JP7339573B2 - New fluorine-containing compound - Google Patents

Description

The present disclosure relates to novel fluorine-containing compounds.

Fluorine-containing compounds have the advantage of being excellent in properties such as heat resistance, oxidation resistance and weather resistance, and various fluorine-containing compounds have been proposed.

ただし、式中の記号は以下の意味を示す。Ｑ^１、Ｑ^２は、それぞれ独立にエーテル性酸素原子を有していてもよい炭素数１～６のペルフルオロアルキレン基であり、Ｑ^１、Ｑ^２の少なくとも一方がエーテル性酸素原子を有する。Ｒ^ｆ１は、エーテル性酸素原子を有していてもよいペルフルオロアルキル基であり、Ｘは酸素原子、窒素原子または炭素原子であって、Ｘが酸素原子の場合ａ＝０であり、Ｘが窒素原子の場合ａ＝１であり、Ｘが炭素原子の場合ａ＝２である。Ｙは、フッ素原子または１価のペルフルオロ有機基。
また、特許文献２には、下式（３ａ－１１）で表される化合物が記載されている。

式中、ａは１を示し、ｂは１を示し、Ｑ^Ｆは単結合またはエーテル性酸素原子を含有していてもよい炭素数１～６のペルフルオロアルキレン基を示す。 For example, in Patent Document 1, a polymer comprising a repeating unit based on a fluorine-containing monomer having radical polymerization reactivity, the repeating unit has a structure having an ionic group represented by the following formula (α) in a side chain. An electrolyte material for a polymer electrolyte fuel cell is described, which is characterized by comprising:

However, the symbols in the formula have the following meanings. Q ¹ and Q ² are each independently a C 1-6 perfluoroalkylene group optionally having an etheric oxygen atom, and at least one of Q ¹ and Q ² has an etheric oxygen atom. R ^f1 is a perfluoroalkyl group optionally having an etheric oxygen atom, X is an oxygen atom, a nitrogen atom or a carbon atom, a=0 when X is an oxygen atom, and X is nitrogen If it is an atom then a=1 and if X is a carbon atom then a=2. Y is a fluorine atom or a monovalent perfluoro organic group.
Further, Patent Document 2 describes a compound represented by the following formula (3a-11).

In the formula, a represents 1, b represents 1, and Q ^F represents a single bond or a C 1-6 perfluoroalkylene group which may contain an etheric oxygen atom.

Japanese Patent No. 5130911 Japanese Patent No. 4792972

An object of the present disclosure is to provide a novel fluorine-containing compound.

The present disclosure provides the following general formula (1):
Rf ¹ -CF ₂ -O-CF=CF-O-CF ₂ -Rf ² (1)
(Wherein, Rf ¹ is —F or a fluorine-containing organic group having 1 to 15 carbon atoms, and Rf ² is a fluorine-containing organic group having 1 to 15 carbon atoms.) A compound (hereinafter also referred to as "first fluorine-containing compound of the present disclosure") is provided.

Rf ¹ is -F, a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated alkenyl group having 2 to 10 carbon atoms, or a fluorinated alkynyl group having 2 to 10 carbon atoms, and Rf ² is a fluorinated alkyl group having 1 to 10 carbon atoms. is preferably a fluorinated alkyl group, a fluorinated alkenyl group having 2 to 10 carbon atoms, or a fluorinated alkynyl group having ² to ¹⁰ carbon atoms, and the fluorinated alkyl group, fluorinated alkenyl group and A fluorinated alkynyl group may have an atom bonded to a carbon atom substituted with a functional group and may contain an etheric oxygen atom.

Rf ¹ above is —F, a fluorinated alkyl group having 1 to 10 carbon atoms, Rf ² is preferably a fluorinated alkyl group having 1 to 10 carbon atoms, and the fluorinated alkyl group for Rf ¹ and Rf ² The group may be substituted with a functional group on the atom attached to the carbon atom and may contain an etheric oxygen atom.

One or both of Rf ¹ and Rf ² are -SO ₂ X, -COX, -POX ₂ (wherein X is a halogen atom, -OH, -OM (M is a monovalent metal atom), - It is preferably a fluorinated alkyl group having 1 to 10 carbon atoms containing SO ₂ NHSO ₂ R or —SO ₂ NHR (R is an alkyl group having 1 to 5 carbon atoms), and the fluorinated alkyl group may contain an etheric oxygen atom.

Both Rf ¹ and Rf ² are groups represented by —Rf ³ —SO ₂ F (wherein Rf ³ is a chain or branched fluorinated alkylene group having 1 to 10 carbon atoms). Preferably.

Rf ¹ above is a group represented by —Rf ⁴ —SO ₂ F (wherein Rf ⁴ is a chain or branched fluorinated alkylene group having 1 to 10 carbon atoms), and Rf ² is , —Rf ⁵ —SO ₂ F (wherein Rf ⁵ is a chain or branched C 1-10 fluorinated alkylene group containing an etheric oxygen atom). preferable.

The present disclosure also provides the following general formula (2):
Rf ⁶ -O-CFX ^a -CFY ^a -O-Rf ⁶ (2)
(wherein Rf ⁶ is the same or different and is -F or a fluorine-containing organic group having 1 to 16 carbon atoms; X ^a and Y ^a are the same or different and are -H, -F, -Cl, —Br or —I, except when both X ^a and Y ^a are —H or —F). to provide a fluorine-containing compound of

Rf ⁶ is preferably the same or different and is -F, a fluorinated alkyl group having 1 to 11 carbon atoms, a fluorinated alkenyl group having 2 to 11 carbon atoms or a fluorinated alkynyl group having 2 to 11 carbon atoms. , the fluorinated alkyl group, fluorinated alkenyl group and fluorinated alkynyl group in Rf ⁶ may be substituted with a functional group at the atom bonded to the carbon atom and may contain an etheric oxygen atom.

The above Rf ⁶ is preferably the same or different and is -F or a fluorinated alkyl group having 1 to 11 carbon atoms, and the fluorinated alkyl group has an atom bonded to a carbon atom substituted with a functional group. may contain an etheric oxygen atom.

One or both of the two Rf ⁶ are -SO ₂ X, -COX, -POX ₂ (wherein X is a halogen atom, -OH, -OM (M is a monovalent metal atom), - SO ₂ NHSO ₂ R or —SO ₂ NHR (R is an alkyl group having 1 to 5 carbon atoms)) is preferably a fluorinated alkyl group having 1 to 11 carbon atoms, and the fluorine in Rf ⁶ The alkyl group may contain an etheric oxygen atom.

Both of the above two Rf ⁶ are groups represented by —Rf ⁷ —SO ₂ F (wherein Rf ⁷ is a chain or branched fluorinated alkylene group having 1 to 11 carbon atoms). Preferably.

One of Rf ⁶ is a group represented by —Rf ⁸ —SO ₂ F (wherein Rf ⁸ is a chain or branched fluorinated alkylene group having 1 to 11 carbon atoms), and Rf The other of ⁶ is a group represented by -Rf ⁹ -SO ₂ F (wherein Rf ⁹ is a chain or branched C 1-11 fluorinated alkylene group containing an etheric oxygen atom). is preferred.

It is preferred that one of X ^a and Y ^a is —F and the other is —H, —Cl, —Br or —I.

The present disclosure provides novel fluorine-containing compounds.

The present disclosure is described in detail below.

The first fluorine-containing compound of the present disclosure has the following general formula (1):
Rf ¹ -CF ₂ -O-CF=CF-O-CF ₂ -Rf ² (1)
(Wherein, Rf ¹ is —F or a fluorine-containing organic group having 1 to 15 carbon atoms, and Rf ² is a fluorine-containing organic group having 1 to 15 carbon atoms.) be.
The fluorine-containing organic group is not particularly limited as long as it is a monovalent organic group containing at least one fluorine atom.
Here, the monovalent organic group is generally a fluorine-containing aliphatic group, and refers to a saturated or unsaturated, straight-chain or branched fluorine-containing aliphatic group. It may be interposed by an atom, a nitrogen atom, a sulfonyl group, an aromatic ring, or the like, and may have a functional group bonded to the carbon atom.
The above functional groups are not particularly limited, but examples include -SO ₂ X, -COX, -POX ₂ (wherein X is a halogen atom, -OH, -OM (M is a monovalent metal atom), -SO ₂ NHSO ₂ R or —SO ₂ NHR (R is an alkyl group having 1 to 5 carbon atoms)).
Examples of the halogen atom for X include -F, -Cl, -Br, and -I.
In the above M, the monovalent metal atom includes Li, Na, K, Rb, Cs, Ag and the like.
Examples of R above include a chain or branched methyl group, ethyl group, propyl group, butyl group, and the like.

The above Rf ¹ is preferably -F, a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated alkenyl group having 2 to 10 carbon atoms, or a fluorinated alkynyl group having 2 to 10 carbon atoms. Atoms bonded to atoms may be substituted with functional groups and may contain etheric oxygen atoms.
Rf ² is preferably a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated alkenyl group having 2 to 10 carbon atoms, or a fluorinated alkynyl group having 2 to 10 carbon atoms, and these are bonded to a carbon atom. Atoms may be substituted with functional groups, and may contain etheric oxygen atoms.
In this specification, when the atoms bonded to the carbon atoms of the fluorinated alkyl group, fluorinated alkenyl group and fluorinated alkynyl group are substituted with a functional group containing a carbon atom, the fluorinated alkyl group, fluorine The number of carbon atoms in the alkenyl group or fluorinated alkenyl group does not include the number of carbon atoms in the functional group.

The fluorinated alkyl groups in Rf ¹ and Rf ² may be linear or branched. The fluorinated alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.

Specific examples of the linear fluorinated alkyl group include CF ₃ —, CF ₃ CH ₂ —, CF 3 CF ₂ —, CF ₃ CH ₂ CH ₂ —, CF ₃ CF _{2 CH 2} —, CF ₃ CF _{2 CF2- , CF3CH2CF2- , CF3CH2CH2CH2- , CF3CF2CH2CH2- , CF3CH2CF2CH2- , CF3CF2CF2CH2 _ _ _ _ _ _ _ _ _ - , CF3CF2CF2CF2- , CF3CF2CH2CF2- , CF3CH2CH2CH2CH2- , CF3CF2CH2CH2CH2- , CF3CH2 _ _ _ _ _ _ _ _ _ CF2CH2CH2- , CF3CF2CF2CH2CH2- , CF3CF2CF2CF2CH2- , CF3CF2CH2CF2CH2- , CF3CF2CH2 _ _ _ _ _ _ _ _ _ _ _ _ CH2CH2CH2- , CF3CF2CF2CF2CH2CH2- , CF3CF2CH2CF2CH2CH2- , HCF2- , HCF2CH2- , HCF2CF2 _ _ _ _ _ _ _ _ _ - , HCF2CH2CH2- , HCF2CF2CH2- , HCF2CH2CF2- , HCF2CF2CH2CH2- , HCF2CH2CF2CH2- , HCF2CF2 _ _ _ _ _ _ CF2CF2- , HCF2CF2CH2CH2CH2- , HCF2CH2CF2CH2CH2- , HCF2CF2CF2CF2CH2- , HCF2CF2CF2CF2 _ _ _ _ _ _ _ _ _ _ _ _ CH2CH2- , FCH2- , FCH2CH2- , FCH2CF2- , FCH2CF2CH2- , FCH2CF2CF2- , CH3CF2CH2- , CH3CF2 _ _ _ CF2- , CH3CF2CH2CF2- , CH3CF2CF2CF2- , CH3CH2CF2CF2- , CH3CF2CH2CF2CH2- , CH3CF2 _ _ _ _ _ _ _ _ _ CF2CF2CH2- , CH3CF2CF2CH2CH2- , CH3CH2CF2CF2CH2- , CH3CF2CH2CF2CH2CH2- , CH3CF2 _ _ _ _ _ _ _ _ _ _ _ _} CH ₂ CF ₂ CH ₂ CH ₂ — and the like.

As a branched fluorinated alkyl group,

etc.

From the viewpoint of chemical durability, the fluorinated alkyl group is preferably a perfluoroalkyl group such as CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ —. , CF ₃ CF(CF ₃ )—, or CF ₃ C(CF ₃ ) ₂ —.

When the atoms bonded to the carbon atoms of Rf ¹ and Rf ² are not substituted with functional groups and are fluorinated alkyl groups containing no etheric oxygen atoms, the first fluorine-containing compound of the present disclosure is F- _CF2 -O-CF=CF-O- _CF2 - _CF3 , _CF3 - _CF2 -O-CF=CF-O- _{CF2 - CF3} , CF3CF2 _- CF2- _O -CF =CF _- O- _{CF2 - CF2CF3} , _{CF3CF2CF2 - CF2 - O} -CF=CF _{- O} - _{CF2 -} CF2CF2CF3 _{, CF3CF2CF2CF2- CF2} -O-CF=CF-O- _{CF2 - CF2CF2CF2CF3} , _CF3CF ( _{CF3 )} -CF2 _{- O} -CF=CF-O- _CF2 -CF( _CF3 ) CF ₃ , CF ₃ C(CF ₃ ) ₂ -CF ₂ -O-CF=CF-O-CF ₂ -C(CF ₃ ) ₂ CF ₃ and the like.

Examples of the fluorinated alkyl group containing an etheric oxygen atom include CF ₃ —O—CH ₂ —, CF ₃ —O—CF ₂ —, CF ₃ CH ₂ —O—CH ₂ —, CF ₃ —O—CH _{2 CH2-} , _CF3CF2 -O- _CH2- , _CF3 - _O -CF2CH2-, _CF3CF2 - _O - _CF2- , _{CF3- O - CF2CF2- , CF3} CH ₂ —O—CF ₂ —, CF ₃ —O—CH ₂ CF ₂ — and the like.
The fluorinated alkyl group is preferably a perfluoroalkyl group, such as CF ₃ —O—CF ₂ —, CF ₃ CF ₂ —O—CF ₂ —, CF ₃ —O—CF ₂ CF ₂ —, or CF _{3 .} CF ₂ --O--CF(CF ₃ )-- is preferred.

When at least one of Rf ¹ and Rf ² is a fluorinated alkyl group containing an etheric oxygen atom in which the atom bonded to the carbon atom is not substituted with a functional group, the first fluorine-containing compound of the present disclosure as CF ₃ -O-CF ₂ -CF ₂ -O-CF=CF-O-CF ₂ -CF ₂ -O-CF ₃ , CF ₃ CF ₂ -O-CF ₂ -CF ₂ -O-CF= CF-O- _CF2 - _CF2 -O- _CF2CF3 , CF3-O- _CF2CF2 - _{CF2 -} O-CF=CF-O- _{CF2 - CF2CF2} - _{O - CF3} , CF ₃ CF ₂ -O-CF(CF ₃ )-CF ₂ -O-CF=CF-O-CF ₂ -CF(CF ₃ )-O-CF ₂ CF ₃ , CF ₃ -CF ₂ -O-CF =CF-O-CF ₂ -CF(CF ₃ )-O-CF ₂ CF ₃ and the like.

The above fluorinated alkenyl groups may be linear or branched. The fluorinated alkenyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
Examples of the fluorinated alkenyl groups include CF ₂ ═CH—, CF ₂ ═CF—, CF ₃ CH═CH—, CF ₂ ═CHCH ₂ —, CF ₃ CF═CH—, CF ₂ ═CFCH ₂ —, CF _{3 CF} =CF-, _CF2 = _CFCF2- , CF3CH=CF-, _CF2 =CHCF2-, HCF=CH-, HCF=CF-, _HCF2CH =CH-, HCF= _{CHCH2- ,} HCF ₂ CF=CH-, HCF=CFCH ₂ -, HCF ₂ CH=CF-, HCF=CHCF ₂ -, CH ₃ CF=CH-, CH ₂ =CFCF ₂ - and the like.
The fluorinated alkenyl group is preferably a perfluoroalkenyl group, preferably CF ₂ =CF-, CF ₃ CF=CF- or CF ₂ =CFCF ₂ -.
When Rf ¹ and Rf ² are fluorinated alkenyl groups, the first fluorine-containing compound of the present disclosure includes CF ₂ =CF-CF ₂ -O-CF=CF-O-CF ₂ -CF=CF ₂ , CF ₃ CF=CF-CF ₂ -O-CF=CF-O-CF ₂ -CF=CFCF ₃ , CF ₂ =CFCF ₂ -CF ₂ -O-CF=CF-O-CF ₂ -CF ₂ CF= CF ₂ and the like.

The above fluorinated alkynyl groups may be linear or branched. The fluorinated alkynyl group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
Examples of the fluorinated alkynyl group include CF≡C—, CF ₃ C≡C—, CF≡CCH ₂ —, CF≡CCF ₂ —, HCF ₂ C≡C—, CH≡CCF ₂ —, and the like.
As the fluorinated alkynyl group, a perfluoroalkynyl group is preferable, and CF≡C—, CF ₃ C≡C—, or CF≡CCF ₂ — is preferable.
When Rf ¹ and Rf ² are fluorinated alkynyl groups, the first fluorine-containing compound of the present disclosure includes CF≡C—CF ₂ —O—CF=CF—O—CF ₂ —C≡CF, CF ₃ C≡C-CF ₂ -O-CF=CF-O-CF ₂ -C≡CCF ₃ , CF≡CCF ₂ -CF ₂ -O-CF=CF-O-CF ₂ -CF ₂ C≡CF, etc. mentioned.

Compounds represented by the general formula (1) are those in which one or both of Rf ¹ and Rf ² are —SO ₂ X, —COX, —POX ₂ (wherein X is a halogen atom, —OH, —OM (M is a monovalent metal atom), —SO ₂ NHSO ₂ R, or —SO ₂ NHR (R is an alkyl group having 1 to 5 carbon atoms)). Preferably, the fluorinated alkyl group may contain an etheric oxygen atom. By having the above functional groups, it can be used, for example, as a monomer for synthesizing a polymer that is a raw material for fuel cell materials (catalyst layer binder, electrolyte membrane).
Such a fluorinated alkyl group has the formula: Y ¹ -Rf ³ - (Rf ³ is a chain or branched fluorinated alkylene group having 1 to 10 carbon atoms and containing an etheric oxygen atom. Y ¹ is —SO ₂ X, —COX, —POX ₂ (wherein X is a halogen atom, —OH, —OM (M is a monovalent metal atom), —SO ₂ NHSO ₂ R , or —SO ₂ NHR (R is an alkyl group having 1 to 5 carbon atoms).
The halogen atom for X is preferably -F, -Cl, -Br or -I, more preferably -F.
When X is a halogen atom, copolymerizability with a fluorine-containing monomer such as tetrafluoroethylene is good, and it is easy to obtain a high-molecular-weight polymer, which is preferable. After the polymerization step, it is usually preferable to convert X to —OH or —OM (M is a monovalent metal atom) by reacting with an alkaline solution or the like.
In the above M, the monovalent metal atom includes Li, Na, K, Rb, Cs, Ag and the like.
In Rf ³ , the number of carbon atoms in the fluorinated alkylene group is preferably 1 to 8, more preferably 1 to 6, even more preferably 1 to 4, because the amount of functional groups per unit weight can be increased.
Examples of Rf ³ include -CF ₂ -*, -CF 2 CF ₂ -*, _{-CF 2 CF 2} CF ₂ -*, -CF(CF ₃ )-*, -CF ₂ CF ₂ CF ₂ CF ₂ -*, -CF(CF ₃ )CF ₂ -*, -CF ₂ -O-CF ₂ -*, -CF ₂ CF ₂ -O-CF ₂ -*, -CF ₂ -O-CF ₂ CF ₂ -* , -CF ₂ CF ₂ -O-CF ₂ CF ₂ -*, -CF ₂ CF ₂ -O-CF(CF ₃ )CF ₂ -*, etc. (* in the above formula binds to Y ¹ side).

In general formula (1), both Rf ¹ and Rf ² are —Rf ³ —SO ₂ F (wherein Rf ³ is a chain or branched C 1-10 fluorinated alkylene group. ) is one of preferred embodiments. In Rf ¹ and Rf ² , Rf ³ may be the same or different. As described above, by having two functional groups, it is possible to synthesize a polymer having a large amount of functional groups per unit weight when used as a monomer. Also, a polymer having a large amount of functional groups per unit weight can improve ion conductivity when used as an electrolyte material. For example, when used as —SO ₃ H in fuel cell materials, it is useful as a binder for electrolyte membranes and catalyst layers. —SO ₃ Li can be used as an electrolyte material for lithium batteries. Moreover, when used for a polymer actuator, it is useful because it can increase the displacement. Also, when added to paints, it is useful because effects such as hydrophilization can be obtained with the addition of a small amount.
Examples of Rf ³ include -CF ₂ -*, -CF ₂ CF ₂ -*, -CF ₂ CF ₂ CF ₂ -*, -CF(CF ₃ )-*, -CF ₂ CF ₂ CF ₂ CF ₂ -* , -CF(CF ₃ )CF ₂ -*, etc., and -Rf ³ - in Rf ¹ and Rf ² may be the same or different (* in the above formula binds to -SO ₂ F side).
Preferred specific examples of such fluorine-containing compounds include FSO ₂ -CF ₂ -CF ₂ -O-CF=CF-O-CF ₂ -CF ₂ -SO ₂ F, FSO ₂ -CF ₂ CF ₂ -CF ₂ - _O -CF=CF-O- _CF2 - _CF2CF2 - _SO2F , _{FSO2 -CF2CF2CF2 - CF2} - _O -CF=CF-O- _{CF2 - CF2CF2} CF ₂ -SO ₂ F, FSO ₂ -CF ₂ CF(CF ₃ )-CF ₂ -O-CF=CF-O-CF ₂ -CF(CF ₃ )CF ₂ -SO ₂ F and the like.

In the general formula (1), Rf ¹ is a group represented by -Rf ⁴ -SO ₂ F (wherein Rf ⁴ is a chain or branched fluorinated alkylene group having 1 to 10 carbon atoms). and Rf ² is —Rf ⁵ —SO ₂ F (wherein Rf ⁵ is a chain or branched C 1-10 fluorinated alkylene group containing an etheric oxygen atom). It is also one of preferred embodiments that the group is
In the above Rf ⁴ , the number of carbon atoms in the fluorinated alkylene group is preferably 1-8, more preferably 1-6, even more preferably 1-4. Rf ⁴ includes -CF ₂ -*, -CF ₂ CF ₂ -*, -CF(CF ₃ )-*, -CF ₂ CF ₂ CF ₂ -*, -CF(CF ₃ )CF ₂ -*, - CF ₂ CF ₂ CF ₂ CF ₂ -*, etc. (* in the above formula indicates the side that bonds to -SO ₂ F).
In the above Rf ⁵ , the number of carbon atoms in the fluorinated alkylene group is preferably 1-8, more preferably 1-6, and even more preferably 1-4. The above Rf ⁵ includes -CF ₂ -O-CF ₂ -*, -CF ₂ -O-CF ₂ CF ₂ -*, -CF(CF ₃ ) -O-CF ₂ -*, -CF(CF ₃ ) —O—CF ₂ CF ₂ —*, etc. (* in the above formula indicates the side that bonds to —SO ₂ F).
Preferred specific examples of the above compounds include the following compounds.
_FSO2 - _CF2 - _CF2 -O-CF=CF-O-CF2- _CF2 - _O -CF2- _SO2F , FSO2 _{- CF2CF2 - CF2} - _O -CF=CF-O _-CF2 - _CF2 -O- _CF2 - _SO2F , FSO2- _CF2CF2CF2 - _{CF2 -O} -CF=CF- _O - _CF2 - _{CF2 -O} - _{CF2- SO2} F, _FSO2 -CF( _CF3 )-CF2 _- O-CF=CF-O- _CF2 - _CF2- O-CF2 _{- SO2F} , FSO2 _- CF( _CF3 )-CF2 _- O -CF=CF-O- _CF2 - _CF2 -O-CF2 _{- SO2F} , FSO2 _- CF2- _{CF2 -O} -CF=CF-O- _CF2 -CF( _CF3 )-O- CF ₂ CF ₂ —SO ₂ F and the like.

The first fluorine-containing compound of the present disclosure is useful, for example, as a monomer for synthesizing polymers. It can also be used for acid catalysts, phase transfer catalysts, ionic liquids, and materials (intermediates) for producing these.

The second fluorine-containing compound of the present disclosure has the following general formula (2):
Rf ⁶ -O-CFX ^a -CFY ^a -O-Rf ⁶ (2)
(wherein Rf ⁶ is the same or different and is -F or a fluorine-containing organic group having 1 to 16 carbon atoms; X ^a and Y ^a are the same or different and are -H, -F, -Cl, —Br or —I, except when both X ^a and Y ^a are —H or —F).
The fluorine-containing organic group is not particularly limited as long as it is a monovalent organic group containing at least one fluorine.
Here, the monovalent organic group is generally a fluorine-containing aliphatic group, and refers to a saturated or unsaturated, straight-chain or branched fluorine-containing aliphatic group. It may be interposed by an atom, a nitrogen atom, a sulfonyl group, an aromatic ring, or the like, and may have a functional group bonded to the carbon atom.
The above functional groups are not particularly limited, but examples include -SO ₂ X, -COX, -POX ₂ (wherein X is a halogen atom, -OH, -OM (M is a monovalent metal atom), -SO ₂ NHSO ₂ R or —SO ₂ NHR (R is an alkyl group having 1 to 5 carbon atoms) is preferred.
Examples of the halogen atom for X include -F, -Cl, -Br, and -I.
In the above M, the monovalent metal atom includes Li, Na, K, Rb, Cs, Ag and the like.
Examples of R above include a chain or branched methyl group, ethyl group, propyl group, butyl group, and the like.

Rf ⁶ is preferably the same or different and is -F, a fluorinated alkyl group having 1 to 11 carbon atoms, a fluorinated alkenyl group having 2 to 11 carbon atoms or a fluorinated alkynyl group having 2 to 11 carbon atoms, In the above fluorinated alkyl group, fluorinated alkenyl group and fluorinated alkynyl group, atoms bonded to carbon atoms may be substituted with functional groups, and may contain etheric oxygen atoms.

The fluorinated alkyl group in Rf ⁶ above may be linear or branched. The fluorinated alkyl group preferably has 1 to 9 carbon atoms, more preferably 1 to 7 carbon atoms, and still more preferably 1 to 5 carbon atoms.
Specific examples of the fluorinated alkyl group include those exemplified for Rf ¹ and Rf ² described above.
The fluorinated alkyl group for Rf ⁶ is preferably a perfluoroalkyl group, such as CF ₃ —, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, CF ₃ CF ₂ CF ₂ CF ₂ —, CF ₃ CF _{2 .} CF ₂ CF ₂ CF ₂ —, CF ₃ CF(CF ₃ )CF ₂ — or CF ₃ C(CF ₃ ) ₂ CF ₂ — are preferred.
Fluorinated alkyl groups containing etheric oxygen atoms include CF ₃ —O—CF ₂ CF ₂ —, CF ₃ CF ₂ —O—CF ₂ CF ₂ —, and CF ₃ —O—CF ₂ CF ₂ CF _{2 .} -, or CF ₃ CF ₂ -O-CF(CF ₃ )CF ₂ - is preferred.

When the above Rf ⁶ is a fluorinated alkyl group in which the atom bonded to the carbon atom is not substituted with a functional group and does not contain an etheric oxygen atom, the second fluorine-containing compound of the present disclosure is CF ₃ -O- _CF2- CFI-O- _CF3 , _CF3CF2 -O _{- CF2 - CFI} -O- _CF2CF3 , _{CF3CF2CF2 -} O- _CF2 -CFI-O- _{CF2 CF2CF3 , CF3CF2CF2CF2 - O - CF2 -} CFI-O- _{CF2CF2CF2CF3 , CF3CF2CF2CF2CF2 - O - CF2 - CFI-} O- _{CF2CF2CF2CF2CF3} , _CF3CF ( _{CF3 )} CF2 _- O- _{CF2 - CFI} -O- _CF2CF ( _{CF3 )} CF3, _CF3C ( _{CF3 ) 2} CF2 _- O- _CF2 -CFI-O- _CF2C ( _{CF3 )} 2CF3, _{CF3 -} O- _CF2 -CFH-O- _CF3 , CF3CF2 _{- O} -CF2 _- CFH- O- _{CF2CF3 , CF3CF2CF2 - O - CF2 -} CFH _- O- _CF2CF2CF3 , _{CF3CF2CF2CF2 -} O-CF2 _{- CFH} -O- _{CF2 CF2CF2CF3 , CF3CF2CF2CF2CF2 - O - CF2 - CFH} -O- _{CF2CF2CF2CF2CF3 , CF3CF} ( _{CF3 ) CF2 - O- CF2} -CFH-O- _CF2CF ( _{CF3 ) CF3} , CF3C( _CF3 ) _2CF2 -O _- CF2- _CFH -O- _CF2C ( _CF3 ) _{2CF3 , CF3} -O-CFCl-CFCl-O- _CF3 , _{CF3CF2 -} O-CFCl-CFCl-O- _{CF2CF3 , CF3CF2CF2 - O} -CFCl-CFCl-O _{- CF2CF2CF 3 , CF3CF2CF2CF2 - O -} CFCl- _CFCl -O _{- CF2CF2CF2CF3 , CF3CF2CF2CF2CF2 -} O _- CFCl-CFCl-O _{- CF2CF 2CF2CF2CF3 , CF3CF} ( _CF3 ) _{CF2 -} O-CFCl-CFCl-O- _CF2CF (CF3) _CF3 , _CF3C ( _{CF3 ) 2CF2 - O} -CFCl -CFCl-O-CF ₂ C(CF ₃ ) ₂ CF ₃ and the like.
When at least one of the two Rf ⁶ in the above general formula (2) is a fluorinated alkyl group containing an etheric oxygen atom in which the atom bonded to the carbon atom is not substituted with a functional group, the As the second fluorine-containing compound, CF ₃ —O—CF ₂ CF ₂ —O—CF ₂ —CFI—O—CF ₂ CF ₂ —O—CF ₃ , CF ₃ CF ₂ —O—CF ₂ CF ₂ — _{O-CF2-CFI-O-CF2CF2-CF2CF3, CF3-O-CF2CF2CF2 - O - CF2 - CFI - O - CF2CF2CF2} - _{O -} CF ₃ , _CF3CF2 - _O -CF( _CF3 )CF2-O- _{CF2 - CFI} -O- _CF2CF ( _CF3 )-O- _CF2CF3 , _CF3CF2 - _O - _CF2 -CFI-O- _{CF2CF ( CF3} )-O- _CF2CF3 , _{CF3-O-CF2CF2 - O - CF2} -CFH-O- _CF2CF2 -O- _CF3 , CF _{3 CF2} -O- _CF2CF2 -O- _{CF2 - CFH} - _O - _{CF2CF2 -CF2CF3} , _CF3- O- _CF2CF2CF2 - _{O -} CF2 _- CFH-O _-CF2CF2CF2 - _O - _CF3 , _CF3CF2 -O-CF( _CF3 )CF2- _O - _{CF2 -} CFH-O- _CF2CF ( _{CF3 )} -O- _{CF2CF 3} , _CF3CF2 - _O - _CF2 -CFH-O- _CF2CF ( _CF3 ) _-O -CF2CF3 _{, CF3-} O- _CF2CF2 - _O -CFCl-CFCl-O-CF _2CF2 -O- _{CF3 , CF3CF2 -} O- _CF2CF2 -O- _CFCl - _CFCl -O _{- CF2CF2} - _{CF2CF3 , CF3} -O _{- CF2CF2CF2} —O—CFCl—CFCl—O—CF ₂ CF ₂ CF ₂ —O—CF ₃ , CF ₃ CF ₂ —O—CF(CF ₃ )CF ₂ —O—CFCl—CFCl—O—CF ₂ CF(CF ₃ )-O-CF ₂ CF ₃ , CF ₃ CF ₂ -O-CFCl-CFCl-O-CF ₂ CF(CF ₃ )-O-CF ₂ CF ₃ and the like.

The above fluorinated alkenyl groups may be linear or branched. The fluorinated alkenyl group preferably has 2 to 9 carbon atoms, more preferably 2 to 7 carbon atoms, and still more preferably 2 to 5 carbon atoms.
Examples of the fluorinated alkenyl groups include CF ₂ ═CH—CF ₂ —, CF ₂ ═CF—CF ₂ —, CF ₃ CH═CH—CF ₂ —, CF ₂ ═CHCH ₂ —CF ₂ —, CF ₃ CF= CH- _CF2- , _CF2 = _CFCH2 -CF2- _, CF3CF= _{CF-CF2-, CF2=CFCF2-CF2- , CF3CH = CF - CF2-, CF2 =} CHCF _{2 -} CF2-, _HCF =CH- _CF2- , HCF=CF-, HCF2CH=CH- _CF2- , HCF=CHCH2 _{- CF2-} , _HCF2CF =CH- _CF2- , HCF= CFCH ₂ -CF ₂ -, HCF ₂ CH=CF-CF ₂ -, HCF=CHCF ₂ -CF ₂ -, CH ₃ CF=CH-CF ₂ -, CH ₂ =CFCF ₂ -CF ₂ - and the like.
The fluorinated alkenyl group is preferably a perfluoroalkenyl group, preferably CF ₂ =CF--CF ₂ --, CF ₃ CF--CF--CF ₂ -- or CF ₂ =CFCF ₂ --CF ₂ --.
When Rf ⁶ is a fluorinated alkenyl group, the second fluorine-containing compound of the present disclosure includes CF ₂ =CF-CF ₂ -O-CF ₂ -CFI-O-CF ₂ -CF=CF ₂ , CF ₃ CF=CF-CF2- _O - _CF2 -CFI-O-CF2- _CF = _CFCF3 , _CF2 = _CFCF2 -CF2- _O - _CF2 -CFI-O- _CF2 - _CF2CF = _CF2 , _CF2 =CF- _CF2 -O-CF2-CFH-O- _CF2 -CF= _CF2 , _CF3 CF=CF- _CF2 - _O -CF2- _CFH -O- _CF2 -CF =CFCF ₃ , CF ₂ =CFCF ₂ -CF ₂ -O-CF ₂ -CFH-O-CF ₂ -CF ₂ CF=CF _{2 , CF 2 =} CF-CF ₂ -O-CFCl-CFCl-O-CF ₂ -CF=CF ₂ , CF ₃ CF=CF-CF ₂ -O-CFCl-CFCl-O-CF ₂ -CF=CFCF ₃ , CF ₂ =CFCF ₂ -CF ₂ -O-CFCl-CFCl-O-CF ₂ -CF ₂ CF=CF ₂ and the like.

The above fluorinated alkynyl groups may be linear or branched. The fluorinated alkynyl group preferably has 2 to 9 carbon atoms, more preferably 2 to 7 carbon atoms, and still more preferably 2 to 5 carbon atoms.
Examples of the fluorinated alkynyl groups include CF≡C—CF ₂ —, CF ₃ C≡C—CF ₂ —, CF≡CCH ₂ —CF ₂ —, CF≡CCF ₂ —CF ₂ —, and HCF ₂ C≡C—. CF ₂ —, CH≡CCF ₂ —CF ₂ — and the like.
The fluorinated alkynyl group is preferably a perfluoroalkynyl group,
CF≡C—CF ₂ —, CF ₃ C≡C—CF ₂ —, or CF≡CCF ₂ —CF ₂ — are preferred.
When Rf ⁶ is a fluorinated alkynyl group, the second fluorine-containing compound of the present disclosure includes CF≡C—CF ₂ —O—CF ₂ —CFI-O—CF ₂ —C≡CF, CF ₃ C ≡C-CF ₂ -O-CF ₂ -CFI-O-CF ₂ -C≡CCF ₃ , CF≡CCF ₂ -CF ₂ -O-CF ₂ -CFI-O-CF ₂ -CF ₂ C≡CF, CF ≡C-CF ₂ -O-CF ₂ -CFH-O-CF ₂ -C≡CF, CF ₃ C≡C-CF ₂ -O-CF ₂ -CFH-O-CF ₂ -C≡CCF ₃ , CF≡ CCF ₂ —CF ₂ —O—CF ₂ —CFH—O—CF ₂ —CF ₂ C≡CF, CF≡C—CF ₂ —O—CFCl—CFCl—O—CF ₂ —C≡CF, CF ₃ C≡ C--CF ₂ --O--CFCl--CFCl--O--CF ₂ --C.ident.CCF ₃ , CF.ident.CCF ₂ --CF ₂ --O--CFCl--CFCl--O--CF ₂ --CF ₂ C.ident.CF and the like.

Rf ⁶ is the same or different, and is preferably -F or a fluorinated alkyl group having 1 to 11 carbon atoms, and the fluorinated alkyl group has an atom bonded to the carbon atom substituted with a functional group. may contain an etheric oxygen atom.

One or both of the two Rf ⁶ in the general formula (2) is —SO ₂ X, —COX, —POX ₂ (wherein X is a halogen atom, —OH, —OM (M is a monovalent metal atom), —SO ₂ NHSO ₂ R, or —SO ₂ NHR (R is an alkyl group having 1 to 5 carbon atoms)), preferably a fluorinated alkyl group having 1 to 11 carbon atoms, The fluorinated alkyl group may contain an etheric oxygen atom.
Such a fluorinated alkyl group has the formula: Y ² —Rf ⁷ — (Rf ⁷ is a linear or branched fluorinated alkylene group having 1 to 11 carbon atoms and containing an etheric oxygen atom. Y ² is —SO ₂ X, —COX, —POX ₂ (wherein X is a halogen atom, —OH, —OM (M is a monovalent metal atom), or —SO ₂ NHR (R is an alkyl group having 1 to 5 carbon atoms).) is preferred.
The halogen atom for X is preferably -F, -Cl, -Br or -I, more preferably -F.
In the above M, the monovalent metal atom includes Li, Na, K, Rb, Cs, Ag and the like.
Examples of Rf ⁷ include -CF ₂ CF ₂ -*, -CF 2 CF ₂ CF ₂ -*, _{-CF 2 CF 2} CF ₂ CF ₂ -*, -CF ₂ CF (CF ₃ ) -*, - CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -*, -CF ₂ CF (CF ₃ ) CF ₂ -*, -CF ₂ CF ₂ -O-CF ₂ -*, -CF ₂ CF ₂ CF ₂ -O-CF ₂ -*, -CF ₂ CF ₂ -O-CF ₂ CF ₂ -*, -CF ₂ CF ₂ CF ₂ -O-CF ₂ CF ₂ -*, -CF ₂ CF ₂ CF ₂ -O-CF(CF ₃ ) CF ₂ -*, etc. (* in the above formula indicates the side that binds to Y ² ).

In general formula (2), both Rf ⁶ are —Rf ⁷ —SO ₂ F (wherein Rf ⁷ is a chain or branched C 1-11 fluorinated alkylene group. ) is one of preferred embodiments. Preferred specific examples of such compounds include the following compounds.
_FSO2 - _CF2 - _CF2 -O- _CF2 -CFI-O- _CF2 -CF2 _-SO2F , FSO2 _{- CF2CF2 - CF2} -O- _CF2 -CFI- _O - _{CF2 -CF2CF2 - SO2F} , _{FSO2- CF2CF2CF2} -CF2-O _{-CF2 - CFI} - _O - _{CF2 - CF2CF2CF2 - SO2F} , FSO2 _- CF ₂ CF(CF ₃ )-CF ₂ -O-CF ₂ -CFI-O-CF ₂ -CF(CF ₃ )CF ₂ -SO ₂ F, FSO ₂ -CF ₂ -CF ₂ -O-CF ₂ -CFH- O- _CF2 - _CF2 - _SO2F , FSO2 _- CF2CF2 _-CF2 -O- _{CF2 - CFH} -O- _{CF2 - CF2CF2 -} SO2F, FSO2 _{- CF2CF 2CF2 - CF2} -O- _CF2 -CFH-O-CF2- _{CF2CF2CF2 -} SO2F _{, FSO2- CF2CF ( CF3} )-CF2-O- _{CF2 - CFH} -O- _CF2 -CF( _CF3 )CF2 _{- SO2F} , FSO2 _- CF2 _{-CF2 -} O-CFCl-CFCl-O- _CF2 - _CF2 - _SO2F , FSO2 _{- CF2 CF2} - _CF2 -O _- CFCl-CFCl-O- _CF2 - _CF2CF2 -SO2F, _{FSO2 - CF2CF2CF2 - CF2} - _O -CFCl-CFCl-O- _CF2- CF ₂ CF ₂ CF ₂ -SO ₂ F, FSO ₂ -CF ₂ CF(CF ₃ )-CF ₂ -O-CFCl-CFCl-O-CF ₂ -CF(CF ₃ )CF ₂ -SO ₂ F, etc. be done.

In the general formula (2), one of the two Rf ⁶ is —Rf ⁸ —SO ₂ F (wherein Rf ⁸ is a chain or branched C 1-11 fluorinated alkylene group. ) and the other of Rf ⁶ is —Rf ⁹ —SO ₂ F (wherein Rf ⁹ is a linear or branched fluorinated alkylene having 1 to 11 carbon atoms containing an etheric oxygen atom is a group) is also one of preferred embodiments.
The above Rf ⁸ includes -CF ₂ CF ₂ -*, -CF ₂ CF ₂ CF ₂ -*, -CF ₂ CF (CF ₃ ) -*, -CF ₂ CF ₂ CF ₂ CF ₂ -*, -CF ₂ CF(CF ₃ )CF ₂ -*, -CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -*, etc. (* in the above formula indicates the side that bonds to -SO ₂ F).
Examples of Rf ⁹ include -CF ₂ CF ₂ -O-CF ₂ -*, -CF ₂ CF ₂ -O-CF ₂ CF ₂ -*, -CF ₂ CF(CF ₃ )-O-CF ₂ -*, -CF ₂ CF(CF ₃ )-O-CF ₂ CF ₂ -* and the like (* in the above formula indicates the side that bonds to -SO ₂ F).
Preferred specific examples of the above compounds include the following compounds.
_FSO2 - _CF2 - _CF2 -O-CF2 _- CFI-O-CF2- _CF2 - _O -CF2 _{- SO2F} , FSO2 _{- CF2CF2} - _CF2 - _O - _CF2- CFI -O- _CF2 - _CF2 -O- _CF2 - _SO2F , FSO2 _- CF2CF2CF2- _{CF2-O -} CF2- _CFI - _O -CF2- _{CF2 - O} - _{CF2 -SO2F} , _FSO2 -CF( _CF3 )-CF2- _O -CF2- _CFI -O-CF2- _{CF2 -} O-CF2 _{- SO2F} , FSO2 _- CF( _CF3 )- CF2 _- O-CF2 _- CFI-O- _CF2 - _CF2 -O-CF2 _- SO2F, _{FSO2 -} CF2 _-CF2 - _O - _CF2 -CFI-O- _CF2- CF( CF ₃ )-O-CF ₂ CF ₂ -SO ₂ F, FSO ₂ -CF ₂ -CF ₂ -O-CF ₂ -CFH-O-CF ₂ -CF ₂ -O-CF ₂ -SO ₂ F, FSO _{2 -CF2CF2} - _CF2 - _O - _CF2 -CFH-O-CF2- _CF2 -O- _{CF2 - SO2F} , _FSO2 - _{CF2CF2CF2 - CF2} - _O - _CF2 -CFI-O- _CF2 - _CF2 -O- _CF2 -SO2F, _FSO2 -CF( _CF3 )-CF2 _- O- _{CF2 -CFH} -O-CF2- _{CF2 -} O-CF _{2- SO2F} , _FSO2 -CF( _CF3 )-CF2- _O -CF2- _CFH -O- _CF2 - _CF2 -O- _{CF2 -SO2F} , FSO2 _- CF2 _{- CF2} -O- _CF2- CFH-O- _CF2 -CF( _CF3 )-O- _CF2CF2 -SO2F, _{FSO2 - CF2 -CF2} - _O -CFCl-CFCl-O- _CF2- CF2 _- O- _CF2 - _SO2F , FSO2 _{- CF2CF2} -CF2-O-CFCl-CFCl-O- _CF2 - _CF2 -O- _{CF2 - SO2F ,} FSO2 _- CF ₂ CF ₂ CF ₂ -CF ₂ -O-CFCl-CFCl-O-CF ₂ -CF ₂ -O-CF ₂ -SO ₂ F, FSO ₂ -CF(CF ₃ )-CF ₂ -O-CFCl-CFCl- O- _CF2 - _CF2 -O- _CF2 - _SO2F , _FSO2 -CF( _CF3 ) _-CF2 -O-CFCl-CFCl-O- _CF2 - _CF2 -O- _{CF2- SO2} F, FSO ₂ -CF ₂ -CF ₂ -O-CFCl-CFCl-O-CF ₂ -CF(CF ₃ )-O-CF ₂ CF ₂ -SO ₂ F and the like.

X ^a and Y ^a in general formula (2) are the same or different and are —H, —F, —Cl, —Br or —I. One of X ^a and Y ^a is preferably —F and the other is —H, —Cl, —Br or —I.

The second fluorine-containing compound of the present disclosure is useful as a material (intermediate) for producing the compound represented by the general formula (1). It can also be used for acid catalysts, phase transfer catalysts, ionic liquids, and materials (intermediates) for producing these.

The first and second fluorine-containing compounds of the present disclosure can be produced by the following method. First, the method for producing the second fluorine-containing compound of the present disclosure will be described.

The second fluorine-containing compound of the present disclosure has the general formula (a1):
Rf ⁶ O—CF=CF ₂
(Wherein, Rf ⁶ is the same as above.) The compound represented by the general formula (a2):
^{Rf6OM1 _}
(Rf ⁶ is the same as above. M ¹ is Na, K, or Ag.) and the general formula (a3):
X ¹ ₂
(X ¹ is —Cl, —I, or Br) in the presence of a compound represented by the general formula (a4):
Rf ⁶ O—CF ₂ —CFX ¹ —ORf ⁶
(Wherein, Rf ⁶ and X ¹ are the same as above.).

The compound represented by the general formula (a1) is not limited as long as it has Rf ⁶ as exemplified for the second fluorine-containing compound, but examples include _CF2 = _CFOCF3 , _CF2 = _{CFOCF2CF3 ,} CF _{2 = CFOCF2CF2SO2F , CF2 = CFOCF2CF} ( _CF3 ) _OCF2CF2SO2F and the like _.

In the step (1), the compound represented by the general formula (a2) is preferably used in an amount of 0.8 to 1.2 mol, per 1 mol of the compound represented by the general formula (a1). It is more preferable to use 1.1 mol.

In step (1), the compound represented by general formula (a3) is preferably used in an amount of 0.9 to 1.6 mol, per 1 mol of the compound represented by general formula (a1). It is more preferable to use 1.3 mol.

The temperature in step (1) is not particularly limited, and may be about room temperature. From the viewpoint of allowing the reaction to proceed efficiently, the temperature is preferably 0°C or higher, more preferably 5°C or higher. Moreover, 50 degrees C or less is preferable and 40 degrees C or less is more preferable.

The pressure in step (1) may be normal pressure and is not particularly limited.

The reaction of step (1) can be carried out in a solvent. Although the solvent is not particularly limited, organic solvents such as diglyme, triglyme, tetraglyme, and acetonitrile are preferred.

Specifically, the reaction of step (1) is performed by adding a compound represented by general formula (a2) into a reaction vessel and, if necessary, a solvent, and then adding a compound represented by general formula (a1) into the reaction vessel. It can be carried out by, for example, adding the compound dropwise.

After the reaction in step (1), the reaction may be terminated with a reducing agent such as sodium thiosulfate.

（Ｒｆ^６ａは、炭素数１～１６の２価のフッ素含有有機基である。）で示される環状化合物（α）と、ハロゲン化金属とを反応させて、Ｒｆ^６ＯＭ^１（Ｒｆ^６及びＭ^１は上記と同じ。）で示される化合物を得る工程（１ａ）を含んでもよい。 In the above production method, before step (1), the following formula (α)

(Rf ^6a is a divalent fluorine-containing ^organic group having ¹ to 16 carbon atoms.) The cyclic compound ( ^α ) represented by ¹ is the same as above.) to obtain the compound shown in (1a).

Examples of Rf ^6a include the fluorinated alkyl group, fluorinated alkenyl group, fluorinated alkynyl group, etc. described above for Rf ⁶ (the atoms bonded to the carbon atoms of these groups may be substituted with functional groups, etheric oxygen atoms may contain), and groups with a structure in which -H or -F is eliminated (when a fluorinated alkyl group or the like is substituted with a functional group, -H or -F in the functional group is may be eliminated to form a ring structure). For example, if Rf ⁶ is -CF ₃ , then Rf ^6a is -CF ₂ -. When Rf ⁶ is -CF ₂ CF ₂ SO ₂ F, Rf ^6a is -CF ₂ CF ₂ SO ₂ -.
Specific examples of Rf ^6a include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF ₂ CF 2 CF ₂ CF _{2 -} , -CF ₂ SO ₂ -, -CF ₂ CF ₂ SO ₂ —, —CF ₂ CF(CF ₃ )—O—CF ₂ CF ₂ SO ₂ —, and the like.
Specific examples of the above compounds include tetrafluoroethane-β-sultone and the like.

Examples of the metal halide include sodium fluoride, potassium fluoride, silver fluoride and the like. The amount of the metal halide in step (1a) is preferably 0.9 to 1.5 mol per 1 mol of the compound represented by Rf ^6a -O.

The temperature in step (1a) can be, for example, -20°C to 20°C. The pressure in step (1a) may be normal pressure and is not particularly limited.

In the step (1a), for example, a metal halide, a solvent, and the like are charged into a reaction vessel, and the cyclic compound (α) is added dropwise into the reaction vessel while the reaction vessel is cooled by an ice bath or the like. can be implemented by In the above step (1a), from the viewpoint of improving the yield, it is also preferable to remove the water in the reaction vessel at the stage of charging the metal halide into the reaction vessel. As a method for removing moisture, a method of heating the flask with a heat gun while being vacuumed may be mentioned, but it is not particularly limited.

The second fluorine-containing compound of the present disclosure also has the following formula (a1):
Rf ⁶ O—CF=CF ₂
(Wherein, Rf ⁶ is the same as above.) The compound represented by the following formula (a5):
^{Rf6OM2 _}
(Rf ⁶ is the same as above. M ² is Ag or Cu.).
The following formula (a6):
Rf ⁶ O--CFH--CF ₂ ORf ⁶
(wherein Rf ⁶ is the same as above).

In step (2), the compound represented by general formula (a5) is preferably used in an amount of 0.9 to 3.0 mol, per 1 mol of the compound represented by general formula (a1). It is more preferred to use 2.0 mol.

In step (2) _, the acid includes _H2SO4 , HCl, _FSO3H , _ClSO3H , _CF3SO3H and _the like. H ₂ SO ₄ or CF ₃ SO ₃ H is preferred, and H ₂ SO ₄ is more preferred.

In step (2), the acid is preferably used in an amount of 1.0 to 2.0 mol, preferably 1.2 to 1.8 mol, per 1 mol of the compound represented by the general formula (a1). more preferred.

The temperature in step (2) is not particularly limited, and may be about room temperature. From the viewpoint of allowing the reaction to proceed efficiently, the temperature is preferably 0°C or higher, more preferably 5°C or higher. Moreover, 60 degrees C or less is preferable and 50 degrees C or less is more preferable.

The pressure in step (2) may be normal pressure and is not particularly limited.

The reaction of step (2) can be carried out in a solvent. Although the solvent is not particularly limited, organic solvents such as diglyme, triglyme, tetraglyme and dimethylsulfoxide are preferred.

Specifically, the reaction in step (2) is carried out by adding dropwise the compound represented by general formula (a1) into a reaction vessel containing the compound represented by general formula (a5), a solvent, etc., followed by stirring. etc. can be implemented. In step (2), HF may be generated due to the use of acid. Therefore, corrosion of the reaction vessel can be suppressed by applying a fluorine resin lining treatment to both the liquid phase portion and the gas phase portion of the reaction vessel so that the reaction vessel does not corrode.

After the reaction in step (2), the solution obtained by the reaction may be added dropwise to a solution containing water and chloroform to terminate the reaction.

In the above production method, the cyclic compound (α) described above is reacted with a metal halide before step (2) to obtain a compound represented by Rf ⁶ OM ² (Rf ⁶ and M ² are the same as above). A step (2a) of obtaining AgF etc. are mentioned as a metal halide in a process (2a).
The amount of the metal halide in step (2a) is preferably 0.9 to 3.0 mol, more preferably 1.0 to 2.5 mol, per 1 mol of the cyclic compound (α). preferable.
Step (2a) can be carried out, for example, at -20°C to 20°C. The pressure in step (2a) may be normal pressure and is not particularly limited.

The second fluorine-containing compound of the present disclosure further has general formula (a7):
_CH2X2 ^- _CH2X2 ^_
(Wherein, X ² is the same or different and is Br, I, or OTs (tosyl group).) and the general formula (a2):
^{Rf6OM1 _}
(Rf ⁶ is the same as above. M ¹ is Ag, Na, or K.) by reacting the compound represented by the general formula (a8):
Rf ⁶ O—CH ₂ —CH ₂ —ORf ⁶
step (3) of obtaining a compound represented by (wherein Rf ⁶ is the same as above);
The compound represented by the general formula (a8) and chlorine gas (Cl ₂ )
is reacted to form the general formula (a9):
Rf ⁶ O—CCl ₂ —CCl ₂ —ORf ⁶
(wherein Rf ⁶ is the same as above) to obtain a compound represented by (4), and
A compound of general formula (a9) is reacted in the presence of _SbF3 and _SbCl5 to give general formula (a10):
Rf ⁶ O--CFCl--CFCl--ORf ⁶
step (5) of obtaining a compound represented by (wherein Rf ⁶ is the same as above);
It can be manufactured by a manufacturing method including

In the step (3), the compound represented by the general formula (a2) is preferably used in an amount of 1.6 to 2.4 mol, per 1 mol of the compound represented by the general formula (a7). It is more preferable to use 2.2 mol.

The temperature in step (3) is not particularly limited, and may be about room temperature. From the viewpoint of allowing the reaction to proceed efficiently, the temperature is preferably 0°C or higher, more preferably 5°C or higher. Moreover, 50 degrees C or less is preferable and 40 degrees C or less is more preferable.

The pressure in step (3) may be normal pressure and is not particularly limited.

The reaction of step (3) can be carried out in a solvent. Although the solvent is not particularly limited, organic solvents such as diglyme, triglyme and tetraglyme are preferred.
Specifically, it can be carried out by dropping the compound represented by the general formula (a) into a reaction vessel containing the compound represented by the general formula (a2), a solvent and the like.

The reaction in step (4) can be carried out by adding the compound represented by general formula (a8) and, if necessary, a solvent into a reaction vessel and blowing _Cl2 into the reaction vessel. The amount of _Cl2 is not particularly limited as long as it is an amount that allows the reaction between the compound represented by general formula (a8) and _Cl2 to proceed sufficiently. For example, it is preferably used in an amount of 4 mol or more, more preferably in an amount of 8 mol or more, per 1 mol of the compound represented by the general formula (a8).

The temperature in step (4) is preferably 50° C. or higher, more preferably 60° C. or higher, from the viewpoint of efficiently proceeding the reaction. Moreover, 100 degrees C or less is preferable and 90 degrees C or less is more preferable.

The pressure in step (4) may be normal pressure and is not particularly limited.

The reaction of step (4) can be carried out in a solvent. Halogenated carbon such as carbon tetrachloride is preferred as the solvent.

In step (5), the amount of SbF ₃ used is preferably 1.5 to 2.5 mol, more preferably 1.8 to 2.2 mol, per 1 mol of the compound represented by general formula (a9). is more preferable.
The amount of SbCl ₅ used is preferably 0.01 to 1.0 mol, more preferably 0.05 to 0.5 mol, per 1 mol of the compound represented by the general formula (a9). more preferred.

The temperature in step (5) is preferably 0° C. or higher, more preferably 20° C. or higher, from the viewpoint of efficiently proceeding the reaction. Moreover, 80 degrees C or less is preferable and 60 degrees C or less is more preferable.

The pressure in step (5) may be normal pressure and is not particularly limited.

Specifically, the reaction in step (5) is performed by adding the compound represented by general formula (a9) obtained in step (4), SbF ₃ , and SbCl ₅ to a reaction vessel and stirring. can be implemented.

In the above production method, the cyclic compound (α) described above is reacted with a metal halide before step (3) to obtain a compound represented by Rf ⁶ OM ¹ (Rf ⁶ and M ¹ are the same as above). A step (3a) of obtaining AgF etc. are mentioned as a metal halide in a process (3a).
The amount of the metal halide in step (3a) is preferably 0.9 to 3.0 mol, more preferably 1.0 to 1 mol, per 1 mol of the cyclic compound (α).
Step (3a) can be carried out at -200°C to 20°C, for example. The pressure in step (2a) may be normal pressure and is not particularly limited.

In the above production method, purification by washing, distillation, or the like may be performed after each step.

The second fluorine-containing compound of the present disclosure can be produced by the production method as described above. In addition, the production of the second fluorine-containing compound of the present disclosure can be carried out by appropriately changing the compounds, conditions, etc. used in the production method described above.
Next, a method for producing the first fluorine-containing compound of the present disclosure will be described.

The first fluorine-containing compound of the present disclosure can be produced using the second fluorine-containing compound of the present disclosure.
The first fluorine-containing compound of the present disclosure has the following general formula (2):
Rf ⁶ -O-CFX ^a -CFY ^a -O-Rf ⁶ (2)
(wherein Rf ⁶ is the same or different and is -F or a fluorine-containing organic group having 1 to 16 carbon atoms; X ^a and Y ^a are the same or different and are -H, -F, -Cl, -Br or -I, except when both X ^a and Y ^a are -H or -F) is reacted in the presence of a catalyst to give the general formula (1 ):
Rf ¹ -CF ₂ -O-CF=CF-O-CF ₂ -Rf ² (1)
(Wherein, Rf ¹ is —F or a fluorine-containing organic group having 1 to 15 carbon atoms, and Rf ² is a fluorine-containing organic group having 1 to 15 carbon atoms.) Step (6) for obtaining a compound represented by It can be obtained by a manufacturing method including
At this time, one of Rf ⁶ in general formula (2) is Rf ¹ -CF ₂ - and the other is Rf ² -CF ₂ -.

First, the case where either X ^a or Y ^a of the compound represented by general formula (2) is —H in step (6) will be described.
When either X ^a or Y ^a of the compound represented by the general formula (2) is —H, examples of the catalyst include lithium diisopropylamide (LDA), lithium (bistrimethylsilyl)amide (LHMDS), and the like. It is preferred to use such a strong base as a catalyst.
The amount of the catalyst may be appropriately determined depending on the type of the compound represented by the general formula (2) and the type of the catalyst. mol, more preferably 0.9 to 3.0 mol.
The temperature in step (6) is preferably −40° C. or higher, more preferably −30° C. or higher, from the viewpoint of efficiently proceeding the reaction. Moreover, 50 degrees C or less is preferable and 20 degrees C or less is more preferable.
The pressure in step (6) may be normal pressure and is not particularly limited.
The reaction of step (6) can be carried out in a solvent. Although the solvent is not particularly limited, organic solvents such as tetrahydrofuran, diglyme and triglyme can be used.
Specifically, the reaction of step (6) can be carried out by adding a compound represented by general formula (2), a solvent, etc. into a reaction vessel, and then adding a catalyst solution into the reaction vessel. can.

Next, the case where neither X ^a nor Y ^a of the compound represented by the general formula (2) is —H in the above step (6) will be described.
When neither X ^a nor Y ^a of the compound represented by the general formula (2) is —H, it is preferable to use Zn, Mg or the like as the catalyst.
The amount of the catalyst is preferably 0.5 to 6.0 mol, more preferably 1.0 to 5.0 mol, per 1 mol of the compound represented by formula (2).
The temperature in step (6) is preferably 60° C. or higher, more preferably 80° C. or higher, from the viewpoint of efficiently proceeding the reaction. Moreover, 120 degrees C or less is preferable and 110 degrees C or less is more preferable.
The pressure in step (6) may be normal pressure and is not particularly limited.
The reaction of step (6) can be carried out in a solvent. Although the solvent is not particularly limited, an organic solvent such as dimethylformamide can be used.
Specifically, the reaction of step (6) can be carried out by adding a catalyst, a solvent, etc. into a reaction vessel and dropping the compound represented by general formula (2) into the reaction vessel.

Next, the novel fluorine-containing compound of the present disclosure will be described with reference to Examples, but the novel fluorine-containing compound of the present disclosure is not limited only to these Examples.

Example 1 (compound (1) synthesis method)
Potassium fluoride (59 g) was added to a 1 L glass flask equipped with a dropping funnel and a Dimroth condenser, and the flask was heated with a heat gun while evacuating to remove moisture absorbed, then diglyme (338 g) was added. The reaction vessel was cooled in an ice bath while stirring, and _{tetrafluoroethane} -β _- sultone ( ₁₈₀ g) was added dropwise from the dropping funnel to obtain a solution (A ).
Iodine (305 g) and diglyme (335 g) were stirred in a 2 L glass flask equipped with a dropping funnel and a Dimroth condenser, and CF ₂ =CFOCF ₂ CF ₂ SO ₂ F (280 g) was dropped from the dropping funnel. After that, the previously prepared solution (A) was dropped from the dropping funnel. After the dropping, the mixture was stirred at room temperature for 24 hours, and the reaction was stopped by dropping a 20% sodium thiosulfate aqueous solution from the dropping funnel. _The organic _layer obtained by _the liquid _separation operation was washed with water, dried with magnesium sulfate and filtered, and the low boiling point components were distilled off to obtain a _compound represented by _{FSO2CF2CF2OCF2CFIOCF2CF2SO2F .} 380 g of compound (1) (gas chromatography (hereinafter referred to as GC) purity 96%) was obtained.

Compound (1) GCMS (EI)
m/e 407, 393, 321, 293, 271, 249, 227, 208, 183, 133, 127, 119, 100, 97, 69, 67

Compound (M1) Synthesis Method Zinc powder (98 g) and dimethylformamide (275 g) were placed in a 1 L glass flask equipped with a dropping funnel, a Dimroth condenser and a stirrer, and the temperature was raised to 100° C. while stirring. Compound (1) (316 g) was added dropwise from the dropping funnel, then dimethylformamide (10 g) was added from the dropping funnel, and the mixture was stirred at 100°C for 5 hours. After cooling the mixture to room temperature, 1N hydrochloric acid (200 g) and pentane (300 g) were added, and an organic layer was obtained by filtration and liquid separation. The organic layer was washed twice with 1N hydrochloric acid (100 g) and twice with water (100 g), and then dried over magnesium sulfate. Pentane was distilled off under reduced pressure, and the resulting mixture was distilled to obtain 141 g of a compound (M1) represented by the following formula with a GC purity of 98%.

Compound (M1) GCMS (EI)
m/e 377, 183, 133, 119, 100, 97, 69, 67

Example 2 (compound (2) synthesis method)
Silver fluoride (25 g) and diglyme (157 g) were added to a 500 mL fluororesin-lined stainless steel container equipped with a dropping funnel. The reaction vessel was cooled in an ice bath while stirring, and tetrafluoroethane-β-sultone (18 g) was added dropwise from the dropping funnel to obtain a solution containing the compound (m2) represented by FSO ₂ CF ₂ CF ₂ OAg. Ta. After returning to room temperature and stirring for 30 minutes, CF ₂ =CFOCF ₂ CF ₂ SO ₂ F (28 g) was added dropwise from the dropping funnel. The reaction vessel was cooled in an ice bath, and 15 g of sulfuric acid was added dropwise from the dropping funnel. The mixture was returned to room temperature and stirred for 120 hours. The reaction was terminated by dropping the reaction solution into a vessel containing water (100 g) and chloroform (100 g). After filtration, the lower layer separated into two layers was collected, washed twice with water (100 g), and dried over magnesium sulfate. By distilling off _chloroform under reduced pressure, 20 _g (purity ₇₃ %) _of liquid _containing compound ₍ 2) represented by _{FSO2CF2CF2OCF2CFHOCF2CF2SO2F} was obtained. Since hydrogen fluoride may be generated after the sulfuric acid is dropped and the reaction vessel may corrode, the reaction vessel is lined not only with the liquid phase but also with the gas phase.

Compound (2) GCMS (EI)
m/e 281, 231, 195, 183, 167, 145, 133, 119, 101, 100, 97, 82, 67

Synthesis Method of Compound (M1) In a 50 mL glass flask equipped with a thermometer, 16.4 g of the liquid synthesized above (73% purity of compound (2)) and 20 g of tetrahydrofuran were added. The reaction vessel was cooled to −20° C. and 2M lithium diisopropylamide (LDA) in THF (20 mL) was added dropwise with stirring. After the dropwise addition was completed, the mixture was stirred at -20°C for 1 hour and further at 0°C for 1 hour, and 1N hydrochloric acid (1 g) was added dropwise to terminate the reaction. Water (20 g) and chloroform (20 g) were added to the reaction mixture, and the lower layer was collected and dried over magnesium sulfate. After the solvent was distilled off, 8.6 g of a compound (M1) represented by the following formula was obtained with a GC purity of 99% by distillation.

Example 3 (compound (3) synthesis method)
Silver fluoride (27 g) and diglyme (84 g) were added to a 200 mL glass flask equipped with a thermometer. The reaction vessel was cooled in an ice bath while stirring, and tetrafluoroethane-β-sultone (36 g) was added dropwise to obtain a solution containing the compound (m2) represented by FSO ₂ CF ₂ CF ₂ OAg. After returning to room temperature and adding 1,2-dibromoethane (19 g) dropwise, the mixture was stirred at room temperature for 24 hours. The reaction solution was filtered, and the filtrate was poured into water (100 g). The separated organic layer was washed with water, dried over magnesium sulfate, and distilled to obtain 67 g of compound (3) represented by FSO ₂ CF ₂ CF ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ SO ₂ F with a GC purity of 95%. Ta.

Compound (3) GCMS (EI)
m/e 407, 227, 213, 207, 183, 163, 149, 143, 141, 133, 127, 119, 111, 100, 99, 97, 95, 93, 79, 67

Compound (4) Synthesis Method Compound (3) (45 g, GC purity 95%) and 43 g of carbon tetrachloride were added to a 200 mL glass flask equipped with a thermometer and a Dimroth condenser, and the temperature was raised to 80°C. The cooling pipe outlet was connected to the abatement tower, and chlorine gas was blown in for 5 hours under fluorescent lamp irradiation. After the chlorine gas was introduced, the mixture was further stirred for 5 hours while maintaining the temperature at 80°C. After returning to room temperature and replacing the gas phase with nitrogen gas, it was washed with an aqueous solution of potassium sulfite (80 g) and then with water (80 g). Carbon tetrachloride _was distilled off under _reduced pressure to obtain ₄₈ g _of crude product ₍ purity 70%) containing compound _{( 4} ) represented by _{FSO2CF2CF2OCCl2CCl2OCF2CF2SO2F} . Ta.

Synthesis method of compound (5) In a container of 60 mL PFA (tetrafluoroethylene/perfluoro(propyl vinyl ether) copolymer), the crude product (compound (4) purity 70%) synthesized in the previous example (40 g), three Antimony fluoride (18 g) and antimony pentachloride (0.72 mL) were added and stirred at 40° C. for 72 hours. After returning to room temperature, the reaction was stopped by dropping the reaction slurry into an ice-cooled 1N hydrochloric acid aqueous solution (50 g). After washing the liberated lower layer with water (50 g) three times, 24 g of compound (5) represented by FSO ₂ CF ₂ CF ₂ OCFClCFClOCF ₂ CF ₂ SO ₂ F with a GC purity of 95% was obtained by distillation.

Compound (5) GCMS (EI)
m/e 335, 333, 331, 265, 183, 136, 134, 133, 132, 119, 100, 97, 67

Compound (M1) synthesis method Zinc powder (5.6 g) and dimethylformamide (38 g) were placed in a 200 mL glass flask equipped with a dropping funnel and a Dimroth condenser, and the temperature was raised to 100°C while stirring. Compound (5) (24 g) diluted with dimethylformamide (10 g) was added dropwise from the dropping funnel, dimethylformamide (5 g) was then added from the dropping funnel, and the mixture was stirred at 100° C. for 4 hours. After cooling the mixture to room temperature, 1N hydrochloric acid (80 g) and pentane (80 g) were added, and an organic layer was obtained by filtration and liquid separation. The organic layer was washed twice with 1N hydrochloric acid (50 g) and twice with water (50 g), and then dried over magnesium sulfate. Pentane was distilled off under reduced pressure, and the resulting mixture was distilled to obtain 10 g of a compound (M1) represented by the following formula with a GC purity of 98%.

Claims (3)

The following general formula (2):
Rf ⁶ -O-CFX ^a -CFY ^a -O-Rf ⁶ (2)
(wherein both Rf ⁶ are —Rf ⁷ —SO ₂ F (wherein Rf ⁷ is a chain or branched C 1-11 fluorinated alkylene group); X ^a and Y ^a are the same or different and are —H, —F, —Cl, —Br or —I, provided that both X ^a and Y ^a are —H or —F ) is a fluorine-containing compound characterized by the following. The following general formula (2):
RF ⁶ -O-CFX ^a -CFY ^a -O-Rf ⁶ (2)
(In the formula, Rf ⁶ one of -Rf ⁸ -SO ₂ F (in the formula, Rf ⁸ is a chain or branched fluorinated alkylene group having 1 to 11 carbon atoms. ) is a group represented by Rf ⁶ is -Rf ⁹ -SO ₂ F (in the formula, Rf ⁹ is a chain or branched C 1-11 fluorinated alkylene group containing an etheric oxygen atom. ) is a group represented by X ^a and Y ^a are the same or different and are -H, -F, -Cl, -Br or -I. However, X ^a and Y ^a are both -H or -F. ) A fluorine-containing compound characterized by being represented by 3. The fluorine-containing compound according to claim 1 , wherein one of X ^a and Y ^a is —F and the other is —H, —Cl, —Br or —I.