Fluorine-containing ether compound and method for producing 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

Fluorine-containing ether compound and method for producing the same

[0001] The present disclosure relates to a fluorinated ether compound and a method for producing the same.

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

[0003] As a fluorine-containing ether, for example, Patent Document 1 describes a compound represented by the general formula: Rh'(O-Rf)m (wherein m=3 to 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 containing two terminal fluorinated alkyl groups and a substituted or unsubstituted oxymethylene group interposed in the chain, each of the fluorinated alkyl groups containing only one hydrogen atom and optionally containing at least one heteroatom in the chain, with the proviso that the hydrogen atom is part of a monofluoromethylene moiety.

[0005] Special table 2008-529975 publication Special table 2009-507840 publication

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

[0007] However, at least one of the two groups bonded to the oxygen of the ether compound is CF ３ -(trifluoromethyl group) and -CF ２ There are no known fluorine-containing ethers formed from groups that do not contain a unit represented by - (difluoromethylene group).

[0008] An object of the present disclosure is to provide a fluorine-containing ether compound in which at least one of two groups bonded to oxygen of the ether compound is a group that does not contain a trifluoromethyl group or a difluoromethylene group.

[0009] According to the present disclosure, a compound represented by the general formula: R １ -R ２ -O-R ３ -R ４ (In the formula, R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I or -CHFI, R ２ represents a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF-, or a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF- and -CH ２ a fluorinated alkylene group having 2 to 10 carbon atoms, consisting only of units represented by -, or a unit represented by -CFH-, -CH ２ R is a fluorine-containing alkylene group having 3 to 10 carbon atoms and consisting only of units represented by - and units represented by -CHI-, 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 is -CH ３ , -CH ２ F or -CHF ２ The present invention provides a fluorine-containing ether compound represented by the formula:

[0010] According to the present disclosure, it is possible to provide a fluorine-containing ether compound in which at least one of the two groups bonded to oxygen of the ether compound is a group that does not contain a trifluoromethyl group or a difluoromethylene group.

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

[0012] The fluorine-containing ether compound of the present disclosure is represented by the general formula: R １ -R ２-O-R ３ -R ４ (In the formula, R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I or -CHFI, and R ２ represents a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF-, or a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF- and -CH ２ a fluorinated alkylene group having 2 to 10 carbon atoms, consisting only of units represented by -, or a unit represented by -CFH-, -CH ２ is a fluorine-containing alkylene group having 3 to 10 carbon atoms and consisting only of units represented by - 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; R ４ is -CH ３ , -CH ２ F or -CHF ２ It is a fluorine-containing ether compound represented by the formula:

[0013] R １ is -CH ３ , -CH ２ F, -CHF ２ , -CH ２ I or -CHFI, preferably -CH ２ F, -CHF ２ or -CHFI, more preferably -CH ２ The fluorine-containing ether compound of the present disclosure is an ether compound in which at least one of the two groups bonded to the oxygen atom of the ether compound is CF at the terminal. ３ One of the features is that it does not have a -(trifluoromethyl group).

[0014] R ２ represents a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF-, or a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF- and -CH ２ a fluorinated alkylene group having 2 to 10 carbon atoms, consisting only of units represented by -, or a unit represented by -CFH-, -CH２ The fluorine-containing ether compound of the present disclosure is a fluorine-containing alkylene group having 3 to 10 carbon atoms, which is composed only of a unit represented by - and a unit represented by -CHI-. In the fluorine-containing ether compound of the present disclosure, at least one of the two groups bonded to oxygen of the ether compound necessarily contains a unit represented by -CHF-, and ２ One of its features is that it does not contain units indicated by -.

[0015] R ２ is a fluorinated alkylene group consisting only of units represented by —CHF—, R ２ Examples of the alkyl group include -(CHF) ｎ１ A fluorinated alkylene group represented by -(n1 is an integer of 1 to 10) is preferred.

[0016] R ２ is represented by -CHF- and -CH ２ When R is a fluorinated alkylene group consisting only of units represented by -, ２ Examples of the alkyl group include -CHF-(CHF-CHF) ｎ２ - (CH ２ ) ｍ１ a fluorinated alkylene group represented by the formula -(n2 is an integer of 1 to 4, and m1 is an integer of 1 or more), -(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), and the like.

[0017] R ２ is represented by -CHF- and -CH ２ When R is a fluorinated alkylene group consisting only of units represented by -, ２ As the group, -(CHF) ｎ２ -CH ２ -(n2 is an integer of 1 to 9), or -(CHF) ｎ７ -CH ２ -CH ２ - (CH ２ ) ｑA fluorinated alkylene group represented by the formula - (wherein n7 is an integer of 1 to 7, and q is an integer of 1 to 6) is preferred, and -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 of 0 to 2, and q is an integer of 1 to 6) is more preferred.

[0018] R ２ is a unit represented by -CFH-, -CH ２ When R is an alkylene group consisting of only units represented by - and units represented by -CHI-, ２ As the group, -(CHF) ｎ７ -CH ２ -CHI- (CH ２ ) ｑ A fluorinated alkylene group represented by the formula - (wherein n7 is an integer of 1 to 7, and q is an integer of 1 to 6) is preferred, and -CHF- (CHF-CHF) ｎ８ -CH ２ -CHI- (CH ２ ) ｑ A fluorinated alkylene group represented by the formula - (wherein n8 is an integer of 0 to 2, and q is an integer of 1 to 6) is more preferred.

[0019] In the general formula representing a fluorine-containing ether compound, R １ -R ２ The group represented by - is CH ２ F-CHF-, or the general formula: CH ２ F-CHF-(CHF-CHF) ｎ３ -CH ２ - (wherein n3 is an integer of 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 - (wherein n8 is an integer of 0 to 2, X １１is I or H, and q is an integer of 1 to 6).

[0020] n3 is preferably 0 or 1.

[0021] 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. 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 in the non-fluorinated alkylene group of R is preferably 1 or 2. ３ The fluorinated alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 or 2 carbon atoms.

[0022] R ３ Examples of the alkylene group include a single bond, a non-fluorinated alkylene group having 1 to 5 carbon atoms, and -(CHF) ｎ４ - (wherein n4 is an integer of 1 to 10), or -(CHF) ｎ５ -CH ２ Fluorinated alkylene groups represented by the formula - (wherein n5 is an integer of 1 to 9) are preferred.

[0023] R ４ is -CH ３ , -CH ２ F or -CHF ２ and -CH ３ or -CH ２ F is preferred.

[0024] In the general formula representing a fluorine-containing ether compound, R ４ -R ３ The group represented by - is a non-fluorinated alkyl group having 1 to 4 carbon atoms, or a group represented by the general formula: CH ２ F-CHF-(CHF-CHF) ｎ６ -CH ２ - (wherein n6 is an integer of 0 to 4) is preferred.

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

[0026] n6 is preferably 0 or 1.

[0027] Examples of the fluorine-containing ether compound include CH ２ FCHFOCH ３ , C.H. ２ FCHFCH ２ OCH ３ , C.H. ２ FCHFCH ２ OCHFCFH ２ , C.H. ２ FCHFCH ２ OCH ２ CH ３ , C.H. 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 -OCH３ At least one selected from the group consisting of:

[0028] The fluorine-containing ether compound of the present disclosure may be, for example, a compound represented by the general formula: R ４ -R ３ -OH (in the formula, R ３ and R ４ is as defined above) in the presence of a basic compound to give a compound represented by the general formula: CH ２ F-CHF-O-R ３ -R ４ (In the formula, R ３ and R ４ is as described above) (hereinafter, this may be referred to as the first production method).

[0029] In the first production method, the basic compound acts as a catalyst. The basic compound is preferably an inorganic basic compound, such as NaOH, KOH, CsOH, LiOH, or Ca(OH). ２ , Ba(OH) ２ Alkali metal hydroxides or alkaline earth metal hydroxides such as are more preferred.

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

[0031] The reaction of CHF═CHF with an alcohol can be carried out in a solvent, such as a polar organic solvent such as water, diethyl ether, glymes, dioxane, tetrahydrofuran, or acetonitrile.

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

[0033] The fluorine-containing ether compound of the present disclosure can be obtained, for example, by adding CHF=CHF to methanol to form a compound of the general formula: CH ２ F-CHF-(CHF-CHF) ｎ３ -CH２ OH (wherein n3 is an integer of 0 to 4), and reacting the fluorine-containing alcohol with R ４ -R ３ -X (wherein, R ３ and R ４ is as described above, X is a halogen atom or —OSO ３ R' (wherein R' is a non-fluorinated alkyl group or a fluorinated alkyl group) to obtain a compound represented by the general formula: CH ２ F-CHF-(CHF-CHF) ｎ３ -CH ２ -O-R ３ -R ４ (In the formula, n3, R ３ and R ４ The fluorine-containing ether compound represented by the formula (I) can be produced by a production method (hereinafter sometimes referred to as the second production method) for producing a fluorine-containing ether compound represented by the formula (I) (I)

[0034] In the second production method, first, CHF=CHF is added to methanol to produce a fluorine-containing alcohol.

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

[0036] The reaction of methanol with 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 radicals, which then abstract hydrogen atoms from the carbon atom to which the hydroxyl group of methanol is bonded, generating methanol radicals, and a reaction (so-called telomerization reaction) in which CHF=CHF is added to the methanol radicals proceeds.

[0037] The radical initiator is preferably an organic peroxide, and examples thereof 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 di-t-butyl peroxide. Of these, di-t-butyl peroxide is preferred as the radical initiator.

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

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

[0040] The temperature for the reaction of methanol with CHF=CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the reaction of methanol with CHF=CHF is preferably equal to or higher than the decomposition temperature of the radical polymerization initiator, and is preferably lower than the decomposition temperatures of the substrate and the product.

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

[0042] In the second production method, the obtained fluorine-containing alcohol is then reacted with R ４ -R ３ By reacting the fluorine-containing alcohol with a compound represented by -X, oxygen in the fluorine-containing alcohol is alkylated to produce a fluorine-containing ether compound.

[0043] When X is a halogen atom, a base such as sodium hydride is reacted with a fluorine-containing alcohol, and the resulting fluorine-containing alkoxide and R ４ -R ３ By reacting a compound represented by -X (X is a halogen atom) with the compound, a fluorine-containing ether compound can be produced.

[0044] Also, X is -OSO ３ When R′ (wherein R′ is a non-fluorinated alkyl group or a fluorinated alkyl group), for example, a fluorine-containing alcohol and R ４ -R ３ -X (X is -OSO ３ R') to produce a fluorine-containing ether compound.

[0045] R ４ -R ３ -X (X is -OSO ３ The compounds represented by (R ４ -R ３ -O-) ２ SO ２ (R ３ and R ４ is as described above) is preferred.

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

[0047] The fluorine-containing ether compound of the present disclosure may be, for example, a compound represented by the following formula: ２ and IF ５ by reacting the compound of the general formula: R １ -CHF-I (wherein R １ Ha-CHF ２ or —CHFI), and CHF═CHF is added to the first fluorine-containing alkyl iodide to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ８ -I (wherein, R １ As described above, n8 is 1 or 2), and reacting the first or second fluorine-containing alkyl iodide with a compound represented by the general formula: CH ２ =CH-(CH ２ ) ｑ-OH (wherein q is an integer of 1 or more), to give an unsaturated compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ８ -CH ２ -CHI- (CH ２ ) ｑ -OH (in the formula, R １ is as described above, n8 is an integer of 0 to 2, and q is an integer of 1 to 6), and optionally reducing the first fluorine-containing alcohol to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ８ -CH ２ -CH ２ - (CH ２ ) ｑ -OH (in the formula, R １ is as described above, n8 is an integer of 0 to 2, and q is an integer of 1 to 6), and ４ -R ３ -X (wherein, R ３ and R ４ is as described above, X is a halogen atom or —OSO ３ R' (wherein R' is a non-fluorinated alkyl group or a fluorinated alkyl group) to form a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ８ -CH ２ -CHX １１ - (CH ２ ) ｑ -O-R ３ -R ４ (wherein n8 is an integer of 0 to 2, X １１ is I or H, q is an integer from 1 to 6, R ３ and R ４ is as described above) (hereinafter, this may be referred to as the third production method).

[0048] In the third production method, first, CHF=CHF and I ２ and IF ５ by reacting the compound of the general formula: R １ -CHF-I (wherein R １Ha-CHF ２ or —CHFI), and CHF═CHF is added to the first fluorine-containing alkyl iodide to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ８ -I (wherein, R １ As described above, the second fluorine-containing alkyl iodide in which n8 is 1 or 2) is produced.

[0049] I ２ and IF ５ The amount of is preferably 0.5 to 2 moles per mole of CHF=CHF.

[0050] CHF = CHF and I ２ and IF ５ The reaction can be carried out in a solvent.

[0051] CHF = CHF and I ２ and IF ５ The reaction temperature can be appropriately selected, but is preferably −78 to 200° C. ２ and IF ５ The pressure of the reaction can be appropriately selected, but is preferably 0 to 5.0 MPaG. ２ and IF ５ The reaction time can be appropriately selected, 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 serves as a telogen and CHF=CHF serves as a taxogen, and a second fluorine-containing alkyl iodide is produced by this reaction.

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

[0054] The reaction of the first fluorine-containing alkyl iodide with CHF=CHF can be carried out in the presence of a radical initiator, such as an organic peroxide or an azo compound.

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

[0056] Examples of the azo compounds include azobisisobutyronitrile.

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

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

[0059] The temperature for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably −78 to 200° C. The temperature for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF is preferably not less than the decomposition temperature of the radical polymerization initiator, and is preferably lower than the decomposition temperatures of the substrate and the product.

[0060] The pressure for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably 0 to 5.0 MPaG. The time for the reaction of the first fluorine-containing alkyl iodide with CHF═CHF can be appropriately selected, but is preferably 0.1 to 96 hours.

[0061] In the third production method, next, the first or second fluorine-containing alkyl iodide and a compound represented by the general formula: CH ２ =CH-(CH ２ ) ｑ -OH (wherein q is an integer of 1 or more), to give an unsaturated compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ８ -CH ２ -CHI- (CH ２) ｑ -OH (in the formula, R １ As described above, n8 is an integer of 0 to 2, and q is an integer of 1 to 6) to produce a fluorine-containing alcohol represented by the formula (1).

[0062] Fluorine-containing alcohol R １ is R of the first or second fluorine-containing alkyl iodide １ is the same as -CHF ２ Or -CHFI.

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

[0064] The reaction of the first or second fluorine-containing alkyl iodide with the unsaturated compound can be carried out in the presence of a compound capable of generating radicals, such as an organic peroxide or an azo compound.

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

[0066] Examples of the azo compounds include azobisisobutyronitrile.

[0067] The amount of the 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 the radical-generating compound used is preferably 0.001 to 1 mole per mole of the first or second fluorine-containing alkyl iodide.

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

[0070] In the third production method, the obtained fluorine-containing alcohol is then reacted with R ４ -R ３ By reacting the fluorine-containing alcohol with a compound represented by -X, oxygen in the fluorine-containing alcohol is alkylated to produce a fluorine-containing ether compound.

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

[0072] Also, X is -OSO ３ When R′ (wherein R′ is a non-fluorinated alkyl group or a fluorinated alkyl group), for example, a fluorine-containing alcohol and R ４ -R ３ -X (X is -OSO ３ R') to produce a fluorine-containing ether compound.

[0073] R ４ -R ３ -X (X is -OSO ３ The compounds represented by (R ４ -R ３ -O-) ２ SO ２ (R ３ and R ４ is as described above) is preferred.

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

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

[0076] The fluorine-containing ether compound of the present disclosure may be, for example, a compound represented by the following formula: ２ and IF ５ by reacting the compound of the general formula: R １ -CHF-I (wherein R １ Ha-CHF ２ or —CHFI), and CHF═CHF is added to the first fluorine-containing alkyl iodide to obtain a compound represented by the general formula: R １ -CHF- (CHF-CHF) ｎ８ -I (wherein, R １ As described above, n8 is 1 or 2), and reacting the first or second fluorine-containing alkyl iodide with a compound represented by the general formula: CH ２ =CH-(CH ２ ) ｑ -O-R ３ -R ４ (wherein q is an integer of 1 or more, R ３ and R ４ represents R contained in the fluorinated ether compound of the present disclosure. ３ and R ４ (as described above) to form a compound represented by the general formula: １ -CHF- (CHF-CHF) ｎ８ -CH ２ -CHI- (CH ２ ) ｑ -O-R ３ -R ４ (In the formula, R １ , R ３ and R４ As described above, n8 is an integer of 0 to 2, and q is an integer of 1 to 6) (hereinafter, this may be referred to as the fourth production method).

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

[0078] a first or second fluorine-containing alkyl iodide and a compound represented by the general formula: CH ２ =CH-(CH ２ ) ｑ -O-R ３ -R ４ The reaction of the first or second fluorine-containing alkyl iodide with an unsaturated compound represented by the general formula: CH ２ =CH-(CH ２ ) ｑ The reaction with the unsaturated compound represented by —OH can be carried out in the same manner as described in the third production method.

[0079] The resulting fluorine-containing ether compound is reduced to give a compound of the general formula: R １ -CHF- (CHF-CHF) ｎ８ -CH ２ -CH ２ - (CH ２ ) ｑ -O-R ３ -R ４ (In the formula, R １ , R ３ and R ４ is as described above, n8 is an integer of 0 to 2, and q is an integer of 1 to 6. The reduction can be carried out, for example, using a metal catalyst and hydrogen, or using zinc as a reducing agent.

[0080] The composition of the present disclosure may contain the above-mentioned fluorine-containing ether compound and a solvent. 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 composition of the present disclosure may contain the above-mentioned fluorinated ether compound and other components such as surfactants, stabilizers, pigments, dyes, colorants, antioxidants, and flame retardants.

[0082] The composition of the present disclosure may contain the above-mentioned fluorinated ether compound and other fluorinated ether compounds different from the above-mentioned fluorinated ether compounds. Examples of other fluorinated ether compounds include hydrofluoroether compounds.

[0083] The fluorinated ether compounds and compositions of the present disclosure can be suitably used as heat transfer fluids, cleaning solvents, cell size adjusters for adjusting the cell size of foam insulation materials, fire extinguishing agents, carrier fluids, working fluids, polymerization solvents, abrasives, drying agents, resist spreaders, resist strippers, etc. For example, they can be used for the applications of the hydrofluoroether compounds described in JP-A-2009-507840.

[0084] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

[0085] The main embodiments of the present disclosure are as follows.

[0086] <1> According to a first aspect of the present disclosure, there is provided a compound represented by the general formula: R １ -R ２ -O-R ３ -R ４ (In the formula, R １ is -CH ３ , -CH ２F, -CHF ２ , -CH ２ I or -CHFI, R ２ represents a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF-, or a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF- and -CH ２ a fluorinated alkylene group having 2 to 10 carbon atoms, consisting only of units represented by -, or a unit represented by -CFH-, -CH ２ R is a fluorine-containing alkylene group having 3 to 10 carbon atoms and consisting only of units represented by - and units represented by -CHI-, 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 is -CH ３ , -CH ２ F or -CHF ２ <2> According to a second aspect of the present disclosure, there is provided a fluorine-containing ether compound represented by the formula: R １ But -CH ２ F, -CHF ２ <3> According to a third aspect of the present disclosure, there is provided a fluorine-containing ether compound, wherein R ２ The general formula: -(CHF) ｎ１ - (wherein n1 is an integer of 1 to 10), or a fluorinated alkylene group represented by the general formula: -(CHF) ｎ２ -CH ２ -(wherein n2 is an integer of 1 to 9), 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), or -(CHF) ｎ７ -CH ２ -CHI- (CH ２ ) ｑAccording to the first or second aspect, there is provided a fluorinated ether compound, wherein R １ -R ２ - but CH ２ F-CHF-, or the general formula: CH ２ F-CHF-(CHF-CHF) ｎ３ -CH ２ - (wherein n3 is an integer of 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 - (wherein n8 is an integer of 0 to 2, X １１ is I or H, and q is an integer of 1 to 6). <5> According to a fifth aspect of the present disclosure, there is provided a fluorinated ether compound according to any one of the first to third aspects, wherein R ３ a single bond, a non-fluorinated alkylene group having 1 to 5 carbon atoms, a group represented by the general formula: -(CHF) ｎ４ - (wherein n4 is an integer of 1 to 10), or a fluorinated alkylene group represented by the general formula: -(CHF) ｎ５ -CH ２ According to a sixth aspect of the present disclosure, there is provided a fluorinated ether compound, wherein R ４ -R ３ - is a non-fluorinated alkyl group having 1 to 4 carbon atoms, or a group represented by the general formula: CH ２ F-CHF-(CHF-CHF) ｎ６ -CH ２ According to a seventh aspect of the present disclosure, there is provided a fluorine-containing ether compound, wherein the fluorine-containing ether compound is a fluorinated alkyl group represented by the formula: ２ FCHFOCH ３ , C.H.２ FCHFCH ２ OCH ３ ,H ２ FCHFCH ２ OCHFCFH ２ 、H ２ FCHFCH ２ OCH ２ CH ３ 、H ２ ΦCHΦCHΦCHΦCH ２ OCH ３ 、\HF ２ -CHF-CH ２ -CHI-H ２ -OCH ３ 、\HF ２ -CHF-CH ２ -CH ２ -CH ２ -OCH ３ 、\HF ２ -CHF-CH ２ -CH ２ -CH ２ -OCHFCFH ２ 、\HF ２ -CHF-CH ２ -CH ２ -CH ２ -OCH ２ CH ３ 、\HF ２ -CHF-CH ２ -CHI-H 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 ３The fluorinated ether compound according to any one of the first to sixth aspects is at least one selected from the group consisting of: <8> According to an eighth aspect of the present disclosure, there is provided a composition containing the fluorinated ether compound according to any one of the first to seventh aspects and 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 a ninth aspect of the present disclosure, there is provided a heat transfer fluid containing the fluorinated ether compound according to any one of the first to seventh aspects or the composition according to the eighth aspect. <10> According to a tenth aspect of the present disclosure, there is provided a cleaning solvent containing the fluorinated ether compound according to any one of the first to seventh aspects or the composition according to the eighth aspect.

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

[0088] Example 1 Synthesis of 1,1,2-trifluoro-2-iodoethane In a 300 mL pressure vessel, 37.1 g of iodine, IF ５ After the vessel was cooled to -78°C, 10 g of (E)-1,2-difluoroethene was added to the vessel, and the vessel was heated at 80°C for 20 hours. After the vessel was cooled with ice water, the contents of the pressure vessel were washed with water and then added with 5% Na ２ S ２ O ４ Further washing with aqueous solution gave the title compound in 5.8 g. １９ F NMR (282MHz, CDCl ３ ): δ-169.1 to -169.4 (m, 1F), -124.0 to -124.3 (m, 1F). １H NMR (400 MHz, 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 with ice water, the contents of the pressure vessel were analyzed by gas chromatography-mass spectrometry. The title compound was found to be produced at an area ratio of 75.9% compared to 24.1% for the starting material, 1,1,2-trifluoro-2-iodoethane. LRMS (EI 70 eV) 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 charged with nitrogen up 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 produced in an area ratio of 65.8% (total of two isomers) relative to the area ratio of the starting material 1,1,2-trifluoro-2-iodoethane, 34.2%. LRMS (EI 70 eV) m / z (%): 197 ([M-I] ＋ , 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 vessel. After adding 4 drops of 2 M aqueous HCl, the vessel was cooled to -78°C, purged with nitrogen, and then stirred at room temperature for 2 hours. Analysis of the contents of the vessel by gas chromatography-mass spectrometry revealed that the raw materials had disappeared and the title compound had been produced. LRMS (EI 70 eV) m / z (%): 166 ([M-CHOH] ＋ , 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 is -CHF ２ , -CH ２ I or -CHFI, R ２ represents a fluorinated alkylene group having 1 to 10 carbon atoms, which is composed only of units represented by -CHF-, or a unit represented by -CHF- and ２ A fluorinated alkylene group having 2 to 10 carbon atoms, which is composed only of units represented by -, or a unit represented by -CFH-, -CH ２ a fluorine-containing alkylene group having 3 to 10 carbon atoms and consisting only of units represented by - and units represented by -CHI-, R ３ represents 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 is -CH ３ , -CH ２ F or -CHF ２ (It is) A fluorine-containing ether compound represented by the formula:

2. R １ But -CHF ２ 2. The fluorine-containing ether compound according to claim 1, which is -CHFI or -CHFI.

3. R ２ but, General formula: - (CHF) ｎ１ (wherein n1 is an integer from 1 to 10) or a fluorinated alkylene group represented by General formula: - (CHF) ｎ２ -CH ２ - (wherein n2 is an integer from 1 to 9) or a fluorinated alkylene group represented by - (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 - (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) The fluorine-containing ether compound according to claim 1, wherein

4. R １ -R ２ -but, General formula: CHF ２ -CHF- (CHF-CHF) ｎ８ -CH ２ -CHX １１ - (CH ２ ) ｑ - (wherein n8 is an integer from 0 to 2; X １１ is I or H, and q is an integer of 1 to 6). The fluorine-containing ether compound according to claim 1, wherein

5. R ３ but, a 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 a fluorinated alkylene group represented by General formula: - (CHF) ｎ５ -CH ２ - (wherein n5 is an integer from 1 to 9) A fluorinated alkylene group represented by the formula: The fluorine-containing ether compound according to claim 1, wherein

6. R ４ -R ３ -but, a non-fluorinated alkyl group having 1 to 4 carbon atoms, or General formula: CH ２ F-CHF-(CHF-CHF) ｎ６ -CH ２ - (wherein n6 is an integer from 0 to 4) A fluorinated alkyl group represented by the formula: The fluorine-containing ether compound according to claim 1, wherein

7. CHF ２ -CHF-CH ２ -CHI-CH ２ -OCH ３ , C.H.F. ２ -CHF-CH ２ -CH ２ -CH ２ -OCH ３ , C.H.F. ２ -CHF-CH ２ -CH ２ -CH ２ -OCHFCFH ２ , C.H.F. ２ -CHF-CH ２ -CH ２ -CH ２ -OCH ２ CH ３ , C.H.F. 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 The fluorine-containing ether compound according to claim 1, which is at least one selected from the group consisting of:

8. The fluorine-containing ether compound according to claim 1, and A composition containing 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. 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.

11. A fluorine-containing ether compound which is at least one selected from the group consisting of CH 2 FCHFCH 2 OCHFCFH 2 , CH 2 FCHFCH 2 OCH 2 CH 3 , and CH 2 FCHFCHFCHFCHCH 2 OCH 3 .

12. The fluorine-containing ether compound according to claim 11, and A composition containing 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.

13. A heat transfer fluid comprising the fluorine-containing ether compound of claim 11 or the composition of claim 12.

14. A cleaning solvent comprising the fluorine-containing ether compound according to claim 11 or the composition according to claim 12.

15. General formula: R 1 -R 2 -O-R 3 -R 4 (In the formula, R 1 is —CH 3 , —CH 2 F, —CHF 2 , —CH 2 I or —CHFI; R 2 is a fluorinated alkylene group having 1 to 10 carbon atoms and consisting only of units represented by -CHF-, or a fluorinated alkylene group having 2 to 10 carbon atoms and consisting only of units represented by -CHF- and -CH 2 -, or a fluorinated alkylene group having 3 to 10 carbon atoms and consisting only of units represented by -CFH-, -CH 2 - and -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 is —CH 3 , —CH 2 F or —CHF 2 . and a fluorine-containing ether compound represented by the formula: A composition containing 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.

16. A heat transfer fluid comprising the composition of claim 15.

17. A cleaning solvent comprising the composition of claim 15.