JP5026040B2 - Novel fluorine-containing spirocyclic acetal compound and method for producing the same - Google Patents

Description

  The present invention includes a bifunctional compound that can be a raw material monomer for a fluorine-containing polymer having performances such as chemical resistance, weather resistance, water and oil repellency, low molecular interaction, low refractive index, and high light transmittance. The present invention relates to a fluorine spiro cyclic acetal compound and a method for producing the same.

It is a well-known fact that bifunctional ester compounds, acid halides and alcohol compounds are useful as monomer components of condensation polymers. In recent years, fluorine-containing polymers have been actively developed focusing on the chemical resistance, weather resistance, water / oil repellency, low-molecular interaction, low refractive index, and high light transmission properties of fluorine compounds. Yes.
For example, an example of a polycondensation type fluorine-containing polymer for an optical waveguide is described in Patent Document 1 and the literature cited therein. In addition, Patent Document 2 and Patent Document 3 and documents cited therein disclose that polymers obtained by cyclopolymerization of fluorine-containing (ω-alkenyl vinyl ethers) are useful for optical materials such as optical fibers. Yes. Furthermore, it is known that homopolymers of perfluorodioxole compounds described in Patent Document 4 and Patent Document 5 and copolymers with tetrafluoroethylene and the like form amorphous polymers and can be used for the same applications as described above. .
On the other hand, a fluorine-containing bifunctional compound and a method for producing the same are described in Patent Document 6, for example.
However, none of the above documents describes the fluorine-containing spirocyclic acetal compound of the present invention and the production method thereof.
WO03 / 099907A1 specification WO03 / 037838A1 specification Japanese Patent Laid-Open No. 5-70522 US Pat. No. 3,978,030 US Pat. No. 4,399,264 WO02 / 004397 specification

  The object of the present invention is to be able to manufacture from inexpensive raw materials without using complicated operations, and has superior performance (chemical resistance, weather resistance, water / oil repellency, low molecular weight) by polymerization. It is an object of the present invention to provide a novel bifunctional fluorine-containing spirocyclic acetal compound that gives a polymer exhibiting properties such as interaction properties, low refractive index properties, and high light transmittance. A second object of the present invention is to provide a process for producing the above bifunctional fluorine-containing spirocyclic acetal compound.

The present inventor considered the structure and properties of conventional polymers, and introducing a cyclic structure and an ether bond into the polymer main chain imparted polymer physical properties such as amorphousness and high glass transition temperature (T _g ). As a result of further investigation, the inventors have developed a spiro ring compound having an ether bond (acetal bond) in the ring component.
That is, the object of the present invention has been achieved by a compound represented by the following general formula (A) and a production method.
(1) A fluorine-containing spiro cyclic acetal compound represented by the following general formula (A).

In the formula, X represents> C (CF ₃ ) (Y ) . Wherein Y _is, -CF 2 OCOR was ¹ or represents _-CH 2 OR ^{3, R 1} represents an alkyl group or a cycloalkyl group having at least one fluorine atom, ^{R 3} represents a hydrogen atom or an acyl group . Alkyl group or cycloalkyl group for R ¹ may have a substituent other than a fluorine atom, an acyl group at or R ³ may have a substituent.
(2) The fluorine-containing spiro cyclic acetal compound according to (1), wherein the compound represented by the general formula (A) is represented by any one of the following general formulas (I 1 ) or ( IV).

In the formula, R ¹ represents an alkyl group or a cycloalkyl group having at least one fluorine atom. The alkyl group or cycloalkyl group in R ¹ may have a substituent in addition to the fluorine atom.
(3) before Symbol R ¹ is characterized in that it is a perfluoroalkyl group (1) or a fluorine-containing spirocyclic acetal compound according to (2).
(4) A fluorine-containing spiro cyclic acetal compound represented by any one of the following general formulas (IV) and (VI).

Where R ⁴ Represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
(5) A fluorine-containing spiro cyclic acetal compound represented by the following general formula (IV).

(6) A fluorine-containing diacrylate compound represented by the following general formula (VI).

Where R ⁴ Represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
(7) R ⁴ Is a hydrogen atom, The fluorine-containing spiro cyclic acetal compound as described in (6) characterized by the above-mentioned.
(8) A perfluoroester compound represented by the following formula (I-1).

(9) It comprises a step of synthesizing acyloxyacetone from hydroxyacetone, a step of dehydrating condensation of acyloxyacetone obtained in this step with pentaerythritol, and a step of fluorinating a compound obtained by the dehydration condensation. The manufacturing method of the fluorine-containing spiro cyclic acetal compound represented by the following general formula (A ').

式中、Ｘは、＞Ｃ（ＣＦ _３ ）（Ｙ）を表す。ここでＹは、−ＣＨ _２ ＯＲ ^３ を表し、Ｒ ^３ は水素原子またはアシル基を表す。Ｒ ^３ におけるアシル基は置換基を有してもよい。
In the formula, X represents> C (CF ₃ ) (Y ) . Wherein Y _represents -CF 2 OCOR ^{1, R 1} has at least one fluorine atom, to display the alkyl group or a cycloalkyl group. Alkyl group or cycloalkyl group for R ¹ is, but it may also have a substituent other than a fluorine atom.
(10) A step of reducing the compound represented by the general formula (A ′) obtained by the method according to (9) to an acid fluoride or an esterification, and A method for producing a fluorine-containing spirocyclic acetal compound represented by the general formula (A ″).

In the formula, X represents> C (CF ₃ ) (Y). Here, Y represents —CH ₂ OR ³ , and R ³ represents a hydrogen atom or an acyl group. The acyl group in R ³ may have a substituent.

The compound of the present invention is useful as a raw material monomer or precursor of a fluorine-containing polymer having performances such as chemical resistance, weather resistance, water / oil repellency, low molecular interaction, low refractive index, and high light transmittance. It is.
Moreover, according to the manufacturing method of this invention, the fluorine-containing compound which has a spiro cyclic acetal structure can be manufactured with a sufficient yield.
Furthermore, according to the production method of the present invention, the fluorine-containing compound having the spiro cyclic acetal structure can be produced from a relatively inexpensive raw material without using a complicated operation.
The polymer of the fluorine-containing spiro cyclic acetal compound represented by the general formula (A) of the present invention is excellent in chemical resistance, weather resistance, optical performance and the like and can be used for various applications such as for optical waveguides.

The compounds of the present invention are described in detail below.
In one general formula (A), X _{is,> C (CF 3) (} Y) or> represents a C = CF _2, in the present invention represents _{a> C (CF 3) (Y} ). Here, Y represents —CF ₂ OCOR ¹ , —COOR ² , —COF, or —CH ₂ OR ^3, and in the present invention, Y represents —CF ₂ OCOR ¹ or —CH ₂ OR ³ .
R ¹ represents an alkyl group or a cycloalkyl group having at least one fluorine atom, R ² represents a hydrogen atom, an alkali metal, an alkaline earth metal, an alkyl group or a cycloalkyl group, and R ³ represents a hydrogen atom or an acyl group Represents.
The alkyl group in R ¹ preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, may be linear or branched, and may further have a substituent.
The cycloalkyl group in R ¹ preferably has 3 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, and may further have a substituent. R ¹ is preferably the above alkyl group.
Examples of the substituent for the alkyl group or cycloalkyl group include the substituents described later in R ² in addition to the fluorine atom. In particular, the alkyl group may have an ether bond, and when an alkyl group is substituted on a cycloalkyl group, the alkyl group may have an ether bond. Examples of the alkyl group having an ether bond include an alkoxy group, an alkenoxy group, a cycloalkoxy group, and an aryloxy group as a group that substitutes for the alkyl group.
R ¹ is preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and more preferably a perfluoroalkyl group. Specific examples include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoro (1-methyl-2-oxapentyl), perfluoro (1,4-dimethyl-2,5- Dioxaoctyl), perfluorocyclohexyl, perfluoroheptyl, perfluorooctyl, perfluorodecyl, perfluoroundecyl, perfluorododecyl, and the like, but the present invention is not limited thereto.

In the general formula (A), R ² represents a hydrogen atom, an alkali metal, an alkaline earth metal, an alkyl group, or a cycloalkyl group. The alkyl group in R ² preferably has 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, which may be linear or branched and may have a substituent. The cycloalkyl group in R ² preferably has 3 to 20 carbon atoms, more preferably a cycloalkyl group having 5 to 10 carbon atoms, and may have a substituent. Examples of the alkyl group and cycloalkyl group in R ² include methyl, ethyl, propyl, isopropyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl and the like. Moreover, these alkyl groups and cycloalkyl groups may have a substituent.

Examples of the substituent that the alkyl group or cycloalkyl group of R ² may have include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group having 20 or less carbon atoms (for example, Methyl, ethyl), an alkenyl group having 20 or less carbon atoms (for example, vinyl, allyl), a cycloalkyl group having 20 or less carbon atoms (for example, cyclopentyl, cyclohexyl), a cycloalkenyl group having 20 or less carbon atoms (for example, cyclohexenyl). ), An aryl group having 30 or less carbon atoms (for example, phenyl, naphthyl), a cyano group, a carboxyl group, an alkoxycarbonyl group having 20 or less carbon atoms (for example, methoxycarbonyl), an aryloxycarbonyl group having 30 or less carbon atoms (for example, Phenoxycarbonyl), a carbamoyl group (eg, carbamoyl, N-phenoxycarbonyl) Nylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group having 20 or less carbon atoms (for example, acetyl), arylcarbonyl group having 30 or less carbon atoms (for example, benzoyl), nitro group, amino group (for example, amino, dimethyl) Amino, anilino), acylamino group having 20 or less carbon atoms (for example, acetamido, ethoxycarbonylamino), sulfonamide group (for example, methanesulfonamide), imide group (for example, succinimide, phthalimide), imino group (for example, benzylideneano) ),

Hydroxy group, alkoxy group having 20 or less carbon atoms (for example, methoxy), aryloxy group having 30 or less carbon atoms (for example, phenoxy), acyloxy group having 20 or less carbon atoms (for example, acetoxy), alkylsulfonyl having 20 or less carbon atoms An oxy group (for example, methanesulfonyloxy), an arylsulfonyloxy group having 30 or less carbon atoms (for example, benzenesulfonyloxy), a sulfo group, a sulfamoyl group (for example, sulfamoyl, N-phenylsulfamoyl), an alkylthio group having 20 or less carbon atoms ( Examples include methylthio), arylthio groups having 30 or less carbon atoms (for example, phenylthio), alkylsulfonyl groups having 20 or less carbon atoms (for example, methanesulfonyl), arylsulfonyl groups having 30 or less carbon atoms (for example, benzenesulfonyl), heterocyclic groups, and the like. Can. The substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. Moreover, you may combine with substituents and may form a ring. Furthermore, the alkyl group in the substituent may form an unsaturated bond at an arbitrary position.
Of the alkyl group and cycloalkyl group represented by R ² , an alkyl group is preferable, and among them, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
Examples of the alkali metal or alkaline earth metal represented by R ² include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium, preferably sodium and potassium, more preferably potassium. It is.

In the general formula (A), R ³ represents a hydrogen atom or an acyl group. As the acyl group, an acyl group having 1 to 20 carbon atoms (for example, formyl, acetyl, butyryl, stearoyl, benzoyl, cyclohexanoyl, acryloyl, methacryloyl, isocrotonoyl, oleyl) is preferable, and the acyl group has a substituent. May be. Examples of the substituent include the substituents described for R ² above. Here, the acyl group is preferably an alkenoyl group (preferably an alkenoyl group of a terminal vinyl) and a hydroxyl alkanoyl group, more preferably an alkenoyl group having a terminal vinyl, and further preferably acryloyl or methacryloyl which may have a substituent. , —CO (R ⁴ ) ═CH ₂ is most preferred. Here, R ⁴ represents a hydrogen atom, a methyl group or a trifluoromethyl group. R ⁴ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Compound represented by the general formula (A), under following general formula (I), the general formula (II), (III) or a compound represented by any one of (IV) or the formula (V) compounds represented or a compound represented by the general formula (VI) is rather preferred, are are in the present invention, the following formula (I), represented by (IV) or (VI), the general formula (II) , (III) or (V) is a reference example . Each of these groups has the same meaning as the corresponding group in the general formula (A), and the preferred range is also the same.
The compound represented by the general formula (I) is preferably a compound represented by the general formula (I-1), and the compound of the reference example represented by the general formula (II) is represented by the general formula (II-1). The compound of the reference example represented by this is preferable.

Although the compound represented with general formula (A) below is shown, this invention is not limited by this.
The compounds represented by (II-1) to (II-5) and (V) are reference examples.

(I-1) R ¹ = CF (CF ₃ ) OCF ₂ CF ₂ CF ₃
(I-2) R ¹ = perfluoromethyl (I-3) R ¹ = perfluoroethyl (I-4) R ¹ = perfluoropropyl (I-5) R ¹ = perfluoroisopropyl (I-6) R ¹ = perfluorobutyl (I-7) R ¹ = perfluoropentyl (I-8) R ¹ = perfluorohexyl (I-9) R ¹ = perfluoro (1-methyl-2-oxabutyl)
(I-10) R ¹ = perfluoro (1,4-dimethyl-2,5-dioxaoctyl)
(I-11) R ¹ = perfluorocyclohexyl (I-12) R ¹ = perfluoroheptyl (I-13) R ¹ = perfluorooctyl (I-14) R ¹ = perfluorodecyl (I-15) R ¹ = perfluoroun Decyl (I-16) R ¹ = perfluorododecyl (I-17) R ¹ = perfluoro (1-methyl-2-oxahexyl)
(I-18) R ¹ = perfluorocyclopentyl (II-1) R ² = CH ₃
(II-2) R ² = K
(II-3) R ² = C ₂ H ₅
(II-4) R ² = Cyclohexyl (II-5) R ² = Na

(VI-1) R ⁴ = H
(VI-2) R ⁴ = F
(VI-3) R ⁴ = CH ₃
(VI-4) R ⁴ = CF ₃

Next, a process for producing a fluorinated spirocyclic acetal compound represented by a general formula (A).
The fluorine-containing spirocyclic acetal compound represented by the general formula (A) can be produced by a process including a step of fluorinating a spiroacetal compound obtained by a reaction of acyloxyacetone or pyruvate with pentaerythritol. it can.
Here, the fluorine-containing spirocyclic acetal compound represented by a general formula (A), for example hydroxyacetone 1 or pyruvic acid ester 4 as shown in the following scheme (I) can be prepared as a starting material.
Among these, the method for producing the fluorine-containing spirocyclic acetal compound represented by the general formula (A) is a spiroacetal 3 or 5 obtained by the reaction of at least acyloxyacetone 2 or pyruvate 4 and pentaerythritol in the following scheme. And (I) or 6 of the resulting fluorinated compound is obtained. Among these, Preferably, it is a process including the process of fluorinating the spiro acetal compound obtained by reaction of acyloxyacetone and pentaerythritol.

Hereinafter, substituents of the compounds described in the following scheme will be described.
In the following reaction scheme, R ¹¹ represents an alkyl group or a cycloalkyl group, and may have a fluorine atom or the substituent described for R ² . R ¹² represents an alkyl group or a cycloalkyl group, and may have a fluorine atom or the substituent described in R ² . R ¹² is preferably an alkyl group. Rf ¹² represents an alkyl group or a cycloalkyl group in which one or more of R ¹² are replaced with a fluorine atom. X ¹ represents a halogen atom.
In addition, R < ¹ > and R < ² > is synonymous with the thing in general formula (A), R < ⁴ > is synonymous with the thing in general formula (VI), and its preferable range is also the same.

Each of the above groups will be further described.
The alkyl group in R ¹¹ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and the cycloalkyl group in R ¹¹ is 3 to 20 carbon atoms, preferably 5 to 5 carbon atoms. Ten cycloalkyl groups are preferred. These groups may have a substituent as described above. The alkyl group in R ¹¹ may have an ether bond in the alkyl chain, and such a group alkyl group is also preferable. The substituent which may be substituted on the alkyl group is preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The cycloalkyl group in R ¹¹ is also preferably a substituted alkyl group which may have an ether bond in the alkyl chain as a substituent of the cycloalkyl group, or a substituted alkyl group substituted with a halogen atom. R ¹¹ is preferably an alkyl group rather than a cycloalkyl group.
R ¹¹ may be an alkyl group or cycloalkyl group containing no fluorine atom, such as methyl, ethyl, propyl, cyclopentyl, cyclohexyl, etc., but is preferably an alkyl group or cycloalkyl group containing a fluorine atom, more preferably The fluorine-containing alkyl group or fluorine-containing cycloalkyl group is such that the fluorine content in the compound 3 is 30% by mass or more. Examples of such an alkyl group or cycloalkyl group include perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoro (1-methyl-2-oxapentyl), perfluoro (1,4-dimethyl- 2,5-dioxaoctyl), perfluorocyclohexyl, perfluoroheptyl, perfluorooctyl, perfluorodecyl, perfluoroundecyl, perfluorododecyl, 2H-tetrahydroethyl, 4H-octafluorobutyl, 6H-dodecafluorohexyl, 8H-hexadecafluoro Examples include octyl.

X ¹ represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom or a chlorine atom.
R ¹² is preferably an alkyl group or a cycloalkyl group in the same meaning as R ^11, and the preferred range is also the same.
R ¹² is preferably an alkyl group, more preferably an alkyl group having a fluorine atom, and particularly preferably a fluorine-containing alkyl group having a fluorine content of 30% by mass or more in the compound 5. Examples of such an alkyl group include 1H, 1H-pentafluoropropyl, 1H, 1H-heptafluorobutyl, 1H, 1H, 2H, 2H-nonafluorohexyl, 1H, 1H, 2H, 2H, 3H, 3H-nonafluoro. Heptyl, 1H, 1H, 2H, 2H-tridecafluorooctyl, 1H, 1H, 2H, 2H, 3H, 3H-tridecafluorononyl, 1H, 1H, 2H, 2H-heptadecafluorodecyl, 2,5-dimethyl -3,6-dioxa-1H, 1H-heptadecafluorononyl, 5-methyl-1H, 1H, 2H, 2H-undecafluorohexyl, 7-methyl-1H, 1H, 2H, 2H-pentadecafluorooctyl, 1H, 1H, 3H-tetrafluoropropyl, 1H, 1H, 5H-octafluoropentyl, 1H, 1H, 7H- Decafluoro heptyl, 1H, 1H, 9H- hexadecafluoro nonyl, 2H- hexafluoro-2-propyl, 1H, 1H, 3H- hexafluoro-butyl and the like.

Rf ¹² is preferably a perfluoroalkyl group in which all hydrogen atoms in R ¹² are replaced with fluorine atoms.

This will be further described using the above scheme (I).
Acyloxyacetone is preferably represented by the above compound 2, and can be obtained, for example, by reaction of hydroxyacetone 1 with a carboxylic acid halide. On the other hand, the pyruvic acid ester is preferably represented as the above compound 4 and is commercially available or can be easily synthesized by esterification of pyruvic acid.
The reaction of these acyloxyalkyl acetone (Compound 2) or pyruvic acid ester (Compound 4) and pentaerythritol, in particular spiroacetal compound (compound 3 or 5) is synthesized by dehydration condensation reaction, the resulting The fluorine-containing spirocyclic acetal compound represented by the general formula (A) can be produced in a step including a step of fluorinating the obtained spiroacetal compound (Compound 3 or 5).
Here, the compound represented by the general formula (I) is synthesized by obtaining the compound 3 from the compound 2 of the above reaction scheme (the compound 2 is synthesized from the compound 1 in the above reaction scheme) and fluorinating the compound 3. it can.
As the compound represented by the general formula (II), the compound represented by the general formula (I) thus obtained is used, or the compound 6 (the compound 6 is obtained after obtaining the compound 5 from the compound 4, Can be synthesized by reacting with R ² OH. Moreover, the general formula of the compound or compounds 6 are represented by (I) F ^- is reacted with ions, a compound represented by the obtained formula (III) can be synthesized by reacting with R ² OH. Here, when R ² is a hydrogen atom, an alkali metal or an alkaline earth metal, the compound in which R ² in the general formula (II) is an alkyl group or a cycloalkyl group can be hydrolyzed and synthesized. It can also be synthesized by hydrolyzing the compound represented by the general formula (III).
Compound represented by the general formula (III), a compound or compounds 6 are represented by the general formula (I) as described above F ^- can be synthesized by reacting an ion. Although the compound represented by the general formula (III) is not described in the above reaction scheme, a method of thermally decomposing the compound represented by the general formula (I) or the compound 6 is also used in the present invention. Is a preferred embodiment.
The compound represented by the formula (IV) can be synthesized by reducing the compound represented by the general formula (II) or the compound represented by the general formula (III) obtained as described above.
The compound represented by the general formula (V) can be synthesized by thermally decomposing the compound represented by the general formula (II) or the general formula (III) obtained as described above.
In the general formula (A), a compound in which X is> C (CF ³ ) (Y), Y is —CH ₂ OR ³ , and R ³ is an acyl group is represented by the general formula (IV). Can be synthesized by acylating the compound. Examples of the acylating agent include acyl halides and organic acid anhydrides of the corresponding acyl moiety, and organic acids are also preferably used. In the said reaction scheme, the compound represented with general formula (VI) which is a preferable compound among this compound was described as a representative. That is, the acylating agent in the compound represented by the general formula (VI) is particularly preferably an acrylic acid derivative represented by Cl—COC (R ⁴ ) ═CH ₂ . This point will be described later.

Hereinafter, each step in the scheme (I) will be described in detail.
Conversion to acyloxyacetone (compound 2) by reaction of hydroxyacetone 1 and carboxylic acid halide is, for example, published by Maruzen Co., Ltd., edited by The Chemical Society of Japan, 4th edition Experimental Chemistry Course 22, Organic Synthesis IV, -Acid / Amino Acid / Peptide-, p. It can be carried out under the general conditions as described in 50-51. To obtain spirocyclic acetal 3 or 5 from compound 2 or 4 and pentaerythritol, see, for example, J. Org. Org. Chem. 26, 2515 (1961), Tetrahedron, 60, 4789 (2004), Chem. Ber. 61, 790 (1928) and the like.
Specifically, the compound 2 or 4 and pentaerythritol are subjected to a dehydration condensation reaction. This dehydration reaction may be any method that can separate or remove water produced under the reaction conditions. For example, a method of removing water azeotropically in the presence of an acid catalyst, or in the presence of a dehydrating agent. A method of carrying out the reaction is preferred.
At this time, the amount of pentaerythritol used is preferably 0.1 to 5 equivalents, more preferably 0.2 to 1 equivalent, and particularly preferably 0.3 to 0.6 equivalents relative to Compound 2 or 4.
Examples of the acid catalyst include hydrogen chloride, hydrogen bromide, sulfuric acid, phosphoric acid, ammonium chloride, sulfonic acid compounds (for example, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (monohydrate), etc.), carboxylic acid compounds (e.g. acetic acid, propionic acid, butanoic acid, adipic acid, and benzoic acid) various Lewis acids (eg boron trifluoride etherate, aluminum chloride, zirconium oxide, etc.), various solid acid catalyst [for example, Nafion (Nafion ^R, trade name ), Amberlite (Amberlite ^R, tradename, those acidic), Montmorillonite K10 (trade name)] and the like. Moreover, you may use combining these. Of these, p-toluenesulfonic acid monohydrate is preferable. As the usage-amount of the said acid catalyst, 0.001-2 equivalent is preferable with respect to the compound 2 or 4, and 0.01-0.5 equivalent is more preferable.
When removing water by azeotropy, it is preferable to use a Dean-Stark trap. In addition, when water is removed with a dehydrating agent, examples of the dehydrating agent include magnesium sulfate, sodium sulfate, zeolite, and molecular sieves. These dehydrating agents are preferably used in an amount that is greater than or equal to the amount capable of retaining the water produced by the reaction. The dehydrating agent may be used in the reaction system, or may be used outside the reaction system by being retained in the reflux tube.
The reaction may be performed without a solvent or in a solvent. Solvents used include benzene, toluene, xylene, petroleum ether, N, N-dimethylformamide, N, N-diethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide (DMSO), sulfolane, carbon tetrachloride, chloroform, hexane, heptane, cyclohexane and the like, and mixed solvents thereof are mentioned, and toluene is more preferable. The amount of the solvent used is preferably 1 to 100 times by mass and more preferably 2 to 50 times by mass of the amount of compound 2 or 4. The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 120 ° C. The reaction time depends on the type, amount, solvent and reaction temperature of the acid used. It is preferable to carry out the reaction within 12 hours, preferably within 6 hours by adjusting these appropriately.

The fluorination reaction from the compound 3 to the compound represented by the general formula (I) and from the compound 5 to the compound 6 is carried out by a method using cobalt trifluoride, an electrolytic fluorination method and direct fluorine using a fluorine gas in the liquid phase. There are known methods for crystallization (hereinafter referred to as liquid phase direct fluorination method), and these reactions can be used in the present invention. The fluorination reaction using cobalt trifluoride or electrolytic fluorination has problems that cause isomerization and main chain cleavage and recombination, making it difficult to obtain the desired compound with high purity. Therefore, in the present invention, it is more preferable to use the liquid phase direct fluorination method.
The fluorination reaction by the liquid phase direct fluorination method can be carried out in the same manner as described in US Pat. No. 5,093,432 and WO 00/56694.

The synthesis of the compound represented by the general formula (I) or the compound 6 represented by the general formula (II), particularly the compound in which R ² is an alkyl group or a cycloalkyl group is represented by the general formula (I). Or an alcohol represented by R ² OH (R ² is an alkyl group or a cycloalkyl group). The reaction temperature is preferably -20 to 100 ° C, more preferably 0 to 50 ° C. In this reaction, a solvent may be used or it may be carried out without a solvent. Further, the reaction may be performed in the presence of a base, or may be performed without a base.
Solvents that can be used include dichloromethane, chloroform, carbon tetrachloride, diethyl ether, tetrahydrofuran, acetone, ethyl acetate, hexane, toluene, xylene, acetonitrile and the like used in the liquid phase fluorination reaction {eg, perfluoroalkane compounds [FC -72 (trade name, manufactured by Sumitomo 3M), etc.], perfluoroether compounds [FC-75, FC-77 (both trade names, manufactured by Sumitomo 3M), etc.], perfluoropolyether compounds [trade name: Krytox (Registered trademark), manufactured by DuPont), foblin (formed by Fomblin (registered trademark), manufactured by AUSIMINT), Galden (produced by Galden (registered trademark), manufactured by AUSIMINT), demnum {manufactured by Daikin Industries, Ltd.}, etc.], chlorofluorocarbon Compound (CFC-11, CFC-113, etc.), chlorofluoropolyether compound, perfluorotrialkylamine compound, inert fluid (trade name: Fluorinert, Fluorinert (registered trademark), manufactured by Sumitomo 3M Ltd.) and the like A mixed solvent can be mentioned. The amount of the solvent used is preferably 1 to 100 times by mass and more preferably 2 to 50 times by mass of the amount of the compound represented by formula (I) or compound 6.

Examples of the base that can be used include organic bases such as pyridine, triethylamine, N, N-diisopropylethylamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate. Moreover, you may use alkali metal fluorides, such as sodium fluoride, potassium fluoride, and a cesium fluoride, as a hydrogen fluoride scavenger.
As the usage-amount of the base used by this invention, 0.5-10 equivalent is preferable with respect to the compound or compound 6 represented by general formula (I), and 1-3 equivalent is more preferable.
The amount of R ² OH to be used is not particularly limited, but in order to complete the reaction, it is preferably 4 equivalents or more, more preferably 4 to 20 equivalents, relative to the compound represented by formula (I) or compound 6. .
In the general formula (II), a compound in which R ² is a hydrogen atom, an alkali metal or an alkaline earth metal is a compound or compound 6 represented by the general formula (I), or R ² is an alkyl in the general formula (II) It can be easily obtained by (alkali) hydrolysis of either a group or a compound that is a cycloalkyl group.

The compound represented by the general formula (I) or the compound 6 can be converted into a compound represented by the general formula (III) by thermal decomposition. At this time, it is preferably carried out in the presence of an alkali metal fluoride such as sodium fluoride, potassium fluoride, or cesium fluoride. The amount of the alkali metal fluoride used is preferably 0.01 to 5 equivalents, more preferably 0.1 to 1 equivalents with respect to the compound represented by the general formula (I) or the compound 6. The reaction temperature is preferably 50 to 300 ° C, more preferably 100 to 250 ° C. The reaction may be performed in the gas phase or in the liquid phase. In the case of a liquid phase reaction, the reaction solvent is compatible with the compound represented by the general formula (I) or the compound 6 and does not react with the compound represented by the general formula (I) or the compound 6 and the product. If there is no particular limitation, for example, the perfluoropolyether compound, the chlorofluoropolyether compound and the like described above may be used. However, in consideration of separation of the solvent and the product, it is preferably performed without a solvent.

The compound represented by the general formula (III) is represented by the general formula (II) under the same conditions as those for converting the compound represented by the general formula (I) to the compound represented by the general formula (II). Can be converted to
The compound represented by the general formula (II) and the compound represented by the general formula (III) can be converted into a compound represented by the formula (IV) by a reduction reaction. As the reduction reaction, for example, published by Maruzen Co., Ltd., edited by The Chemical Society of Japan, 4th edition, Experimental Chemistry Course 26, Organic Synthesis VIII, -Asymmetric Synthesis / Reduction / Sugar / Labeled Compound- Various reduction methods such as those described in 159-266 can be used. As a preferable reduction method, a method using a metal hydride complex compound such as sodium borohydride, lithium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride (trade name Red-Al, Vitride) [for example, J. Org. Am. Chem. Soc. 116, 4135 (1994); Org. Chem. 26, 2943 (1961), J. Am. Org. Chem. 41, 1470 (1976); Am. Chem. Soc. 115, 8954 (1993). Or a method by catalytic reduction using a hydrogen / transition metal catalyst (for example, see US Pat. No. 2,666,797).
The compound represented by the general formula (V) is a compound represented by the general formula (II) (R ² is preferably an alkali metal or an alkaline earth metal, more preferably sodium or potassium) or a compound represented by the formula (III) Can be obtained by thermal decomposition. As the conditions for the thermal decomposition, for example, Methods of Organic Chemistry, 4, Vol. 10b, Part 1, p. 703, J. et al. Fluorine Chem. 94, 65 (1999), J. Am. Fluorine Chem. 123, 43 (2003), J.A. Org. Chem. , 34, 1841 (1969), J. Am. Org. Chem. , 51, 326 (1986) and the like.
The compound represented by the general formula (IV) can be converted into a compound represented by the general formula (VI) by an esterification reaction with an acrylic acid derivative. Examples of acrylic acid derivatives include carboxylic acids represented by CH ₂ ═CH (R ⁴ ) CO ₂ H, CH ₂ ═CH (R ⁴ ) COX ¹ (X ¹ is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. An acid halide represented by a halogen atom, preferably a chlorine atom), an acid anhydride represented by [(CH ₂ ═CH (R ⁴ ) CO) ₂ ] O (wherein R ⁴ is a general formula) Esterification reaction with the compound represented by the general formula (IV) is, for example, published by Maruzen Co., Ltd., edited by The Chemical Society of Japan, 4th edition, Experimental Chemistry Course. 22, Organic Synthesis IV, -Acid / Amino Acid / Peptide-, p. General methods such as those described in 43-53 can be performed under conditions.

Bifunctional ester of the present invention represented by general formula (II) or acid fluoride represented by general formula (III) and polyfunctional alcohol or phenol (for example, 2 of the present invention represented by general formula (IV)) A polyester can be produced by condensation polymerization of a functional alcohol, ethylene glycol, 1,3-propanediol, bisphenol, hydroquinone, or the like. Examples of the polyester production method include Maruzen Co., Ltd., edited by The Chemical Society of Japan, 4th edition, Experimental Chemistry Course 28, Polymer Synthesis, p. It can be performed according to the method described in 217-231.
The bifunctional ester of the present invention represented by the general formula (II) or the acid fluoride represented by the general formula (III) is a polyfunctional amine or aniline (for example, ethylenediamine, 1,3-diaminopropane, bis ( 4-aminophenyl) ether, 4,4′-diaminodiphenylmethane, etc.) can be subjected to polycondensation to produce polyamide. As a method for producing polyamide, for example, published by Maruzen Co., Ltd., edited by The Chemical Society of Japan, 4th edition, Experimental Chemistry Course 28, Polymer Synthesis, p. 260-277 and the like.
Furthermore, the bifunctional alcohol of the present invention represented by the general formula (IV) is a polyfunctional electrophile (for example, 1,2-dibromoethane, 1,3-dibromopropane, 4,4′-dichlorobenzophenone, 4,4′-difluorobenzophenone, bis (4-chlorophenyl) sulfone, etc.) can be subjected to polycondensation to produce a polyether. As a method for producing polyether, for example, published by Maruzen Co., Ltd., edited by The Chemical Society of Japan, 4th edition, Experimental Chemistry Course 28, Polymer Synthesis, p. 185, and can be carried out according to the conditions of aromatic nucleophilic substitution polymerization.
Polyesters, polyamides, polyethers, and the like thus obtained have a high fluorine content, and have properties specific to the fluorine-containing compound polymer such as high light transmittance, low refractive index, water repellency and oil repellency.

Example 1

  Hereinafter, the present invention will be described in more detail based on examples. The present invention is not limited to these examples.

Hereinafter, specific production examples of the compound represented by the general formula (A) will be described.
According to the following route, the compounds represented by the general formulas (I-1), (II-1), (III), (IV) and (V) and the compounds (II-2) and (VI-1) are produced. did.
Among these, the compounds represented by the general formulas (II-1), (III), and (V), and the compound (II-2) are reference examples.

Preparation of Compound 2-1 Undecafluoro (2-methyl-3-oxahexanoic acid) fluoride in a solution of hydroxyacetone (7.4 g) and pyridine (8.1 ml) in ethyl acetate (100 ml) at room temperature (25 ° C.) (10 g) was added dropwise. After stirring at room temperature for 2 hours, the reaction solution was poured into dilute hydrochloric acid water. After liquid separation, the organic layer was washed with water and saturated brine, and dried over magnesium sulfate. The concentrated residue was purified by column chromatography (developing solvent: ethyl acetate / hexane) to give Compound 2-1 (10.2 g, yield 88%).
¹ H NMR (CDCl ₃ ) δ 2.22 (s, 3H), 4.85 (d, J = 16.2 Hz, 1H), 4.96 (d, J = 16.2 Hz, 1H)
¹⁹ F NMR (CDCl ₃ ) δ-80.3 (1F), -81.8 (3F), -82.5 (3F), -86.7 (1F), -130.2 (2F), -132 .8 (1F)

Production of Compound 3-1 Compound 2-1 (9.9 g), pentaerythritol (1.74 g), p-toluenesulfonic acid monohydrate (0.25 g) and toluene (50 ml) were refluxed for 4 hours while dehydrating. did. The reaction mixture was washed with aqueous sodium hydrogen carbonate solution, water and saturated brine, and dried over sodium sulfate. The concentrated residue was purified by column chromatography (developing solvent: ethyl acetate / hexane) to obtain Compound 3-1 (5.9 g, yield 53%).
¹ H NMR (CDCl ₃ ) δ 1.41 (s, 3H), 3.64 to 3.85 (m, 4H), 4.31 (d, J = 11.1 Hz, 1H), 4.48 (d , J = 11.1Hz, 1H)
¹⁹ F NMR (CDCl ₃ ) δ-80.2 (1F), -81.7 (3F), -82.5 (3F), -86.8 (1F), -130.1 (2F), -132 .3 (1F)

Production of Compound Represented by Formula (I-1) 300 ml provided with a raw material supply port, a fluorine supply port, a helium gas supply port, and an exhaust port connected to a fluorine trap via a reflux device cooled with dry ice 180-ml FC-72 was put into a Teflon (registered trademark) container, and helium gas was blown at an internal temperature of 20 ° C. at a flow rate of 50 ml / min for 30 minutes. Subsequently, 20% F ₂ / N ₂ gas was blown at 100 ml / min for 30 minutes, and the fluorine flow rate was kept as it was, and a solution of compound 3-1 (4.25 g) in FC-72 (13.5 ml) and hexafluorobenzene ( 1 g) of FC-72 (5 ml) was added at a rate of 6.2 ml / h each. Further, 20% F ₂ / N ₂ gas was blown at 100 ml / min for 30 minutes and helium gas was blown at 200 ml / min for 30 minutes. After concentration of FC-72 at normal pressure and further under reduced pressure, the compound represented by the formula (I-1) (5.1 g, crude yield 88%) was almost a single product (oil Product).
¹⁹ F NMR (CDCl ₃ ) δ −60.6 to 64.4 (m, 8F), −76.7 (s, 6F), −79.8 to −80.0 (m, 1F), −80. 3 to -80.6 (m, 1F), 82.0 (m, 6F), 82.1 (s, 6F), -83.4 to -83.8 (m, 4F), -86.7 ( bs, 1F), -86.9 (bs, 1F), -130.2 (s, 4F), -132.0 (s, 1F), -132.1 (s, 1F)

Preparation of compounds of reference examples represented by general formulas (III) and (II-1) General formula (I-1) (5.1 g) and sodium fluoride (0.06 g) obtained above The mixture was stirred at 120 ° C. for 24 hours. At this time, a water-cooled cooler was attached to the reaction vessel, and the low boiling point product was refluxed. The compound represented by the general formula (III) (0.5 g, yield 22%) was obtained by distillation under reduced pressure.
Further, methanol (20 ml) was added to the distillation residue, and the mixture was stirred at room temperature for 3 hours. The reaction was poured into an ethyl acetate / sodium bicarbonate solution. The organic layer was washed with water and saturated brine, and dried over magnesium sulfate. The concentrated residue was purified by column chromatography (developing solvent: ethyl acetate / hexane) to obtain the compound represented by the general formula (II-1) (1.2 g, yield 51%).
General formula (III): ¹⁹ F NMR (CDCl ₃ ) δ 30.2 to 30.3 (m, 2F), −62.8 to −64.2 (m, 4F), −70.6 to −71. 8 (m, 4F), -80.9 to -81.0 (m, 6F) Melting point: 26-28 ° C, boiling point: 135 ° C
General formula (II-1): ¹ H NMR (CDCl ₃ ) δ 3.99 (s, 3H)
¹⁹ F NMR (CDCl ₃ ) δ −62.5 to −63.8 (m, 4F), −69.9 to −71.3 (m, 4F), −81.2 (s, 3F), −81 .4 (s, 3F) Melting point 48-55 ° C

Manufacturing of the compound represented by the general formula (IV)
Lithium aluminum hydride (0.038 g) was added at 5 ° C. to a solution of the compound represented by the general formula (II-1) (0.28 g) in diethyl ether (10 ml). After stirring at room temperature for 4 hours, dilute aqueous hydrochloric acid was slowly added to the reaction solution. After extraction with ethyl acetate, the organic layer was washed with water and saturated brine, and dried over magnesium sulfate. The concentrated residue was purified by column chromatography (developing solvent: ethyl acetate / hexane) to obtain the compound represented by the formula (IV) (0.2 g, yield 80%).
¹ H NMR (CDCl ₃ ) δ 2.20 (bs, 1H), 4.21 (bs, 2H),
¹⁹ F NMR (CDCl ₃ ) δ −56.2 to −58.6 (m, 4F), −66.0 to −67.3 (m, 4F), 80.9 to 81.0 (m, 6F) Melting point: 106-108 ° C

Production of Compound (VI-1)
Potassium carbonate (4.8 g) is added to a solution of the compound represented by the general formula (IV) (3.7 g) in 1-methyl-2-pyrrolidone (30 ml), and acrylic acid chloride (2.4 ml) is slowly added dropwise. did. The reaction solution was stirred at room temperature for 3 hours and then poured into ethyl acetate (150 ml) / dilute hydrochloric acid (150 ml). The organic layer was washed with aqueous sodium hydrogen carbonate solution, water and saturated brine, and dried over magnesium sulfate. The concentrated residue was purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/5) to obtain Compound (VI-1) (3.5 g, yield 78%).
¹ H NMR (CDCl ₃ ) δ 4.75 (s, 4H), 5.98 (dd, J = 10.5 Hz, 1.2 Hz, 2H), 6.16 (dd, J = 17.1 Hz, 10. 5Hz, 2H), 6.51 (dd, J = 17.1 Hz, 1.2 Hz, 2H)
¹⁹ F NMR (CDCl ₃ ) δ −57.0 to −58.3 (m, 4F), −66.1 to −67.0 (m, 4F), −81.2 (s, 3F), −81 .3 (s, 3F) Melting point 34-35 ° C

Production of compound of reference example represented by general formula (V)
To a methanol (200 ml) / water (40 ml) solution of the compound (16.2 g) represented by the general formula (II-1), 10 ml of an 8N potassium hydroxide aqueous solution was added dropwise at room temperature. The reaction solution was stirred at room temperature for 2 hours, and then the solvent was distilled off under reduced pressure. 30 ml of water was added to the concentrated residue, and further concentrated hydrochloric acid was added dropwise with a pH test paper until it showed acidity. The precipitated white crystals were filtered, dispersed in water (30 ml), and 1N aqueous potassium hydroxide solution was added dropwise to adjust pH = 8. The reaction solution was concentrated under reduced pressure, and the residue was sufficiently dried with a vacuum pump at 100 ° C. to obtain compound (II-2) (16.5 g, yield 93%). The obtained compound (II-2) was thermally decomposed at 280 ° C. under reduced pressure (4 mmHg), and volatile components were collected by a trap at −78 ° C. The obtained liquid was distilled under reduced pressure to obtain a compound represented by the formula (V) (0.98 g, yield 74%).
¹⁹ F NMR (CDCl ₃ ) δ-70.7 (s, 8F), -111.2 (s, 4F), b. p. 55 ° C (20mmHg)

Test example 1
Compound (VI-1) (2 g) and Irgacure 907 (trade name, photopolymerization initiator manufactured by Ciba-Geigy Co., Ltd.) (0.1 g) were dissolved in methyl ethyl ketone to prepare a 30% by mass solution, and then the pore size was 0.25 μm. The solution was filtered through a polytetrafluoroethylene filter. The curable resin composition thus prepared was applied onto a PET substrate using a bar coater. The solvent was dried (room temperature 30 minutes + 120 ° C., 2 minutes), then irradiated with ultraviolet rays (500 mJ × 2 times) in a nitrogen atmosphere, and further heated at 120 ° C. for 2 minutes to obtain a transparent cured resin coating film.
A cured resin film was prepared in exactly the same manner except that the compound (VI-1) was replaced with equimolar amounts of the compound (VII) and the compound (VIII).
The cured resin films of the compound (VI-1), (VII) or (VIII) prepared as described above are all made of an amorphous polymer.

The results of evaluating the pencil hardness, refractive index, adhesion, and contact angle of these films are summarized in Table 1 below.
In addition, each evaluation followed the following method.
Pencil hardness: Measured according to JIS K5400.
Refractive index: Measured using an Abbe refractometer (manufactured by Atago Co., Ltd.).
Adhesion: A peel test was performed according to JIS K5400. (○: no peeling, Δ: peeling less than 5%, x: peeling more than 5%)
Contact angle: The contact angle with respect to pure water was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.).
Chemical resistance: 0.5 ml of 5% aqueous sodium hydroxide solution was dropped, and the state of the film surface after wiping for 12 hours was observed. (○: No change, Δ: Some change was observed, ×: Large change was observed.)

  From the results of Table 1, the polymer using the compound (VII) of Comparative Example has a large refractive index, a remarkably small contact angle, inferior water repellency, and insufficient chemical resistance. Moreover, the polymer using the compound (VIII) of the comparative example does not have sufficient adhesion. On the other hand, the polymer using the compound (VI-1) of the present invention is excellent in pencil hardness, refractive index, adhesion, contact angle, and chemical resistance.

Reference example 1
A mixture of 0.5 g of the compound represented by the general formula (V) and 6 mg of perfluorobenzoyl peroxide was sufficiently deoxygenated by nitrogen bubbling and allowed to stand at 30 ° C. for 3 days under sealing. The obtained solid was filtered, washed with acetone, and dried to obtain a white polymer (0.2 g, mp 300 ° C. or higher). When 1% by mass of this white polymer was added to ester oil, and the pin wear amount was measured with a FALEX friction tester (conditions: 80 ° C., 250 lb, 1 hour) manufactured by Falex Corporation, In comparison with this, a significant reduction in the amount of wear is observed.

Claims (10)

The fluorine-containing spiro cyclic acetal compound represented by the following general formula (A).

In the formula, X represents> C (CF ₃ ) (Y ) . Wherein Y _is, -CF 2 OCOR was ¹ or represents _-CH 2 OR ^{3, R 1} has at least one fluorine atom, an alkyl group or a cycloalkyl group, an ^{R 3} is a hydrogen atom or an acyl group To express. Alkyl group or cycloalkyl group for R ¹ may have a substituent other than a fluorine atom, an acyl group at or R ³ may have a substituent. The fluorine-containing spiro cyclic acetal compound of Claim 1 by which the compound represented by the said general formula (A) is represented by either the following general formula (I ) or ( IV).

In the formula, R ¹ represents an alkyl group or a cycloalkyl group having at least one fluorine atom. The alkyl group or cycloalkyl group in R ¹ may have a substituent in addition to the fluorine atom. Fluorinated spirocyclic acetal compound according to claim 1 or 2 before Symbol R ¹ is characterized in that it is a perfluoroalkyl group. The fluorine-containing spiro cyclic acetal compound represented by either the following general formula (IV) or (VI).

Where R ⁴ Represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. A fluorine-containing spiro cyclic acetal compound represented by the following general formula (IV).

A fluorine-containing diacrylate compound represented by the following general formula (VI).

In the formula, R ⁴ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ⁴ Is a hydrogen atom, The fluorine-containing spiro cyclic acetal compound of Claim 6 characterized by the above-mentioned. A perfluoroester compound represented by the following formula (I-1).

The following general formula, which comprises a step of the fluorination step, the acyloxyalkyl acetone obtained in about該工 pentaerythritol step of dehydration condensation, a compound obtained by dehydration condensation of synthesizing acyloxyalkyl acetone hydroxyacetone The manufacturing method of the fluorine-containing spiro cyclic acetal compound represented by (A ') .

In the formula, X represents> C (CF ₃ ) (Y ) . Wherein Y _represents -CF 2 OCOR ^{1, R 1} has at least one fluorine atom, to display the alkyl group or a cycloalkyl group. Alkyl group or cycloalkyl group for R ¹ is, but it may also have a substituent other than a fluorine atom. The compound represented by the general formula (A ′) obtained by the method according to claim 9 is reduced to an acid fluoride or esterified, and then the following general formula (A ") The manufacturing method of the fluorine-containing spiro cyclic acetal compound represented.

Where X is> C (CF ₃ ) (Y). Where Y is -CH ₂ OR ³ Represents R ³ Represents a hydrogen atom or an acyl group. R ³ The acyl group in may have a substituent.