Fluorine-containing ether compounds and methods for producing the same

Abstract

Provided is a fluorine-containing ether compound represented by the general formula: R1-R2-O-R3-R4 (in the formula, R1 is -CH3, -CH2F, -CHF2, -CH2I, or -CHFI, R2 is a fluorinated C1-10 alkylene group constituted from only units represented by -CHF-, a fluorinated C2-10 alkylene group constituted from only units represented by -CHF- and units represented by -CH2, or a fluorine-containing C3-10 alkylene group constituted from only units represented by -CFH-, units represented by -CH2, and units represented by -CHI-, R3 is a single bond, a non-fluorinated C1-5 alkylene group, or a fluorinated C1-10 alkylene group, and R4 is -CH3, -CH2F, or -CHF2).

Description

[Technical Field]

[0001] This disclosure relates to fluorine-containing ether compounds and methods for producing the same. [Background technology]

[0002] Fluorine-containing ethers are used not only as solvents but also in a wide range of other applications.

[0003] As an example of a fluorine-containing ether, Patent Document 1 describes a compound represented by the general formula: Rh'(O-Rf)m (wherein m=3~4, Rf is independently a perfluoroaliphatic group, and Rh' is independently a linear or branched hydrocarbon having 3 to about 8 carbon atoms).

[0004] For example, Patent Document 2 describes a hydrofluoroether compound comprising two terminally fluorinated alkyl groups and a substituted or unsubstituted oxymethylene group interposed in the chain, wherein each of the fluorinated alkyl groups contains only one hydrogen atom, and optionally contains at least one heteroatom in the chain, wherein the hydrogen atom is part of the monofluoromethylene moiety. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Special Publication No. 2008-529975 [Patent Document 2] Special Publication No. 2009-507840 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Patent documents 1 and 2 describe how, in this manner, at least one of the two groups bonded to the oxygen of an ether compound is composed of a perfluoroaliphatic group, or at least one of the groups is composed of a fluorinated alkyl group containing only one hydrogen atom.

[0007] However, no fluorine-containing ethers are known in which at least one of the two groups bonded to the oxygen of the ether compound is composed of a group that does not contain the units represented by CF3- (trifluoromethyl group) and -CF2- (difluoromethylene group).

[0008] The object of this disclosure is to provide a fluorine-containing ether compound having at least one of the two groups bonded to oxygen in the ether compound that does not contain a trifluoromethyl group or a difluoromethylene group. [Means for solving the problem]

[0009] According to this disclosure, the general formula is: R 1 -R 2 -OR 3 -R 4 (In the formula, R 1 These are -CH3, -CH2F, -CHF2, -CH2I, or -CHFI. R 2 This refers to a fluorinated alkylene group having 1 to 10 carbon atoms, consisting only of units represented by -CHF-, or a fluorinated alkylene group having 2 to 10 carbon atoms, consisting only of units represented by -CHF- and -CH2-, or a fluorinated alkylene group having 3 to 10 carbon atoms, consisting only of units represented by -CFH-, -CH2-, and -CHI-. R 3 This 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 (These are -CH3, -CH2F, or -CHF2) A fluorine-containing ether compound represented by the following is provided.

Effects of the Invention

[0010] According to the present disclosure, a fluorine-containing ether compound can be provided, in which, among the two groups bonded to oxygen of the ether compound, at least one group has a group that does not contain a trifluoromethyl group and a difluoromethylene group.

Modes for Carrying Out the Invention

[0011] Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0012] The fluorine-containing ether compound of the present disclosure has the general formula: R 1 -R 2 -O-R 3 -R 4 (In the formula, R 1 is -CH3, -CH2F, -CHF2, -CH2I or -CHFI, and R 2 is a fluorinated alkylene group having 1 to 10 carbon atoms and composed only of units represented by -CHF-, or a fluorinated alkylene group having 2 to 10 carbon atoms and composed only of units represented by -CHF- and units represented by -CH2-, or a fluorine-containing alkylene group having 3 to 10 carbon atoms and composed only of units represented by -CFH-, units represented by -CH2- and units represented by -CHI-, and 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, and R 4 is -CH3, -CH2F or -CHF2).

[0013] R 1The group is -CH3, -CH2F, -CHF2, -CH2I, or -CHFI, preferably -CH2F, -CHF2, or -CHFI, and more preferably -CH2F. One feature of the fluorine-containing ether compounds of this disclosure is that at least one of the two groups bonded to the oxygen of the ether compound does not have a CF3- (trifluoromethyl group) at its terminus.

[0014] R 2 This refers to 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-. One characteristic of the fluorinated ether compounds of this disclosure is that at least one of the two groups bonded to the oxygen of the ether compound always contains a unit represented by -CHF- and does not contain a unit represented by -CF2-.

[0015] R 2 If R is a fluorinated alkylene group consisting only of units represented by -CHF-, 2 For example, -(CHF) n1 A fluorinated alkylene group represented by -(n1 is an integer from 1 to 10) is preferred.

[0016] R 2 If R is a fluorinated alkylene group composed only of units represented by -CHF- and units represented by -CH2-, 2 For example, -CHF-(CHF-CHF) n2 -(CH2) m1 -(n2 is an integer between 1 and 4, m1 is an integer greater than or equal to 1) fluorinated alkylene group, -(CHF) n7 -CH2-CH2-(CH2) q Examples include fluorinated alkylene groups represented by -(wherein n7 is an integer from 1 to 7, and q is an integer from 1 to 6).

[0017] R 2 If R is a fluorinated alkylene group composed only of units represented by -CHF- and units represented by -CH2-, 2 For example, -(CHF) n2 A fluorinated alkylene group represented by -CH2- (where n2 is an integer from 1 to 9), or -(CHF) n7 -CH2-CH2-(CH2) q A fluorinated alkylene group represented by -(wherein n7 is an integer from 1 to 7, and q is an integer from 1 to 6) is preferred, and -CHF-(CHF-CHF) n3 A fluorinated alkylene group represented by -CH2- (where n3 is an integer from 0 to 4), or -CHF- (CHF-CHF) n8 -CH2-CH2-(CH2) q - (where n8 is an integer from 0 to 2 and q is an integer from 1 to 6) is more preferable.

[0018] R 2 If the alkylene group is composed only of units represented by -CFH-, -CH2-, and -CHI-, then R 2 For example, -(CHF) n7 -CH2-CHI-(CH2) q A fluorinated alkylene group represented by -(wherein n7 is an integer from 1 to 7, and q is an integer from 1 to 6) is preferred, and -CHF-(CHF-CHF) n8 -CH2-CHI-(CH2) q A fluorinated alkylene group represented by -(wherein n8 is an integer from 0 to 2, and q is an integer from 1 to 6) is more preferred.

[0019] In the general formula for fluorine-containing ether compounds, R 1 -R 2 The group represented by - is CH2F-CHF-, or the general formula: CH2F-CHF-(CHF-CHF) n3 A fluorinated alkyl group represented by -CH2- (where n3 is an integer from 0 to 4), Alternatively, the general formula is: CHF2-CHF-(CHF-CHF) n8 -CH2-CHX 11 -(CH2)q -(In the formula, n8 is an integer between 0 and 2, X 11 A fluorinated alkyl group represented by I or H (where q is an integer from 1 to 6) is preferred.

[0020] n3 is preferably 0 or 1.

[0021] R 3 This is a single bond, a non-fluorinated alkylene group with 1 to 5 carbon atoms, or a fluorinated alkylene group with 1 to 10 carbon atoms. 3 The number of carbon atoms is preferably 0 to 5, more preferably 0 to 3, and even more preferably 0 or 1. 3 The number of carbon atoms in the non-fluorinated alkylene group is preferably 1 or 2. 3 The number of carbon atoms in the fluorinated alkylene group is preferably 1 to 5, and more preferably 1 or 2.

[0022] R 3 Examples include single bonds, non-fluorinated alkylene groups with 1 to 5 carbon atoms, and -(CHF) n4 -(wherein n4 is an integer from 1 to 10) fluorinated alkylene group, or -(CHF) n5 A fluorinated alkylene group represented by -CH2- (wherein n5 is an integer from 1 to 9) is preferred.

[0023] R 4 The protein is -CH3, -CH2F, or -CHF2, with -CH3 or -CH2F being preferred.

[0024] In the general formula for fluorine-containing ether compounds, R 4 -R 3 The group indicated by - is a non-fluorinated alkyl group having 1 to 4 carbon atoms, or the general formula: CH2F-CHF-(CHF-CHF) n6 -CH2- A fluorinated alkyl group represented by (wherein n6 is an integer from 0 to 4) is preferred.

[0025] R 4 -R 3When the group indicated by - is a non-fluorinated alkyl group, the number of carbon atoms in the non-fluorinated alkyl group is preferably 1 or 2.

[0026] n6 is preferably 0 or 1.

[0027] As the fluorine-containing ether compound, 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-CHI-CH2-CH2-CH2-CH2-OCH3, and CHF2-CHF-CH2-CH2-CH2-CH2-CH2-CH2-OCH3 is preferred.

[0028] The fluorine-containing ether compounds of this disclosure include, for example, CHF=CHF and the general formula: R 4 -R 3 -OH(in the formula, R 3 and R 4 The alcohol represented by (as described above) is reacted in the presence of a basic compound to produce the general formula: CH2F-CHF-OR 3 -R 4 (In the formula, R 3 and R 4 It can be produced by a manufacturing method for producing fluorine-containing ether compounds as shown above (hereinafter sometimes referred to as the first manufacturing method).

[0029] In the first manufacturing method, the basic compound acts as a catalyst. Inorganic basic compounds are preferred as the basic compound, and alkali metal hydroxides or alkaline earth metal hydroxides such as NaOH, KOH, CsOH, LiOH, Ca(OH)2, and Ba(OH)2 are more preferred.

[0030] The amount of basic compound used is preferably 0.01 to 1.0 mole, and more preferably 0.2 to 0.8 moles, per mole of alcohol.

[0031] The reaction between CHF=CHF and alcohol can be carried out in a solvent. Examples of solvents include water, diethyl ether, glymes, dioxane, tetrahydrofuran, and acetonitrile, which are polar organic solvents.

[0032] The pressure for the reaction between CHF=CHF and alcohol is preferably 1.0 to 2.0 MPaG. The temperature for the reaction between CHF=CHF and alcohol is preferably 20 to 95°C.

[0033] The fluorine-containing ether compounds of this disclosure include, for example, By adding CHF=CHF to methanol, the general formula is: CH2F-CHF-(CHF-CHF) n3 A fluorine-containing alcohol represented by -CH2OH (where n3 is an integer from 0 to 4) is produced. Fluorine-containing alcohol and R 4 -R 3 -X(where R 3 and R 4 As described above, X is reacted with a compound represented by a halogen atom or -OSO3R' (wherein R' is a non-fluorinated alkyl group or a fluorinated alkyl group) to form a compound of the general formula: CH2F-CHF-(CHF-CHF) n3 -CH2-OR 3 -R 4 (In the formula, n3, R 3 and R 4 The above describes how to produce fluorine-containing ether compounds. It can be manufactured by the manufacturing method (hereinafter sometimes referred to as the second manufacturing method).

[0034] In the second manufacturing method, a fluorine-containing alcohol is first produced by adding CHF=CHF to methanol.

[0035] In fluorine-containing alcohols, n3 represents the degree of polymerization of CHF=CHF. n3 is an integer between 0 and 4, preferably 0 or 1.

[0036] The reaction between methanol and CHF=CHF can be carried out in the presence of a radical initiator. When the reaction is carried out in the presence of a radical initiator, the radical initiator decomposes to generate a radical, which then abstracts a hydrogen atom from the carbon atom to which the hydroxyl group of methanol is bonded, thereby producing a methanol radical. A reaction then proceeds in which CHF=CHF is added to the methanol radical (a so-called telomerization reaction).

[0037] As radical initiators, organic peroxides are preferred, including dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate and t-butyl peroxypivalate, and dialkyl peroxides such as dit-butyl peroxide. Among these, dit-butyl peroxide is preferred as a radical initiator.

[0038] The amount of CHF=CHF used is preferably 0.01 to 100 moles per mole of methanol.

[0039] The amount of radical initiator used is preferably 0.01 to 2 moles per mole of methanol.

[0040] The reaction temperature between methanol and CHF=CHF can be selected as appropriate, but is preferably -78 to 200°C. Furthermore, the reaction temperature between methanol and CHF=CHF is preferably above the decomposition temperature of the radical polymerization initiator, and preferably below the decomposition temperature of the substrate and product.

[0041] The pressure of the reaction between methanol and CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The reaction time between methanol and CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0042] In the second production method, next, the obtained fluorinated alcohol is reacted with a compound represented by R 4 -R 3 -X to alkylate the oxygen of the fluorinated alcohol, thereby producing a fluorinated ether compound.

[0043] When X is a halogen atom, a base such as sodium hydride is allowed to act on the fluorinated alcohol, and the resulting fluorinated alkoxide is reacted with a compound represented by R 4 -R 3 -X (X is a halogen atom) to produce a fluorinated ether compound.

[0044] Also, when X is -OSO3R' (where R' is a non-fluorinated alkyl group or a fluorinated alkyl group), for example, in an aqueous solution of a hydroxide, the fluorinated alcohol is reacted with a compound represented by R 4 -R 3 -X (X is -OSO3R') to produce a fluorinated ether compound.

[0045] R 4 -R 3 As the compound represented by -X (X is -OSO3R'), (R 4 -R 3 -O-)2SO2 (R 3 and R 4 are as described above) is preferred.

[0046] The pressure of the reaction between the fluorinated alcohol and the compound represented by R 4 -R 3 -X is preferably 0.1 to 2.0 MPaG. The pressure of the reaction between the fluorinated alcohol and the compound represented by R 4 -R 3The temperature of the reaction with the compound represented by -X is preferably 20 to 95 °C.

[0047] The fluorine-containing ether compound of the present disclosure is, for example, By reacting CHF=CHF with I2 and IF5, a first fluorine-containing alkyl iodide represented by the general formula: R 1 -CHF-I (where R 1 is -CHF2 or -CHFI) is produced, and CHF=CHF is added to the first fluorine-containing alkyl iodide to obtain a general formula: R 1 -CHF-(CHF-CHF) n8 -I (where R 1 is as described above, n8 is 1 or 2) to produce a second fluorine-containing alkyl iodide, Reacting the first or second fluorine-containing alkyl iodide with an unsaturated compound represented by the general formula: CH2=CH-(CH2) q -OH (where q is an integer of 1 or more) to obtain a first fluorine-containing alcohol represented by the general formula: R 1 -CHF-(CHF-CHF) n8 -CH2-CHI-(CH2) q -OH (where R 1 is as described above, n8 is an integer of 0 to 2, q is an integer of 1 to 6), Optionally, the first fluorine-containing alcohol is reduced to obtain a first fluorine-containing alcohol represented by the general formula: R 1 -CHF-(CHF-CHF) n8 -CH2-CH2-(CH2) q -OH (where R 1 is as described above, n8 is an integer of 0 to 2, q is an integer of 1 to 6), Reacting the first or second fluorine-containing alcohol with R 4 -R 3 -X (where R 3 and R 4 are as described above, X is a halogen atom or -OSO3R’ (where R’ is a non-fluorinated alkyl group or a fluorinated alkyl group)) to obtain a compound represented by the general formula: R 1 -CHF-(CHF-CHF)n8 -CH2-CHX 11 -(CH2) q -OR 3 -R 4 (In the formula, 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 It can be produced by the manufacturing method for producing fluorine-containing ether compounds as shown above (hereinafter sometimes referred to as the third manufacturing method).

[0048] In the third manufacturing method, CHF=CHF is first reacted with I2 and IF5 to produce the general formula: R 1 -CHF-I (wherein, R 1 A first fluorine-containing alkyl iodide is produced, represented by -CHF2 or -CHFI), and by adding CHF=CHF to the first fluorine-containing alkyl iodide, the general formula: R 1 -CHF-(CHF-CHF) n8 -I (where R 1 As described above, n8 produces a second fluorine-containing alkyl iodide represented by 1 or 2).

[0049] The amounts of I2 and IF5 used are preferably 0.5 to 2 moles per mole of CHF = CHF.

[0050] The reaction between CHF=CHF and I2 and IF5 can be carried out in a solvent.

[0051] The reaction temperature of CHF=CHF with I2 and IF5 can be selected as appropriate, but is preferably -78 to 200°C. The reaction pressure of CHF=CHF with I2 and IF5 can be selected as appropriate, but is preferably 0 to 5.0 MPaG. The reaction time of CHF=CHF with I2 and IF5 can be selected as appropriate, but is preferably 0.1 to 96 hours.

[0052] The reaction between the first fluorine-containing alkyl iodide and CHF=CHF is a telomerization reaction in which the first fluorine-containing alkyl iodide acts as the telogen and CHF=CHF acts as the taxogen, and this reaction produces a second fluorine-containing alkyl iodide.

[0053] In the second fluorine-containing alkyl iodide, n8 represents the degree of polymerization of CHF=CHF. n8 is 1 or 2, preferably 1.

[0054] The reaction between the first fluorinated alkyl iodide and CHF=CHF can be carried out in the presence of a radical initiator. Examples of radical initiators include organic peroxides and azo compounds.

[0055] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate, and t-butyl peroxypivalate, and dialkyl peroxides such as dit-butyl peroxide.

[0056] Examples of azo compounds include azobisisobutyronitrile.

[0057] The amount of CHF=CHF used is preferably 0.01 to 100 moles per mole of fluorine-containing alkyl iodide.

[0058] The amount of radical initiator used is preferably 0.01 to 2 moles per mole of fluorine-containing alkyl iodide.

[0059] The reaction temperature between the first fluorine-containing alkyl iodide and CHF=CHF can be appropriately selected, but is preferably -78 to 200°C. Furthermore, the reaction temperature between the first fluorine-containing alkyl iodide and CHF=CHF is preferably above the decomposition temperature of the radical polymerization initiator, and preferably below the decomposition temperature of the substrate and product.

[0060] The reaction pressure between the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The reaction time between the first fluorinated alkyl iodide and CHF=CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0061] In the third manufacturing method, the first or second fluorine-containing alkyl iodide and the general formula: CH2=CH-(CH2) q By reacting with an unsaturated compound represented by -OH (where q is an integer greater than or equal to 1), the general formula: R 1 -CHF-(CHF-CHF) n8 -CH2-CHI-(CH2) q -OH(in the formula, R 1 As described above, this process produces a fluorine-containing alcohol represented by n8 (where n8 is an integer from 0 to 2, and q is an integer from 1 to 6).

[0062] R of fluorine-containing alcohols 1 R of the first or second fluorine-containing alkyl iodide 1 It is the same as -CHF2 or -CHFI.

[0063] The n8 of the fluorine-containing alcohol is an integer between 0 and 2, preferably 0 or 1.

[0064] The reaction between the first or second fluorinated alkyl iodide and the unsaturated compound can be carried out in the presence of a radical-generating compound. Examples of such compounds include organic peroxides and azo compounds.

[0065] Examples of organic peroxides include dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and disec-butyl peroxydicarbonate, peroxyesters such as 2-ethylhexanoyl (tert-butyl) peroxide, t-butyl peroxyisobutyrate, and t-butyl peroxypivalate, and dialkyl peroxides such as dit-butyl peroxide.

[0066] Examples of azo compounds include azobisisobutyronitrile.

[0067] The amount of unsaturated compound used is preferably 0.01 to 100 moles per mole of the first or second fluorine-containing alkyl iodide.

[0068] The amount of radical-generating compound used is preferably 0.001 to 1 mole per mole of the first or second fluorine-containing alkyl iodide.

[0069] The reaction temperature of the first or second fluorine-containing alkyl iodide and the unsaturated compound can be appropriately selected, but is preferably 50 to 200°C. The reaction pressure of the first or second fluorine-containing alkyl iodide and the unsaturated compound can be appropriately selected, but is preferably 0.1 to 5 MPaG. The reaction time of the first or second fluorine-containing alkyl iodide and the unsaturated compound can be appropriately selected, but is preferably 0.1 to 96 hours.

[0070] In the third manufacturing method, the obtained fluorine-containing alcohol and R 4 -R 3 By reacting it with the compound indicated by -X, the oxygen of the fluorine-containing alcohol is alkylated to produce a fluorine-containing ether compound.

[0071] When X is a halogen atom, a fluorine-containing alcohol is reacted with a base such as sodium hydride, and the resulting fluorine-containing alkoxide and R 4 -R 3Fluorine-containing ether compounds can be produced by reacting them with a compound represented by -X (where X is a halogen atom).

[0072] Furthermore, if X is -OSO3R' (wherein R' is a non-fluorinated alkyl group or a fluorinated alkyl group), for example, in an aqueous solution of hydroxide, a fluorinated alcohol and R 4 -R 3 Fluorine-containing ether compounds can be produced by reacting them with a compound represented by -X (where X is -OSO3R').

[0073] R 4 -R 3 Compounds denoted by -X (where X is -OSO3R') include (R 4 -R 3 -O-)2SO2(R 3 and R 4 (As stated above) is preferable.

[0074] Fluorine-containing alcohol and R 4 -R 3 The pressure for the reaction with the compound indicated by -X is preferably 0.1 to 2.0 MPaG. Fluorine-containing alcohol and R 4 -R 3 The reaction temperature with the compound indicated by -X is preferably 20 to 95°C.

[0075] In the third manufacturing method, the first fluorine-containing alcohol may be reduced to the second fluorine-containing alcohol. The reduction can be carried out, for example, by using a metal catalyst and hydrogen, or by using zinc as a reducing agent.

[0076] The fluorine-containing ether compounds of this disclosure include, for example, By reacting CHF=CHF with I2 and IF5, the general formula is R 1 -CHF-I (wherein, R 1 A first fluorine-containing alkyl iodide is produced, represented by -CHF2 or -CHFI), and by adding CHF=CHF to the first fluorine-containing alkyl iodide, the general formula: R1 -CHF-(CHF-CHF) n8 -I (where R 1 As described above, n8 produces a second fluorine-containing alkyl iodide represented by 1 or 2), A first or second fluorine-containing alkyl iodide and the general formula: CH2=CH-(CH2) q -OR 3 -R 4 (In the formula, q is an integer greater than or equal to 1, R 3 and R 4 The fluorine-containing ether compounds of this disclosure have R 3 and R 4 As described above, by reacting with an unsaturated compound represented by the general formula: R 1 -CHF-(CHF-CHF) n8 -CH2-CHI-(CH2) q -OR 3 -R 4 (In the formula, R 1 , R 3 and R 4 As described above, it can be produced by a manufacturing method for producing a fluorine-containing ether compound represented by n8 (where n8 is an integer from 0 to 2, and q is an integer from 1 to 6) (hereinafter sometimes referred to as the fourth manufacturing method).

[0077] The methods for producing the first and second fluorine-containing alkyl iodides are as described in the third method.

[0078] A first or second fluorine-containing alkyl iodide and the general formula: CH2=CH-(CH2) q -OR 3 -R 4 The reaction with the unsaturated compound shown is between the first or second fluorine-containing alkyl iodide and the compound with the general formula: CH2=CH-(CH2) q The reaction with the unsaturated compound represented by -OH can be carried out by the same method as described in the third production method.

[0079] The obtained fluorine-containing ether compound is reduced to obtain the general formula: R 1-CHF-(CHF-CHF) n8 -CH2-CH2-(CH2) q -OR 3 -R 4 (In the formula, R 1 , R 3 and R 4 As described above, a fluorine-containing ether compound represented by n8 (where n8 is an integer from 0 to 2 and q is an integer from 1 to 6) may be produced. Reduction can be carried out, for example, by using a metal catalyst and hydrogen, or by using zinc as a reducing agent.

[0080] The compositions of this disclosure may contain the above-mentioned fluorine-containing ether compounds and solvents. The solvent may be at least one selected from the group consisting of alcohols, ethers, alkanes, alkenes, perfluorinated carbons, perfluorinated tertiary amines, perfluorinated ethers, cycloalkanes, esters, ketones, aromatic compounds, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, and hydrofluorocarbons.

[0081] Furthermore, the compositions of this disclosure may contain the above-mentioned fluorine-containing ether compounds, as well as other components such as surfactants, stabilizers, pigments, dyes, colorants, antioxidants, and flame retardants.

[0082] Furthermore, the compositions of this disclosure may contain the above-mentioned fluorine-containing ether compounds and other fluorine-containing ether compounds different from the above-mentioned fluorine-containing ether compounds. Examples of other fluorine-containing ether compounds include hydrofluoroether compounds.

[0083] The fluorine-containing ether compounds and compositions of this disclosure can be suitably used as heat transfer fluids, cleaning solvents, bubble size adjusters for adjusting the bubble size of foamed insulation materials, fire extinguishing agents, carrier fluids, working fluids, polymerization solvents, abrasives, drying agents, resist developing agents, resist stripping agents, and the like. For example, they can be used in the applications of the hydrofluoroether compounds described in Japanese Patent Publication No. 2009-507840.

[0084] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0085] The main embodiments of this disclosure are as follows:

[0086] <1> According to the first aspect of this disclosure, General formula: R 1 -R 2 -OR 3 -R 4 (In the formula, R 1 These are -CH3, -CH2F, -CHF2, -CH2I, or -CHFI. R 2 This refers to a fluorinated alkylene group having 1 to 10 carbon atoms, consisting only of units represented by -CHF-, or a fluorinated alkylene group having 2 to 10 carbon atoms, consisting only of units represented by -CHF- and -CH2-, or a fluorinated alkylene group having 3 to 10 carbon atoms, consisting only of units represented by -CFH-, -CH2-, and -CHI-. R 3 This 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 (These are -CH3, -CH2F, or -CHF2) A fluorine-containing ether compound is provided as shown. <2> According to the second aspect of this disclosure, R 1 However, fluorine-containing ether compounds are provided that are -CH2F, -CHF2, or -CHFI in a first respect. <3> According to the third aspect of this disclosure, R 2 but, General formula: -(CHF) n1 -(In the formula, n1 is an integer between 1 and 10) A fluorinated alkylene group represented by, General formula: -(CHF) n2 -CH2- (wherein n2 is an integer from 1 to 9) A fluorinated alkylene group represented by, -(CHF) n7 -CH2-CH2-(CH2) q -(wherein n7 is an integer from 1 to 7, and q is an integer from 1 to 6) represents a fluorinated alkylene group, or -(CHF) n7 -CH2-CHI-(CH2) q - (wherein n7 is an integer from 1 to 7, and q is an integer from 1 to 6) fluorinated alkylene group A fluorine-containing ether compound is provided according to a first or second aspect. <4> According to the fourth aspect of this disclosure, R 1 -R 2 -but, CH2F-CHF-, or, General formula: CH2F-CHF-(CHF-CHF) n3 A fluorinated alkyl group represented by -CH2- (where n3 is an integer between 0 and 4), or General formula: CHF2-CHF-(CHF-CHF) n8 -CH2-CHX 11 -(CH2) q -(In the formula, n8 is an integer between 0 and 2, X 11 Fluorinated alkyl groups represented by I or H (where q is an integer from 1 to 6). A fluorine-containing ether compound is provided according to any of the first to third aspects. <5> According to the fifth aspect of this disclosure, R 3 but, Single bond, non-fluorinated alkylene group with 1 to 5 carbon atoms, General formula: -(CHF) n4 -(In the formula, n4 is an integer between 1 and 10) A fluorinated alkylene group represented by, General formula: -(CHF) n5 -CH2- (wherein n5 is an integer from 1 to 9) Fluorinated alkylene group shown A fluorine-containing ether compound is provided according to any of the first to fourth aspects. <6> According to the sixth aspect of this disclosure, R 4 -R 3 -but, Non-fluorinated alkyl groups having 1 to 4 carbon atoms, or General formula: CH2F-CHF-(CHF-CHF) n6 -CH2- (wherein n6 is an integer between 0 and 4) Fluorinated alkyl groups represented by A fluorine-containing ether compound is provided according to any of the first to fifth aspects. <7> According to the seventh aspect of this disclosure, A fluorine-containing ether compound is provided, 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-CHI-CH2-CH2-CH2-CH2-OCH3, and CHF2-CHF-CH2-CH2-CH2-CH2-CH2-CH2-OCH3, according to any of the first to sixth viewpoints. <8> According to the eighth aspect of this disclosure, Fluorine-containing ether compounds according to any of the first to seventh aspects, A composition is provided that contains at least one selected from the group consisting of alcohols, ethers, alkanes, alkenes, perfluorinated carbons, perfluorinated tertiary amines, perfluorinated ethers, cycloalkanes, esters, ketones, aromatic compounds, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, and hydrofluorocarbons. <9> According to the ninth aspect of this disclosure, A heat transfer fluid is provided that contains a fluorine-containing ether compound according to any of the first to seventh aspects or a composition according to the eighth aspect. <10> According to the tenth aspect of this disclosure, A cleaning solvent is provided that contains a fluorine-containing ether compound according to any of the first to seventh aspects or a composition according to the eighth aspect. [Examples]

[0087] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to such embodiments.

[0088] Example 1: Synthesis of 1,1,2-trifluoro-2-iodoethane 37.1 g of iodine and 16.1 g of IF5 were added to a 300 mL pressure vessel, and the vessel was sealed. After cooling the vessel to -78°C, 10 g of (E)-1,2-difluoroethene was introduced into the vessel, and the vessel was heated at 80°C for 20 hours. After cooling the vessel with ice water, the contents of the pressure vessel were washed with water, and then further washed with a 5% Na2S2O4 aqueous solution to obtain 5.8 g of the compound described in the title. 19 F NMR (282MHz, CDCl3): δ-169.1~-169.4(m,1F), -124.0~-124.3(m,1F). 1 H NMR(400MHz,CDCl3):δ 6.79(d with fine coupling,J = 48.0 Hz,1H),7.26(td with fine coupling,J = 54.8,3.6 Hz,1H). LRMS (EI 70eV) m / z (%):210(M+,100),190(8),171(3),83(62),64(37),51(14).

[0089] Example 2 Synthesis of 4,5,5-trifluoro-2-iodopentanol 1.84 g of 1,1,2-trifluoro-2-iodoethane, 509 mg of allyl alcohol, and 288 mg of azobisisobutyronitrile were placed in a 10 mL pressure vessel. The vessel was then heated at 80°C for 22 hours. After cooling the vessel in ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The results showed that the title compound was formed at an area ratio of 75.9% compared to 24.1% of the starting material, 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70eV) m / z (%):268(M+,1),251(1),185(2),141(95),73(100),51(38).

[0090] Example 3 Synthesis of 1,1,2-trifluoro-4-iodo-8-methoxyoctane 500 mg of 1,1,2-trifluoro-2-iodoethane, 272 mg of 6-methoxyhexene, and 117 mg of azobisisobutyronitrile were placed in a 10 mL pressure vessel. The vessel was cooled to -78°C, purged with nitrogen, and then nitrogen was added to 0.5 MPa. The vessel was heated at 80°C for 13 hours. After cooling the vessel with ice water, a mixture containing the target compound was obtained. Analysis of the contents by gas chromatography-mass spectrometry revealed that the title compound was formed at an area ratio of 65.8% (total of two isomers) compared to an area ratio of 34.2% for the starting material 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70eV) m / z (%):197([MI] + ,37),165(100),45(50).

[0091] Example 4 Synthesis of 1,1,2-trifluoro-8-methoxyoctane 200 mg of 1,1,2-trifluoro-4-iodo-8-methoxyoctane, 0.4 mL of methanol, and 80.7 mg of Zn were placed in a 10 mL glass container. After adding 4 drops of 2 M aqueous HCl solution, the container was cooled to -78°C, purged with nitrogen, and stirred at room temperature for 2 hours. Analysis of the contents of the container by gas chromatography-mass spectrometry revealed that the starting materials had disappeared and the title compound had been formed. LRMS (EI 70eV) m / z (%):166([M-CH3OH] + ,11),138(27),51(9),45(100).

Claims

1. General formula: R １ -R ２ -O-R ３ -R ４ (In the formula, R １ -R ２ -teeth, 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, and q is an integer from 1 to 6) is a fluorinated alkyl group, R ３ This is a single bond, a non-fluorinated alkylene group having 1 to 3 carbon atoms, or a fluorinated alkylene group having 1 to 3 carbon atoms. R ４ is, -CH ３ or -CH ２ (It is F) A fluorine-containing ether compound represented by [the formula shown].

2. R ３ but, Single bond, non-fluorinated alkylene group with 1 to 3 carbon atoms, General formula: - (CHF) ｎ４ - (In the formula, n4 is an integer between 1 and 3) A fluorinated alkylene group represented by, General formula: - (CHF) ｎ５ -CH ２ - (In the formula, n5 is an integer between 1 and 2) Fluorinated alkylene group shown The fluorine-containing ether compound according to claim 1.

3. R ４ -R ３ -but, Non-fluorinated alkyl groups having 1 to 4 carbon atoms, or General formula: CH ２ F-CHF-(CHF-CHF) ｎ６ -CH ２ Fluorinated alkyl groups represented by - (where n6 is 0 in the formula) The fluorine-containing ether compound according to claim 1.

4. CHF ２ -CHF-CH ２ -CHI-CHI 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-CHI 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 The fluorine-containing ether compound according to claim 1, which is at least one selected from the group consisting of the following.