JP2012184185A - Novel perfluoroalkylating agent and method for producing perfluoroalkyl group-containing compound by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To propose a novel perfluoroalkylmagnesium-zirconium ate complex.SOLUTION: A perfluoroalkylating agent is prepared by reacting a perfluoromagnesium halide with a metallocene dihalide represented by general formula (2) (wherein M is a titanium atom or a zirconium atom; and X is a halogen atom) and a perfluoroalkyl iodide, and various perfluoroalkyl group-containing compounds are prepared by using the same.

Description

  The present invention relates to a novel perfluoroalkylating agent and a method for producing a perfluoroalkyl group-containing compound using the same. Perfluoroalkyl group-containing compounds are useful compounds as intermediates for the production of various medical and agricultural chemicals.

  The novel perfluoroalkylating agent of the present invention is not known.

  Conventionally, a perfluoroalkyl magnesium halide is known as a synthetic reagent for fluorine-containing compounds, and a method for synthesizing various fluorine-containing compounds using the reagent is known (Non-patent Document 1).

J. et al. Fluorine Chemistry (1975), 5 (2), 115-125

  Conventionally known perfluoroalkylmagnesium halides exist stably only at a temperature of -30 ° C. or lower, and decompose by raising the temperature, so that the use conditions thereof are limited. Further, the reaction is limited to perfluoroalkylation of only carbonyl compounds represented by acetaldehyde and acetone.

  As a result of intensive studies on a method for solving the above problems, the present inventor has found a novel perfluoroalkylating agent prepared from alkylmagnesium halide, perfluoroalkyl iodide and metallocene dihalide, and the perfluoroalkylating agent Shows high reactivity to various carbonyl compounds, and also shows high reactivity to cyano compounds and esters that have not been known so far, and gives perfluoroalkylated products in high yield. As a result, the present invention has been completed.

That is, the present invention
[Claim 1] The following general formula (1)

R ¹ MgX (1)

(Wherein R ¹ represents a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, and X represents a halogen atom)
And an alkylmagnesium halide represented by the following general formula (2)

(Wherein M represents a titanium atom or a zirconium atom, and X represents a halogen atom)
And metallocene dihalide represented by the following general formula (3)

Rf-I (3)

(Wherein Rf represents a trifluoromethyl group, a pentafluoroethyl group, a linear, branched or cyclic perfluoroalkyl group or a perfluoroaryl group having 3 to 9 carbon atoms)
A perfluoroalkylating agent prepared by reacting a perfluoroalkyl iodide represented by the formula:

[Item 2] The perfluoroalkylating agent according to Item 1 and the following general formula (4)

(Wherein R ² and R ³ are each independently a hydrogen atom, a methyl group, an ethyl group, or a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, a naphthyl group, a pyridyl group, a phenyl group, An ethylenyl group, a substituted alkyl group or a substituted phenyl group, R ² and R ³ may be condensed, and R ² and R ³ are not hydrogen atoms)
The following general formula (5), characterized in that a carbonyl compound represented by the formula:

(Wherein Rf, R ² and R ³ are the same as above)
The manufacturing method of fluorine-containing alcohol represented by these.

[Item 3] The perfluoroalkylating agent according to Item 1 and the following general formula (6)

R ⁴ -CN (6)

(Wherein R ⁴ is a methyl group, an ethyl group, or a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, a naphthyl group, a pyridyl group, a phenylethylenyl group, a substituted alkyl group, or a substituted phenyl group. Indicate)
Or a cyano compound represented by the following general formula (7)

R ⁴ —CO ₂ R ⁵ (7)

(In the formula, R ⁴ is the same as above, R ⁵ represents a methyl group or an ethyl group)
The following general formula (8):

(Wherein R ⁴ and Rf are the same as above)
The manufacturing method of perfluoroalkyl ketones represented by these.

[Item 4] The perfluoroalkylating agent according to Item 1 and the following general formula (9)

(Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, a naphthyl group, a pyridyl group, a methoxy group, A carbonyl group, a phenylethynyl group, a substituted alkyl group, a substituted phenyl group, a substituted alkenyl group, and a substituted acetylene group)
The following general formula (10), characterized by reacting an epoxy compound represented by

(Wherein R ⁶ , R ⁷ and Rf are the same as above)
The manufacturing method of the fluorine-containing compound represented by these is provided.

  The perfluoroalkylating agent of the present invention can be perfluoroalkylated on carbonyl compounds, cyano compounds and epoxy compounds, which have been difficult to perfluoroalkylate.

  Hereinafter, embodiments of the present invention will be described.

  The substituted alkyl group of the present invention represents a 2- (tert-butyldiphenylsilyloxy) ethyl group.

  The substituted alkenyl group of the present invention represents a 3-benzyloxy-1-propynyl group or a 1-bromo-2-phenylethenyl group.

  The substituted phenyl group of the present invention represents a 4-methoxyphenyl group, a 4-nitrophenyl group, or a 4-methoxycarbonylphenyl group.

  The substituted acetylene group of the present invention is a phenylethynyl group, a 4-methoxyphenylethynyl group, or a 4- (tert-butyldiphenylsilyloxy) -1-butynyl group.

  Specific examples of the alkylmagnesium halide represented by the formula (1) of the present invention include, for example, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmaunecumum chloride, ethylmagnesium bromide, ethyl Magnesium iodide, n-propylmagnesium chloride, n-propylmagnesium bromide, n-propylmagnesium iodide, iso-propylmagnesium chloride, iso-propylmagnesium bromide, iso-propylmagnesium iodide, n-butylmagnesium chloride, n- Butylmagnesium bromide, n-butylmagnesium iodide, iso-butylmagnesium chloride, iso-butylmagnesium bromide Amide, iso- butyl magnesium iodide, tert- butyl magnetic shim chloride, tert- butyl magnesium bromide, and tert- butyl magnesium iodide and the like.

  The metallocene dihalide represented by the general formula (2) of the present invention is titanium sendiodichloride or zirconocene dichloride.

  Specific examples of the perfluoroalkyl iodide represented by the general formula (3) of the present invention include trifluoromethyl iodide, pentafluoroethyl iodide, n-heptafluoropropyl iodide, and iso-heptafluoro. Propyl iodide, n-nonafluorobutyl iodide, iso-nonafluorobutyl iodide, tert-nonafluorobutyl iodide, n-undecafluoropentyl iodide, n-tridecafluorohexyl iodide, n-pentadeca Examples thereof include fluoroheptyl iodide and n-heptadecafluorooctyl iodide.

  The perfluoroalkylating agent of the present invention comprises an alkylmagnesium halide represented by the general formula (1) and a metallocene dihalide represented by the general formula (2) at a temperature of −40 ° C. or lower in a solvent inert to the reaction. And the perfluoroalkyl iodide represented by the general formula (3) is mixed, then heated to 0 to -30 ° C., and stirred for a predetermined time.

  In preparing the perfluoroalkylating agent of the present invention, the alkylmagnesium halide represented by the general formula (1) is used in an amount of 2.0 mol or more based on the metallocene dihalide represented by the general formula (2). If it is, there is no problem, but usually 2.0 to 2.2 mol amount is used.

  In the preparation of the perfluoroalkylating agent of the present invention, the perfluoroalkyl iodide represented by the general formula (3) is sufficient in an equimolar amount or more with respect to the metallocene dihalide represented by the general formula (2). However, preferably 1.2 to 2.0 molar amounts are used.

  As the solvent applicable to the preparation of the perfluoroalkylating agent of the present invention, any solvent can be used as long as it is inert to the reaction. Preferably, ether solvents such as diethyl ether and tetrahydrofuran are used for the reaction. It is used in an amount of 10 to 200 times by weight based on the metallocene dihalide represented by the general formula (2).

  The preparation time of the perfluoroalkylating agent of the present invention is an alkylmagnesium halide represented by the general formula (1), a metallocene dihalide represented by the general formula (2) and a general formula (3) at -40 ° C or lower. After the perfluoroalkyl iodide represented is mixed, it is maintained for 1 to 3 hours, then heated to 0 to −30 ° C., and maintained for 1 to 3 hours.

  The perfluoroalkylating agent of the present invention is used for reactions with various substrates after preparation without isolation and purification.

  Specific examples of the carbonyl compounds represented by the general formula (4) of the present invention include acetaldehyde, propionaldehyde, 2-methylpropionaldehyde, 2,2-dimethylpropionaldehyde, n-butanal, and n-pentanal. N-hexanal, n-heptanal, n-octanal, n-nonanal, cyclopentanecarbaldehyde, cyclohexanecarbaldehyde, benzaldehyde, cinnamaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, acetone, 2-butanone, 2-pentanone 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, 2-decanone, cyclopentanone, cyclo-2-pentenone, cyclohexanone, cyclo-2-hexenone, 2-adamantanone, acetophene , Benzophenone, 2-acetylpyridine, 3-acetylpyridine, 4-acetylpyridine, benzalacetone, 1-indanone, 2-indanone, α-tetralone, β-tetralone, 2-n-pentyl-2-cyclopentenone , 2-phenylpropionaldehyde, 3-O-methylesterone and the like.

Specific examples of the fluorine-containing alcohol represented by the general formula (5) of the present invention include 1,1,1-trifluoro-2-hydroxypropane, 1,1,1-trifluoro-2- Hydroxybutane, 1,1,1-trifluoro-2-hydroxy-3-methylbutane, 1,1,1-trifluoro-2-hydroxy-3,3-dimethylbutane, 1,1,1-trifluoro-2 -Hydroxypentane, 1,1,1-trifluoro-2-hydroxyhexane, 1,1,1-trifluoro-2-hydroxyheptane, 1,1,1-trifluoro-2-hydroxyoctane, 1,1, 1-trifluoro-2-hydroxynonane, 1,1,1-trifluoro-2-hydroxydecane, 2,2,2-trifluoro-1-hydroxy-1-cyclopentylethane, , 2,2-trifluoro-1-hydroxy-1-cyclohexylethane, 2,2,2-trifluoro-1-hydroxy-1-phenylethane, 1,1,1-trifluoro-2-hydroxy-4- Phenyl-3-butene, 2,2,2-trifluoro-1-hydroxy-1- (1-naphthyl) ethane, 2,2,2-trifluoro-1-hydroxy-1- (2-naphthyl) ethane, 1,1,1-trifluoro-2-hydroxy-2-methylpropane, 1,1,1-trifluoro-2-hydroxy-2-methylbutane, 1,1,1-trifluoro-2-hydroxy-2- Methylpentane, 1,1,1-trifluoro-2-hydroxy-2-methylhexane, 1,1,1-trifluoro-2-hydroxy-2-methylheptane, 1,1,1-trifluoro Ro-2-hydroxy-2-methyloctane, 1,1,1-trifluoro-2-hydroxy-2-methylnonane, 1,1,1-trifluoro-2-hydroxy-2-methyldecane, 1-trifluoromethyl -1-hydroxycyclopentane, 1-trifluoromethyl-1-hydroxy-2-cyclopentene, 1-trifluoromethyl-1-hydroxycyclohexane, 1-trifluoromethyl-1-hydroxy-2-cyclohexene, 2,2, 2-trifluoro-1-hydroxy-1-methyl-1- (2-adamantyl) ethane, 2,2,2-trifluoro-1-hydroxy-1-methyl-1-phenylethane, 2,2,2- Trifluoro-1-hydroxy-1,1-diphenylethane, 2,2,2-trifluoro-1-hydroxy-1-methyl Ru-1- (2-pyridyl) ethane, 2,2,2-trifluoro-1-hydroxy-1-methyl-1- (3-pyridyl) ethane, 2,2,2-trifluoro-1-hydroxy- 1-methyl-1- (4-pyridyl) ethane, 1,1,1-trifluoro-2-hydroxy-2-methyl-4-phenyl-3-butene, 1-trifluoromethyl-1-hydroxyindane, 2 -Trifluoromethyl-2-hydroxyindane, 1-trifluoromethyl-1-hydroxy-1,2,3,4-tetrahydronaphthalene, 2-trifluoromethyl-2-hydroxy-1,2,3,4-tetrahydro Naphthalene, 1-trifluoromethyl-1-hydroxy-2-n-pentyl-2-cyclopentene, 1,1,1-trifluoro-2-hydroxy-3-phenylbutane (8R, 9S, 13S, 14S, 17S) -3-methoxy-13-methyl-17-trifluoromethyl-7,8,9,11,12,13,14,15,16,17-decahydro- 6H-cyclopenta [a] phenanthrene-17-ol, 1,1,1,2,2-pentafluoro-3-hydroxybutane, 1,1,1,2,2-pentafluoro-3-hydroxypentane, 1, 1,1,2,2-pentafluoro-3-hydroxy-4-methylpentane, 1,1,1,2,2-pentafluoro-3-hydroxy-4,4-dimethylbutane, 1,1,1, 2,2-pentafluoro-3-hydroxyhexane, 1,1,1,2,2-pentafluoro-3-hydroxyheptane, 1,1,1,2,2-pentafluoro-3-hydroxyoctane, 1,1,1,2,2-pentafluoro-3-hydroxynonane, 1,1,1,2,2-pentafluoro-3-hydroxydecane, 1,1,1,2,2-pentafluoro-3- Hydroxyundecane, 2,2,3,3,3-pentafluoro-1-hydroxy-1-cyclopentylpropane, 2,2,3,3,3-pentafluoro-1-hydroxy-1-cyclohexylpropane, 2,2 , 3,3,3-pentafluoro-1-hydroxy-1-phenylpropane, 1,1,1,2,2-pentafluoro-3-hydroxy-5-phenyl-4-pentene, 2,2,3, 3,3-pentafluoro-1-hydroxy-1- (1-naphthyl) propane, 2,2,3,3,3-pentafluoro-1-hydroxy-1- (2-naphthyl) propane, 1,1, 1, 2,2-pentafluoro-3-hydroxy-3-methylbutane, 1,1,1,2,2-pentafluoro-3-hydroxy-3-methylpentane, 1,1,1,2,2-pentafluoro- 3-hydroxy-3-methylhexane, 1,1,1,2,2-pentafluoro-3-hydroxy-3-methylheptane, 1,1,1,2,2-pentafluoro-3-hydroxy-3- Methyloctane, 1,1,1,2,2-pentafluoro-3-hydroxy-3-methylnonane, 1,1,1,2,2-pentafluoro-3-hydroxy-3-methyldecane, 1,1,1 , 2,2-pentafluoro-3-hydroxy-3-methylundecane, 1-pentafluoroethyl-1-hydroxycyclopentane, 1-pentafluoroethyl-1-hydroxy-2-sic Pentene, 1-pentafluoroethyl-1-hydroxycyclohexane, 1-pentafluoroethyl-1-hydroxy-2-cyclohexene, 2,2,3,3,3-pentafluoro-1-hydroxy-1-methyl-1- (2-adamantyl) propane, 2,2,3,3,3-pentafluoro-1-hydroxy-1-methyl-1-phenylpropane, 2,2,3,3,3-pentafluoro-1-hydroxy- 1,1-diphenylpropane, 2,2,3,3,3-pentafluoro-1-hydroxy-1-methyl-1- (2-pyridyl) propane, 2,2,3,3,3-pentafluoro- 1-hydroxy-1-methyl-1- (3-pyridyl) propane, 2,2,3,3,3-pentafluoro-1-hydroxy-1-methyl-1- (4-pyridyl) Lopan, 1,1,1,2,2-pentafluoro-3-hydroxy-3-methyl-5-phenyl-4-pentene, 1-pentafluoroethyl-1-hydroxyindane, 2-pentafluoroethyl-2- Hydroxyindane, 1-pentafluoroethyl-1-hydroxy-1,2,3,4-tetrahydronaphthalene, 2-pentafluoroethyl-2-hydroxy-1,2,3,4-tetrahydronaphthalene, 1-pentafluoroethyl -1-hydroxy-2-n-pentyl-2-cyclopentene, 1,1,1,2,2-pentafluoro-3-hydroxy-4-phenylpentane, (8R, 9S, 13S, 14S, 17S) -3 -Methoxy-13-methyl-17-pentafluoroethyl-7,8,9,11,12,13,14,15,16,17 Decahydro-6H-cyclopenta [a] phenanthrene-17-ol, 1,1,1,2,2,3,3-heptafluoro-4-hydroxypentane, 1,1,1,2,2,3,3 -Heptafluoro-4-hydroxyhexane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-5-methylhexane, 1,1,1,2,2,3,3-hepta Fluoro-4-hydroxy-5,5-dimethylpentane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxyhexane, 1,1,1,2,2,3,3-hepta Fluoro-4-hydroxyoctane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxynonane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxydecane 1,1,1,2,2,3,3- Ptafluoro-4-hydroxyundecane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxydodecane, 2,2,3,3,4,4,4-heptafluoro-1-hydroxy- 1-cyclopentylbutane, 2,2,3,3,4,4,4-heptafluoro-1-hydroxy-1-cyclohexylbutane, 2,2,3,3,4,4,4-heptafluoro-1- Hydroxy-1-phenylbutane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-6-phenyl-5-hexene, 2,2,3,3,4,4,4- Heptafluoro-1-hydroxy-1- (1-naphthyl) butane, 2,2,3,3,4,4,4-heptafluoro-1-hydroxy-1- (2-naphthyl) butane, 1,1, 1,2,2,3,3-heptafluo -4-hydroxy-4-methylpentane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-4-methylhexane, 1,1,1,2,2,3,3- Heptafluoro-4-hydroxy-4-methylheptane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-4-methyloctane, 1,1,1,2,2,3 3-heptafluoro-4-hydroxy-4-methylnonane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-4-methyldecane, 1,1,1,2,2,3 3-heptafluoro-4-hydroxy-4-methylundecane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-4-methyldodecane, 1-heptafluoropropyl-1-hydroxycyclo Pentane, 1-heptuff Fluoropropyl-1-hydroxy-2-cyclopentene, 1-heptafluoropropyl-1-hydroxycyclohexane, 1-heptafluoropropyl-1-hydroxy-2-cyclohexene, 2,2,3,3,4,4,4-hepta Fluoro-1-hydroxy-1-methyl-1- (2-adamantyl) butane, 2,2,3,3,4,4,4-heptafluoro-1-hydroxy-1-methyl-1-phenylbutane, 2 , 2,3,3,4,4,4-heptafluoro-1-hydroxy-1,1-diphenylbutane, 2,2,3,3,4,4,4-heptafluoro-1-hydroxy-1- Methyl-1- (2-pyridyl) butane, 2,2,3,3,4,4,4-heptafluoro-1-hydroxy-1-methyl-1- (3-pyridyl) butane, 2,2,3 3,4,4,4-heptafluoro-1-hydroxy-1-methyl-1- (4-pyridyl) butane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-4 -Methyl-6-phenyl-5-hexene, 1-heptafluoropropyl-1-hydroxyindane, 2-heptafluoropropyl-2-hydroxyindane, 1-heptafluoropropyl-1-hydroxy-1,2,3,4 -Tetrahydronaphthalene, 2-heptafluoropropyl-2-hydroxy-1,2,3,4-tetrahydronaphthalene, 1-heptafluoropropyl-1-hydroxy-2-n-pentyl-2-cyclopentene, 1,1,1 , 2,2,3,3-heptafluoro-4-hydroxy-5-phenylhexane, (8R, 9S, 13S, 14S, 17S)- -Methoxy-13-methyl-17-n-heptafluoropropyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta [a] phenanthren-17-ol, 1,1,2,2,3,3,4,4-nonafluoro-5-hydroxyhexane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxyheptane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-6-methylheptane, 1,1,1,2,2,3,3,4,4-nonafluoro-5 Hydroxy-6,6-dimethylhexane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxyheptane, 1,1,1,2,2,3,3,4, 4-nonafluoro-5-hydroxynonane, 1,1,1,2 2,3,3,4,4-nonafluoro-5-hydroxydecane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxyundecane, 1,1,1,2 , 2,3,3,4,4-nonafluoro-5-hydroxydodecane, 1,1,1,2,2,3,3,4


4-nonafluoro-5-hydroxytridecane, 2,2,3,3,4,4,5,5,5-nonafluoro-1-hydroxy-1-cyclopentylpentane, 2,2,3,3,4,4 , 5,5,5-nonafluoro-1-hydroxy-1-cyclohexylpentane, 2,2,3,3,4,4,5,5,5-nonafluoro-1-hydroxy-1-phenylpentane, 1,1 , 1,2,2,3,3,4,4-nonafluoro-5-hydroxy-7-phenyl-6-heptene, 2,2,3,3,4,4,5,5,5-nonafluoro-1 -Hydroxy-1- (1-naphthyl) pentane, 2,2,3,3,4,4,5,5,5-nonafluoro-1-hydroxy-1- (2-naphthyl) pentane, 1,1,1 , 2,2,3,3,4,4-nonafluoro-5-hydro Ci-5-methylhexane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-5-methylheptane, 1,1,1,2,2,3,3 4,4-nonafluoro-5-hydroxy-5-methyloctane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-5-methylnonane, 1,1,1,2 , 2,3,3,4,4-nonafluoro-5-hydroxy-5-methyldecane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-5-methylundecane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-5-methyldodecane, 1,1,1,2,2,3,3,4,4-nonafluoro-5 -Hydroxy-5-methyltridecane, 1-n-nonafluorobutyl-1-hydro Cycyclopentane, 1-n-nonafluorobutyl-1-hydroxy-2-cyclopentene, 1-n-nonafluorobutyl-1-hydroxycyclohexane, 1-n-nonafluorobutyl-1-hydroxy-2-cyclohexene, 2 , 2,3,3,4,4,5,5,5-nonafluoro-1-hydroxy-1-methyl-1- (2-adamantyl) pentane, 2,2,3,3,4,4,5 5,5-nonafluoro-1-hydroxy-1-methyl-1-phenylpentane, 2,2,3,3,4,4,5,5,5-nonafluoro-1-hydroxy-1,1-diphenylpentane, 2,2,3,3,4,4,5,5,5-nonafluoro-1-hydroxy-1-methyl-1- (2-pyridyl) pentane, 2,2,3,3,4,4,5 , 5,5-Nonafluoro -1-hydroxy-1-methyl-1- (3-pyridyl) pentane, 2,2,3,3,4,4,5,5,5-nonafluoro-1-hydroxy-1-methyl-1- (4 -Pyridyl) pentane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-5-methyl-7-phenyl-6-heptene, 1-nonafluorobutyl-1-hydroxy Indan, 2-nonafluorobutyl-2-hydroxyindane, 1-nonafluorobutyl-1-hydroxy-1,2,3,4-tetrahydronaphthalene, 2-nonafluorobutyl-2-hydroxy-1,2,3 4-tetrahydronaphthalene, 1-nonafluorobutyl-1-hydroxy-2-n-pentyl-2-cyclopentene, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydride Xyl-6-phenylheptane, (8R, 9S, 13S, 14S, 17S) -3-methoxy-13-methyl-17-n-nonafluorobutyl-7,8,9,11,12,13,14,15 , 16,17-decahydro-6H-cyclopenta [a] phenanthrene-17-ol, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxyheptane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxyoctane, 1,1,1,2,2,3,3,4,4,5 , 5-Undecafluoro-6-hydroxy-7-methyloctane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxy-7,7- Dimethylheptane, 1,1,1,2,2,3,3,4,4,5,5- Ndecafluoro-6-hydroxyoctane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxydecane, 1,1,1,2,2,3 3,4,4,5,5-undecafluoro-6-hydroxyundecane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxydodecane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxytridecane, 1,1,1,2,2,3,3,4,4 5,5-undecafluoro-6-hydroxytetradecane, 2,2,3,3,4,4,5,5,6,6,6-undecafluoro-1-hydroxy-1-cyclopentylhexane, 2, 2,3,3,4,4,5,5,6,6,6-undecafluoro-1-hydroxy-1-si Chlohexylhexane, 2,2,3,3,4,5,5,6,6,6-undecafluoro-1-hydroxy-1-phenylhexane, 1,1,1,2,2,3 , 3,4,4,5,5-undecafluoro-6-hydroxy-8-phenyl-7-octene, 2,2,3,3,4,4,5,5,6,6,6-un Decafluoro-1-hydroxy-1- (1-naphthyl) hexane, 2,2,3,3,4,4,5,5,6,6,6-undecafluoro-1-hydroxy-1- (2 -Naphthyl) hexane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxy-6-methylheptane, 1,1,1,2,2, 3,3,4,4,5,5-undecafluoro-6-hydroxy-6-methyloctane, 1,1,1,2,2,3,3 4,4,5,5-undecafluoro-6-hydroxy-6-methylnonane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxy- 6-methyldecane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxy-6-methylundecane, 1,1,1,2,2,3 , 3,4,4,5,5-undecafluoro-6-hydroxy-6-methyldodecane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro- 6-hydroxy-6-methyltridecane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxy-6-methyltetradecane, 1-n-un Decafluoropentyl-1-hydroxycyclopentane, 1-n-undecafluoropentyl-1 Hydroxy-2-cyclopentene, 1-n-undecafluoropentyl-1-hydroxycyclohexane, 1-n-undecafluoropentyl-1-hydroxy-2-cyclohexene, 2,2,3,3,4,4,5 , 5,6,6,6-undecafluoro-1-hydroxy-1-methyl-1- (2-adamantyl) hexane, 2,2,3,3,4,4,5,5,6,6 6-undecafluoro-1-hydroxy-1-methyl-1-phenylhexane, 2,2,3,3,4,4,5,5,6,6,6-undecafluoro-1-hydroxy-1 1,2-diphenylhexane, 2,2,3,3,4,5,5,6,6,6-undecafluoro-1-hydroxy-1-methyl-1- (2-pyridyl) hexane, , 2,3,3,4,4,5,5,6,6 , 6-Undecafluoro-1-hydroxy-1-methyl-1- (3-pyridyl) hexane, 2,2,3,3,4,4,5,5,6,6,6-undecafluoro- 1-hydroxy-1-methyl-1- (4-pyridyl) hexane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxy-6-methyl -8-phenyl-7-octene, 1-undecafluoropentyl-1-hydroxyindane, 2-undecafluoropentyl-2-hydroxyindane, 1-undecafluoropentyl-1-hydroxy-1,2,3 4-tetrahydronaphthalene, 2-undecafluoropentyl-2-hydroxy-1,2,3,4-tetrahydronaphthalene, 1-undecafluoropentyl-1-hydroxy-2-n-pentyl-2 Cyclopentene, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxy-7-phenyloctane, (8R, 9S, 13S, 14S, 17S) -3 -Methoxy-13-methyl-17-n-undecafluoropentyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta [a] phenanthren-17-ol, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxyoctane, 1,1,1,2,2,3,3,4 , 4,5,5,6,6-tridecafluoro-7-hydroxynonane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro- 7-hydroxy-8-methyloctane, 1,1,1,2,2,3,3,4 , 5,5,6,6-tridecafluoro-7-hydroxy-8,8-dimethyloctane, 1,1,1,2,2,3,3,4,4,5,5,6,6- Tridecafluoro-7-hydroxynonane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxyundecane, 1,1,1, 2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxydodecane, 1,1,1,2,2,3,3,4,4,5,5 , 6,6-tridecafluoro-7-hydroxytridecane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxytetradecane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxypentadecane, 2,2,3,3 4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxy-1-cyclopentylheptane, 2,2,3,3,4,4,5,5,6 6,7,7,7-tridecafluoro-1-hydroxy-1-cyclohexylheptane, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro -1-hydroxy-1-phenylheptane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-9-phenyl-8- Nonene, 2,2,3,3,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxy-1- (1-naphthyl) heptane, 2,2,3 , 3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxy-1- (2-naphthyl) heptane, 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyloctane, 1,1,1,2,2,3 3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methylnonane, 1,1,1,2,2,3,3,4,4,5,5,6 6-tridecafluoro-7-hydroxy-7-methyldecane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7- Methylundecane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyldodecane, 1,1,1,2, 2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyltridecane, 1,1,1,2,2,3,3,4 4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyltetradecane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tri Decafluoro-7-hydroxy-7-methylpentadecane, 1-n-tridecafluorohexyl-1-hydroxycyclopentane, 1-n-tridecafluorohexyl-1-hydroxy-2-cyclopentene, 1-n-trideca Fluorohexyl-1-hydroxycyclohexane, 1-n-tridecafluorohexyl-1-hydroxy-2-cyclohexene, 2,2,3,3,4,4,5,5,6,6,7,7,7 -Tridecafluoro-1-hydroxy-1-methyl-1- (2-adamantyl) heptane, 2,2,3,3,4,4,5,5,6,6,7,7,7-trideca Fluoro-1-hydride Roxy-1-methyl-1-phenylheptane, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxy-1,1-diphenyl Heptane, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxy-


1-methyl-1- (2-pyridyl) heptane, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxy-1-methyl -1- (3-pyridyl) heptane, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxy-1-methyl-1- (4-Pyridyl) heptane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyl-9-phenyl-8 -Nonene, 1-tridecafluorohexyl-1-hydroxyindane, 2-tridecafluorohexyl-2-hydroxyindane, 1-tridecafluorohexyl-1-hydroxy-1,2,3,4-tetrahydronaphthalene, 2 -Tridecafluorohexyl-2-hydroxy-1, , 3,4-tetrahydronaphthalene, 1-tridecafluorohexyl-1-hydroxy-2-n-pentyl-2-cyclopentene, 1,1,1,2,2,3,3,4,4,5,5 , 6,6-tridecafluoro-7-hydroxy-8-phenylnonane, (8R, 9S, 13S, 14S, 17S) -3-methoxy-13-methyl-17-n-tridecafluorohexyl-7,8 9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta [a] phenanthrene-17-ol, 1,1,1,2,2,3,3,4,4,5 , 5,6,6,7,7-pentadecafluoro-8-hydroxynonane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7- Pentadecafluoro-8-hydroxydecane, 1,1,1, , 2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-9-methyldecane, 1,1,1,2,2,3,3,4 , 4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-9,9-dimethylnonane, 1,1,1,2,2,3,3,4,4,5, 5,6,6,7,7-pentadecafluoro-8-hydroxyundecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-penta Decafluoro-8-hydroxydodecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxytridecane, 1, 1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxytetradecane, 1,1,1,2,2,3 , 3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxypentadecane, 1,1,1,2,2,3,3,4,4,5,5 6,6,7,7-pentadecafluoro-8-hydroxyhexadecane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro -1-hydroxy-1-cyclopentyloctane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1- Cyclohexyloctane, 2,2,3,3,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1-phenyloctane, 1,1, 1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-10-fe Ru-9-decene, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1- (1-naphthyl) ) Octane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1- (2-naphthyl) octane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-8-methylnonane, 1,1,1,2, 2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-8-methyldecane, 1,1,1,2,2,3,3,4 4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-8-methylundecane, 1,1,1,2,2,3,3,4,4,5,5,6 , 6 7,7-pentadecafluoro-8-hydroxy-8-methyldodecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro -8-hydroxy-8-methyltridecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-8 -Methyltetradecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-8-methylpentadecane, 1,1 , 1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-8-methylhexadecane, 1-n-pentadecafluoroheptyl-1 -Hydroxycyclopentane, 1-n-pentadecafluoroheptyl-1-hydroxy-2-si Clopentene, 1-n-pentadecafluoroheptyl-1-hydroxycyclohexane, 1-n-pentadecafluoroheptyl-1-hydroxy-2-cyclohexene, 2,2,3,3,4,4,5,5,6 , 6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1-methyl-1- (2-adamantyl) octane, 2,2,3,3,4,4,5,5 6,6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1-methyl-1-phenyloctane, 2,2,3,3,4,4,5,5,6,6 , 7,7,8,8,8-pentadecafluoro-1-hydroxy-1,1-diphenyloctane, 2,2,3,3,4,4,5,5,6,6,7,7, 8,8,8-pentadecafluoro-1-hydroxy-1-methyl-1- (2- Lysyl) octane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1-methyl-1- (3 -Pyridyl) octane, 2,2,3,3,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1-methyl-1- ( 4-pyridyl) octane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-8-methyl-10- Phenyl-9-decene, 1-pentadecafluoroheptyl-1-hydroxyindane, 2-pentadecafluoroheptyl-2-hydroxyindane, 1-pentadecafluoroheptyl-1-hydroxy-1,2,3,4-tetrahydro Naphthalene, 2-pentadecafluoroheptyl-2 Hydroxy-1,2,3,4-tetrahydronaphthalene, 1-pentadecafluoroheptyl-1-hydroxy-2-n-pentyl-2-cyclopentene, 1,1,1,2,2,3,3,4 4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-9-phenyldecane, (8R, 9S, 13S, 14S, 17S) -3-methoxy-13-methyl-17-n Pentadecafluoroheptyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta [a] phenanthrene-17-ol, 1,1,1,2,2, 3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxydecane, 1,1,1,2,2,3,3,4,4 , 5,5,6,6,7,7,8,8-heptade Cafluoro-9-hydroxyundecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy-10 -Methylundecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy-10,10- Dimethyldecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxydodecane, 1,1, 1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxytridecane, 1,1,1,2,2, 3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxytetradecane, 1,1,1,2,2,3,3 4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxypentadecane, 1,1,1,2,2,3,3,4,4,5,5 , 6,6,7,7,8,8-heptadecafluoro-9-hydroxyhexadecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7, 7,8,8-heptadecafluoro-9-hydroxyheptadecane, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9- Heptadecafluoro-1-hydroxy-1-cyclopentylnonane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro -1-hydroxy-1-cyclohexylnonane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluor -1-hydroxy-1-phenylnonane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9- Hydroxy-11-phenyl-10-undecene, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1- Hydroxy-1- (1-naphthyl) nonane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1 -Hydroxy-1- (2-naphthyl) nonane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro- 9-hydroxy-9-methyldecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy- 9-methylundecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy-9-methyl Dodecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy-9-methyltridecane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy-9-methyltetradecane, 1,1 , 1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8-heptadecafluoro-9-hydroxy-9-methylpentadecane, 1,1,1, 2,2,3,3,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy-9-methylhexadecane, 1,1,1 2,2,3,3,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy-9-methylheptadecane, 1-n-heptadecafluorooctyl -1-hydroxycyclopentane, 1-n-heptadecafluorooctyl-1-hydroxy-2-cyclopentene, 1-n-heptadecafluorooctyl-1-hydroxycyclohexane, 1-n-heptadecafluorooctyl-1-hydroxy -2-cyclohexene, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1-hydroxy-1-methyl -1- (2-adamantyl) nonane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1- Hydroxy-1-methyl-1-fe Lunonane, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1-hydroxy-1,1-diphenylnonane 2,2,3,3,4,4,5,5,6,7,7,8,8,9,9,9-heptadecafluoro-1-hydroxy-1-methyl-1- ( 2-pyridyl) nonane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1-hydroxy-1- Methyl-1- (3-pyridyl) nonane, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1 -Hydroxy-1-methyl-1- (4-pyridyl) nonane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8- Heptadecafluoro-9-G Droxy-9-methyl-11-phenyl-10-undecene, 1-heptadecafluorooctyl-1-hydroxyindane, 2-heptadecafluorooctyl-2-hydroxyindane, 1-heptadecafluorooctyl-1-hydroxy-1 , 2,3,4-Tetrahydride


Lonaphthalene, 2-heptadecafluorooctyl-2-hydroxy-1,2,3,4-tetrahydronaphthalene, 1-heptadecafluorooctyl-1-hydroxy-2-n-pentyl-2-cyclopentene, 1,1, 1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9-hydroxy-10-phenylundecane, (8R, 9S, 13S, 14S, 17S) -3-Methoxy-13-methyl-17-n-heptadecafluorooctyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta [a] And phenanthrene-17-ol.

  Specific examples of the cyano compounds represented by the general formula (6) of the present invention include acetonitrile, propionitrile, n-butyronitrile, 1-cyano-n-butane, 1-cyano-n-pentane, Cyanocyclopentane, 1-cyano-n-hexane, cyanocyclohexane, 1-cyano-n-heptane, 1-cyano-n-octane, benzonitrile, 1-naphthonitrile, 2-naphthonitrile, 1-cyanopyridine, 2 -Cyanopyridine, 3-cyanopyridine, 1-cyano-2-phenylethane and the like.

  Specific examples of the esters represented by the general formula (7) of the present invention include methyl acetate, ethyl acetate, methyl propionate, ethyl n-propionate, methyl n-butanoate, and ethyl n-butanoate. , Methyl n-pentanoate, methyl cyclopentanecarboxylate, ethyl cyclopentanecarboxylate, methyl n-hexanoate, ethyl n-hexanoate, methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, methyl n-heptanoate, n-heptane Ethyl acetate, methyl n-octanoate, methyl n-nonanoate, ethyl n-nonanoate, methyl benzoate, ethyl benzoate, methyl cinnamate, ethyl cinnamate, phthalide, 5,6-dihydro-2H-pyran-2 -One, diethyl oxalate, methyl 1-methyl-2-cyclopentanone-1-carboxylate , Phthalide, and the like.

  Specific examples of the perfluoroalkyl ketones represented by the general formula (8) of the present invention include trifluoromethyl methyl ketone, trifluoromethyl ethyl ketone, trifluoromethyl n-propyl ketone, and trifluoromethyl n-butyl ketone. , Trifluoromethyl n-pentyl ketone, trifluoromethyl cyclopentyl ketone, trifluoromethyl n-hexyl ketone, trifluoromethyl cyclohexyl ketone, trifluoromethyl n-heptyl ketone, trifluoromethyl n-octyl ketone, trifluoromethyl phenyl ketone 1,1,1-trifluoro-4-phenyl-3-buten-2-one, 1-trifluoromethyl-1,3-dihydroisobenzofuran-1-ol, 2-trifluoromethyl-5,6 -Dihydro-2H-pyran-2-ol, ethyl 3,3,3-trifluoro-2,2-dihydroxypropionate, methyl 2-hydroxy-1-methyl-2- (trifluoromethyl) cyclopentanecarboxylate, 1-trifluoromethyl-1-hydroxy-1,3-dihydroisobenzofuran, pentafluoroethyl methyl ketone, pentafluoroethyl ethyl ketone, pentafluoroethyl n-propyl ketone, pentafluoroethyl n-butyl ketone, pentafluoroethyl n-pentyl ketone , Pentafluoroethyl cyclopentyl ketone, pentafluoroethyl n-hexyl ketone, pentafluoroethyl cyclohexyl ketone, pentafluoroethyl n-heptyl ketone, pentafluoroethyl n-octyl Ketone, pentafluoroethyl phenyl ketone, 1,1,1,2,2-pentafluoro-5-phenyl-4-buten-3-one, 1-pentafluoroethyl-1,3-dihydroisobenzofuran-1-ol 2-pentafluoroethyl-5,6-dihydro-2H-pyran-2-ol, 3,3,4,4,4-pentafluoro-2,2-dihydroxybutanoic acid, methyl 2-hydroxy-1- Methyl-2- (pentafluoroethyl) cyclopentanecarboxylate, 1-pentafluoroethyl-1-hydroxy-1,3-dihydroisobenzofuran, n-heptafluoropropyl methyl ketone, n-heptafluoropropyl ethyl ketone, n-heptafluoro Propyl n-propyl ketone, n-heptafluoropropyl n-butyl Ketone, n-heptafluoropropyl n-pentyl ketone, n-heptafluoropropyl cyclopentyl ketone, n-heptafluoropropyl n-hexyl ketone, n-heptafluoropropyl cyclohexyl ketone, n-heptafluoropropyl n-heptyl ketone, n- Heptafluoropropyl n-octyl ketone, n-heptafluoropropyl phenyl ketone, 1,1,1,2,2,3,3-heptafluoro-6-phenyl-5-buten-4-one, 1-n-hepta Fluoropropyl-1,3-dihydroisobenzofuran-1-ol, 2-n-heptafluoropropyl-5,6-dihydro-2H-pyran-2-ol, 3,3,4,4,5,5,5 -Ethyl heptafluoro-2,2-dihydroxypentanoate, methyl -Hydroxy-1-methyl-2- (n-heptafluoropropyl) cyclopentanecarboxylate, 1-n-heptafluoropropyl-1-hydroxy-1,3-dihydroisobenzofuran, n-nonafluorobutyl methyl ketone, n- Nonafluorobutyl ethyl ketone, n-nonafluorobutyl n-propyl ketone, n-nonafluorobutyl n-butyl ketone, n-nonafluorobutyl n-pentyl ketone, n-nonafluorobutyl cyclopentyl ketone, n-nonafluorobutyl n-hexyl Ketone, n-nonafluorobutyl cyclohexyl ketone, n-nonafluorobutyl n-heptyl ketone, n-nonafluorobutyl n-octyl ketone, n-nonafluorobutyl phenyl ketone, 1,1,1,2,2,3 3, , 4-nonafluoro-7-phenyl-6-buten-5-one, 1-n-nonafluorobutyl-1,3-dihydroisobenzofuran-1-ol, 2-n-nonafluorobutyl-5,6-dihydro -2H-pyran-2-ol, 3,3,4,4,5,5,6,6,6-nonafluoro-2,2-dihydroxyhexanoic acid ethyl, methyl 2-hydroxy-1-methyl-2- ( n-nonafluorobutyl) cyclopentanecarboxylate, 1-n-nonafluorobutyl-1-hydroxy-1,3-dihydroisobenzofuran, n-undecafluoropentyl methyl ketone, n-undecafluoropentyl ethyl ketone, n-un Decafluoropentyl n-propyl ketone, n-undecafluoropentyl n-butyl ketone, n-undecaful Lopentyl n-pentyl ketone, n-undecafluoropentyl cyclopentyl ketone, n-undecafluoropentyl n-hexyl ketone, n-undecafluoropentyl cyclohexyl ketone, n-undecafluoropentyl n-heptyl ketone, n-undeca Fluoropentyl n-octyl ketone, n-undecafluoropentyl phenyl ketone, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-8-phenyl-7-butene- 6-one, 1-n-undecafluoropentyl-1,3-dihydroisobenzofuran-1-ol, 2-n-undecafluoropentyl-5,6-dihydro-2H-pyran-2-ol, 3, 3,4,4,5,5,6,6,7,7,7-undecafluoro-2,2-dihydroxy Ethyl butanoate, methyl 2-hydroxy-1-methyl-2- (n-undecafluoropentyl) cyclopentanecarboxylate, 1-n-undecafluoropentyl-1-hydroxy-1,3-dihydroisobenzofuran, n -Tridecafluorohexyl methyl ketone, n-tridecafluorohexyl ethyl ketone, n-tridecafluorohexyl n-propyl ketone, n-tridecafluorohexyl n-butyl ketone, n-tridecafluorohexyl n-pentyl ketone, n-trityl ketone Decafluorohexyl cyclopentyl ketone, n-tridecafluorohexyl n-hexyl ketone, n-tridecafluorohexyl cyclohexyl ketone, n-tridecafluorohexyl n-heptyl ketone, n-tridecafluorohexyl n-octyl ketone, n-tridecafluorohexyl phenyl ketone, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-9-phenyl-8- Buten-7-one, 1-n-tridecafluorohexyl-1,3-dihydroisobenzofuran-1-ol, 2-n-tridecafluorohexyl-5,6-dihydro-2H-pyran-2-ol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-2,2-dihydroxyoctanoate, methyl 2-hydroxy-1-methyl-2 -(N-tridecafluorohexyl) cyclopentanecarboxylate, 1-n-tridecafluorohexyl-1-hydroxy-1,3-dihydroisobenzofuran, n-pentadecafluoroheptyl methyl ketone n-pentadecafluoroheptyl ethyl ketone, n-pentadecafluoroheptyl n-propylketone, n-pentadecafluoroheptyl n-butylketone, n-pentadecafluoroheptyl n-pentylketone, n-pentadecafluoroheptyl cyclopentylketone, n -Pentadecafluoroheptyl n-hexyl ketone, n-pentadecafluoroheptyl cyclohexyl ketone, n-pentadecafluoroheptyl n-heptyl ketone, n-pentadecafluoroheptyl n-octyl ketone, n-pentadecafluoroheptyl phenylketone, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-10-phenyl-9-buten-8-one, 1-n- Pentadecafluoroheptyl-1,3 -Dihydroisobenzofuran-1-ol, 2-n-pentadecafluoroheptyl-5,6-dihydro-2H-pyran-2-ol, 3,3,4,4,5,5,6,6,7, 7,8,8,9,9,9-pentadecafluoro-2,2-dihydroquinanoate, 2-hydroxy-1-methyl-2- (n-pentadecafluoroheptyl) cyclopentanecarboxylate, 1 -N-pentadecafluoroheptyl-1-hydroxy-1,3-dihydroisobenzofuran, n-heptadecafluorooctyl methyl ketone, n-heptadecafluorooctyl ethyl ketone, n-heptadecafluorooctyl n-propyl ketone, n-hepta Decafluorooctyl n-butyl ketone, n-heptadecafluorooctyl n-pentyl ketone, n-he Putadecafluorooctyl cyclopentyl ketone, n-heptadecafluorooctyl n-hexyl ketone, n-heptadecafluorooctyl cyclohexyl ketone, n-heptadecafluorooctyl n-heptyl ketone, n-heptadecafluorooctyl n-octyl ketone, n -Heptadecafluorooctyl phenyl ketone, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-11-phenyl- 10-buten-9-one, 1-n-heptadecafluorooctyl-1,3-dihydroisobenzofuran-1-ol, 2-n-heptadecafluorooctyl-5,6-dihydro-2H-pyran-2- All, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10- Ethyl ptadecafluoro-2,2-dihydroxidenoate, 2-hydroxy-1-methyl-2- (n-heptadecafluorooctyl) cyclopentanecarboxylate, 1-n-heptadecafluorooctyl-1-hydroxy- 1,3-dihydroisobenzofuran and the like can be mentioned.

  Specific examples of the epoxy compound represented by the general formula (9) of the present invention include styrene oxide, 4-methoxystyrene oxide, 4-nitrostyrene oxide, 1,2-epoxy-4-phenyl-1 , 3-butadiene, 1,2-epoxy-3-bromo-4-phenyl-1,3-butadiene, epoxyindene, 3,4-dihydro-2H-spiro [naphthalene] -1,2'-oxirane, 2- Phenylethylenyloxirane, 2- (4-methoxyphenyl) ethylenyloxirane, tert-butyl [[4- (2-methyloxiran-2-yl) but-3-in-1-yl] oxy] diphenylsilane and the like Can be mentioned.

  Specific examples of the fluorine-containing compounds represented by the general formula (10) of the present invention include 1,1,1-trifluoro-2-hydroxy-3-phenylpropane, 1,1,1-trimethyl and the like. Fluoro-2-hydroxy-3- (4-methoxyphenyl) propane, 1,1,1-trifluoro-2-hydroxy-3- (4-nitrophenyl) propane, 1,1,1-trifluoro-2- Hydroxy-5-phenyl-4-pentene, 1,1,1-trifluoro-4-bromo-2-hydroxy-5-phenyl-4-pentene, 2-trifluoromethyl-2-hydroxyindene, 2,2, 2-trifluoro-1-hydroxy-1- [1- (1,2,3,4-tetrahydronaphthyl)] ethane, 1,1,1-trifluoro-2-hydroxy-5-phenyl-4-pent 1,1,1-trifluoro-2-hydroxy-5- (4-methoxyphenyl) -4-pentyne, 8-[(tert-butyldiphenylsilyl) oxy] -1,1,1-trifluoro-3 -Hydroxy-4-methyl-5-heptine, 1,1,1,2,2-pentafluoro-3-hydroxy-4-phenylbutane, 1,1,1,2,2-pentafluoro-3-hydroxy- 4- (4-methoxyphenyl) butane, 1,1,1,2,2-pentafluoro-3-hydroxy-4- (4-nitrophenyl) butane, 1,1,1,2,2-pentafluoro- 3-hydroxy-6-phenyl-5-hexene, 1,1,1,2,2-pentafluoro-5-bromo-3-hydroxy-6-phenyl-5-hexene, 2-pentafluoroethyl-2-hydroxy Indene, 2,2,3,3,3-pentafluoro-1-hydroxy-1- [1- (1,2,3,4-tetrahydronaphthyl)] propane, 1,1,1,2,2-penta Fluoro-3-hydroxy-6-phenyl-5-hexyne, 1,1,1,2,2-pentafluoro-3-hydroxy-6- (4-methoxyphenyl) -5-hexyne, 8-[(tert- Butyldiphenylsilyl) oxy] -1,1,1,2,2-pentafluoro-3-hydroxy-4-methyl-5-octyne, 1,1,1,2,2,3,3-heptafluoro-4 -Hydroxy-5-phenylpentane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-5- (4-methoxyphenyl) pentane, 1,1,1,2,2,3 , 3-Heptafluoro-4-hydroxy Ci-5- (4-nitrophenyl) pentane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-7-phenyl-6-heptene, 1,1,1,2,2 , 3,3-heptafluoro-6-bromo-4-hydroxy-7-phenyl-6-heptene, 2-n-heptafluoropropyl-2-hydroxyindene, 2,2,3,3,4,4,4 -Heptafluoro-1-hydroxy-1- [1- (1,2,3,4-tetrahydronaphthyl)] butane, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-7 -Phenyl-6-heptine, 1,1,1,2,2,3,3-heptafluoro-4-hydroxy-7- (4-methoxyphenyl) -6-heptine, 8-[(tert-butyldiphenylsilyl) ) Oxy] -1,1,1,2,2 3,3-heptafluoro-3-hydroxy-4-methyl-5-nonine, 1,1,1,2,2,3,3,4,4,4-nonafluoro-5-hydroxy-6-phenylhexane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-6- (4-methoxyphenyl) hexane, 1,1,1,2,2,3,3,4 4-nonafluoro-5-hydroxy-6- (4-nitrophenyl) hexane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-8-phenyl-7-octene, 1,1,1,2,2,3,3,4,4-nonafluoro-7-bromo-5-hydroxy-8-phenyl-7-octene, 2-n-nonafluorobutyl-2-hydroxyindene, 2 , 2,3,3,4,4,5,5,5-nonafluoro- -Hydroxy-1- [1- (1,2,3,4-tetrahydronaphthyl)] pentane, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-8-phenyl -7-octyne, 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-8- (4-methoxyphenyl) -7-octyne, 8-[(tert-butyldiphenyl Silyl) oxy] -1,1,1,2,2,3,3,4,4-nonafluoro-3-hydroxy-4-methyl-5-decyne, 1,1,1,2,2,3,3 , 4,4,5,5-undecafluoro-6-hydroxy-7-phenylheptane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6- Hydroxy-7- (4-methoxyphenyl) heptane, 1,1,1,2,2,3,3 4,4,5,5-undecafluoro-6-hydroxy-7- (4-nitrophenyl) heptane, 1,1,1,2,2,3,3,4,4,5,5-undeca Fluoro-6-hydroxy-9-phenyl-8-nonene, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-8-bromo-6-hydroxy-9- Phenyl-8-nonene, 2-n-undecafluoropentyl-2-hydroxyindene, 2,2,3,3,4,4,5,5,6,6,6-undecafluoro-1-hydroxy- 1- [1- (1,2,3,4-tetrahydronaphthyl)] hexane, 1,1,1,2,2,3,3,4,4,5,5-undecafluoro-6-hydroxy- 9-phenyl-8-nonine, 1,1,1,2,2,3,3,4,4,5,5-undecafluor -6-hydroxy-9- (4-methoxyphenyl) -8-nonine, 8-[(tert-butyldiphenylsilyl) oxy] -1,1,1,2,2,3,3,4,4,5 , 5-Undecafluoro-3-hydroxy-4-methyl-5-undetine, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7 -Hydroxy-8-phenyloctane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-8- (4-methoxyphenyl) Octane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-8- (4-nitrophenyl) octane, 1,1, 1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-10- Enyl-9-decene, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-9-bromo-7-hydroxy-10-phenyl-9- Decene, 2-n-tridecafluorohexyl-2-hydroxyindene, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-hydroxy- 1- [1- (1,2,3,4-tetrahydronaphthyl)] heptane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro- 7-hydroxy-10-phenyl-9-decyne, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-10- (4 -Methoxyphenyl) -9-decyne, 8-[(tert-butyldiphenylsilyl) oxy] -1,1,1,2,2 , 3,3,4,4,5,5,6,6-tridecafluoro-3-hydroxy-4-methyl-5-dodecine, 1,1,1,2,2,3,3,4,4 , 5,5,6,6,7,7-pentadecafluoro-8-hydroxy-9-phenylnonane, 1,1,1,2,2,3,3,4,4,5,5,6 6,7,7-pentadecafluoro-8-hydroxy-9- (4-methoxyphenyl) nonane, 1,1,1,2,2,3,3,4,4,5,5,6,6 7,7-pentadecafluoro-8-hydroxy-9- (4-nitrophenyl) nonane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7, 7-pentadecafluoro-8-hydroxy-11-phenyl-10-undecene, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pen Decafluoro-10-bromo-8-hydroxy-11-phenyl-10-undecene, 2-n-pentadecafluoroheptyl-2-hydroxyindene, 2,2,3,3,4,4,5,5,6 , 6,7,7,8,8,8-pentadecafluoro-1-hydroxy-1- [1- (1,2,3,4-tetrahydronaphthyl)] octane, 1,1,1,2,2 , 3,3,4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-11-phenyl-10-undecyne, 1,1,1,2,2,3,3 , 4,4,5,5,6,6,7,7-pentadecafluoro-8-hydroxy-11- (4-methoxyphenyl) -10-undecyne, 8-[(tert-butyldiphenylsilyl) oxy] -1,1,1,2,2,3,3,4,4,5 , 6,6,7,7-pentadecafluoro-3-hydroxy-4-methyl-5-tridecine, 1,1,1,2,2,3,3,4,4,5,5,6,6 , 7,7,8,8-heptadecafluoro-9-hydroxy-10-phenyldecane, 1,1,1,2,2,3,4,4,4,5,5,6,6,7, 7,8,8-heptadecafluoro-9-hydroxy-10- (4-methoxyphenyl) decane, 1,1,1,2,2,3,3,4,4,5,5,6,6, 7,7,8,8-heptadecafluoro-9-hydroxy-10- (4-nitrophenyl) decane, 1,1,1,2,2,3,3,4,4,5,5,6 6,7,7,8,8-heptadecafluoro-9-hydroxy-12-phenyl-11-dodecene, 1,1,1,2,2,3,3,4,4,5 5,6,6,7,7,8,8-heptadecafluoro-11-bromo-9-hydroxy-12-phenyl-11-dodecene, 2-n-heptadecafluorooctyl-2-hydroxyindene, 2, 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-1-hydroxy-1- [1- (1,2, 3,4-tetrahydronaphthyl)] decane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9- Hydroxy-12-phenyl-11-dodecine, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-9- Hydroxy-12- (4-methoxyphenyl) -11-dodecine, 8-[(tert-butyldiphenylsilyl) o Si] -1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-3-hydroxy-4-methyl-5 -Tetradetin etc. are mentioned.

  The reaction of the perfluoroalkylating agent of the present invention with various substrates is carried out in the temperature range of 0 to −40 ° C. in the perfluoroalkylating agent prepared by the above-described predetermined operation, in an amount of 0.5 to 1.0 mol. The reaction is completed by adding the above substrate and carrying out the reaction in the temperature range of 0 to 40 ° C. for 0.5 to 4.0 hours.

  In the reaction of the perfluoroalkylating agent of the present invention with various substrates, 1.0 to 3.0 moles with respect to the perfluoroalkylating agent of the present invention in order to inhibit the adverse effects of by-produced magnesium halide. An amount of 1,4-dioxane may be added, and for the purpose of accelerating the reaction, 1.0 to 3.0 mol of diethylaluminum chloride or methylaluminoxane with respect to the perfluoroalkylating agent of the present invention. An aluminum-based Lewis acid such as may be added.

  The post-treatment after the reaction between the perfluoroalkylating agent of the present invention and various substrates can be carried out by a known operation. For example, 1N-hydrochloric acid is added to stop the reaction, and the organic layer is extracted with ether. The combined product is dried over sodium sulfate, filtered, and the solvent is distilled off under reduced pressure to obtain a crude product, which is then purified by silica gel column chromatography to obtain the desired product.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.

  Example 1 Preparation of 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-phenyl-1-hydroxyheptane

I-Propylmagnesium chloride (2.0 M ether solution, 0.24 mL) was added to a solution of titanium sen dichloride (Cp ₂ TiCl ₂ , 59.8 mg, 0.24 mmol) in ether (2.4 mL) cooled to −78 ° C. 0.48 mmol), 1,4-dioxane (46 μL, 0.54 mmol) and n-tridecafluorohexyl iodide (C ₆ F ₁₃ I, 78 μL, 0.36 mmol) were added, and the temperature was adjusted to −50 ° C. Stir for hours. Subsequently, benzaldehyde (20 μL, 0.20 mmol) was added, the temperature was raised, and the mixture was stirred at room temperature for 1 hour.

After completion of the reaction, 1N-hydrochloric acid was added to stop the reaction, followed by extraction three times with ether. The organic layers were combined, dried over sodium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1 (v / v)) to obtain the desired product 2,2,3,3,4,4,5,5,6, 6,7,7,7-Tridecafluoro-1-phenyl-1-hydroxyheptane was obtained (85.2 mg, yield:> 99%).
¹ H NMR (300 MHz, CDCl ₃ ) δ 2.54 (d, J = 5.1 Hz, 1H), 5.21 (ddd, J _HF = 17.7 and 5.4 Hz, J = 5.4 Hz, 1H), 7.41-7.49 (m, 5H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 72.3 (dd, J _CF = 28.5 and 22.5 Hz), 104.6-122.9 (m, (CF ₂ ) ₅ CF ₃ ), 128.0 128.6, 129.7, 133.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.3 Hz, 3F), -117.4-(-127.3) (m, 10F).
_{HRMS (APCI-TOF) Calcd forC} 13 H 6 F 13 O [M-H] -: 425.0211, Found: 425.0198.
IR (KBr) 702, 819, 1060, 1203, 1355, 1451, 1458, 1959, 3038, 3416 cm ⁻¹ .

  Example 2 Preparation of 2,2,3,3,4,4,4-heptafluoro-1- (1-naphthyl) -1-hydroxybutane

The same operation as in Example 1 was carried out except that n-heptafluoropropyl iodide was used instead of n-tridecafluorohexyl iodide and 1-naphthaldehyde was used instead of benzaldehyde. , 3,3,4,4,4-heptafluoro-1- (1-naphthyl) -1-hydroxybutane was obtained in 81% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.70 (d, J = 5.1 Hz, 1H), 6.12 (ddd, J _HF = 19.8 and 3.9 Hz, J = 3.9 Hz, 1H) 7.51-7.61 (m, 3H), 7.83-8.03 (m, 4H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 67.5 (dd, J _CF = 30.0 and 21.8 Hz), 106.4-128.5 (m, (CF ₂ ) ₂ CF ₃ ), 122.7 124.8, 125.2, 126.6, 126.9, 129.0, 130.2, 130.3, 131.4, 133.7.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.7 (t, J _FF = 10.2 Hz, 3F), -115.9-(-117.0) (m, 1F), -124.4 (-127.9) (m, 3F).
_{HRMS (APCI-TOF) Calcd forC} 14 H 8 F 7 O [M-H] -: 325.0463, Found: 325.0454.
IR (KBr) 785,963,1231,1348,1513,1698,1932,3052,3513cm < ^-1 >.

  Example 3 Preparation of 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-6-phenyl-heptane

The same procedure as in Example 1 was carried out except that n-nonafluorobutyl iodide was used instead of n-tridecafluorohexyl iodide of Example 1 and 2-phenylpropionaldehyde was used instead of benzaldehyde. 1,1,2,2,3,3,4,4-Nonafluoro-5-hydroxy-6-phenyl-heptane was obtained in 79% yield. The product was a mixture of two isomers with a ratio of 67/33.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.44 (dd, J = 6.9 and 1.2 Hz, 3H, major), 1.47 (dd, J = 7.5 and 2.1 Hz, 3H, minor ), 1.85 (d, J = 8.4 Hz, 1H, minor), 2.11 (d, J = 7.5 Hz, 1H, major), 3.29-3.37 (m, 1H), 4 .18-4.34 (brm, 1H), 7.28-7.40 (m, 5H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 13.9, 18.9, 39.1, 39.8, 72.5 (dd, J _CF = 26.3 and 20.3 Hz), 73.1 (dd, _{J CF = 27.8 and 21.8Hz),} 104.9-123.6 (m, (CF 2) 3 CF 3), 127.2,127.6,128.5,128.8,128.8 128.9, 140.0, 143.1.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-81.0 (s, 3F), -116.0- (-127.8) (m, 6F).
_{HRMS (APCI-TOF) Calcd forC} 13 H 10 F 9 O [M-H] -: 353.0588, Found: 353.0583.
IR (neat) 706, 1025, 1134, 1235, 1358, 1453, 1603, 1717, 2940, 3341 cm ⁻¹ .

  Example 4 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2-hydroxy-2- (2- Preparation of pyridyl) decane

The same procedure as in Example 1 was carried out except that n-tridecafluorohexyl iodide in Example 1 was replaced with n-heptadecafluoroheptyl iodide, and 2-acetylpyridine was used in place of benzaldehyde. 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2-hydroxy-2- (2-pyridyl) decane % Yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.75 (s, 3H), 6.51 (s, 1H), 7.36 (dd, J = 7.8 and 4.8 Hz, 1H), 7.51 (D, J = 7.8 Hz, 1H), 7.80 (td, J = 7.8 and 1.5 Hz, 1H), 8.58 (d, J = 4.8 Hz, 1H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 23.0, 75.4 (t, J _CF = 24.0 Hz), 104.5-124.1 (m, (CF ₂ ) ₇ CF ₃ ), 121.6 (T, J _CF = 3.0 Hz), 123.8, 137.5, 147.1, 155.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.9 Hz, 3F), -115.9-(-119.0) (m, 4F), -121.8- (-122.0) (m, 6F), -122.8 (s, 2F), -126.2 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 15 H 7 F 17 NO [M-H] -: 540.0256, Found: 540.0270.
IR (KBr) 661,764,963,1142,1203,1410,1596,1719,2963,3285 cm < ^-1 >.

  Example 5 Preparation of 1-n-nonafluorobutyl-1-hydroxy-1,2,3,4-tetrahydronaphthalene

The same operation as in Example 1 was carried out except that n-tridecafluorohexyl iodide in Example 1 was replaced by n-nonafluorobutyl iodide and 1-tetralone was used in place of benzaldehyde, and the target 1-nonafluoro was obtained. Butyl-1-hydroxy-1,2,3,4-tetrahydronaphthalene was obtained in 99% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.89-2.16 (m, 3H), 2.36-2.43 (m, 1H), 2.51 (s, 1H), 2.83-2 .87 (m, 2H), 7.19 (d, J = 6.9 Hz, 1H), 7.20-7.34 (m, 2H), 7.71 (d, J = 7.2 Hz, 1H) .
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 18.5, 29.5, 33.0 (dd, J _CF = 7.5 and 3.8 Hz), 74.8 (dd, J _CF = 22.5 and 21 .0 Hz), 104.2-123.8 (m, (CF ₂ ) ₃ CF ₃ ), 126.6, 127.6 (t, J _CF = 3.8 Hz), 129.1, 129.5, 134 0.0, 138.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.8 (t, J _FF = 7.9 Hz, 3F), -110.4 (d, J _FF = 286.5 Hz, 1F), -116.8- (-118.8) (m, 2F), -120.3- (-121.4) (m, 1F), -124.2-(-125.4) (m, 1F), -126.5 -(-127.7) (m, 1F).
_{HRMS (APCI-TOF) Calcd forC} 14 H 10 F 9 O [M-H] -: 365.0588, Found: 365.0597.
IR (neat) 692, 733, 1025, 1134, 1235, 1358, 1446, 1487, 2954, 3484 cm ⁻¹ .

  Example 6 Preparation of 2-n-pentyl-1-heptadecafluorooctyl-1-hydroxy-2-cyclopentene

The same as Example 1 except that n-heptadecafluorooctyl iodide was used instead of n-tridecafluorohexyl iodide and 2-n-pentyl-2-cyclopenten-1-one was used instead of benzaldehyde. The operation was performed to obtain the desired 2-n-pentyl-1-heptadecafluorooctyl-1-hydroxy-2-cyclopentene in 80% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.90 (t, J = 6.9 Hz, 3H), 1.31-1.36 (m, 3H), 1.46-1.63 (m, 2H) 1.99-2.17 (m, 3H), 2.25 (s, 1H), 2.30-2.58 (m, 3H), 5.83 (s1H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 14.0, 22.5, 26.8, 27.8, 29.2, 31.8, 34.5, 87.7 (dd, J _CF = 25.5) and 20.3 Hz), 104.1-122.9 (m, (CF ₂ ) ₇ CF ₃ ), 132.5, 142.6.
¹⁹ -NMR (282 MHz, CDCl ₃ ) δ-81.0 (t, J _FF = 9.6 Hz, 3F), -116.8-(-119.7) (m, 4F), -121.8 (brm , 6F), -122.8 (s, 2F), -126.3 (s, 2F).
_{HRMS (APCI-TOF) Calcd for} C 18 H 16 F 17 O [M-H] -: 571.0930, Found: 571.0937.
IR (neat) 1072, 1147, 1208, 1242, 1371, 1467, 1609, 2859, 2933, 3464 cm ⁻¹ .

  Example 7 Preparation of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyl-9-phenyl-8-nonene

Example 1 , 1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyl-9-phenyl-8-nonene was obtained in 94% yield .
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.63 (s, 3H), 2.39 (s, 1H), 6.34 (d, J = 16.2 Hz, 1H), 6.87 (d, J = 16.2 Hz, 1H), 7.26-7.44 (m, 5H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 23.3, 76.1 (t, J _CF = 24.0 Hz), 104.8-123.6 (m, (CF ₂ ) ₅ CF ₃ ), 126.7 , 127.0, 128.5, 128.9, 131.5, 136.0.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.9 Hz, 3F), -117.8-(-121.9) (m, 6F), -122.8 ( s, 2F), -126.2 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 16 H 10 F 13 O [M-H] -: 465.0524, Found: 465.0504.
IR (KBr) 565, 743, 977, 1238, 1368, 1493, 1706, 1953, 3025, 3636 cm ⁻¹ .

  Example 8 Preparation of 1-n-heptadecafluorooctyl-1-hydroxycyclohexane

The same operation as in Example 1 was performed except that n-heptadecafluorooctyl iodide and cyclohexanone were used instead of n-heptadecafluorooctyl iodide and benzaldehyde in place of n-tridecafluorohexyl iodide of Example 1, and the target 1-n-hepta was obtained. Decafluorooctyl-1-hydroxycyclohexane was obtained in 76% yield.
^{1 H-NMR (300MHz, CDCl} 3) δ1.18-1.25 (m, 1H), 1.63-1.74 (m, 7H), 1.83-1.92 (m, 3H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 20.3, 25.0, 29.9 (t, J _CF = 2.3 Hz), 75.3 (t, J _CF = 22.5 Hz), 105.1- 123.3 (m, (CF ₂ ) ₇ CF ₃ ).
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-81.0 (t, J _FF = 9.9 Hz, 3F), -119.1 (s, 2F), -121.6-(-126.2) ( m, 6F), -122.9 (s, 2F), -122.9 (s, 2F), -126.2 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 14 H 10 F 17 O [M-H] -: 517.0460, Found: 517.0456.
IR (KBr) 644, 909, 991, 1052, 1228, 1464, 1717, 2947, 3457, 3606 cm ⁻¹ .

  Example 9 Preparation of 2-n-heptafluoropropyl-2-hydroxyadamantane

The same operation as in Example 1 was carried out except that n-heptafluoropropyl iodide and n-heptafluoropropyl iodide in place of Example 1 and 2-adamantanone in place of benzaldehyde were used. -Heptafluoropropyl-2-hydroxyadamantane was obtained in 92% yield.
¹ H-NMR (300 MHz, C ₆ D ₆ ) δ 1.21-1.26 (m, 3H), 1.43-1.58 (m, 6H), 1.95-2.04 (m, 6H) .
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 26.3, 27.0, 33.0, 33.2 (t, J _CF = 3.8 Hz), 33.5, 38.4, 76.7 (t, _{J CF = 21.8Hz), 107.1-125.0 (} m, (CF 2) 2 CF 3).
¹⁹ F-NMR (282 MHz, C ₆ D ₆ ) δ-80.3 (t, J _FF = 10.2 Hz, 3F), -113.0 (brm, 2F), -122.9 (s, 2F) .
_{HRMS (APCI-TOF) Calcd forC} 13 H 14 F 7 O [M-H] -: 319.0933, Found: 319.0928.
IR (KBr) 558, 730, 881, 943, 1225, 1335, 1458, 1719, 2928, 3478 cm < ^-1 >.

  Example 10 (8R, 9S, 13S, 14S, 17S) -3-Methoxy-13-methyl-17-pentafluoroethyl-7,8,9,11,12,13,14,15,16,17-decahydro Preparation of -6H-cyclopenta [a] phenanthrene-17-ol

The same procedure as in Example 1 was carried out except that pentafluoroethyl iodide and 3-O-methylesterone were used in place of n-tridecafluorohexyl iodide and benzaldehyde in place of Example 1 (8R , 9S, 13S, 14S, 17S) -3-Methoxy-13-methyl-17-pentafluoroethyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta [ a] Phenanthren-17-ol was obtained in 95% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.00 (s, 3H), 1.28-1.60 (m, 4H), 1.71-1.96 (m, 6H), 2.09 (brs 3H), 2.26 (td, J = 11.1 and 4.2, 1H), 2.3-2.49 (m, 2H), 2.86-2.91 (m, 2H), 3 .79 (s, 3H), 6.65 (d, J = 2.7 Hz, 1H), 6.73 (dd, J = 8.4 and 7.2 Hz, 1H), 7.21 (d, J = 8.4 Hz, 1H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 15.2, 24.5, 26.7, 27.6, 29.7, 33.2 (dd, J _CF = 6.8 and 2.3 Hz), 33. 5 (t, J _CF = 3.0 Hz), 39.5, 43.1, 50.4, 51.2, 55.2, 84.5 (t, J _CF = 22.5 Hz), 111.5, 112.7-126.6 m, CF ₂ CF ₃ ), 113.8, 126.3, 132.2, 137.8, 157.6.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-77.1 (s, 3F), -118.5 (d, J _FF = 272.7 Hz, 1F), -119.9 (d, J _FF = 272. 7Hz, 1F).
_{HRMS (APCI-TOF) Calcd forC} 21 H 24 F 5 O 2 [M-H] -: 403.1697, Found: 403.1693.
IR (KBr) 737, 908, 1218, 1506, 1609, 1719, 1871, 2069, 2928, 3629 cm ⁻¹ .

  Example 11 Preparation of pentafluoroethyl 1-naphthyl ketone

The same operation as in Example 1 was carried out except that pentafluoroethyl iodide and methyl 1-naphthalenecarboxylate were used instead of n-tridecafluorohexyl iodide and benzaldehyde in Example 1, and the target product, pentafluoroethyl, was obtained. 1-Naphthyl ketone was obtained in 71% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.55-7.71 (m, 3H), 7.92-7.95 (m, 1H), 8.13-8.17 (m, 2H), 8 .56 (d, J = 8.7 Hz, 1H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 104.2-129.8 (m, CF ₂ CF ₃ ), 124.2, 125.0, 127.3, 128.2, 129.1, 129.4 130.6 (t, J _CF = 6.0 Hz), 131.0, 134.1, 135.7, 186.0 (t, J _CF = 25.5 Hz).
¹⁹ F NMR- (282 MHz, CDCl ₃ ) δ-81.1 (s, 3F), -114.3 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 13 H 7 F 5 O [M] -: 274.0417, Found: 274.0410.
IR (neat) 719, 773, 889, 1005, 1228, 1344, 1507, 1576, 1704, 3056 cm ⁻¹ .

  Example 12 Preparation of n-heptadecafluorooctyl n-hexyl ketone

The same operation as in Example 1 was performed except that n-heptadecafluorooctyl iodide and methyl octanoate were used instead of n-heptadecafluorooctyl iodide and benzaldehyde instead of n-tridecafluorohexyl iodide of Example 1, and the target n-hepta Decafluorooctyl n-hexyl ketone was obtained in> 99% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.88 (t, J = 6.9 Hz, 3H), 1.28-1.31 (m, 8H), 1.62-1.69 (m, 2H) ), 2.74 (t, J = 7.2 Hz, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 13.9, 22.4, 22.5, 28.6, 28.8, 31.5, 37.9, 104.0-123.2 (m, (CF _{2) 7 CF 3), 194.1} (t, J CF = 25.5Hz).
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.9 Hz, 3F), -120.4 (t, J _FF = 12.7 Hz, 2F), -121.4 ( s, 2F), -122.0-(-122.3) (m, 6F), -122.8 (s, 2F), -126.2 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 16 H 14 F 17 O [M-H] -: 545.0773, Found: 545.0753.
IR (neat) 659, 1079, 1147, 1235, 1330, 1364, 1467, 1759, 2866, 2933 cm ⁻¹ .

  Example 13 Preparation of n-Tridecafluorohexyl Cyclohexyl Ketone

The same procedure as in Example 1 was carried out except that n-tridecafluorohexyl iodide was used instead of n-tridecafluorohexyl iodide in Example 1, and methylcyclohexanecarboxylate was used in place of benzaldehyde. Tridecafluorohexyl cyclohexyl ketone was obtained in 80% yield.
¹ H NMR (300 MHz, CDCl ₃ ) δ 1.21-1.48 (m, 5H), 1.69-1.73 (m, 1H), 1.82-1.90 (m, 4H), 2. 89 (t, J = 11.1 Hz, 1H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 25.3, 25.5, 28.3, 46.3, 104.3-123.5 (m, (CF ₂ ) ₅ CF ₃ ), 197.6 (t , J _CF = 24.8 Hz).
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-81.2 (t, J _FF = 9.9 Hz, 3F), -119.9 (t, J _FF = 12.4 Hz, 2F), -121.7 ( s, 2F), -122.2 (s, 2F), -123.1 (s, 2F), -126.5 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 13 H 10 F 13 O [M-H] -: 429.0524, Found: 429.0519.
IR (neat) 733, 991, 1147, 1201, 1235, 1364, 1453, 1745, 2859, 2940 cm ⁻¹ .

  Example 14 Preparation of ethyl 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2,2-dihydroxydecanoate

The same operation as in Example 1 was carried out except that n-pentadecafluorooctyl iodide in place of n-tridecafluorohexyl iodide in Example 1 and diethyl oxalate in place of benzaldehyde were used. 69% ethyl 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2,2-dihydroxydecanoate Obtained in yield.
^{1 H-NMR (300MHz, CDCl} 3) δ1.37 (t, J = 7.2Hz, 3H), 4.41 (q, J = 7.2Hz, 2H), 4.62 (brs, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 13.9, 65.0, 92.0 (t, J _CF = 19.5 Hz), 107.8-123.5 (m, (CF ₂ ) ₇ CF ₃ ) , 167.1.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-81.0 (t, J _FF = 9.9 Hz, 3F), −120.4 (s, 2F), −121.2 (s, 2F), −122 0 (s, 2F), -122.9 (s, 2F), -126.3 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 12 H 6 F 17 O 4 [M-H] -: 536.9995, Found: 537.0012.
IR (neat) 658, 726, 855, 1018, 1147, 1235, 1371, 1745, 2995, 3450 cm ⁻¹ .

  Example 15 Preparation of 1-n-nonafluorobutyl-1-hydroxy-1,3-dihydroisobenzofuran

The same operation as in Example 1 was carried out except that n-nonafluorobutyl iodide was used instead of n-tridecafluorohexyl iodide and phthalide was used instead of benzaldehyde. Butyl-1-hydroxy-1,3-dihydroisobenzofuran was obtained in 90% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 3.62 (brs, 1H), 5.18 (d, J = 12.6 Hz, 1H), 5.28 (d, J = 12.6 Hz, 1H), 7 .31 (d, J = 7.5 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.50 (t, J = 7.2 Hz, 1H), 7.57 (d, J = 7.8 Hz, 1H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 73.6, 106.7 (dd, J _CF = 30.8 and 24.8 Hz), 107.4-130.5 (m, (CF ₂ ) ₃ CF ₃ ) 121.1, 124.2, 128.4, 130.9, 134.8, 137.1, 139.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J = 8.5 Hz, 3F), -119.1-(-122.3) (m, 4F), -125.6 (dt , J _FF = 291.6 and 13.3 Hz, 1F), -126.9 (dt, J _FF = 295.5 and 14.7 Hz, 1F).
_{HRMS (APCI-TOF) Calcd forC} 12 H 6 F 9 O 2 [M-H] -: 353.0224, Found: 353.0241.
IR (KBr) 617, 726, 971, 1201, 1358, 1467, 1711, 1922, 2906, 3368 cm ⁻¹ .

  Example 16 Preparation of 2-n-tridecafluorohexyl-2-hydroxy-5,6-dihydro-2H-pyran

Same as Example 1 except that n-tridecafluorohexyl iodide was used instead of n-tridecafluorohexyl iodide and 5,6-dihydro-2H-pyran-2-one was used instead of benzaldehyde. The target product, 2-n-tridecafluorohexyl-2-hydroxy-5,6-dihydro-2H-pyran, was obtained in 69% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.96-2.04 (m, 1H), 2.31-2.43 (m, 1H), 3.09 (s, 1H), 3.94-4 0.08 (s, 2H), 5.85 (d, J = 10.5 Hz, 1H), 6.29-6.34 (m, 1H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 23.7, 59.2, 93.2 (t, J _CF = 25.5 Hz), 106.8-119.6 (m, (CF ₂ ) ₅ CF ₃ ) , 121.7, 132.8.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.3 Hz, 3F), -119.0-(-126.2) (m, 10F).
_{HRMS (APCI-TOF) Calcd forC} 11 H 6 F 13 O 2 [M-H] -: 417.0160, Found: 417.0155.
IR (KBr) 672, 998, 1235, 1473, 1657, 1717, 2390, 2947, 3015, 3491 cm ⁻¹ .

  Example 17 Preparation of 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-phenylnonan-3-one

The same procedure as in Example 1 was carried out except that n-tridecafluorohexyl iodide was used instead of n-tridecafluorohexyl iodide in Example 1, and 2-phenyl-1-cyanoethane was used in place of benzaldehyde. Of 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-phenylnonan-3-one in 83% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 3.02 (t, J = 6.8 Hz, 2H), 3.10 (t, J = 6.8 Hz, 2H), 7.21-7.36 (m, 5H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 28.4, 39.7, 104.1-123.3 (m, (CF ₂ ) ₅ CF ₃ ), 126.7, 128.2, 128.7, 139 .2, 193.1 (t, J _CF = 25.5 Hz).
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-81.0 (t, J _FF = 18.3 Hz, 3F), -120.4 (t, J _FF = 16.1 Hz, 2F), -121.7 ( s, 2F), -122.3 (s, 2F), -122.9 (s, 2F), -126.3 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 15 H 8 F 13 O [M-H] -: 451.0368, Found: 451.0356.
IR (neat) 699, 746, 1147, 1242, 1364, 1371, 1500, 1759, 2940, 3035 cm ⁻¹ .

  Example 18 Preparation of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-phenyl-2-hydroxyoctane

The same operation as in Example 1 was carried out except that n-tridecafluorohexyl iodide in place of Example 1 and styrene oxide in place of benzaldehyde were used instead of n-tridecafluorohexyl iodide. 4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-phenyl-2-hydroxyoctane was obtained in 54% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.28 (d, J = 6.3 Hz, 1H), 2.87 (dd, J = 14.1 and 10.5 Hz, 1H), 3.15 (d, J = 14.1 Hz, 1H), 4.26-4.38 (m, 1H), 7.27-7.42 (m, 5H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 35.5, 71.1 (dd, J _CF = 28.5 and 21.8 Hz), 104-2-123.4 (m, (CF ₂ ) ₅ CF ₃ ) , 127.2, 128.8, 129.5, 135.7.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-81.1 (t, J _FF = 9.9 Hz, 3F), -119.9-(-127.6), (m, 10F).
_{HRMS (APCI-TOF) Calcd forC} 14 H 8 F 13 O [M-H] -: 439.0368, Found: 439.0353.
IR (neat) 651, 706, 1147, 1201, 1249, 1358, 1460, 1500, 3035, 3531 cm ⁻¹ .

  Example 19 Preparation of 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1-phenyl-1-hydroxyheptane

To a solution of zirconocene dichloride (Cp ₂ ZrCl ₂ , 70.2 mg, 0.24 mmol) cooled to −78 ° C. in ether (2.4 mL) was added n-propylmagnesium chloride (2.0 M ether solution, 0.12 mL, 0 .24 mmol) was added, and the mixture was warmed to 0 ° C. and stirred for 30 minutes. Next, after cooling again to −78 ° C., 1,4-dioxane (23 μL, 0.27 mmol) and n-tridecafluorohexyl iodide (C ₆ F ₁₃ I, 78 μL, 0.36 mmol) were charged. After stirring at temperature for 1 hour, benzaldehyde (20 μL, 0.20 mmol) was added, the temperature was raised, and the mixture was stirred at room temperature for 2 hours.

  After completion of the reaction, 1N-hydrochloric acid was added to stop the reaction, followed by extraction three times with ether. The organic layers were combined, dried over sodium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1 (v / v)) to obtain the desired product 2,2,3,3,4,4,5,5,6, 6,7,7,7-Tridecafluoro-1-phenyl-1-hydroxyheptane was obtained (85.2 mg, yield:> 99%).

  Example 20 Preparation of 2,2,3,3,4,4,4-heptafluoro-1- (1-naphthyl) -1-hydroxybutane

  The same procedure as in Example 19 was performed, except that n-heptafluoropropyl iodide was used instead of n-tridecafluorohexyl iodide of Example 19 and 1-naphthaldehyde was used instead of benzaldehyde. 3,3,4,4,4-heptafluoro-1- (1-naphthyl) -1-hydroxybutane was obtained in 97% yield.

  Example 21 Preparation of 1,1,1,2,2,3,3,4,4-nonafluoro-5-hydroxy-6-phenyl-heptane

  The same operation as in Example 19 was carried out except that n-nonafluorobutyl iodide was used instead of n-tridecafluorohexyl iodide and 2-phenylpropionaldehyde was used instead of benzaldehyde. 1,1,2,2,3,3,4,4-Nonafluoro-5-hydroxy-6-phenyl-heptane was obtained in 96% yield. The product was a mixture of two isomers with a ratio of 67/33.

  Example 22 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2-hydroxy-2- (2- Preparation of pyridyl) decane

  The same operation as in Example 19 was carried out except that n-tridecafluorohexyl iodide in Example 19 was replaced with n-heptadecafluoroheptyl iodide and 2-acetylpyridine was used in place of benzaldehyde. 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2-hydroxy-2- (2-pyridyl) decane % Yield.

  Example 23 Preparation of 1-n-nonafluorobutyl-1-hydroxy-1,2,3,4-tetrahydronaphthalene

  The same operation as in Example 19 was carried out except that n-tridecafluorohexyl iodide in Example 19 was replaced with n-nonafluorobutyl iodide and 1-tetralone was used in place of benzaldehyde. Butyl-1-hydroxy-1,2,3,4-tetrahydronaphthalene was obtained in 93% yield.

  Example 24 Preparation of 2-n-pentyl-1-heptadecafluorooctyl-1-hydroxy-2-cyclopentene

  The same as Example 19 except that n-heptadecafluorooctyl iodide was used instead of n-tridecafluorohexyl iodide of Example 19, and 2-n-pentyl-2-cyclopenten-1-one was used instead of benzaldehyde. The operation was carried out to obtain the desired 2-n-pentyl-1-heptadecafluorooctyl-1-hydroxy-2-cyclopentene in 95% yield.

  Example 25 Preparation of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyl-9-phenyl-8-nonene

  The same operation as in Example 19 was performed except that n-tridecafluorohexyl iodide was used instead of n-tridecafluorohexyl iodide and benzaldehyde acetone was used instead of benzaldehyde. , 1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-7-hydroxy-7-methyl-9-phenyl-8-nonene was obtained in 84% yield. .

  Example 26 Preparation of 1-n-heptadecafluorooctyl-1-hydroxycyclohexane

  The same operation as in Example 19 was performed except that n-heptadecafluorooctyl iodide was used instead of n-tridecafluorohexyl iodide and cyclohexanone was used instead of benzaldehyde in Example 19, and the target 1-n-hepta was obtained. Decafluorooctyl-1-hydroxycyclohexane was obtained in 83% yield.

  Example 27 Preparation of 2-n-heptafluoropropyl-2-hydroxyadamantane

  The same operation as in Example 19 was performed except that n-heptafluoropropyl iodide was used instead of n-tridecafluorohexyl iodide of Example 19 and 2-adamantanone was used instead of benzaldehyde. -Heptafluoropropyl-2-hydroxyadamantane was obtained in 84% yield.

  Example 28 (8R, 9S, 13S, 14S, 17S) -3-Methoxy-13-methyl-17-pentafluoroethyl-7,8,9,11,12,13,14,15,16,17-decahydro Preparation of -6H-cyclopenta [a] phenanthrene-17-ol

  The same procedure as in Example 19 was carried out except that pentafluoroethyl iodide and 3-O-methylstyrene were used instead of n-tridecafluorohexyl iodide and benzaldehyde in Example 19, and the target product (8R, 9S) was used. , 13S, 14S, 17S) -3-Methoxy-13-methyl-17-pentafluoroethyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta [a] Phenanthrene-17-ol was obtained in 91% yield.

  Example 29 Preparation of pentafluoroethyl 1-naphthyl ketone

  The same operation as in Example 19 was performed except that pentafluoroethyl iodide and methyl 1-naphthalenecarboxylate were used instead of n-tridecafluorohexyl iodide and benzaldehyde in Example 19, and the target product, pentafluoroethyl, was obtained. 1-Naphthyl ketone was obtained in 39% yield.

  Example 30 of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2,2-dihydroxydecanoate Preparation

  The same operation as in Example 19 was carried out except that n-pentadecafluorooctyl iodide was used instead of n-tridecafluorohexyl iodide in Example 19 and diethyl oxalate was used in place of benzaldehyde. As a result, 81% of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-2,2-dihydroxydecanoate was obtained. Obtained at a rate.

  Example 31 Preparation of methyl 4- (2,2,3,3,4,4,5,5,5-nonafluoro-1-hydroxypentyl) benzoate

The same operation as in Example 19 was performed except that n-nonafluorobutyl iodide was used instead of n-tridecafluorohexyl iodide of Example 19 and 4-methoxycarbonylbenzaldehyde was used instead of benzaldehyde. -(2,2,3,3,4,4,5,5,5-nonafluoro-1-hydroxypentyl) benzoate was obtained in 56% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 3.09 (brs, 1H), 3.92 (s, 3H), 5.28 (dd, J _HF = 17.1 and 6.0 Hz, 1H), 7. 54 (d, J = 8.1 Hz, 2H), 8.05 (d, J = 8.1 Hz, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 52.5, 72.0 (dd, J _CF = 28.5 and 22.5 Hz), 104.6-130.6 (m, (CF ₂ ) ₃ CF ₃ ) , 128.2, 129.9, 131.3, 138.9, 166.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 8.3 Hz, 3F), -117.3-(-127.5) (m, 6F).
_{HRMS (APCI-TOF) Calcd forC} 13 H 8 F 9 O 3 [M-H] -: 383.0330, Found: 383.0329.
IR (KBr) 537, 723, 888, 1211, 1307, 1444, 1706, 1953, 2970, 3458 cm ⁻¹ .

  Example 32 Preparation of methyl (1S, 2S) -2-hydroxy-1-methyl-2- (pentafluoroethyl) cyclopentanecarboxylate

Implemented except that instead of n-tridecafluorohexyl iodide in Example 19, pentafluoroethyl iodide, benzaldehyde was replaced with methyl (1S) -1-methyl-2-cyclopentanone-1-carboxylate The same operation as in Example 19 was performed to obtain the desired product methyl (1S, 2S) -2-hydroxy-1-methyl-2- (pentafluoroethyl) cyclopentanecarboxylate in 56% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.41 (s, 3H), 1.71-1.81 (m, 1H), 1.84-2.20 (m, 4H), 2.42-2 .52 (m, 1H), 2.45 (s, 1H), 3.69 (s, 3H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 18.8, 20.6, 33.2 (t, J _CF = 5.3 Hz), 52.3, 56.8, 85.6 (dd, J _CF = 26 3 and 21.0 Hz), 106.5-123.1 (m, (CF ₂ ) ₅ CF ₃ ), 175.2.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.2 Hz, 3F), -114.7-(− 115.9) (m, 1F), −119.5 (-121.4) (m, 2F), -121.7- (-121.8) (brm, 2F), -122.8 (s, 2F), -126.2 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 14 H 12 F 13 O 3 [M-H] -: 475.0579, Found: 475.0590.
IR (KBr) 644, 855, 1005, 1141, 1235, 1364, 1467, 1717, 2968, 3477 cm ⁻¹ .

  Example 33 Preparation of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-phenyl-2-hydroxyoctane

  The same operation as in Example 19 was carried out except that n-tridecafluorohexyl iodide and styrene oxide were used instead of n-tridecafluorohexyl iodide instead of n-tridecafluorohexyl iodide of Example 19, 4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-phenyl-2-hydroxyoctane was obtained in 43% yield.

  Example 34 Preparation of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-phenyl-2-hydroxyoctane

  The same operations as in Example 33 were performed under the same conditions as in Example 33, except that diethylaluminum chloride (1.2 mol) was further added, and the target product 3,3,4,4,5,5,6,6 was obtained. , 7,7,8,8,8-tridecafluoro-1-phenyl-2-hydroxyoctane was obtained in 75% yield.

  Example 35 Preparation of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-phenyl-2-hydroxyoctane

To a solution of zirconocene dichloride (Cp ₂ ZrCl ₂ , 70.2 mg, 0.24 mmol) cooled to −78 ° C. in ether (2.4 mL) was added n-propylmagnesium chloride (2.0 M ether solution, 0.12 mL, 0 .24 mmol), 1,4-dioxane (23 μL, 0.27 mmol) and n-tridecafluorohexyl iodide (C ₆ F ₁₃ I, 78 μL, 0.36 mmol) were added, followed by stirring at the same temperature for 1 hour. . Next, methylaluminoxane (10% toluene solution, 0.16 mL, 0.24 mmol) was added, and the mixture was warmed to 0 ° C. and stirred for 2 minutes. To this was added styrene oxide (23 μL, 0.20 mmol), and then the mixture was warmed to room temperature and stirred for 1 hour.

  After completion of the reaction, 1N-hydrochloric acid was added to stop the reaction, followed by extraction three times with ether. The organic layers were combined, dried over sodium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1 (v / v)) to obtain 3,3,4,4,5,5,6,6,7, 7,8,8,8-Tridecafluoro-1-phenyl-2-hydroxyoctane was obtained (77.5 mg, yield: 88%).

  Example 36 Preparation of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1- (4-methoxyphenyl) -2-hydroxyoctane

Example 4 8,8,8-Tridecafluoro-1-phenyl-2-hydroxyoctane was obtained in 43% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.09 (d, J = 6.3 Hz, 1H), 2.82 (dd, J = 14.1 and 10.2 Hz, 1H), 3.07 (d, J = 14.1 Hz, 1H), 3.80 (s, 3H), 4.28-4.31 (m, 1H), 6.88 (d, J = 8.4 Hz, 2H), 7.18 ( d, J = 8.4 Hz, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 34.6, 55.3, 71.1 (dd, J _CF = 28.5 and 23.3 Hz), 100.2-123.4 (m, (CF ₂ ) ₅ CF ₃ ), 114.3, 127.3, 130.6, 158.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.6 Hz, 3F), -119.8-(-127.3) (m, 10F).
_{HRMS (APCI-TOF) Calcd forC} 15 H 10 F 13 O 2 [M-H] -: 469.0473, Found: 469.0488.
IR (neat) 748, 885, 967, 1124, 1131, 1240, 1357, 2921, 3030, 3454 cm ⁻¹ .

  Example 37 Preparation of (E) -5,5,6,6,7,7,8,8,8-nonafluoro-1-phenyl-4-hydroxy-1-octene

Example 35 except that n-nonafluorobutyl iodide was used instead of n-tridecafluorohexyl iodide and 3,4-epoxy-1-phenyl-1,3-butadiene was used instead of styrene oxide. The target product (E) -5,5,6,6,7,7,8,8,8-nonafluoro-1-phenyl-4-hydroxy-1-octene was obtained in 71% yield. Obtained.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.24 (d, J = 7.2 Hz, 1H), 2.58-2.68 (m, 1H), 2.72-2.79 (m, 1H) , 4.21-4.35 (m, 1H), 6.18-6.28 (m, 1H), 6.61 (d, J = 15.6 Hz, 1H), 7.26-7.42 ( m, 5H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 33.2, 93.2 (dd, J _CF = 27.8 and 22.5 Hz), 107.1-119.8 (m, (CF ₂ ) ₃ CF ₃ ) , 122.7, 126.3, 127.9, 128.7, 135.3, 136.5.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.0 Hz, 3F), -120.1-(-127.6) (m, 6F).
_{HRMS (APCI-TOF) Calcd forC} 14 H 10 F 9 O [M-H] -: 365.0588, Found: 365.0584.
IR (KBr) 748, 885, 967, 1124, 1131, 1240, 1357, 2921, 3030, 3454 cm ⁻¹ .

  Example 38 (Z) -2-bromo-5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-1-phenyl-4-hydroxy-1 -Preparation of decene

The same procedure as in Example 35 was performed except that 3,4-epoxy-2-bromo-1-phenyl-1,3-butadiene was used instead of styrene oxide in Example 35, and the target product (Z) -2- Bromo-5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-1-phenyl-4-hydroxy-1-decene obtained in 78% yield It was.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.37 (d, J = 6.3 Hz, 1H), 2.92-3.07 (m, 2H), 4.57-4.71 (m, 1H) 6.95 (s, 1H), 7.30-7.41 (m, 3H), 7.60 (d, J = 6.9 Hz, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 43.5, 68.2 (dd, J _CF = 28.9 and 23.3 Hz), 107.0-123.2 (m, (CF ₂ ) ₅ CF ₃ ) 119.5, 128.4, 128.5, 129.1, 132.9, 135.2.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.8 (t, J _FF = 9.6 Hz, 3F), -119.7-(-127.3) (m, 10F).
_{HRMS (APCI-TOF) Calcd forC} 16 H 9 BrF 13 O [M-H] -: 542.9629, Found: 545.9630.
IR (neat) 692, 753, 916, 1147, 1242, 1317, 1371, 1446, 3056, 3410 cm ⁻¹ .

  Example 39 Preparation of (E) -8-benzyloxy-1,1,1,2,2,3,3-heptafluoro-4-hydroxy-6-octene

Example 35 except that n-heptafluoropropyl iodide was used instead of n-tridecafluorohexyl iodide and 1,2-epoxy-5-benzyloxy-1,3-pentadiene was used instead of styrene oxide. The same operation as 35 was performed to obtain the target product (E) -8-benzyloxy-1,1,1,2,2,3,3-heptafluoro-4-hydroxy-6-octene in 78% yield. It was.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.35-2.45 (m, 1H), 2.50-2.57 (m, 1H), 2.78 (d, J = 6.6 Hz, 1H) , 4.53 (s, 3H), 5.68-5.86 (m, 2H), 7.28-7.39 (m, 5H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 32.4, 68.9 (dd, J _CF = 28.5 and 23.3 Hz), 72.5, 106.1-123.5 (m, (CF ₂ ) ₂ CF _3), 127.1,127.8,127.8,128.5,131.7,137.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 10.2 Hz, 3F), -121.0 (dd, J _FF = 282.4 Hz and J _FH = 5.5 Hz, 1F ), -124.7-(-128.3) (m, 3F).
_{HRMS (APCI-TOF) Calcd forC} 15 H 14 F 7 O 2 [M-H] -: 359.0882, Found: 359.0871.
IR (neat) 733, 916, 978, 1114, 1228, 1351, 1460, 2859, 2933, 3395 cm ⁻¹ .

  Example 40 Preparation of 2-n-heptadecafluorooctyl-2-hydroxy-2,3-dihydro-1H-indene

The same operation as in Example 35 was carried out except that n-heptadecafluoro p-octyl iodide instead of n-tridecafluorohexyl iodide in Example 35 and 1,2-epoxyindene were used instead of styrene oxide. The product 2-n-heptadecafluorooctyl-2-hydroxy-2,3-dihydro-1H-indene was obtained in 73% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.23 (s, 1H), 3.10 (d, J = 16.8 Hz, 1H), 3.58 (d, J = 16.8 Hz, 1H), 7 24-7.31 (m, 4H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 42.8, 84.0 (t, J _CF = 25.5 Hz), 104.8-120.7 (m, (CF ₂ ) ₇ CF ₃ ), 125.2. 127.5, 138.4.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 9.6 Hz, 3F), -118.4 (s, 2F), -119.4 (s, 2F), -121 .8-(-121.8) (brm, 6F), -122.8 (s, 2F), -126.2 (s, 2F).
_{HRMS (APCI-TOF) Calcd forC} 17 H 8 F 17 O [M-H] -: 551.0304, Found: 551.0300.
IR (KBr) 659, 753, 1072, 1208, 1480, 1725, 1935, 2390, 3035, 3579 cm ⁻¹ .

  Example 41 Preparation of 2,2,3,3,3-pentafluoro-1-hydroxy-1- (1-1,2,3,4-tetrahydronaphthyl) propane

Implemented except that pentafluoroethyl iodide was used instead of n-tridecafluorohexyl iodide in Example 35, and 3,4-dihydro-2H-spiro [naphthalene] -1,2'-oxirane was used instead of styrene oxide. The same operation as in Example 35 was performed to obtain the desired 2-n-heptadecafluorooctyl-2-hydroxy-2,3-dihydro-1H-indene in 78% yield. The obtained target product was a mixture of isomers, and the ratio was 52/48.
¹ H-NMR (300 MHz, CDCl ₃ ) δ1.59-1.71 (m, 1H), 1.87-2.09 (m, 4H), 2.68-2.92 (m, 2H), 3 .38-3.43 (brm, 1H), 4.02-4.15 (m, 1H, major), 4.57-4.69 (m, 1H, minor), 7.12-7.24 ( m, 4H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 18.4, 21.8, 22.6 (d, J _CF = 3.8 Hz), 28.1 (d, J _CF = 3.0 Hz), 28.5 29.9, 37.5, 38.2, 71.7 (dd, J _CF = 28.5 and 22.5 Hz), 72.3 (dd, J _CF = 27.0 and 19.5 Hz), 110. 4-125.0 (m, CF ₂ CF ₃ ), 126.0, 126.6, 126.7, 127.5, 127.9, 129.9, 130.2, 130.9 (d, J _CF = 3.8 Hz), 132.3, 135.1, 139.1, 140.2.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-81.8 (s, 3F, minor), −82.8 (s, 3F, major), −120.1 (d, J _FF = 276.0 Hz, 1F) , Major), −123.0 (d, J _FF = 276.1 Hz, 1F, minor), −127.9 (dd, J _FF = 276.1 Hz and J _FH = 22.3 Hz, 1F, minor), − 131.6 (dd, J _FF = 276.0 Hz and J _FH = 22.4 Hz, 1F, major).
_{HRMS (APCI-TOF) Calcd forC} 13 H 12 F 5 O [M-H] -: 279.0808, Found: 279.0806.
IR (neat) 740, 1038, 1120, 1195, 1244, 1453, 1493, 2872, 2947, 3538 cm ⁻¹ .

  Example 42 Preparation of 5,5,6,6,7,7,8,8,8-nonafluoro-1-phenyl-4-hydroxy-1-octyne

The same procedure as in Example 35 was performed, except that nonafluorobutyl iodide was used instead of n-tridecafluorohexyl iodide of Example 35, and 2- (phenylethynyl) oxirane was used instead of styrene oxide. 5,5,6,6,7,7,8,8,8-Nonafluoro-1-phenyl-4-hydroxy-1-octyne was obtained in 55% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.69 (d, J = 6.9 Hz, 1H), 2.86-3.02 (m, 2H), 4.38-4.44 (m, 1H) , 7.29-7.45 (m, 5H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 21.8 (t, J _CF = 0.4 Hz), 68.3 (dd, J _CF = 29.3 and 22.5 Hz), 82.5, 84.4 99.8-129.5 (m, (CF ₂ ) ₃ CF ₃ ), 122.6, 128.5, 128.7, 131.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.9 (t, J _FF = 8.3 Hz, 3F), -119.6-(-128.5) (m, 6F).
_{HRMS (APCI-TOF) Calcd forC} 14 H 8 F 9 O [M-H] -: 363.0431, Found: 363.0433.
IR (neat) 755, 885, 1131, 1233, 1350, 1493, 1678, 2927, 3064, 3488 cm ⁻¹ .

  Example 43 Preparation of 5,5,6,6,7,7,8,8,8-nonafluoro-1- (4-methoxyphenyl) -4-hydroxy-1-octyne

The same operation as in Example 35 was conducted except that n-nonafluorobutyl iodide was used instead of n-tridecafluorohexyl iodide and 2- [4-methoxyphenyl) ethynyl] oxirane was used instead of styrene oxide. The target product 5,5,6,6,7,7,8,8,8-nonafluoro-1- (4-methoxyphenyl) -4-hydroxy-1-octyne was obtained in 54% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 2.70 (d, J = 7.2 Hz, 1H), 2.84-3.00 (m, 2H), 3.91 (s, 3H), 4.34 -4.46 (m, 1H), 6.84 (d, J = 8.7 Hz, 2H), 7.36 (d, J = 8.7 Hz, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 21.8, 55.4, 68.3 (dd, J _CF = 29.3 and 22.5 Hz), 81.0, 84.4, 106.4-129. _{0 (m, (CF 2)} 5 CF 3), 114.1,114.7,133.3,159.9.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-80.8 (t, J _FF = 9.3 Hz, 3F), -119.8-(-128.3) (m, 10F).
_{HRMS (APCI-TOF) Calcd forC} 17 H 10 F 13 O 2 [M-H] -: 493.0473, Found: 493.0459.
IR (KBr) 695,826,1032,1245,1506,1603,1719,2852, 1970,3313 cm < ^-1 >.

  Example 44 Preparation of 8-[(tert-butyldiphenylsilyl) oxy] -1,1,1,2,2-pentafluoro-3-hydroxy-4-methyl-5-octyne

Instead of n-tridecafluorohexyl iodide in Example 35, pentafluoroethyl iodide and tert-butyl [[4- (2-methyloxiran-2-yl) but-3-yne-1 instead of styrene oxide] The same operation as in Example 35 was performed except that -yl] oxy] diphenylsilane was used, and the target 8-[(tert-butyldiphenylsilyl) oxy] -1,1,1,2,2-pentafluoro-3 was obtained. -Hydroxy-4-methyl-5-octyne was obtained in 84% yield. The obtained target product was a mixture of isomers, and the ratio was 64/36.
Major
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.07 (s, 9H), 1.28 (d, J = 7.2 Hz, 3H), 2.38-2.46 (m, 3H), 2.98 -3.01 (brm, 1H), 3.76 (t, J = 6.9 Hz, 2H), 4.07-4.19 (m, 1H), 7.37-7.47 (m, 6H) , 7.67-7.70 (m, 4H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 15.0, 19.2, 22.8, 26.7, 28.0, 62.5, 70.5 (dd, J _CF = 27.0 and 20.3 Hz) ), 80.6, 80.7, 109.5-124.6 (m, CF ₂ CF ₃ ), 127.7, 129.7, 133.6, 135.6.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-82.7 (s, 3F), -121.4 (d, J _FF = 276.9 Hz, 1F), -130.0 (dd, J _FF = 276. 9 Hz and J _FH = 20.9 Hz, 1F).
_{HRMS (APCI-TOF) Calcd forC} 25 H 28 F 5 O 2 Si [M-H] -: 483.1779, Found: 483.1764.
IR (neat) 699, 733, 822, 1059, 1106, 1195, 1426, 2859, 2933, 3524 cm ⁻¹ .
Minor
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.06 (s, 9H), 1.33 (d, J = 6.9 Hz, 3H), 2.44 (td, J = 6.6 and 2.1 Hz, 2H), 2.69 (d, J = 10.5 Hz, 1H), 3.03-3.06 (m, 1H), 3.75 (t, J = 6.6 Hz, 2H), 3.79- 3.84 (m, 1H), 7.36-7.47 (m, 6H), 7.66-7.69 (m, 4H).
¹³ C-NMR (75 MHz, CDCl ₃ ) δ 19.2, 19.4, 22.8, 26.7, 27.3, 62.4, 70.8 (dd, J _CF = 28.5 and 21.8 Hz) ), 77.9, 83.5, 112.7-126.3 (m, CF ₂ CF ₃ ), 127.7, 129.7, 133.5, 135.5.
¹⁹ F-NMR (282 MHz, CDCl ₃ ) δ-82.3 (s, 3F), -122.0 (d, J _FF = 276.1 Hz, 1F), -132.6 (dd, J _FF = 276. 1 Hz and J _FH = 19.9 Hz, 1F).
_{HRMS (APCI-TOF) Calcd forC} 25 H 28 F 5 O 2 Si [M-H] -: 483.1779, Found: 483.1761.
IR (neat) 699, 733, 1018, 1106, 1201, 1426, 1589, 2859, 2933, 3491 cm ⁻¹ .

  According to the present invention, a novel perfluoroalkylating agent can be proposed, and various fluorine-containing compounds using the same can be produced.

Claims (4)

The following general formula (1)

R ¹ MgX (1)

(Wherein R ¹ represents a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, and X represents a halogen atom)
Perfluoromagnesium halide represented by the following general formula (2)

(Wherein M represents a titanium atom or a zirconium atom, and X represents a halogen atom)
And metallocene dihalide represented by the following general formula (3)

Rf-I (3)

(Wherein Rf represents a trifluoromethyl group, a pentafluoroethyl group, a linear, branched or cyclic perfluoroalkyl group or a perfluoroaryl group having 3 to 9 carbon atoms)
A perfluoroalkylating agent prepared by reacting a perfluoroalkyl iodide represented by the formula: The perfluoroalkylating agent according to claim 1 and the following general formula (4)

(Wherein R ² and R ³ are each independently a hydrogen atom, a methyl group, an ethyl group, or a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, a naphthyl group, a pyridyl group, a phenyl group, An ethylenyl group, a substituted alkyl group or a substituted phenyl group, R ² and R ³ may be condensed, and R ² and R ³ are not hydrogen atoms)
The following general formula (5), characterized in that a carbonyl compound represented by the formula:

(Wherein Rf, R ² and R ³ are the same as above)
The manufacturing method of fluorine-containing alcohol represented by these. The perfluoroalkylating agent according to claim 1 and the following general formula (6)

R ⁴ -CN (6)

(Wherein R ⁴ is a methyl group, an ethyl group, or a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, a naphthyl group, a pyridyl group, a phenylethylenyl group, a substituted alkyl group, or a substituted phenyl group. Indicate)
Or a cyano compound represented by the following general formula (7)

R ⁴ —CO ₂ R ⁵ (7)

(In the formula, R ⁴ is the same as above, R ⁵ represents a methyl group or an ethyl group)
The following general formula (8):

(Wherein R ⁴ and Rf are the same as above)
The manufacturing method of perfluoroalkyl ketones represented by these. The perfluoroalkylating agent according to claim 1 and the following general formula (9)

(Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, a naphthyl group, a pyridyl group, a methoxy group, A carbonyl group, a phenylethynyl group, a substituted alkyl group, a substituted phenyl group, a substituted alkenyl group, and a substituted acetylene group)

The following general formula (10), characterized by reacting an epoxy compound represented by

(Wherein R ⁶ , R ⁷ and Rf are the same as above)
The manufacturing method of the fluorine-containing compound represented by these.