead of CuCl2 and the blending amounts were changed as shown in Table 1 below.

[0064] [Example 11: Production of fluorine-containing compounds] The following compound (X1) was used to attempt the production of the fluorine-containing compound (1). The following compound (X1) was synthesized by adding triphenylphosphine and carbon tetrabromide to 2,3,3,4,4,5,5,6,6,7,7,7-Dodecafluoro-2-(trifluoromethyl)-1-heptanol and reacting them in dichloromethane. However, the compound (X1) was unstable and decomposed back into alcohol during purification. Therefore, it was found to be unsuitable for synthesizing the fluorine-containing compound (1).

[0065] [ka]

[0066] Table 1 shows the blending ratio of each component in the synthesis of Examples 1 to 10 and the yield of the target product obtained. The eq (equivalent) and mol% in Table 1 are based on the number of triflate groups in the electrophilic agent. A hyphen (-) in the table indicates that no addition was made. The yield is the amount of the target product. 19 Quantitative determination was carried out using F-NMR by the internal standard method (internal standard: hexafluorobenzene) and calculated using the following formula. Yield = target product / compound (A1-1) × 100 [%]

[0067] [Table 1]

[0068] As shown in Table 1, the production methods of Examples 1 and 3 to 10, which involve reacting compound (A1-1), which is a compound having a partial structure represented by formula (a), with a Grignard reagent in the presence of a transition metal compound, have shown that the target fluorine-containing compound can be synthesized under relatively mild reaction conditions. The following Examples 12 and 13 demonstrate that various compounds can be synthesized by this production method.

[0069] [Example 12: Production of fluorine-containing compound (2)] (Synthesis Example 12-1: Synthesis of Compound (12-1)) 2,2'-[(1,1,2,2-Tetrafluoro-1,2-Othanediyl)bis(oxy)]bis[2,3,3,3-tetrafluoro-1-propanol] (3.85 g), dichloromethane (100 mL), and pyridine (2.2 mL) were added and cooled to 0°C. Trifluoromethanesulfonic anhydride (7.18 g) was added and stirred at room temperature for 3 hours. After washing twice with water, the mixture was dried over sodium sulfate. After filtration, the solvent was distilled off, and hexane was added. After stirring for 30 minutes, the mixture was filtered and dried under reduced pressure to obtain 2.73 g of the following compound (12-1). The NMR measurement results of the compound (12-1) are shown below. 1 H-NMR(400MHz,Chloroform-d)δ 3.86(m,4H). 19 F-NMR(376MHz,Chloroform-d)δ -72(m),-82(m),-92(m),-136(m).

[0070] [ka]

[0071] (Synthesis Example 12-2: Synthesis of Fluorine-Containing Compound (2)) The above compound (12-1) (0.66 g) and CuCl (2.6 mg) were added and cooled to 10°C, and then a THF solution of n-butylmagnesium chloride (0.88 M, 10.2 mL) was added dropwise and stirred at room temperature for 1 hour. After cooling to 0°C, 1 M hydrochloric acid was added and the mixture was extracted with AE-3000. After adding sodium sulfate and drying, the mixture was filtered and concentrated, and then subjected to flash column chromatography using silica gel to obtain 0.09 g of the following fluorine-containing compound (2). The NMR measurement results of compound (2) are shown below. 1 H-NMR (400MHz, Chloroform-d) δ 2.5~1.8(m,4H),1.6~1.1(m,12H),1.0~0.8(m,6H). 19 F-NMR(376MHz,Chloroform-d) δ -72(m),-82(m),-92(m),-126(m).

[0072] [ka]

[0073] [Example 13: Production of fluorine-containing compound (3)] (Synthesis Example 13-1: Compound (13-1)) For the following compound (13-1), HFPO Alcohol FEOH-2500 manufactured by Sanming Hexafluoro Chemicals was used. CF3-CF2-CF2-O-(CF(CF3)-CF2-O) n6 -CF(CF3)-CH2OH...Formula (13-1) The average number of repeating units n6 is 14.

[0074] (Synthesis Example 13-2: Synthesis of Compound (13-2)) 4.00 g of the compound (13-1), 2,6-lutidine (0.759 g), and AE-3000 (28.0 g) were added and stirred at 0° C. Trifluoromethanesulfonic anhydride (0.987 g) was added, and the mixture was stirred at room temperature. After washing with water, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 3.73 g of the following compound (13-2). CF3-CF2-CF2-O-(CF(CF3)-CF2-O) n7 -CF(CF3)-CH2OTf...Formula (13-2) The average number of repeating units, n7, is 14, and OTf is triflate: -OS(=O)2(-CF3).

[0075] NMR spectrum of compound (13-2); 1 H-NMR(400MHz,Chloroform-d) δ 4.95(m,2H). 19 F-NMR(376MHz,Chloroform-d) δ -80~-85(m),-131.5(m),-136(m).

[0076] (Synthesis Example 13-3: Synthesis of Compound (13-3)) Diethyldiallylmalonate (60.0 g), lithium chloride (23.7 g), water (6.45 g), and dimethyl sulfoxide (263 g) were added and stirred at 160°C. After cooling to room temperature, water was added and extracted with ethyl acetate. Hexane was added to the organic layer, which was washed with saturated saline and dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 39.5 g of the following compound (13-3).

[0077] [ka]

[0078] NMR spectrum of compound (13-3); 1H-NMR (400MHz, Chloroform-d) δ(ppm):(ddt,J=17.1,10.1,7.0Hz,2H),5.06~4.94(m,4H),4.09(q,J=7.1Hz,2H),2.47(ddd,J=14.0 ,8.0,6.1Hz,1H),2.33(dt,J=14.9,7.5Hz,2H),2.22(dt,J=14.1,6.5Hz,2H),1.21(t,J=7.1Hz,3H).

[0079] (Synthesis Example 13-4: Synthesis of compound (13-4)) After adding THF (260 mL) and diisopropylamine (29.8 g), the solution was cooled to -78 °C. A hexane solution of n-butyllithium (2.76 M, 96.6 mL) was added, and the mixture was heated to 0 °C. After stirring, the mixture was cooled to -78 °C to prepare a THF solution of lithium diisopropylamide (LDA). The above compound (13-3) (39.5 g) was added to the THF solution, and after stirring, allyl bromide (24.1 mL) was added. The mixture was heated to 0 °C, 1 M hydrochloric acid (100 mL) was added, and the THF was evaporated under reduced pressure. Extraction with dichloromethane was followed by the addition of sodium sulfate. After filtration, the solvent was evaporated, and the mixture was subjected to flash column chromatography using silica gel to obtain 45.0 g of compound (13-4).

[0080] [ka]

[0081] NMR spectrum of compound (13-4); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.74~5.62(m,3H),5.04(dd,J=13.6,1.9Hz,6H),4.10(q,J=7.1Hz,2H),2.29(d,J=7.4Hz,6H),1.22(t,J=7.1Hz,3H).

[0082] (Synthesis Example 13-5: Synthesis of compound (13-5)) The above compound (13-4) (45.0 g) was dissolved in THF (620 mL) and cooled to 0°C. A THF solution (104 mL) of lithium aluminum hydride was added and stirred. Water and a 15% aqueous sodium hydroxide solution were added, and the mixture was stirred at room temperature and then diluted with dichloromethane. After filtration, the solvent was distilled off, and flash column chromatography using silica gel was performed to obtain 31.3 g of the following compound (13-5).

[0083] [ka]

[0084] NMR spectrum of compound (13-5); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.90~5.76(m,3H),5.10~5.02(m,6H),3.38(s,2H),2.03(dt,J=7.5,1.2Hz,6H),1.45(s,1H).

[0085] (Synthesis Example 13-6: Synthesis of compound (13-6)) Acetonitrile (380 mL), the compound (13-5) (31.3 g), triphenylphosphine (64.3 g), and carbon tetrachloride (33.9 g) were added and stirred at 90°C. After concentration, ethyl acetate / hexane was added and stirred. After filtration and concentration, 28.2 g of the following compound (13-6) was obtained by distillation.

[0086] [ka]

[0087] NMR spectrum of compound (13-6); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.83~5.67(m,3H),5.16~5.01(m,6H),3.32(s,2H),2.05(dt,J=7.5,1.1Hz,6H).

[0088] (Synthesis Example 13-7: Synthesis of compound (13-7)) To magnesium (2.36 g), THF (35 mL) and iodine (0.180 g) were added and stirred at room temperature. A solution of the compound (13-6) (14.0 g) in THF (35 mL) was added, and the mixture was heated under reflux for 2 hours to prepare a solution (1.0 M) of the following compound (13-7).

[0089] [ka]

[0090] (Synthesis Example 13-8: Synthesis of fluorine-containing compound (3)) CuCl2 (16.0 mg), 1-phenyl-1-propyne (0.052 g), 1,3-bistrifluoromethylbenzene (24 mL), and the compound (13-1) (2.3 g) were added, followed by the compound (13-7) (5.0 mL, 1.0 M). After stirring at room temperature, the mixture was washed with 1 M hydrochloric acid and dried over sodium sulfate. After filtration, the solvent was distilled off, and AC-6000 was added. After washing with MeOH, flash column chromatography using silica gel was performed to obtain 0.227 g of the following fluorine-containing compound (3). AC-6000 is CF 13 It is C2H5.

[0091] [ka] The average number of repeating units n8 is 10.

[0092] NMR spectrum of compound (3); 1 H-NMR (400MHz, Chloroform-d) δ 1.5(m),1.8~2.4(m),5.0(m,6H),5.8(m,3H). 19 F-NMR(376MHz,Chloroform-d) δ -80~-85(m),-94(m),-105.5(m),-131.5(m),-136(m). [Industrial Applicability]

[0093] According to the present invention, fluorine-containing compounds used in a variety of fields, such as agricultural chemicals, pharmaceuticals, and functional materials, can be synthesized using readily available compounds under relatively mild reaction conditions. Furthermore, for example, by using a Grignard reagent having a carbon-carbon double bond, a double bond can be easily added to compound (A), thereby obtaining compounds that are useful as raw materials for synthesizing various compounds.

[0094] This application claims priority based on Japanese Patent Application No. 2021-034906, filed on March 5, 2021, the disclosure of which is incorporated herein in its entirety.

Claims

1. A compound having a partial structure represented by the following formula (a): with a Grignard reagent in the presence of a transition metal compound, A method for producing a fluorine-containing compound. -C(-R ａ )(-R ｂ )-CH ２ -L Formula (a) However, in the formula, R ａ is a fluorine atom or a fluoroalkyl group, R ｂ is a hydrogen atom or a fluoroalkyl group, L is a sulfonate group.

2. The method for producing a fluorine-containing compound according to claim 1, wherein the compound having a partial structure represented by formula (a) is a compound represented by the following formula (A1) or formula (A2): G １ -C(-R ａ )(-R ｂ )-CH ２ -L Formula (A1) L-CH ２ -{C(-R ａ )(-R ｂ )-G ２}- ｎ C(-R ａ )(-R ｂ )-CH ２ -L Formula (A2) However, in the formula, R ａ is a fluorine atom or a fluoroalkyl group, and R ａ If there are multiple R ａ may be the same or different, R ｂ is a hydrogen atom or a fluoroalkyl group, and R ｂ If there are multiple R ｂ may be the same or different, G １ represents a monovalent group having a (poly)oxyfluoroalkylene chain, a hydrogen atom, an alkyl group, or a fluoroalkyl group, G ２ represents a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, an alkylene group, or a fluoroalkylene group, L represents a sulfonate group, and in formula (A2), a plurality of Ls may be the same or different. n is 0 or 1.

3. In formula (A1), G １ The method for producing a fluorine-containing compound according to claim 2, wherein is a monovalent group having a (poly)oxyfluoroalkylene chain or a perfluoroalkyl group.

4. In formula (A2), n is 0, or n is 1, and G ２ The method for producing a fluorine-containing compound according to claim 2, wherein is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, or a perfluoroalkylene group.

5. The method for producing a fluorine-containing compound according to any one of claims 1 to 4, wherein the Grignard reagent is represented by the following formula (B): R-MgX formula (B) In the formula, R is a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, and X is a halogen atom.

6. The method for producing a fluorine-containing compound according to claim 5 , wherein the Grignard reagent is represented by the following formula (B1): R １ -CH ２ -MgX formula (B1) In the formula, R １ is a hydrogen atom or a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, and X is a halogen atom.

7. The method for producing a fluorine-containing compound according to any one of claims 1 to 6, wherein L is a triflate group.

8. The method for producing a fluorine-containing compound according to any one of claims 1 to 7, wherein the transition metal compound contains copper.

9. A fluorine-containing compound represented by the following formula (A1) or (A2): G １ -C(-R ａ )(-R ｂ )-CH ２ -L Formula (A1) L-CH ２ -{C(-R ａ )(-R ｂ )-G ２}- ｎ C(-R ａ )(-R ｂ )-CH ２ -L Formula (A2) However, in the formula, R ａ is a fluorine atom or a fluoroalkyl group, and R ａ If there are multiple R ａ may be the same or different, R ｂ is a hydrogen atom or a fluoroalkyl group, and R ｂ If there are multiple R ｂ may be the same or different, G １ represents a monovalent group having a (poly)oxyfluoroalkylene chain, a hydrogen atom, an alkyl group, or a fluoroalkyl group, G ２ represents a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, an alkylene group, or a fluoroalkylene group, L represents a sulfonate group, and in formula (A2), a plurality of Ls may be the same or different. n is 0 or 1.

10. In formula (A1), G １ The fluorine-containing compound according to claim 9 , wherein is a monovalent group having a (poly)oxyfluoroalkylene chain or a perfluoroalkyl group.

11. In formula (A2), n is 0, or n is 1, and G ２ The fluorine-containing compound according to claim 9 , wherein is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, or a perfluoroalkylene group.

12. The fluorine-containing compound according to any one of claims 9 to 11, wherein L is a triflate group.

13. A fluorine-containing compound represented by the following formula (C1) or formula (C2): G １ -C(-R ａ )(-R ｂ )-CH ２ -R Formula (C1) R-CH ２ -{C(-R ａ )(-R ｂ )-G ２}- ｎ C(-R ａ )(-R ｂ )-CH ２ -R Formula (C2) However, in the formula, R ａ is a fluorine atom or a fluoroalkyl group, and R ａ If there are multiple R ａ may be the same or different, R ｂ is a hydrogen atom or a fluoroalkyl group, and R ｂ If there are multiple R ｂ may be the same or different, G １ represents a monovalent group having a (poly)oxyfluoroalkylene chain, a hydrogen atom, an alkyl group, or a fluoroalkyl group, G ２ represents a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, an alkylene group, or a fluoroalkylene group, R is a hydrocarbon group which may have a substituent and which may have a heteroatom in the carbon chain, n is 0 or 1.

14. In formula (C1), G １ The fluorine-containing compound according to claim 13, wherein is a monovalent group having a (poly)oxyfluoroalkylene chain or a perfluoroalkyl group.

15. In formula (C2), n is 0, or n is 1, and G ２ The fluorine-containing compound according to claim 13, wherein is a divalent group having a (poly)oxyfluoroalkylene chain, a single bond, or a perfluoroalkylene group.

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