Fluorine-containing ether compound and method for producing same

Abstract

Provided is a fluorine-containing ether compound which is represented by the general formula: R1-R2-O-R3-R4 (in the formula, R1 is-CH3,-CH2F,-CHF2,-CH2I or-CHFI; r2 represents a fluorinated alkylene group having 1 to 10 carbon atoms and comprising only a unit represented by-CHF-, a fluorinated alkylene group having 2 to 10 carbon atoms and comprising only a unit represented by-CHF-and a unit represented by-CH2-, or a fluorine-containing alkylene group having 3 to 10 carbon atoms and comprising only a unit represented by-CFH-, a unit represented by-CH2-and a unit represented by-CHI-; and R3 represents a single bond, a non-fluorinated alkylene group having 1-5 carbon atoms, or a fluorinated alkylene group having 1-10 carbon atoms, and R4 represents-CH3,-CH2F, or-CHF2).

Description

Technical Field

[0001] The present disclosure relates to fluorine-containing ether compounds and methods for making the same. Background Art

[0002] Fluorinated ethers are used not only as solvents but also in a wide range of applications.

[0003] As fluorinated ethers, for example, Patent Document 1 describes compounds represented by the general formula: Rh'(O-Rf)m (wherein m=3-4, Rf is independently a perfluoroaliphatic group, and Rh' is independently a straight-chain or branched hydrocarbon having 3 to about 8 carbon atoms).

[0004] For example, Patent Document 2 describes a hydrofluoroether compound comprising two terminal fluorinated alkyl groups and a substituted or unsubstituted oxymethylene group in the chain, wherein the fluorinated alkyl groups each contain only one hydrogen atom and, depending on the circumstances, contain at least one heteroatom in the chain, wherein the hydrogen atom is part of the monofluoromethylene moiety.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application No. 2008-529975

[0008] Patent Document 2: Japanese Patent Application No. 2009-507840 Summary of the invention

[0009] Problems to be solved by the invention

[0010] Patent Documents 1 and 2 describe that, of the two groups bonded to the oxygen of the ether compound, at least one group is composed of a perfluoroaliphatic group and at least one group is composed of a fluorinated alkyl group containing only one hydrogen atom.

[0011] However, it is not known that at least one of the two groups bonded to the oxygen of the ether compound is composed of a group not containing CF. 3 -(trifluoromethyl) and -CF 2 - is a fluorine-containing ether composed of a group of the unit (difluoromethylene) represented by -.

[0012] In the present disclosure, an object is to provide a fluorine-containing ether compound having a group not containing a trifluoromethyl group and a difluoromethylene group as at least one of two groups bonded to oxygen of an ether compound.

[0013] Means for solving problems

[0014] According to the present disclosure, a fluorine-containing ether compound is provided, which has the general formula: R 1 -R 2-OR 3 -R 4 Indicated.

[0015] (Where,

[0016] R 1 -CH 3 、-CH 2 F, -CHF 2 、-CH 2 I or -CHFI,

[0017] R 2 It is a fluorinated alkylene group having 1 to 10 carbon atoms consisting only of a unit represented by -CHF-, or a fluorinated alkylene group consisting only of a unit represented by -CHF- and -CH 2 -a fluorinated alkylene group having 2 to 10 carbon atoms, or a unit represented by -CFH-, -CH 2 A fluorinated alkylene group having 3 to 10 carbon atoms consisting of a unit represented by - and a unit represented by -CHI-,

[0018] R 3 is a single bond, a non-fluorinated alkylene group having 1 to 5 carbon atoms, or a fluorinated alkylene group having 1 to 10 carbon atoms,

[0019] R 4 -CH 3 、-CH 2 F or -CHF 2 )

[0020] Effects of the Invention

[0021] According to the present disclosure, there can be provided a fluorine-containing ether compound having a group not including a trifluoromethyl group and a difluoromethylene group as at least one of two groups bonded to oxygen of an ether compound. DETAILED DESCRIPTION

[0022] Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0023] The fluorine-containing ether compound disclosed herein is of the general formula: R 1 -R 2 -OR 3 -R 4 The fluorinated ether compounds shown.

[0024] (Where R 1 -CH 3 、-CH 2 F, -CHF 2 、-CH 2 I or -CHFI,R 2It is a fluorinated alkylene group having 1 to 10 carbon atoms consisting only of a unit represented by -CHF-, or a fluorinated alkylene group consisting only of a unit represented by -CHF- and -CH 2 -a fluorinated alkylene group having 2 to 10 carbon atoms, or a unit represented by -CFH-, -CH 2 - and -CHI-, and a fluorinated alkylene group having 3 to 10 carbon atoms, R 3 is a single bond, a non-fluorinated alkylene group having 1 to 5 carbon atoms, or a fluorinated alkylene group having 1 to 10 carbon atoms, R 4 -CH 3 、-CH 2 F or -CHF 2 )

[0025] R 1 -CH 3 、-CH 2 F, -CHF 2 、-CH 2 I or -CHFI, preferably -CH 2 F, -CHF 2 or -CHFI, more preferably -CH 2 F. One of the characteristics of the fluorinated ether compound disclosed in the present invention is that at least one of the two groups bonded to the oxygen of the ether compound does not have a CF at the terminal. 3 -(trifluoromethyl).

[0026] R 2 It is a fluorinated alkylene group having 1 to 10 carbon atoms consisting only of a unit represented by -CHF-, or a fluorinated alkylene group consisting only of a unit represented by -CHF- and -CH 2 -a fluorinated alkylene group having 2 to 10 carbon atoms, or a unit represented by -CFH-, -CH 2 A fluorinated alkylene group having 3 to 10 carbon atoms, which is composed of a unit represented by -CHF- and a unit represented by -CHI-. One of the characteristics of the fluorinated ether compound disclosed in the present invention is that at least one of the two groups bonded to the oxygen of the ether compound must contain a unit represented by -CHF- and does not contain -CF 2 - The unit shown.

[0027] In R 2 In the case of a fluorinated alkylene group consisting of only units represented by -CHF-, R 2 , for example, preferably -(CHF) n1 -(n1 is an integer of 1 to 10).

[0028] In R 2 For units represented by only -CHF- and -CH 2In the case of a fluorinated alkylene group consisting of a unit represented by -, as R 2 , for example -CHF-(CHF-CHF) n2 -(CH 2 ) m1 -(n2 is an integer of 1 to 4, m1 is an integer of 1 or more) represented by a fluorinated alkylene group, -(CHF) n7 -CH 2 -CH 2 -(CH 2 ) q -(wherein n7 is an integer of 1 to 7, and q is an integer of 1 to 6).

[0029] In R 2 For units represented by only -CHF- and -CH 2 In the case of a fluorinated alkylene group consisting of a unit represented by -, as R 2 , preferably -(CHF) n2 -CH 2 -(n2 is an integer of 1 to 9) represented by a fluorinated alkylene group, or -(CHF) n7 -CH 2 -CH 2 -(CH 2 ) q -(wherein n7 is an integer of 1 to 7, and q is an integer of 1 to 6), more preferably -CHF-(CHF-CHF) n3 -CH 2 -(n3 is an integer of 0 to 4) or -CHF-(CHF-CHF) n8 -CH 2 -CH 2 -(CH 2 ) q -(wherein n8 is an integer from 0 to 2, and q is an integer from 1 to 6).

[0030] In R 2 A unit represented by only -CFH-, -CH 2 In the case of an alkylene group consisting of a unit represented by - and a unit represented by -CHI-, R 2 , preferably -(CHF) n7 -CH 2 -CHI-(CH 2 ) q -(wherein n7 is an integer of 1 to 7, and q is an integer of 1 to 6), more preferably -CHF-(CHF-CHF) n8 -CH 2 -CHI-(CH 2 )q -(wherein n8 is an integer of 0 to 2, and q is an integer of 1 to 6).

[0031] In the general formula representing the fluorine-containing ether compound, R 1 -R 2 -, preferably CH 2 F-CHF-, or general formula: CH 2 F-CHF-(CHF-CHF) n3 -CH 2 - (where n3 is an integer from 0 to 4) or a fluorinated alkyl group represented by the general formula: CHF 2 -CHF-(CHF-CHF) n8 -CH 2 -CHX 11 -(CH 2 ) q -(where n8 is an integer from 0 to 2, X 11 is I or H, q is an integer of 1 to 6).

[0032] n3 is preferably 0 or 1.

[0033] R 3 R is a single bond, a non-fluorinated alkylene group having 1 to 5 carbon atoms, or a fluorinated alkylene group having 1 to 10 carbon atoms. 3 The number of carbon atoms in R is preferably 0 to 5, more preferably 0 to 3, and even more preferably 0 or 1. 3 The number of carbon atoms of the non-fluorinated alkylene group is preferably 1 or 2. 3 The fluorinated alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 or 2 carbon atoms.

[0034] As R 3 , preferably a single bond, a non-fluorinated alkylene group having 1 to 5 carbon atoms, -(CHF) n4 -(wherein n4 is an integer from 1 to 10) or -(CHF) n5 -CH 2 -(wherein n5 is an integer of 1 to 9).

[0035] R 4 -CH 3 、-CH 2 F or -CHF 2 , preferably -CH 3 or -CH 2 F.

[0036] In the general formula representing the fluorine-containing ether compound, R 4 -R 3-, preferably a non-fluorinated alkyl group having 1 to 4 carbon atoms, or a group of the general formula: CH 2 F-CHF-(CHF-CHF) n6 -CH 2 -(wherein n6 is an integer of 0 to 4).

[0037] R 4 -R 3 When the group represented by - is a non-fluorinated alkyl group, the non-fluorinated alkyl group preferably has 1 or 2 carbon atoms.

[0038] n6 is preferably 0 or 1.

[0039] As the fluorine-containing ether compound, it is preferred to be selected from the group consisting of CH 2 FCHFOCH 3 , CH 2 FCHFCH 2 OCH 3 , CH 2 FCHFCH 2 OCHFCFH 2 , CH 2 FCHFCH 2 OCH 2 CH 3 , CH 2 FCHFCHFCHFCH 2 OCH 3 , CHF 2 -CHF-CH 2 -CHI-CH 2 -OCH 3 , CHF 2 -CHF-CH 2 -CH 2 -CH 2 -OCH 3 , CHF 2 -CHF-CH 2 -CH 2 -CH 2 -OCHFCFH 2 , CHF 2 -CHF-CH 2 -CH 2 -CH 2 -OCH 2 CH 3 , CHF 2 -CHF-CH 2 -CHI-CH 2 -CH 2 -CH 2 -CH 2 -OCH3 and CHF 2 -CHF-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -OCH 3 At least one of the group consisting of.

[0040] The fluorine-containing ether compound disclosed herein can be prepared by reacting CHF=CHF with a general formula: R 4 -R 3 -OH (where R 3 and R 4 As described above), the alcohol represented by the formula: CH 2 F-CHF-OR 3 -R 4 (Where R 3 and R 4 The fluorine-containing ether compound can be produced by the method for producing a fluorine-containing ether compound as described above (hereinafter sometimes referred to as the first production method).

[0041] In the first production method, the basic compound acts as a catalyst. As the basic compound, an inorganic basic compound is preferred, and NaOH, KOH, CsOH, LiOH, Ca(OH) 2 、Ba(OH) 2 Such as alkali metal hydroxides or alkaline earth metal hydroxides.

[0042] The amount of the basic compound used is preferably 0.01 mol to 1.0 mol, more preferably 0.2 mol to 0.8 mol, based on 1 mol of the alcohol.

[0043] The reaction of CHF=CHF and alcohol can be carried out in a solvent. Examples of the solvent include polar organic solvents such as water, diethyl ether, glyme, dioxane, tetrahydrofuran, and acetonitrile.

[0044] The pressure of the reaction of CHF=CHF and alcohol is preferably 1.0 MPaG to 2.0 MPaG. The temperature of the reaction of CHF=CHF and alcohol is preferably 20°C to 95°C.

[0045] The fluorine-containing ether compound disclosed in the present invention can be produced, for example, by the following production method (hereinafter sometimes referred to as the second production method):

[0046] By adding CHF=CHF to methanol, the general formula: CH 2 F-CHF-(CHF-CHF) n3 -CH 2OH (wherein n3 is an integer from 0 to 4),

[0047] Make fluorinated alcohol and R 4 -R 3 -X(where R 3 and R 4 As mentioned above, X is a halogen atom or -OSO 3 R' (wherein R' is a non-fluorinated alkyl group or a fluorinated alkyl group)) to produce a compound of the general formula: CH 2 F-CHF-(CHF-CHF) n3 -CH 2 -OR 3 -R 4 (In the formula, n3, R 3 and R 4 As described above).

[0048] In the second production method, first, a fluorine-containing alcohol is produced by adding CHF═CHF to methanol.

[0049] n3 in the fluorine-containing alcohol represents the polymerization degree of CHF=CHF. n3 is an integer of 0 to 4, and is preferably 0 or 1.

[0050] The reaction of methanol and CHF=CHF can be carried out in the presence of a free radical initiator. When the reaction is carried out in the presence of a free radical initiator, the free radical initiator decomposes to generate free radicals, and the generated free radicals extract the hydrogen atom on the carbon to which the hydroxyl group of methanol is bonded, thereby generating methanol free radicals, and a reaction of adding CHF=CHF to the methanol free radical is carried out (so-called telomerization reaction).

[0051] As the free radical initiator, preferably an organic peroxide, dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate, dialkyl peroxides such as di-tert-butyl peroxide, etc. can be cited. As the free radical initiator, di-tert-butyl peroxide is particularly preferred.

[0052] The amount of CHF=CHF used is preferably 0.01 mol to 100 mol relative to 1 mol of methanol.

[0053] The amount of the radical initiator used is preferably 0.01 mol to 2 mol per 1 mol of methanol.

[0054] The reaction temperature of methanol and CHF=CHF can be appropriately selected, and is preferably -78°C to 200°C. The reaction temperature of methanol and CHF=CHF is preferably not less than the decomposition temperature of the radical polymerization initiator and preferably less than the decomposition temperature of the substrate and the product.

[0055] The pressure of the reaction of methanol and CHF=CHF can be appropriately selected, and is preferably 0 to 5.0 MPaG. The time of the reaction of methanol and CHF=CHF can be appropriately selected, and is preferably 0.1 to 96 hours.

[0056] In the second production method, the obtained fluorinated alcohol is then reacted with R 4 -R 3 -X to alkylate the oxygen of the fluorinated alcohol to produce a fluorinated ether compound.

[0057] When X is a halogen atom, a base such as sodium hydride is reacted with a fluorinated alcohol to form a fluorinated alcohol salt. 4 -R 3 By reacting a compound represented by -X (X is a halogen atom), a fluorine-containing ether compound can be produced.

[0058] In addition, in X is -OSO 3 In the case of R' (wherein R' is a non-fluorinated alkyl group or a fluorinated alkyl group), for example, a fluorinated alcohol is reacted with R in an aqueous solution of a hydroxide. 4 -R 3 -X (X is -OSO 3 R') is reacted with a compound represented by the formula (A), thereby producing a fluorine-containing ether compound.

[0059] As R 4 -R 3 -X (X is -OSO 3 R'), preferably (R 4 -R 3 -O-) 2 SO 2 (R 3 and R 4 as described above).

[0060] Fluorinated alcohol and R 4 -R 3 The reaction pressure of the compound represented by -X is preferably 0.1 MPaG to 2.0 MPaG. 4 -R 3 The reaction temperature of the compound represented by -X is preferably 20°C to 95°C.

[0061] The fluorine-containing ether compound disclosed in the present invention can be produced, for example, by the following production method (hereinafter sometimes referred to as the third production method):

[0062] By making CHF = CHF and I 2 and IF 5 Reaction to produce general formula: R 1 -CHF-I (where R 1 -CHF 2 or -CHFI), and preparing a first fluorinated alkyl iodide represented by the general formula: R by adding CHF=CHF to the first fluorinated alkyl iodide. 1 -CHF-(CHF-CHF) n8 -I(where R 1 As described above, n8 is 1 or 2) represented by the second fluorine-containing alkyl iodide,

[0063] By reacting the first fluorinated alkyl iodide or the second fluorinated alkyl iodide with a compound of the general formula: CH 2 =CH-(CH 2 ) q -OH (wherein q is an integer greater than 1) to produce an unsaturated compound represented by the general formula: R 1 -CHF-(CHF-CHF) n8 -CH 2 -CHI-(CH 2 ) q -OH (where R 1 As described above, n8 is an integer from 0 to 2, q is an integer from 1 to 6),

[0064] Optionally, the first fluorinated alcohol is reduced to produce a compound of the general formula: R 1 -CHF-(CHF-CHF) n8 -CH 2 -CH 2 -(CH 2 ) q -OH (where R 1 As described above, n8 is an integer from 0 to 2, q is an integer from 1 to 6),

[0065] The first fluorinated alcohol or the second fluorinated alcohol is reacted with R 4 -R 3 -X(where R 3 and R 4 As mentioned above, X is a halogen atom or -OSO 3 R' (wherein R' is a non-fluorinated alkyl group or a fluorinated alkyl group)) to produce a compound represented by the general formula: R 1 -CHF-(CHF-CHF) n8 -CH 2 -CHX 11 -(CH 2 )q -OR 3 -R 4 (where n8 is an integer from 0 to 2, X 11 is I or H, q is an integer from 1 to 6, R 3 and R 4 As described above).

[0066] In the third manufacturing method, first, CHF=CHF and I 2 and IF 5 Reaction to produce general formula: R 1 -CHF-I (where R 1 -CHF 2 or -CHFI), and preparing a first fluorinated alkyl iodide represented by the general formula: R by adding CHF=CHF to the first fluorinated alkyl iodide. 1 -CHF-(CHF-CHF) n8 -I(where R 1 As described above, n8 is the second fluorine-containing alkyl iodide represented by 1 or 2).

[0067] I 2 and IF 5 The amount of O used is preferably 0.5 mol to 2 mol relative to 1 mol of CHF=CHF.

[0068] CHF=CHF and I 2 and IF 5 The reaction can be carried out in a solvent.

[0069] CHF=CHF and I 2 and IF 5 The reaction temperature can be appropriately selected, preferably -78°C to 200°C. CHF=CHF and I 2 and IF 5 The reaction pressure can be appropriately selected, preferably 0 to 5.0 MPaG. CHF = CHF and I 2 and IF 5 The reaction time can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0070] The reaction of the first fluorinated alkyl iodide and CHF=CHF is a telogenation reaction of a product having CHF=CHF as a main chain using the first fluorinated alkyl iodide as a telogen, and the second fluorinated alkyl iodide is produced by this reaction.

[0071] n8 in the second fluorine-containing alkyl iodide represents the polymerization degree of CHF=CHF. n8 is 1 or 2, and preferably 1.

[0072] The reaction of the first fluorine-containing alkyl iodide and CHF=CHF may be carried out in the presence of a radical initiator. Examples of the radical initiator include organic peroxides and azo compounds.

[0073] Examples of the organic peroxide include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0074] Examples of the azo compound include azobisisobutyronitrile and the like.

[0075] The amount of CHF=CHF used is preferably 0.01 mol to 100 mol relative to 1 mol of the fluorine-containing alkyl iodide.

[0076] The amount of the radical initiator used is preferably 0.01 mol to 2 mol per 1 mol of the fluorine-containing alkyl iodide.

[0077] The reaction temperature of the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, and is preferably -78°C to 200°C. The reaction temperature of the first fluorinated alkyl iodide and CHF=CHF is preferably not less than the decomposition temperature of the radical polymerization initiator and preferably less than the decomposition temperature of the substrate and the product.

[0078] The pressure of the reaction of the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, and is preferably 0 to 5.0 MPaG. The time of the reaction of the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, and is preferably 0.1 to 96 hours.

[0079] In the third production method, the first fluorinated alkyl iodide or the second fluorinated alkyl iodide is reacted with a compound of the general formula: CH 2 =CH-(CH 2 ) q -OH (wherein q is an integer greater than 1) to produce an unsaturated compound represented by the general formula: R 1 -CHF-(CHF-CHF) n8 -CH 2 -CHI-(CH 2 ) q -OH (where R 1 As described above, n8 is an integer of 0 to 2, and q is an integer of 1 to 6).

[0080] Fluorinated alcohol R 1 and R of the first fluorinated alkyl iodide or the second fluorinated alkyl iodide 1 Same as -CHF2 or -CHFI.

[0081] n8 of the fluorine-containing alcohol is an integer of 0 to 2, and is preferably 0 or 1.

[0082] The reaction of the first fluorine-containing alkyl iodide or the second fluorine-containing alkyl iodide with the unsaturated compound may be carried out in the presence of a compound that generates free radicals. Examples of such a compound include organic peroxides and azo compounds.

[0083] Examples of the organic peroxide include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate, and dialkyl peroxides such as di-tert-butyl peroxide.

[0084] Examples of the azo compound include azobisisobutyronitrile and the like.

[0085] The amount of the unsaturated compound used is preferably 0.01 mol to 100 mol per 1 mol of the first fluorine-containing alkyl iodide or the second fluorine-containing alkyl iodide.

[0086] The amount of the radical-generating compound used is preferably 0.001 mol to 1 mol per 1 mol of the first fluorine-containing alkyl iodide or the second fluorine-containing alkyl iodide.

[0087] The temperature of the reaction of the first fluorinated alkyl iodide or the second fluorinated alkyl iodide with the unsaturated compound can be appropriately selected, and is preferably 50° C. to 200° C. The pressure of the reaction of the first fluorinated alkyl iodide or the second fluorinated alkyl iodide with the unsaturated compound can be appropriately selected, and is preferably 0.1 MPaG to 5 MPaG. The time of the reaction of the first fluorinated alkyl iodide or the second fluorinated alkyl iodide with the unsaturated compound can be appropriately selected, and is preferably 0.1 hour to 96 hours.

[0088] In the third production method, the obtained fluorinated alcohol is then reacted with R 4 -R 3 -X to alkylate the oxygen of the fluorinated alcohol to produce a fluorinated ether compound.

[0089] When X is a halogen atom, a base such as sodium hydride is reacted with a fluorinated alcohol to form a fluorinated alcohol salt. 4 -R 3 By reacting a compound represented by -X (X is a halogen atom), a fluorine-containing ether compound can be produced.

[0090] In addition, in X is -OSO 3In the case of R' (wherein R' is a non-fluorinated alkyl group or a fluorinated alkyl group), for example, in an aqueous solution of a hydroxide, a fluorinated alcohol is reacted with R 4 -R 3 -X (X is -OSO 3 R') is reacted with a compound represented by the formula (A), thereby producing a fluorine-containing ether compound.

[0091] As R 4 -R 3 -X (X is -OSO 3 R'), preferably (R 4 -R 3 -O-) 2 SO 2 (R 3 and R 4 as described above).

[0092] Fluorinated alcohol and R 4 -R 3 The reaction pressure of the compound represented by -X is preferably 0.1 MPaG to 2.0 MPaG. 4 -R 3 The reaction temperature of the compound represented by -X is preferably 20°C to 95°C.

[0093] In the third production method, the first fluorine-containing alcohol may be reduced to the second fluorine-containing alcohol. The reduction may be performed, for example, using a metal catalyst and hydrogen, or using zinc as a reducing agent.

[0094] The fluorine-containing ether compound disclosed in the present invention can be produced, for example, by the following production method (hereinafter sometimes referred to as the fourth production method):

[0095] By making CHF = CHF and I 2 and IF 5 Reaction to produce general formula: R 1 -CHF-I (where R 1 -CHF 2 or -CHFI), and preparing a first fluorinated alkyl iodide represented by the general formula: R by adding CHF=CHF to the first fluorinated alkyl iodide. 1 -CHF-(CHF-CHF) n8 -I(where R 1 As described above, n8 is 1 or 2) represented by the second fluorine-containing alkyl iodide,

[0096] By reacting the first fluorinated alkyl iodide or the second fluorinated alkyl iodide with a compound of the general formula: CH 2 =CH-(CH 2 ) q -OR 3 -R4 (wherein, q is an integer greater than 1, R 3 and R 4 As the fluorine-containing ether compound of the present disclosure has R 3 and R 4 The unsaturated compound shown in the above description) is reacted to produce the general formula: R 1 -CHF-(CHF-CHF) n8 -CH 2 -CHI-(CH 2 ) q -OR 3 -R 4 (Where R 1 , R 3 and R 4 As described above, n8 is an integer of 0 to 2, and q is an integer of 1 to 6).

[0097] The method for producing the first fluorine-containing alkyl iodide and the second fluorine-containing alkyl iodide is the same as described in the third production method.

[0098] As the first fluorinated alkyl iodide or the second fluorinated alkyl iodide and the general formula: CH 2 =CH-(CH 2 ) q -OR 3 -R 4 The reaction of the unsaturated compound shown in the figure, the first fluorinated alkyl iodide or the second fluorinated alkyl iodide and the general formula: CH 2 =CH-(CH 2 ) q The reaction of the unsaturated compound represented by -OH can be carried out by the same method as that described in the third production method.

[0099] The obtained fluorinated ether compound can be reduced to produce a compound of the general formula: R 1 -CHF-(CHF-CHF) n8 -CH 2 -CH 2 -(CH 2 ) q -OR 3 -R 4 (Where R 1 , R 3 and R 4 As described above, n8 is an integer of 0 to 2, and q is an integer of 1 to 6). The reduction can be performed, for example, using a metal catalyst and hydrogen, or using zinc as a reducing agent.

[0100] The composition of the present disclosure may contain the above-mentioned fluorinated ether compound and a solvent. As the solvent, at least one selected from the group consisting of alcohols, ethers, alkanes, olefins, perfluorocarbons, perfluorinated tertiary amines, perfluorinated ethers, cycloalkanes, esters, ketones, aromatic compounds, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons and hydrofluorocarbons.

[0101] In addition, the composition of the present disclosure may contain the above-mentioned fluorine-containing ether compound, and other components such as a surfactant, a stabilizer, a pigment, a dye, a colorant, an antioxidant, and a flame retardant.

[0102] In addition, the composition of the present disclosure may contain the above-mentioned fluorine-containing ether compound and other fluorine-containing ether compounds different from the above-mentioned fluorine-containing ether compound. Examples of other fluorine-containing ether compounds include hydrofluoroether compounds.

[0103] The fluorinated ether compound and the composition of the present disclosure can be suitably used as a heat transfer fluid, a cleaning solvent, a bubble size regulator for adjusting the bubble size of a foamed thermal insulation material, a fire extinguishing agent, a carrier fluid, a working fluid, a polymerization solvent, an abrasive, a desiccant, a resist developer, a resist stripper, etc. For example, they can be used for the use of the hydrofluoroether compound described in Japanese Unexamined Patent Application Publication No. 2009-507840.

[0104] Although the embodiments have been described above, it should be understood that various modifications may be made to the embodiments and details without departing from the spirit and scope of the claims.

[0105] The main embodiments of the present disclosure are as follows.

[0106] <1> According to a first aspect of the present disclosure, there is provided a fluorine-containing ether compound having the general formula: R 1 -R 2 -OR 3 -R 4 Indicated.

[0107] (Where,

[0108] R 1 -CH 3 、-CH 2 F, -CHF 2 、-CH 2 I or -CHFI,

[0109] R 2 It is a fluorinated alkylene group having 1 to 10 carbon atoms consisting only of a unit represented by -CHF-, or a fluorinated alkylene group consisting only of a unit represented by -CHF- and -CH 2 -a fluorinated alkylene group having 2 to 10 carbon atoms, or a unit represented by -CFH-, -CH2 A fluorinated alkylene group having 3 to 10 carbon atoms, which is composed of a unit represented by - and a unit represented by -CHI-,

[0110] R 3 is a single bond, a non-fluorinated alkylene group having 1 to 5 carbon atoms, or a fluorinated alkylene group having 1 to 10 carbon atoms, R 4 -CH 3 、-CH 2 F or -CHF 2 )

[0111] <2> According to a second aspect of the present disclosure, there is provided a fluorine-containing ether compound according to the first aspect, wherein R 1 -CH 2 F, -CHF 2 or -CHFI.

[0112] <3> According to a third aspect of the present disclosure, there is provided a fluorine-containing ether compound according to the first aspect or the second aspect, wherein R 2 for:

[0113] General formula: -(CHF) n1 -(wherein n1 is an integer from 1 to 10); or

[0114] General formula: -(CHF) n2 -CH 2 -(wherein n2 is an integer from 1 to 9); or

[0115] -(CHF) n7 -CH 2 -CH 2 -(CH 2 ) q -(wherein n7 is an integer of 1 to 7, and q is an integer of 1 to 6); or

[0116] -(CHF) n7 -CH 2 -CHI-(CH 2 ) q -(wherein n7 is an integer of 1 to 7, and q is an integer of 1 to 6).

[0117] <4> According to a fourth aspect of the present disclosure, there is provided a fluorine-containing ether compound according to any one of the first aspect to the third aspect, wherein R 1 -R 2 -for:

[0118] CH 2 F-CHF-; or

[0119] General formula: CH 2 F-CHF-(CHF-CHF) n3 -CH 2 -(wherein n3 is an integer from 0 to 4) represented by a fluorinated alkyl group; or

[0120] General formula: CHF 2 -CHF-(CHF-CHF) n8 -CH 2 -CHX 11 -(CH 2 ) q -(where n8 is an integer from 0 to 2, X 11 is I or H, q is an integer of 1 to 6).

[0121] <5> According to a fifth aspect of the present disclosure, there is provided a fluorine-containing ether compound according to any one of the first aspect to the fourth aspect, wherein R 3 for:

[0122] single bond;

[0123] A non-fluorinated alkylene group having 1 to 5 carbon atoms;

[0124] General formula: -(CHF) n4 -(wherein n4 is an integer from 1 to 10) represented by a fluorinated alkylene group; or

[0125] General formula: -(CHF) n5 -CH 2 -(wherein n5 is an integer of 1 to 9).

[0126] <6> According to a sixth aspect of the present disclosure, there is provided a fluorine-containing ether compound according to any one of the first aspect to the fifth aspect, wherein R 4 -R 3 -for:

[0127] A non-fluorinated alkyl group having 1 to 4 carbon atoms; or

[0128] General formula: CH 2 F-CHF-(CHF-CHF) n6 -CH 2 -(wherein n6 is an integer of 0 to 4).

[0129] <7> According to a seventh aspect of the present disclosure, there is provided a fluorinated ether compound according to any one of the first aspect to the sixth aspect, wherein the fluorinated ether compound is selected from the group consisting of CH 2 FCHFOCH 3 , CH 2 FCHFCH 2 OCH 3, CH 2 FCHFCH 2 OCHFCFH 2 , CH 2 FCHFCH 2 OCH 2 CH 3 , CH 2 FCHFCHFCHFCH 2 OCH 3 , CHF 2 -CHF-CH 2 -CHI-CH 2 -OCH 3 , CHF 2 -CHF-CH 2 -CH 2 -CH 2 -OCH 3 , CHF 2 -CHF-CH 2 -CH 2 -CH 2 -OCHFCFH 2 , CHF 2 -CHF-CH 2 -CH 2 -CH 2 -OCH 2 CH 3 , CHF 2 -CHF-CH 2 -CHI-CH 2 -CH 2 -CH 2 -CH 2 -OCH 3 and CHF 2 -CHF-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -OCH 3 At least one of the group consisting of.

[0130] <8> According to an eighth aspect of the present disclosure, there is provided a composition comprising:

[0131] A fluorine-containing ether compound according to any one of the first to seventh aspects; and

[0132] At least one selected from the group consisting of alcohols, ethers, alkanes, olefins, perfluorocarbons, perfluorinated tertiary amines, perfluorinated ethers, cycloalkanes, esters, ketones, aromatic compounds, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons and hydrofluorocarbons.

[0133] <9> According to a ninth aspect of the present disclosure, there is provided a heat transfer fluid comprising the fluorine-containing ether compound according to any one of the first to seventh aspects or the composition according to the eighth aspect.

[0134] <10> According to a tenth aspect of the present disclosure, there is provided a cleaning solvent comprising the fluorine-containing ether compound according to any one of the first aspect to the seventh aspect or the composition according to the eighth aspect.

[0135] Example

[0136] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to the examples.

[0137] Example 1 Synthesis of 1,1,2-trifluoro-2-iodoethane

[0138] Add 37.1 g iodine and IF into a 300 mL pressure-resistant container. 5 16.1 g, the container was sealed. After cooling the container to -78°C, 10 g of (E)-1,2-difluoroethylene was introduced into the container, and the container was heated at 80°C for 20 hours. After cooling the container with ice water, the contents of the pressure container were washed with water, and then further washed with 5% Na 2 S 2 O 4 The mixture was washed with aqueous solution to obtain 5.8 g of the title compound.

[0139] 19 F NMR (282 MHz, CDCl 3 ): δ-169.1~-169.4(m,1F), -124.0~-124.3(m,1F).

[0140] 1 H NMR (400MHz, CDCl3): δ6.79 (d with fine coupling, J=48.0Hz, 1H), 7.26 (tdwith fine coupling, J=54.8, 3.6Hz, 1H).

[0141] LRMS (EI 70eV) m / z (%): 210 (M+, 100), 190 (8), 171 (3), 83 (62), 64 (37), 51 (14).

[0142] Example 2 Synthesis of 4,5,5-trifluoro-2-iodopentanol

[0143] 1.84 g of 1,1,2-trifluoro-2-iodoethane, 509 mg of allyl alcohol, and 288 mg of azobisisobutyronitrile were added to a 10 mL pressure vessel. The vessel was then heated at 80° C. for 22 hours. The vessel was cooled with ice water, and the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The result showed that the title compound was generated at an area ratio of 75.9% relative to the area ratio of 24.1% of the raw material 1,1,2-trifluoro-2-iodoethane.

[0144] LRMS (EI 70eV) m / z (%): 268 (M+, 1), 251 (1), 185 (2), 141 (95), 73 (100), 51 (38).

[0145] Example 3 Synthesis of 1,1,2-trifluoro-4-iodo-8-methoxyoctane

[0146] In a 10 mL pressure-resistant container, 500 mg of 1,1,2-trifluoro-2-iodoethane, 272 mg of 6-methoxyhexene, and 117 mg of azobisisobutyronitrile were added. The container was cooled to -78°C, replaced with nitrogen, and nitrogen was added to 0.5 MPa. The container was heated at 80°C for 13 hours. After cooling the container with ice water, a mixture containing the target compound was obtained. The contents were analyzed by gas chromatography-mass spectrometry, and the title compound was generated with an area ratio of 65.8% (total of 2 isomers) relative to the area ratio of 34.2% of the raw material 1,1,2-trifluoro-2-iodoethane.

[0147] LRMS(EI 70eV)m / z(%): 197([MI] + ,37),165(100),45(50).

[0148] Example 4 Synthesis of 1,1,2-trifluoro-8-methoxyoctane

[0149] 200 mg of 1,1,2-trifluoro-4-iodo-8-methoxyoctane, 0.4 mL of methanol, and 80.7 mg of Zn were added to a 10 mL glass container. After adding 4 drops of 2M HCl aqueous solution, the container was cooled to -78°C, replaced with nitrogen, and stirred at room temperature for 2 hours. The contents of the container were analyzed by gas chromatography-mass spectrometry, and the raw materials disappeared, and the title compound was generated.

[0150] LRMS(EI 70eV)m / z(%): 166([M-CH 3 OH] + ,11),138(27),51(9),45(100).

Claims

1. A fluorine-containing ether compound having the general formula: R 1 -R 2 -OR 3 -R 4 It is indicated that In the formula, R 1 is -CH3, -CH2F, -CHF2, -CH2I or -CHFI, R 2 is a fluorinated alkylene group having 1 to 10 carbon atoms consisting only of a unit represented by -CHF-, or a fluorinated alkylene group having 2 to 10 carbon atoms consisting only of a unit represented by -CHF- and a unit represented by -CH2-, or a fluorinated alkylene group having 3 to 10 carbon atoms consisting only of a unit represented by -CFH-, a unit represented by -CH2-, and a unit represented by -CHI-, R 3 is a single bond, a non-fluorinated alkylene group having 1 to 5 carbon atoms, or a fluorinated alkylene group having 1 to 10 carbon atoms, R 4 It is -CH3, -CH2F or -CHF2.

2. The fluorine-containing ether compound according to claim 1, wherein R 1 It is -CH2F, -CHF2 or -CHFI.

3. The fluorine-containing ether compound according to claim 1 or 2, wherein R 2 for: General formula: -(CHF) n1 -, wherein n1 is an integer from 1 to 10; or General formula: -(CHF) n2 -CH2-, wherein n2 is an integer from 1 to 9; or -(CHF) n7 -CH2-CH2-(CH2) q -, wherein n7 is an integer from 1 to 7, and q is an integer from 1 to 6; or -(CHF) n7 -CH2-CHI-(CH2) q -, wherein n7 is an integer of 1 to 7, and q is an integer of 1 to 6.

4. The fluorine-containing ether compound according to any one of claims 1 to 3, wherein R 1 -R 2 -for: CH2F-CHF-; or General formula: CH2F-CHF-(CHF-CHF) n3 -CH2-, wherein n3 is an integer from 0 to 4; or General formula: CHF2-CHF-(CHF-CHF) n8 -CH2-CHX 11 -(CH2) q - fluorinated alkyl, wherein n8 is an integer from 0 to 2, and X 11 is I or H, and q is an integer of 1-6.

5. The fluorine-containing ether compound according to any one of claims 1 to 4, wherein R 3 for: single bond; A non-fluorinated alkylene group having 1 to 5 carbon atoms; General formula: -(CHF) n4 -, wherein n4 is an integer from 1 to 10; or General formula: -(CHF) n5 A fluorinated alkylene group represented by -CH2-, wherein n5 is an integer of 1 to 9.

6. The fluorine-containing ether compound according to any one of claims 1 to 5, wherein R 4 -R 3 -for: A non-fluorinated alkyl group having 1 to 4 carbon atoms; or General formula: CH2F-CHF-(CHF-CHF) n6 A fluorinated alkyl group represented by -CH2-, wherein n6 is an integer of 0 to 4.

7. The fluorine-containing ether compound according to any one of claims 1 to 6, which is at least one selected from the group consisting of CH2FCHFOCH3, CH2FCHFCH2OCH3, CH2FCHFCH2OCHFCFH2, CH2FCHFCH2OCH2CH3, CH2FCHFCHFCHFCH2OCH3, CHF2-CHF-CH2-CHI-CH2-OCH3, CHF2-CHF-CH2-CH2-CH2-OCH3, CHF2-CHF-CH2-CH2-CH2-OCHFCFH2, CHF2-CHF-CH2-CH2-CH2-OCH2CH3, CHF2-CHF-CH2-CH2-CH2-OCHFCFH2, CHF2-CHF-CH2-CH2-CH2-OCH2CH3, CHF2-CHF-CH2-CH2-CHI-CH2-CH2-CH2-CH2-OCH3 and CHF2-CHF-CH2-CH2-CH2-CH2-CH2-CH2-OCH3.

8. A composition comprising: The fluorine-containing ether compound according to any one of claims 1 to 7; and At least one selected from the group consisting of alcohols, ethers, alkanes, olefins, perfluorocarbons, perfluorinated tertiary amines, perfluorinated ethers, cycloalkanes, esters, ketones, aromatic compounds, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons and hydrofluorocarbons. 9 . A heat transfer fluid comprising the fluorine-containing ether compound according to claim 1 or the composition according to claim 8 . 10 . A cleaning solvent comprising the fluorine-containing ether compound according to claim 1 or the composition according to claim 8 .