Method for producing fluorine-containing compounds and method for producing surface treatment agents

Abstract

The purpose of the present invention is to provide a method for producing a fluorine compound using easily available compounds under relatively mild reaction conditions and a method for producing a surface treatment agent using a fluorine compound obtained by said production method.　The method is for producing a fluorine compound represented by formula (C1) or (C2) and comprises reacting a compound represented by formula (A1) or (A2) with a compound represented by formula (B1).　Formula (A1): G1-L1-CR1R2-X1 Formula (A2): X2-CR3R4-L2-G2-L3-CR5R6-X3 Formula (B1): R11-MgR12 Formula (C1): G1-L1-CR1R2-R11 Formula (C2): R11-CR3R4-L2-G2-L3-CR5R6-R11 The symbols in the formulae are as described in the specification.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a fluorine-containing compound and a method for producing a surface treatment agent. [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] Furthermore, Non-Patent Document 1 discloses a compound represented by the following formula as an electrophilic perfluoroalkylating agent.

[0005] [ka] However, R f nC m F 2m+1 , Tf is SO2CF3, and R is H or F.

[0006] Furthermore, Example 1A of Patent Document 2 describes the reaction of CF3(CF2)6(CH2)2-I with hexylmagnesium chloride in tetrahydrofuran (THF) in the presence of isoprene. [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. 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. Furthermore, the method of Patent Document 2 has the problem that the longer the perfluoroalkyl chain and the larger the molecular weight, the lower the reactivity. This is thought to be because the longer the perfluoroalkyl chain, the lower the solubility in solvents.

[0010] The present invention aims to provide a method for producing a fluorine-containing compound in a good yield under relatively mild reaction conditions using easily available compounds, and a method for producing a surface treatment agent using the fluorine-containing compound obtained by the production method. [Means for solving the problem]

[0011] The present invention provides a method for producing a fluorine-containing compound and a method for producing a surface treatment agent having the following constitutions [1] to

[10] . [1] A method for producing a fluorine-containing compound represented by the following formula (C1) or formula (C2), comprising reacting a compound represented by the following formula (A1) or formula (A2) with a compound represented by the following formula (B1): G1 -L 1 -CR 1 R 2 -X 1 Formula (A1) X 2 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -X 3 Formula (A2) R 11 -MgR 12 Formula (B1) G 1 -L 1 -CR 1 R 2 -R 11 Formula (C1) R 11 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -R 11 Formula (C2) However, in the formula, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, L 1 , L 2 and L 3 are each independently a single bond or a divalent organic group, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R 11 is a hydrocarbon group which may have a substituent or may have a heteroatom, and R 11 If there are multiple R 11may be the same or different from each other, R 12 represents a halogen atom or a hydrocarbon group which may have a substituent or a hetero atom, X 1 , X 2 and X 3 are each independently a halogen atom. [2] A method for producing a fluorine-containing compound represented by the following formula (C1) or (C2), which comprises reacting a compound represented by the following formula (A3) or (A4) with a compound represented by the following formula (B2): G 1 -L 1 -CR 1 R 2 -MgR 12 Formula (A3) R 12 Mg-CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -MgR 12 Formula (A4) R 11 -X 4 Formula (B2) G 1 -L 1 -CR 1 R 2 -R 11 Formula (C1) R 11 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -R 11 Formula (C2) However, in the formula, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, L 1 , L 2 and L3 are each independently a single bond or a divalent organic group, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R 11 are each independently a hydrocarbon group which may have a substituent or may have a heteroatom, and R 11 If there are multiple R 11 may be the same or different from each other, R 12 is a halogen atom or a hydrocarbon group which may have a substituent or may have a hetero atom, and R 12 If there are multiple R 12 may be the same or different from each other, X 4 is a halogen atom. [3] A method for producing a fluorine-containing compound represented by the following formula (C1) or formula (C2), comprising reacting a compound represented by the following formula (A1) or formula (A2), a compound represented by the following formula (B2), and a compound represented by the following formula (B3): G 1 -L 1 -CR 1 R 2 -X 1 Formula (A1) X 2 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -X 3 Formula (A2) R 11 -X 4 Formula (B2) R 14 -CR 15 R 16 -MgR 12 Formula (B3) G 1 -L1 -CR 1 R 2 -R 11 Formula (C1) R 11 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -R 11 Formula (C2) However, in the formula, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, L 1 , L 2 and L 3 are each independently a single bond or a divalent organic group, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R 11 is a hydrocarbon group which may have a substituent or may have a heteroatom, and R 11 If there are multiple R 11 may be the same or different from each other, R 12 represents a halogen atom or a hydrocarbon group which may have a substituent or a hetero atom, R 14 , R 15 and R 16 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent or a hetero atom, X 1 , X 2 , X 3 and X 4 are each independently a halogen atom. [4] Said L1 -CR 1 R 2 , said L 2 -CR 3 R 4 , and the L 3 -CR 5 R 6 At least one of the following is true: 7 R 8 -CR 9 R 10 ) n1 The method for producing a fluorine-containing compound according to any one of [1] to [3], In the formula, R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R 7 , R 8 , R 9 or R 10 If there are multiple R 7 , R 8 , R 9 or R 10 may be the same or different from each other, n1 is an integer from 1 to 20. [5] Said L 1 -CR 1 R 2 , said L 2 -CR 3 R 4 , and the L 3 -CR 5 R 6 At least one of them is (CH2CH2) n2 The method for producing a fluorine-containing compound according to any one of [1] to [4], In the formula, n2 is an integer of 1 to 20. [6] R 11 The method for producing a fluorine-containing compound according to any one of [1] to [5], wherein: (CH2=CH-R 21 -) a (R 22 -) 3-a CR 23 -* Formula (D1) However, in the formula, R 21 is a single bond or an alkylene group having 1 to 18 carbon atoms which may have a fluorine atom, and R 21 If there are multiple R 21 may be the same or different from each other, R 22 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R 22 If there are multiple R 22 may be the same or different from each other, R 23 represents a single bond or an alkylene group having 1 to 19 carbon atoms, a is an integer from 1 to 3, * is a bond. [7] X 1 , X 2 , X 3 and X 4 The method for producing a fluorine-containing compound according to any one of [1] to [6], wherein at least one of the following is an iodine atom: [8] The method for producing a fluorine-containing compound according to any one of [1] to [7], wherein the reaction is carried out in the presence of a transition metal compound. [9] The method for producing a fluorine-containing compound according to [8], wherein the transition metal compound contains one or more elements selected from Cu, Ni, Pd and Co.

[10] A method for producing a surface treatment agent, comprising producing a fluorine-containing compound represented by formula (C1) or (C2) by the production method according to any one of [1] to [9], and introducing a reactive silyl group into the fluorine-containing compound. [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, and a method for producing a surface treatment agent using the fluorine-containing compound obtained by the production method. DETAILED DESCRIPTION OF THE INVENTION

[0013] In this specification, the compound represented by formula (A1) will be referred to as compound (A1), and the same applies to compounds represented by other formulas. "(Poly)oxyfluoroalkylene" is a general term for oxyfluoroalkylene and polyoxyfluoroalkylene. A fluoroalkyl group is a general term that includes perfluoroalkyl groups and partial fluoroalkyl groups. A perfluoroalkyl group refers to a group in which all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms. A partial fluoroalkyl group is an alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms and which also has one or more hydrogen atoms. In other words, a fluoroalkyl group is an alkyl group that has one or more fluorine atoms. The term "reactive silyl group" refers collectively to a hydrolyzable silyl group and a silanol group (Si-OH), and the term "hydrolyzable silyl group" refers to a group that can undergo a hydrolysis reaction to form a silanol group. The term "organic group" refers to a hydrocarbon group that may have a substituent and may have a heteroatom or other bond in the carbon chain. The term "hydrocarbon group" refers to an aliphatic hydrocarbon group (such as a straight-chain alkylene group, a branched alkylene group, or a cycloalkylene group), an aromatic hydrocarbon group (such as a phenylene group), or a group consisting of a combination thereof. The term "surface layer" refers to a layer formed on the surface of a substrate. 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 present production method) is a suitable production method capable of introducing any substituent into a compound having a (poly)oxyfluoroalkylene chain by subjecting an organohalogen compound having a (poly)oxyfluoroalkylene chain (compound (A1), compound (A2)) or an organomagnesium compound having a (poly)oxyfluoroalkylene chain (compound (A3), compound (A4)) to a coupling reaction with a specific organomagnesium compound or organohalogen compound. This production method uses a compound having a (poly)oxyfluoroalkylene chain as the reaction substrate. It is presumed that while compounds having long-chain perfluoroalkyl groups are poorly soluble and the reaction does not proceed smoothly, the use of a compound having an ether chain improves solubility and increases reactivity. According to the present production method, even when a compound having a (poly)oxyfluoroalkylene chain with a relatively high molecular weight (long chain) is used, the reaction efficiency is high, and the yield of the target product can be increased while suppressing the reaction temperature and reaction time. For example, according to the present production method, even when a compound having a (poly)oxyfluoroalkylene chain with a molecular weight of 200 to 30,000 is used, the target product can be suitably produced. Furthermore, according to the present production method, for example, a fluorine-containing compound with a molecular weight of 1,000 to 30,000 can be suitably produced. The three production methods belonging to this production method will be explained in more detail below.

[0015] <First manufacturing method> The first method for producing a fluorine-containing compound of the present invention is a method for producing a fluorine-containing compound represented by the following formula (C1) or formula (C2), which comprises reacting a compound represented by the following formula (A1) or formula (A2) with a compound represented by the following formula (B1): G 1 -L 1 -CR 1 R 2 -X 1 Formula (A1) X 2 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -X 3 Formula (A2) R 11 -MgR 12 Formula (B1) G 1 -L 1 -CR 1 R 2 -R 11 Formula (C1) R 11-CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -R 11 Formula (C2) However, in the formula, G 1 is a monovalent group having a (poly)oxyfluoroalkylene chain, G 2 is a divalent group having a (poly)oxyfluoroalkylene chain, L 1 , L 2 and L 3 are each independently a single bond or a divalent organic group, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R 11 is a hydrocarbon group which may have a substituent or may have a heteroatom, and R 11 If there are multiple R 11 may be the same or different from each other, R 12 represents a halogen atom or a hydrocarbon group which may have a substituent or a hetero atom, X 1 , X 2 and X 3 are each independently a halogen atom.

[0016] The first production method is a method for synthesizing compound (C1) or compound (C2) by a coupling reaction between compound (A1) or compound (A2), which is an organic halogen compound, and compound (B1), which is an organic magnesium compound. Although the reaction pathway of this reaction is partly speculative, it is believed that the reaction pathway is a reaction between I of compound (A1) or compound (A2) and MgR of compound (B1). 12is presumed to undergo an exchange reaction in the reaction system (in a solvent) to produce compound (A3) or compound (A4) in the second production method described below and compound (B2), while a coupling reaction proceeds to synthesize compound (C1) or compound (C2).

[0017] G 1 The monovalent group having a (poly)oxyfluoroalkylene chain in 1 (L 1 If is a single bond, CR 1 R 2 ) 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, Rf7 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 is an integer of 1 to 200. When the obtained compound (C1) is used as a surface treatment agent or a raw material thereof, it is preferable that m1+m2+m3+m4+m5+m6 is an integer of 1 to 200, that is, G 1 is preferably a polyoxyfluoroalkylene chain. 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)~(R f6 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 L 1 (L 1 If is a single bond, CR 1 R 2 ) is bonded to -O-. When m7 is 1, G 1 L 1 (L 1 If is a single bond, CR 1 R 2 ) is bonded to the carbon atom (R f7 (the terminal carbon atom of The fluoroalkylene group having 3 to 6 carbon atoms may be a straight-chain fluoroalkylene group, or may be a fluoroalkylene group having a branched or cyclic structure.

[0018] R f1Specific examples include -CF2- and -CHF-. R f2 Specific examples include -CF2CF2-, -CHFCF2-, -CHFCHF-, -CH2CF2-, -CH2CHF-, etc. R f3 Specific examples of the alkyl group include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CHF-, - Examples include CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F)-CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2-, and -CH(CH2F)-CH2-. R f4Specific examples of the alkyl group include -CF2CF2CF2CF2-, -CHFCF2CF2CF2-, -CH2CF2CF2CF2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2C Examples include HFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, -cycloC4F6-, and the like. R f5 Specific examples of the group include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, -cycloC5F8-, and the like. R f6 Specific examples of the alkyl group include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, -cycloCF 10 - and more. Also, R f0 and R f7 Specific examples of R f1 ~R f6 Examples include those similar to those listed above. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, a specific example of which is perfluorocyclobutane-1,2-diyl, -cycloC5F8- means a perfluorocyclopentanediyl group, a specific example of which is perfluorocyclopentane-1,3-diyl, -cycloC6F 10 - means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0019] When the obtained compound (C1) is used as a surface treatment agent or a raw material thereof, G 1 Among these, it is preferable that the compound has a structure represented by the following formulae (F1) to (F3), because it has excellent water and oil repellency, abrasion resistance, and fingerprint stain removability. (R f1 O) m1 -(R f2 O) m2 Formula (F1) (R f2 O) m2 -(R f4 O) m4 Formula (F2) (R f3 O) m3 Formula (F3) However, the symbols in formulas (F1) to (F3) are the same as those in formula (G1-1).

[0020] In formula (F1) and formula (F2), (R f1 O) and (R f2 O), (R f2 O) and (R f4 O) can be bonded in any order. For example, (R f1 O) and (R f2 O) may be alternated, and (R f1 O) and (R f2 O) may be arranged in blocks or randomly. The same applies to formula (F3). In formula (F1), m1 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20. Furthermore, m2 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20. In formula (F2), m2 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20. Furthermore, m4 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20. In formula (F3), m3 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20.

[0021] G 2 In the formula (A2), the divalent group having a (poly)oxyfluoroalkylene chain is represented by L 2 or L 3 (L 2 or L 3 If is a single bond, CR 3 R 4 or CR 5 R 6 ) 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 f6 The bonding order of the groups (O) is arbitrary, as explained in the formula (G1-1) above. When m7 is 0, G 2 L 3 (L 3 If is a single bond, CR 5 R 6 ) is bound to one end -O-. When m7 is 1, G 2 L 3 (L 3 If is a single bond, CR 5 R 6 ) is bonded to the carbon atom (R f7 (The terminal carbon atom of the ) Also, when m0 is 1, G 2 L 2 (L 2 If is a single bond, CR 3 R 4 ) is bound to -O-. When m0 is 0, G 2 L 2 (L 2 If is a single bond, CR 3 R 4 ) 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. When the obtained compound (C2) is used as a surface treatment agent or a raw material thereof, it is preferable that m1+m2+m3+m4+m5+m6 is an integer of 1 to 200, that is, G 2 is preferably a polyoxyfluoroalkylene chain.

[0022] When the obtained compound (C2) is used as a surface treatment agent or a raw material thereof, G 2Among these, it is preferable that the compound has a structure represented by the following formula (F4) to formula (F6), because it has excellent water and oil repellency, abrasion resistance, and fingerprint stain removability. -(O) m0 -(R f1 O) m1 -(R f2 O) m2 Formula (F4) -(O) m0 -(R f2 O) m2 -(R f4 O) m4 Formula (F5) -(O) m0 -(R f3 O) m3 Formula (F6) However, the symbols in formulas (F4) to (F6) are the same as those in formula (G2-1).

[0023] In formula (F4) and formula (F5), (R f1 O) and (R f2 O), (R f2 O) and (R f4 O) can be bonded in any order. For example, (R f1 O) and (R f2 O) may be alternated, and (R f1 O) and (R f2 O) may be arranged in blocks or randomly. The same applies to formula (F6). In formula (F4), m1 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20. Furthermore, m2 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20. In formula (F5), m2 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20. Furthermore, m4 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20. In formula (F6), m3 is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, and particularly preferably 1 to 20.

[0024] G 1 and G 2 The proportion of fluorine atoms in the (poly)oxyfluoroalkylene chain [{number of fluorine atoms / (number of fluorine atoms+number of hydrogen atoms)}×100(%)] is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more, in terms of excellent water and oil repellency and fingerprint removability. Furthermore, the molecular weight of the (poly)oxyfluoroalkylene chain portion is preferably from 200 to 30,000, more preferably from 600 to 25,000, and even more preferably from 1,000 to 20,000, from the viewpoint of abrasion resistance.

[0025] L 1 , L 2 and L 3 Each of L is independently a single bond or a divalent organic group. 1 , L 2 and L 3 The organic group in may have a substituent, and may have a heteroatom or other bond (B 1 ) may be mentioned. Examples of the hydrocarbon group include aliphatic hydrocarbon groups (such as linear alkylene groups, branched alkylene groups, and cycloalkylene groups), aromatic hydrocarbon groups (such as phenylene groups), and groups formed by combinations thereof. The aliphatic hydrocarbon groups may have a double or triple bond in the carbon chain. Examples of combinations include groups in which an alkylene group and an arylene group are directly linked via a heteroatom or other bond. Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxy group, an amino group, a nitro group, a sulfo group, etc., and from the viewpoint of the stability of the compound in the present production method, a halogen atom is preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0026] Heteroatoms or other bonds (B 1 ) is exemplified by -C(O)NR 26 -, -C(O)O-, -C(O)-, -O-, -NR 26-, -S-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 26 -,-SO2NR 26 -, -Si(R 26 )2-, -OSi(R 26 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and divalent organopolysiloxane residues. 26 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 26 The alkyl group preferably has 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0027] L 1 , L 2 and L 3 Specific examples of R include a single bond and an alkylene group R which may have a substituent. 28 an alkylene group R which may have a substituent; 28 and the above B 1 Combinations with (e.g., -R 28 -B 1 -, -B 1 -R 28 -B 1 -, -R 28 -B 1 -R 28 -) and others.

[0028] R 1 , R 2 , R 3 , R 4 , R 5 and R 6are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of the alkyl group include linear and branched alkyl groups. Examples of the substituent that the alkyl group may have include a halogen atom, a hydroxy group, an amino group, a nitro group, and a sulfo group, with a halogen atom being preferred from the viewpoint of the stability of the compound in the present production method. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Of these, a fluorine atom is preferred as the halogen atom from the viewpoint of stability. Specific examples of the alkyl group which may have a substituent include CH3-, CH2F-, CHF2-, CF3-, CH3CH2-, CF3CH2-, CF3CF2-, CH3CH2CH2-, CF3CH2CH2-, CF3CF2CH2-, CF3CF2CF2-, CH3CH(CH3)-, CF3CH(CH3)-, CF3CH(CF3)-, CF3CF(CF3)-, CH3CH2CH2CH2-, CF3CF2CF2CF2-, CH3CH2CH(-CH2CH3)-, CF3CF2CF(-CF2CF3)-, CH3CH2CH2CH(-CH2CH3)-, CF3CF2CF2CF(-CF2CF3)-, and the like. 1 , R 2 , R 3 , R 4 , R 5 and R 6 The alkyl groups which may have a substituent may be the same or different. R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is preferably a hydrogen atom from the viewpoint of reactivity.

[0029] In this production method, in view of the ease of synthesis of the raw materials and the reactivity of the compound (A1), the compound (A2) with the compound (B2), etc., it is preferable to use the compound (A1) or the compound (A2) containing L. 1 -CR 1 R 2 , L 2 -CR 3 R 4 , and L 3 -CR5 R 6 At least one of the following is true: 7 R 8 -CR 9 R 10 ) n1 It is preferable that the compound has a structure represented by the following formula: In the formula, R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R 7 , R 8 , R 9 or R 10 If there are multiple R 7 , R 8 , R 9 or R 10 may be the same or different from each other, n1 is an integer from 1 to 20. For example, L 1 -CR 1 R 2 (CR 7 R 8 -CR 9 R 10 ) n1 In this case, the compound (A1) is represented by the following formula (A1a): 2 -CR 3 R 4 and L 3 -CR 5 R 6 (CR 7 R 8 -CR 9 R 10 ) n1 In this case, the compound (A2) is represented by the following formula (A2a): The compounds (A3), (A4), (C1), and (C2) described below also have the same meanings. G 1 -(CR 7 R 8 -CR 9 R 10 ) n1 -X 1 Formula (A1a) X 2 -(CR 9R 10 -CR 7 R 8 ) n1 -L 2 -G 2 -(CR 7 R 8 -CR 9 R 10 ) n1 -X 3 Formula (A2a)

[0030] R 7 , R 8 , R 9 and R 10 The alkyl group in R 1 ~R 6 In terms of reactivity, R 9 and R 10 is a hydrogen atom, that is, (CR 7 R 8 -CR 9 R 10 ) n1 (CR 7 R 8 -CH2) n1 It is preferable that the group is a group represented by (CR 7 R 8 -CH2) n1 In the formula, the bond of "CH2" is X of compound (A1) or compound (A2). 1 , X 2 , or X 3 Compound (A1) and compound (A2) bond to each other. 11 ” (However, X 11 is X 1 , X 2 , or X 3 ) structure, the reactivity of the coupling in the present production method is improved. X 1 , X 2 , and X 3 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and an iodine atom is preferred in terms of further improving reactivity.

[0031] (CR 7 R8 -CH2) n1 Specific examples include CH2CH2, CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, CH(-CH3)CH2, CH(-CF3)CH2, CH(-CH2F)CH2, CH(-CHF2)CH2, C(-CH3)(-CH3)CH2, C(-CF3) (-CF3)CH2, C(-CH2CH3)(-CH2CH3)CH2, C(-CF2CF3)(-CF2CF3)CH2, C(-CH2CH2CH3)(-CH2CH2CH3)CH2, C(-CF2CF2CF3)(-CF2CF2CF3)CH2, C(-CH2CH2 CH2CH3)(-CH2CH2CH2CH3)CH2, C(-CF2CF2CF2CF3)(-CF2CF2CF2CF3)CH2, C(-CH2CH2CH2CH2CH3)(-CH2CH2CH2CH2CH3)CH2, C(-CF2CF2CF2CF2CF3)(- CF2CF2CF2CF2CF3)CH2, C(-CH2CH2CH2CH2CH2CH3)(-CH2CH2CH2CH2CH2CH3)CH2, C(-CF2CF2CF2CF2CF2CF3)(-CF2CF2CF2CF2CF2CF3)CH2, and the like.

[0032] Furthermore, in this production method, in view of the ease of synthesis of the raw materials and the reactivity of the compound (A1), the compound (A2) with the compound (B2), etc., it is particularly preferable to use R 7 is a hydrogen atom, and R 8 is preferably a hydrogen atom or a methyl group, and R 7 and R 8 It is more preferable that both of L and L in the compound (A1) or the compound (A2) are hydrogen atoms. 1 -CR 1 R 2 , L 2 -CR 3 R 4 , and L 3 -CR 5 R 6 At least one of them is (CH2CH2) n2 It is preferable that the compound has a structure represented by the following formula: where n2 is an integer of 1 to 20, preferably 1 to 12, and more preferably 1 to 6.

[0033] Specific preferred examples of the compound (A1) and the compound (A2) include the following.

[0034] [ka] Here, n11 to n28 represent the number of repeating units, and each independently represents an integer of 1 to 200.

[0035] Compound (A1) and compound (A2) can be produced, for example, by reacting compounds represented by the following formulas (A1-2) and (A2-2) with triphenylphosphine and iodomethane to form iodination, or by reacting compounds represented by the following formulas (A1-2) and (A2-2) with triphenylphosphine and iodine to form iodination, etc. Alternatively, commercially available products having the desired structure may be used. G 1 -L 1 -CR 1 R 2 -OH formula (A1-2) HO-CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -OH formula (A2-2) However, the symbols in the formula are as described above.

[0036] As an example of synthesis of compound (A1), a compound represented by the following formula (A1-3) can also be produced by adding an initiator, a metal catalyst, an organic catalyst, etc., and ethylene to the following formula (A1-4) and reacting them. G 1 -L 1 -CH2CH2-X 1 Formula (A1-3) G 1 -L 1 -X 1 Formula (A1-4) The initiator, metal catalyst, and organic catalyst can be appropriately selected from known initiators. Examples of initiators include azo initiators, organic peroxides, and redox initiators. Examples of metal catalysts include simple metals such as copper and iron, copper acetate, and copper chloride. Examples of organic catalysts include triethoxyphosphine. In addition, other olefin compounds may be used in place of ethylene to obtain a compound (A1) having the desired structure.

[0037] In compound (B1), R 11 is a substituent introduced into the compound (A1) and the compound (A2), and can be appropriately selected and used depending on the intended use of the resulting compound (C1) and compound (C2). R 11 The hydrocarbon group in may have a substituent, and may not have a heteroatom or other bond (B 1 ) may be mentioned. Examples of the hydrocarbon group include aliphatic hydrocarbon groups (such as linear alkyl groups, branched alkyl groups, and cycloalkyl groups), aromatic hydrocarbon groups (such as phenyl groups), and groups formed from combinations thereof. The aliphatic hydrocarbon groups may have a double or triple bond in the carbon chain. Examples of combinations include groups in which an alkylene group and an aryl group are directly linked via a heteroatom or other bond. Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxy group, an amino group, a nitro group, a sulfo group, etc. From the viewpoint of the stability of the compound in the present production method, a halogen atom is preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Specific examples of heteroatoms or other bonds include the above-mentioned B 1 The same as those mentioned above can be mentioned.

[0038] When further introducing another substituent into the obtained compound (C1) or compound (C2), for example, R 11is preferably an alkyl group having a double bond. 11 is an alkyl group having a double bond, it is possible to suitably obtain compound (C1) or compound (C2) having a double bond introduced therein, into which other substituents can be easily introduced, while suppressing side reactions in the production method of the present invention. Such an R 11 Among these, a substituent represented by the following formula (D1) is preferred. (CH2=CH-R 21 -) a (R 22 -) 3-a CR 23 -* Formula (D1) However, in the formula, R 21 is a single bond or an alkylene group having 1 to 18 carbon atoms which may have a fluorine atom, and R 21 If there are multiple R 21 may be the same or different from each other, R 22 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R 22 If there are multiple R 22 may be the same or different from each other, R 23 represents a single bond or an alkylene group having 1 to 19 carbon atoms, a is an integer from 1 to 3, * is a bond.

[0039] (CH2=CH-R 21 The group represented by (-) may include an isomerized structure. For example, (CH2=CH-R 21 When the group represented by -) is a group represented by CH2=CH-CH2-, it may also contain a group represented by CH3CH=CH-. Also, (CH2=CH-R 21 -) a When a in the group represented by the formula (I) is 2 or more, each group may be the same or different. R 21 The number of carbon atoms may be 1 to 18, and preferably 1 to 8.

[0040] R 12 is a halogen atom or a hydrocarbon group which may have a substituent or a hetero atom. R 12 In terms of reactivity, the halogen atom in 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.

[0041] R 12 The hydrocarbon group in 11 The same as R 12 is a hydrocarbon group, in the reaction of this production method, R 11 instead of R 12 may be introduced, and for example, the following compounds (C3) to (C6) may be produced. G 1 -L 1 -CR 1 R 2 -R 12 Formula (C3) R 11 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -R 12 Formula (C4) R 12 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -R 12 Formula (C5) R 11 -R 12 Formula (C6) However, the symbols in the formula are as described above.

[0042] In this regard, the following can be addressed: R 11 and R 12By using a substituent having the same structure as the compound (C1), the by-products (C3) to (C5) become the same compound as the compound (C1) or (C2). R 12 R 11 By using a substituent that is less reactive than R, it is possible to suppress the formation of the by-products (C3) to (C5). 11 -R 31 -CH2-(where R 31 is a hydrocarbon group), and R 12 -R 31 -CR 32 R 33 -(However, R 31 is a hydrocarbon group, and R 32 and R 33 are each independently a hydrogen atom or an alkyl group, and at least one of them is an alkyl group, 11 is introduced as a priority. Furthermore, when compounds (C3) to (C6) are produced, they may be separated by column chromatography or the like as necessary, and further, depending on the application of compound (C1) or (C2), the mixture containing compounds (C3) to (C6) may be used as is. These may be appropriately selected depending on the application of the compound (C1) or the compound (C2).

[0043] Specific preferred examples of the compound (B1) include the following:

[0044] [ka]

[0045] [ka] However, R 12 is as mentioned above.

[0046] Compound (B1) can be produced, for example, by reacting the compound represented by the following formula (B1-1) with metallic magnesium and, if necessary, with the compound represented by the following formula (B1-2). Alternatively, a commercially available product having the desired structure may be used. R 11 -X 5 Formula (B1-1) R 12a -X 5 Formula (B1-2) However, R 11 is as mentioned above, and R 12a is a hydrocarbon group which may have a substituent or may have a hetero atom, and X 5 is a halogen atom. By reacting the compound (B1-1) with metallic magnesium, R 12 Compound (B1) in which R is a halogen atom can be obtained. 12 Compound (B1) having a hydrocarbon group is obtained.

[0047] In this production method, the amount of compound (B1) used is determined based on the amount of X contained in compound (A1) or compound (A2) from the viewpoint of improving the yield of the target compound. 1 ~X 3 Relative to the total number of equivalents, 1 to 30 equivalents is preferred, 1.2 to 20 equivalents is more preferred, and 1.5 to 10 equivalents is even more preferred.

[0048] The transition metal compound can be appropriately selected from known catalysts. As the transition metal compound, a compound containing an element of Groups 3 to 12 of the periodic table as a transition metal is preferred, and among these, a compound containing an element of Groups 8 to 11 is preferred. Among these, the element of Groups 8 to 11 preferably contains one or more elements selected from copper, nickel, palladium, and cobalt, and more preferably further contains copper.

[0049] When the transition metal compound contains copper, the copper may be any of zero-, monovalent, divalent, and trivalent compounds, but 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. Note that copper chloride may be anhydrous or hydrated, but from the viewpoint of catalytic activity, copper chloride anhydride is more preferred.

[0050] When the transition metal compound contains nickel, the nickel may be a zero-valent, monovalent, divalent, or trivalent compound. However, from the viewpoints of catalytic activity and stability, a salt or complex salt of zero-valent or divalent nickel is preferred. Furthermore, from the viewpoints of availability, nickel chloride (NiCl) is more preferred. Note that nickel chloride may be anhydrous or hydrated, but from the viewpoint of catalytic activity, anhydrous nickel chloride is more preferred.

[0051] When the transition metal compound contains palladium, the palladium may be either a zero-valent or divalent compound, but from the viewpoint of catalytic activity and stability, a salt or complex salt of zero-valent or divalent palladium is preferred. Furthermore, from the viewpoint of ease of availability, tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) and palladium acetate (Pd(OAc)2) are more preferred. Note that tris(dibenzylideneacetone)dipalladium and palladium acetate may be anhydrides or hydrates, but from the viewpoint of catalytic activity, tris(dibenzylideneacetone)dipalladium anhydride and palladium acetate anhydride are more preferred.

[0052] When the transition metal compound contains cobalt, the cobalt may be a zero-, monovalent, divalent, or trivalent compound. However, from the viewpoint of catalytic activity, a salt or complex salt of divalent or trivalent cobalt is preferred. Furthermore, from the viewpoint of availability, divalent cobalt chloride (CoCl) is more preferred. Note that cobalt chloride may be anhydrous or hydrated, but from the viewpoint of catalytic activity, anhydrous cobalt chloride is more preferred.

[0053] The amount of the transition metal compound used is, for example, 0.05 to 50 equivalents, preferably 0.1 to 30 equivalents, and more preferably 0.15 to 20 equivalents relative to the total number of I's contained in compound (A1) or compound (A2).

[0054] 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. However, in this production method, sufficient yield can be obtained without using a ligand, so the use of the ligand is not necessary. Examples of the ligand include 1,3-butadiene, tricyclohexylphosphine, 1,1-bis(diphenylphosphino)ferrocenephenylpropyne, 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 I atoms contained in compound (A1) or compound (A2), from the viewpoint of improving the yield of the target product.

[0055] The reaction in this production method is usually carried out in a solvent. The solvent can be appropriately selected from solvents capable of dissolving compound (A1) or compound (A2) and compound (B1). The solvent may be a single solvent or a mixed solvent of two or more solvents. For example, the solvent is not particularly limited as long as it is inert to the reaction. Among solvents inert to the reaction, ether solvents such as diethyl ether, tetrahydrofuran (THF), and dioxane are preferred because they have a high affinity with the ether chain, and tetrahydrofuran is more preferred. For compounds with a relatively high fluorine atom content such as compound (A1) and compound (A2), a fluorine-based solvent is more preferred, and a mixed solvent combining the above-mentioned ether-based solvent with a fluorine-based solvent is even more 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. Among these, hydrofluoroethers (for example, CF3CH2OCF2CF2H (AE-3000)) are preferred as fluorine-based solvents.

[0056] In the first manufacturing method, for example, (I): A method in which a solution containing compound (A1) or compound (A2) is prepared, a transition metal compound and, if necessary, a ligand are added, and then a separately prepared compound (B1) is added; (II): A method in which a solution containing compound (B1), a transition metal compound, and optionally a ligand is prepared, and then compound (A1) or compound (A2) is gradually added thereto. From the viewpoint of suppressing by-products and improving the yield of compound (C1) or compound (C2), the above method (II) is preferred.

[0057] The reaction temperature of the compound (A1) or (A2) with the compound (B1) may be appropriately adjusted depending on the combination of the compound (A1) or (A2) with the compound (B1), for example, −20° C. to 66° C. (the boiling point of tetrahydrofuran), preferably 25° C. to 60° C.

[0058] <Second manufacturing method> The second method for producing a fluorine-containing compound of the present invention is a method for producing a fluorine-containing compound represented by the following formula (C1) or formula (C2), which comprises reacting a compound represented by the following formula (A3) or formula (A4) with a compound represented by the following formula (B2). G 1 -L 1 -CR 1 R 2 -MgR 12 Formula (A3) R 12 Mg-CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -MgR 12 Formula (A4) R 11 -X 4 Formula (B2) G 1 -L 1 -CR 1 R 2 -R 11 Formula (C1) R 11 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -R 11 Formula (C2) However, X 4 is a halogen atom, and a preferred embodiment is X 1 ~X 3 The other symbols in the formula are the same as those described in the first production method, and the preferred embodiments are also the same.

[0059] The second production method is a method for synthesizing a compound (C1) or a compound (C2) by a coupling reaction between an organomagnesium compound (A3) or a compound (A4) and an organohalogen compound (B2). In the second production method, the compounds (A3) and (A4) having a (poly)oxyfluoroalkylene chain are organomagnesium compounds, and the introduced substituent R 11 The second production method differs from the first production method in that the compound (B2) having the formula (I) is an organic halogen compound. The second production method will be described below, but a description of the contents common to the first production method will be omitted here.

[0060] Compound (A3) and compound (A4) can be produced by, for example, reacting compounds of the following formula (A3-2) and (A4-2), respectively, with metallic magnesium, and, if necessary, with compounds of the following formula (B1-2). Alternatively, commercially available products having the desired structures may be used. G 1 -L 1 -CR 1 R 2 -X 6 Formula (A3-2) X 7 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -X 8 Formula (A4-2) R 12a -X 9 Formula (B1-2) However, X 6 ~X 9 are each independently a halogen atom, and the other symbols in the formula are as defined above.

[0061] Specific preferred examples of the compound (A3) and the compound (A4) include the following.

[0062] [ka] However, R 12 is as described above, and n30 to n47 represent the number of repeating units and are each independently an integer of 1 to 200.

[0063] Compound (B2) can be produced, for example, by reacting a compound represented by the following formula (B2-2) with triphenylphosphine and iodomethane to iodinate it, or by reacting it with triphenylphosphine and iodine to iodinate it, etc. Alternatively, a commercially available product having the desired structure may be used. R 11 -OH formula (B2-2) However, R in the formula 11 is as mentioned above.

[0064] Specific preferred examples of the compound (B2) include the following:

[0065] [ka]

[0066] [ka]

[0067] The solvent, catalyst, ratio of raw materials, reaction temperature, etc. in the second production method can be the same as those in the first production method, and the preferred embodiments are also the same.

[0068] <Third manufacturing method> The third method for producing a fluorine-containing compound of the present invention is a method for producing a fluorine-containing compound represented by the following formula (C1) or formula (C2), which comprises reacting a compound represented by the following formula (A1) or formula (A2), a compound represented by the following formula (B2), and a compound represented by the following formula (B3). G 1 -L 1 -CR 1 R 2 -X 1 Formula (A1) X 2 -CR3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -X 3 Formula (A2) R 11 -X 4 Formula (B2) R 14 -CR 15 R 16 -MgR 12 Formula (B3) G 1 -L 1 -CR 1 R 2 -R 11 Formula (C1) R 11 -CR 3 R 4 -L 2 -G 2 -L 3 -CR 5 R 6 -R 11 Formula (C2) However, the symbols in the formula are as described above, and R 14 , R 15 and R 16 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent or a hetero atom.

[0069] In the third production method, various reaction pathways are assumed, but the main reaction is first the reaction of X of compound (B2) 4 and compound (B3) MgR 12 It is presumed that an exchange reaction occurs, followed by a coupling reaction with compound (A1) or compound (A2) to synthesize compound (C1) or compound (C2). The third manufacturing method will be described below, but a description of the contents common to the first or second manufacturing method will be omitted here.

[0070] R 14 , R 15 , R 16 The hydrocarbon group in R 11Among them, the compound (B2) X 4 and compound (B3) MgR 12 From the viewpoint that the exchange reaction of R 14 , R 15 , R 16 Preferably, at least two of the above groups are hydrocarbon groups which may have a substituent or a heteroatom. By bonding the carbon atom directly bonded to Mg to two or more alkyl groups, a direct coupling reaction with compound (A1) or compound (A2) can be suppressed.

[0071] The solvent, catalyst, ratio of raw materials, reaction temperature, etc. in the third production method can be the same as those in the first production method, and the preferred embodiments are also the same.

[0072] As explained above, the first to third production methods can be used to obtain compounds (C1) or (C2) in which various substituents have been introduced into the (poly)oxyfluoroalkylene chain. Fluorine-containing compounds have excellent properties such as low refractive index, low dielectric constant, water and oil repellency, heat resistance, chemical resistance, chemical stability, and transparency, and can be used in a wide variety of fields, including electrical and electronic materials, semiconductor materials, optical materials, and surface treatment agents.

[0073] Furthermore, a surface treatment agent can also be produced by introducing a reactive silyl group into the compound (C1) or compound (C2) obtained by the first to third production methods. Fluorine-containing compounds having a (poly)oxyfluoroalkylene chain and a hydrolyzable silyl group are suitable for use in surface treatment agents because they can form a surface layer on the surface of a substrate that exhibits high lubricity, water repellency, oil repellency, etc.

[0074] The method for introducing a reactive silyl group into compound (C1) or (C2) may be appropriately selected depending on the substituents possessed by compound (C1) or compound (C2). For example, when compound (C1) or compound (C2) has a double bond, the double bond can be introduced by subjecting the double bond to a hydrosilylation reaction with compound (E1) or (E2) shown below. HSi(R 40 ) 3-c (L)c Formula (E1) HSi(R 41 ) 3-k [-(OSi(R 42 )2) p -O-Si(R 40 ) 3-c (L) c ] k Formula (E2) However, in the formula, R 40 is an alkyl group, and R 40 If there are multiple R 40 may be the same or different, L is a hydrolyzable group or a hydroxyl group, and a plurality of Ls may be the same or different; R 41 is an alkyl group, and R 41 If there are multiple R 41 may be the same or different, R 42 is an alkyl group, a phenyl group, or an alkoxy group, and two R 42 may be the same or different, c is 2 or 3; k is 2 or 3; p is an integer of 0 to 5, and when p is 2 or more, 2 or more (OSi(R 42 )2) may be the same or different. Compound (E2) can be produced, for example, by the method described in the specification of WO 2019 / 208503.

[0075] In compounds (C1) and (C2), R 11 is a group represented by the formula (D1), a surface treatment agent represented by the following formula can be obtained.

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka] In the formula, n6 to n10 represent the number of repeating units, and each independently represents an integer of 1 to 200.

[0080] A reactive silyl group is a group in which either or both of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, a hydrolyzable silyl group becomes a silanol group (Si-OH) through a hydrolysis reaction. The silanol group further undergoes a dehydration condensation reaction between molecules to form a Si-O-Si bond. Furthermore, the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. The halogen atom is preferably a chlorine atom. As the hydrolyzable group, an alkoxy group or a halogen atom is preferred from the viewpoint of ease of production. As the hydrolyzable group, an alkoxy group having 1 to 4 carbon atoms is preferred from the viewpoint of less outgassing during application and excellent storage stability of the present compound, an ethoxy group is particularly preferred when long-term storage stability of the present compound is required, and a methoxy group is particularly preferred when the reaction time after coating the surface treatment agent on the substrate is to be short.

[0081] The substrate may be a substrate that is required to be water- and oil-repellent, such as a substrate that may come into contact with other articles (e.g., a stylus) or human fingers, a substrate that may be held with human fingers during operation, or a substrate that may be placed on other articles (e.g., a mounting table). The substrate may be made of metal, resin, glass, sapphire, ceramic, stone, or a composite of these materials. The glass may be chemically strengthened. A base film such as a SiO2 film may be formed on the surface of the substrate. The substrate is preferably a substrate for a touch panel, a substrate for a display, or a lens for glasses, and is particularly preferably a substrate for a touch panel.The material of the substrate for a touch panel is preferably glass or a transparent resin. Further, the substrate is preferably a glass or resin film used for the exterior parts (excluding the display part) of devices such as mobile phones (for example, smartphones), personal digital assistants (for example, tablet terminals), game consoles, and remote controls.

[0082] Such a surface treatment agent containing a fluorine-containing compound is preferably used as a surface treatment agent for applications requiring long-term maintenance of the performance of preventing deterioration of water and oil repellency even when the surface layer is repeatedly rubbed with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface layer by wiping (fingerprint stain removability), for example, as a surface treatment agent for members constituting the surfaces of touch panels that are touched with fingers, eyeglass lenses, and displays of wearable devices. [Example]

[0083] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. Examples 1 to 20 are examples.

[0084] [Example 1] [Synthesis Example 1-1: Synthesis of Compound (1-1)] According to the method described in Example 11 of WO 2013 / 121984, the following compound (1-1) was obtained. CF3-O-(CF2CF2O-CF2CF2CF2CF2O) n (CF2CF2O)-CF2CF2CF2-CH2CH2I...Formula (1-1) The average number of repeating units, n, is 13.

[0085] [Synthesis Example 1-2: Synthesis of Compound (2-1)] Diethyldiallylmalonate (60.0 g), lithium chloride (23.7 g, 559 mmol), water (6.45 g, 360 mmol), 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 (2-1).

[0086] [ka]

[0087] NMR spectrum of compound (2-1); 1 H-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).

[0088] [Synthesis Example 1-3: Synthesis of Compound (2-2)] After adding THF (260 mL) and diisopropylamine (29.8 mL), 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 (2-1) (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 (2-2).

[0089] [ka]

[0090] NMR spectrum of compound (2-2); 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).

[0091] [Synthesis Example 1-4: Synthesis of Compound (2-3)] The above compound (2-2) (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 (2-3).

[0092] [ka]

[0093] NMR spectrum of compound (2-3); 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).

[0094] [Synthesis Example 1-5: Synthesis of Compound (3-1)] Acetonitrile (380 mL), the compound (2-3) (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 (3-1) was obtained by distillation.

[0095] [ka]

[0096] NMR spectrum of compound (3-1); 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).

[0097] [Synthesis Example 1-6: Synthesis of Compound (3-2)] 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 (3-1) (14.0 g) in THF (35 mL) was added and heated to reflux to prepare a solution (0.80 M) of the following compound (3-2).

[0098] [ka]

[0099] NMR spectrum of compound (3-2); 1 H-NMR(400MHz,Chloroform-d) δ(ppm):5.88(m,3H),5.11(m,6h),1.85(m,6h),1.22(s,2h).

[0100] [Synthesis Example 1-7: Synthesis of Compound (1-2)] The compound (1-1) (1.03 g) was suspended in dehydrated THF (5 ml), and copper chloride (0.0025 g) was added and stirred at room temperature. The compound (3-2) (0.31 g), adjusted to 17 wt %, was slowly added dropwise to the mixed solution, and the mixture was stirred at 55°C. After the mixed solution was cooled to room temperature, water was added, and the AE - After extraction with 3000 ml (5 ml), sodium sulfate was added. After filtration, the solvent was distilled off. Flash column chromatography using silica gel was performed to obtain a mixture containing compound (1-2). NMR measurement confirmed that compound (1-2) was obtained with a selectivity of 84%.

[0101] [ka]

[0102] NMR spectrum of compound (1-2); 1 H-NMR (400MHz, Chloroform-d) δ(ppm):5.80(ddt,J=20.3,9.3,7.4Hz,3H),5.01(dd,J=13.5,1.7Hz,6H),2. 13~2.01(m,2H),1.97(d,J=7.5Hz,6H),1.67~1.55(m,2H),1.27~1.18(m,2H). 19 F-NMR(376MHz,Chloroform-d) δ(ppm):-55.25,-82.83,-88.06,-90.16(d,J=8.1 Hz),-114.18,-125.26,-126.59.

[0103] [Examples 2-20] Compound (1-2) was produced in the same manner as in Synthesis Example 1-7 of Example 1 above, except that various conditions were changed as shown in Table 1 below. The equivalent weight is based on compound (1-1). The raw material conversion rate is the rate at which compound (1-1) is converted, and the target product selectivity is the rate at which the target compound (1-2) is selected from the compounds converted from compound (1-1). The ligand can be used within the suitable equivalent range as described above relative to compound (1-1).

[0104] [Table 1]

[0105] The abbreviations in Table 1 are as follows: Pd2(dba)3: Tris(dibenzylideneacetone)dipalladium Pd(OAc)2: Palladium acetate PCy3: Tricyclohexylphosphine dppf: 1,1'-ferrocenediyl-bis(diphenylphosphine) AE - 3000:CF3CH2OCF2CF2H THF: tetrahydrofuran [Industrial Applicability]

[0106] 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 compound (B1) having a carbon-carbon double bond, a double bond can be easily added to compound (A1) or compound (A2), and a compound useful as a raw material for synthesizing various compounds can be obtained.

[0107] This application claims priority based on Japanese Patent Application No. 2021-35322, filed on March 5, 2021, the disclosure of which is incorporated herein in its entirety.

Claims

1. A method for producing a fluorine-containing compound represented by the following formula (C1) or (C2), comprising reacting a compound represented by the following formula (A1) or (A2) with a compound represented by the following formula (B1), wherein the reaction is carried out in the presence of a transition metal compound. G １ -L １ -CR １ R ２ -X １ Formula (A1) X ２ -CR ３ R ４ -L ２ -G ２ -L ３ -CR ５ R ６ -X ３ Formula (A2) R １１ -MgR １２ Formula (B1) G １ -L １ -CR １ R ２ -R １１ Formula (C1) R １１ -CR ３ R ４ -L ２ -G ２ -L ３ -CR ５ R ６ -R １１ Formula (C2) However, in the formula, G １ is a monovalent group having a (poly)oxyfluoroalkylene chain, G ２ is a divalent group having a (poly)oxyfluoroalkylene chain, L １ , L ２ and L ３ are each independently a single bond or a divalent organic group, R １ , R ２ , R ３ , R ４ , R ５ and R ６ each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R １１ is a hydrocarbon group which may have a substituent or may have a hetero atom, and R １１ If there are multiple R １１ may be the same or different from each other, R １２ represents a halogen atom or a hydrocarbon group which may have a substituent or a hetero atom, X １ , X ２ and X ３ are each independently a halogen atom.

2. A method for producing a fluorine-containing compound represented by the following formula (C1) or (C2), which comprises reacting a compound represented by the following formula (A3) or formula (A4) with a compound represented by the following formula (B2): G １ -L １ -CR １ R ２ -MgR １２ Formula (A3) R １２ Mg - Cr ３ R ４ -L ２ -G ２ -L ３ -Cr ５ R ６ -MgR １２ Formula (A4) R １１ -X ４ Equation (B2) G １ -L １ -CR １ R ２ -R １１ Formula (C1) R １１ -CR ３ R ４ -L ２ -G ２ -L ３ -CR ５ R ６ -R １１ Formula (C2) However, in the formula, G １ is a monovalent group having a (poly)oxyfluoroalkylene chain, G ２ is a divalent group having a (poly)oxyfluoroalkylene chain, L １ , L ２ and L ３ are each independently a single bond or a divalent organic group, R １ , R ２ , R ３ , R ４ , R ５ and R ６ each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R １１ are each independently a hydrocarbon group which may have a substituent or a heteroatom, and R １１ If there are multiple R １１ may be the same or different from each other, R １２ is a halogen atom or a hydrocarbon group which may have a substituent or a hetero atom, and R １２ If there are multiple R １２ may be the same or different from each other, X ４ is a halogen atom.

3. A method for producing a fluorine-containing compound represented by the following formula (C1) or (C2), which comprises reacting a compound represented by the following formula (A1) or (A2), a compound represented by the following formula (B2), and a compound represented by the following formula (B3): G １ -L １ -CR １ R ２ -X １ Formula (A1) X ２ -CR ３ R ４ -L ２ -G ２ -L ３ -CR ５ R ６ -X ３ Formula (A2) R １１ -X ４ Equation (B2) R １４ -CR １５ R １６ -MgR １２ Formula (B3) G １ -L １ -CR １ R ２ -R １１ Formula (C1) R １１ -CR ３ R ４ -L ２ -G ２ -L ３ -CR ５ R ６ -R １１ Formula (C2) However, in the formula, G １ is a monovalent group having a (poly)oxyfluoroalkylene chain, G ２ is a divalent group having a (poly)oxyfluoroalkylene chain, L １ , L ２ and L ３ are each independently a single bond or a divalent organic group, R １ , R ２ , R ３ , R ４ , R ５ and R ６ each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, R １１ is a hydrocarbon group which may have a substituent or may have a hetero atom, and R １１ If there are multiple R １１ may be the same or different from each other, R １２ represents a halogen atom or a hydrocarbon group which may have a substituent or a hetero atom, R １４ , R １５ and R １６ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent or a hetero atom, X １ , X ２ , X ３ and X ４ are each independently a halogen atom.

4. Said L １ -CR １ R ２ , said L ２ -CR ３ R ４ , and the L ３ -CR ５ R ６ At least one of the following is true: ７ R ８ -CR ９ R １０ ) ｎ１ The method for producing a fluorine-containing compound according to any one of claims 1 to 3, represented by the formula: In the formula, R ７ , R ８ , R ９ and R １０ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and R ７ , R ８ , R ９ or R １０ If there are multiple R ７ , R ８ , R ９ or R １０ may be the same or different from each other, n1 is an integer from 1 to 20.

5. Said L １ -CR １ R ２ , L ２ -CR ３ R ４ , and the L ３ -CR ５ R ６ At least one of the ２ CH ２ ) ｎ２ The method for producing a fluorine-containing compound according to any one of claims 1 to 4, wherein the compound is represented by the formula: In the formula, n2 is an integer of 1 to 20.

6. The R １１ The method for producing a fluorine-containing compound according to any one of claims 1 to 5, wherein the compound is represented by the following formula (D1): (CH) ２ =CH-R ２１ -) ａ (R) ２２ -) ３－ａ C-R ２３ -* Formula (D1) However, in the formula, R ２１ is a single bond or an alkylene group having 1 to 18 carbon atoms which may have a fluorine atom, and R ２１ If there are multiple R ２１ may be the same or different from each other, R ２２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a fluorine atom, and R ２２ If there are multiple R ２２ may be the same or different from each other, R ２３ represents a single bond or an alkylene group having 1 to 19 carbon atoms, a is an integer from 1 to 3, * indicates a bond.

7. The X １ , X ２ 4. The method for producing a fluorine-containing compound according to claim 1, wherein at least one of X and X3 is an iodine atom.

8. The method for producing a fluorine-containing compound according to claim 2 or 3, wherein X 4 is an iodine atom.

9. The method for producing a fluorine-containing compound according to claim 2 or 3, wherein the reaction is carried out in the presence of a transition metal compound.

10. The method for producing a fluorine-containing compound according to claim 1 or 9, wherein the transition metal compound contains one or more elements selected from Cu, Ni, Pd and Co.

11. A method for producing a surface treatment agent, comprising producing a fluorine-containing compound represented by formula (C1) or formula (C2) by the production method according to any one of claims 1 to 10, and introducing a reactive silyl group into the fluorine-containing compound.

Images