JPS649976B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula (In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, Ar is a substituted or unsubstituted phenyl group, and X is a group represented by -OSO ₂ Y, a group represented by -OCOZ, a halogen atom) ,
BF ₄ , ClO ₄ , PF ₄ , PF ₆ , AsF ₄ , AsF ₆ , SbF ₆ ,
Or _SbF4 . However, Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, an OM group, an alkoxy group, a phenoxy group, or a perhaloalkyl group, and Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted It is a substituted aryl group or perhaloalkyl group. M is a hydrogen atom, an alkali metal atom, an ammonium residue, a pyridinium residue, or a group represented by the formula: R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or an aryl group, R ⁹ is a hydrogen atom,
It is an alkyl group or an aryl group. n is 0 or 1
It is. R ¹ and R ⁵ can be combined to form a cyclic structure. ) The present invention relates to a method for producing a perfluoroalkyl-substituted ester represented by The perfluoroalkyl-substituted ester represented by the general formula () obtained by the present invention can serve as an intermediate for the synthesis of useful substances having surface activity. For example, among the perfluoroalkyl-substituted esters represented by the general formula (), formic acid 2-(perfluoroalkyl)ethyl ester and acetic acid 2-
(Perfluoroalkyl)ethyl ester can be led to 2-(perfluoroalkyl)ethanol by hydrolysis [R&D Report "Chemistry and Industry of Fluorine Compounds" (1977, CMC Publishing) p. 388 and J・Org.Chem., 23 ,
1166 (1958)]. This alcohol is useful as an intermediate for surfactants, water and oil repellents, surface treatment agents for paper, leather, textiles, etc., fire extinguishers, oil collecting agents, lubricating oil additives, etc. [Organic Synthetic Chemistry, Vol. 31] roll,
No. 6, p. 508 (1973), R&D report “Chemistry and Industry of Fluorine Compounds” (1977, CMC Publishing)]. Furthermore, formic acid or acetic acid 4-(perfluoroalkyl)-2-butenyl ester can be led to 4-(perfluoroalkyl)-2-buten-1-ol by hydrolysis (Reference Examples 1 and 2). reference). 4-(perfluoroalkyl)-2-
Buten-1-ol is a surfactant, water and oil repellent,
It is useful as an intermediate for surface treatment agents for paper, leather, fibers, etc., fire extinguishers, oil collecting agents, lubricating oil additives, fluorine rubber, resists for integrated circuits, etc. For example, 1, which is useful as a monomer for fluorine polymers that easily have surface activity by performing a dehydration reaction.
-(Perfluoroalkyl)-1,3-butadiene (Reference Example 3, US Patent No.
2892824, 2912407 and 3398128).
In addition, by reacting 4-(perfluoroalkyl)-2-buten-1-ol with methacrylic acid chloride, we have developed a fluorine methacrylate ester polymer that is useful as a water and oil repellent for textiles and as a resist for integrated circuits. Methacrylic acid 4-(perfluoroalkyl)-2-butenyl ester, which is a monomer for coalescence, can be produced (Reference Example 4, R
&D Report “Cutting-edge application technology of fluorine compounds”
(See p. 138 and “Chemistry and Industry of Fluorine Compounds” p. 391). 4-(perfluoroalkyl) methacrylate
-2-Butenyl ester is a completely new type of water and oil repellent agent and monomer for producing resists for integrated circuits, which has an unsaturated bond between the acid moiety and the perfluoroalkyl group moiety. As a conventional method for producing 1-(perfluoroalkyl)-1,3-butadiene, for example, when the perfluoroalkyl group is a trifluoromethyl group, (1) trifluoroacetylacetone is heated at high pressure and high temperature (150
The diol is obtained by reducing it with Raney nickel under conditions (atmospheric pressure, 100°C), converting it into diacetate with acetic anhydride, and then thermally decomposing it at 470°C [J. Amer.Chem.Soc., 76 , 5147 (1954)], and (2) 5,5,5-trifluorolaebulic acid (5, 5,5-trifluorolaevolic
acid) with lithium aluminum hydride,
After diol and further diacetate, 520
℃ thermal decomposition method (Tetrahedron, 1960 , 164
), and further (3) 3,3,3-trifluoro-1-
⁶⁰ CO in a mixture of propyne and ethyl alcohol
A method of obtaining adducts by irradiating them with gamma rays for a long time and dehydrating them with phosphorus pentoxide
14044) is known. However, methods (1) and (2) have long reaction paths and the final thermal decomposition reaction is carried out at a high temperature of around 500°C, which is not preferable from the viewpoint of energy saving. Method (3) uses ⁶⁰ Co, which is a radioactive substance, and has a low yield. From the above points, the conventional method for producing 1-(perfluoroalkyl)-1,3-butadiene is unsatisfactory as an industrial production method. Conventionally, as a method for producing perfluoroalkyl-substituted esters represented by the general formula (), iodoperfluoroalkane and ethylene are reacted under radical-generating conditions to produce 2-(perfluoroalkyl).
Method of obtaining ethyl iodide, followed by reaction with (1) dimethylformamide at high temperature (140°C) and hydrolysis [J.Chem.Soc., 1949 , 2856 and R&D report, "Chemistry and industry of fluorine compounds" (1977, CMC Publishing) p. 388] or (2) treatment with silver acetate [J.Org.Chem., 23 , 1166 (1958)] are known. However, the conventional method of reacting iodoperfluoroalkane with ethylene is under radical reaction conditions, so polymerization reactions tend to occur simultaneously and reaction control is difficult, and the next method (1) of reacting with dimethylformamide requires high temperatures. Therefore, it is not desirable from the viewpoint of energy saving. Also, a method using silver acetate
Method (2) is economically disadvantageous because it uses expensive silver salt. From the above points, the conventional method is unsatisfactory as an industrial production method. As a result of intensive studies to overcome the conventional drawbacks, the present inventors have discovered a method for easily producing perfluoroalkyl-substituted esters under mild conditions, and have completed the present invention. The present invention is based on the general formula (In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, Ar is a substituted or unsubstituted phenyl group, and X is a group represented by -OSO ₂ Y, a group represented by -OCOZ, a halogen atom) ,
BF ₄ , ClO ₄ , PF ₄ , PF ₆ , AsF ₄ , AsF ₆ , SbF ₆ or SbF ₄ . However, Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, an OM group, an alkoxy group, a phenoxy group, or a perhaloalkyl group, and Z is a substituted or unsubstituted alkyl group, a substituted or It is an unsubstituted aryl group or perhaloalkyl group. M is a hydrogen atom, an alkali metal atom, an ammonium residue, a pyridinium residue, or a group represented by the formula. ) and a perfluoroalkylaryl iodonium compound represented by the general formula R ¹ R ² C(=CR ³ −CR ⁴ (= _o CR ⁵ R ⁶ −() (R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or an aryl group. n is 0 or 1. R ¹
and R ⁵ can be combined to form a cyclic structure. ) and the general formula (In the formula, R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, alkyl groups or aryl groups.) By reacting with an amide compound represented by the formula (wherein R 7 , R 8 and R 9 are a hydrogen atom, an alkyl group or an aryl group) and then hydrolyzing the compound, This method produces perfluoroalkyl-substituted esters. The perfluoroalkylaryl iodonium compound represented by the above general formula (), which is a raw material of the present invention, is a di(trifluoroacetoxy)iodoperfluoroalkane or a difluoroacetyl iodoperfluoroalkane obtained by oxidizing or fluorinating an industrially available iodized perfluoroalkane. Iodoperfluoroalkane [Zh.Org.Khim・6 , 329 (1970), J.Fluorine
Chem., 8 , 177 (1976) and J.Amer.Chem.Soc.,
91, 3054 (1969)] with substituted or unsubstituted benzene in the presence of an acid; a method of reacting with substituted or unsubstituted benzene and then treating with an alkali metal halide; It can be obtained by a method of reacting iodonium chloride and silver salt [Zh.
Org Khim. 7 , 1473 (1971), Zh.Org.Khim.
16, 232 (1980), West German Published Patent No. 3021226, French Published Patent No. 2458527, and Japanese Patent Application Laid-open No. 162763/1983]. In addition, in the perfluoroalkylaryl iodonium compound represented by the general formula (), when X is -OSO ₂ Y (Y=OM) and M is an alkali metal atom, ammonium residue or pyridinium residue, the general formula () is used. The perfluoroalkyl iodonium compound (X=OSO ₂ Y, Y
=OH) with the corresponding base. As the perfluoroalkylaryl iodonium compound represented by the general formula (), n
-heneicosafluorodecyl phenyl iodonium trifluoromethanesulfonate, 7-trifluoromethyl-hexadecafluorooctyl phenyl iodonium trifluoromethanesulfonate, n-heptadecafluorooctyl phenyl iodonium trifluoromethanesulfonate,
n-pentadecafluoroheptyl phenyl iodonium trifluoromethanesulfonate, n-tridecafluorohexylphenyl iodonium trifluoromethanesulfonate, i-heptafluoropropylphenyl iodonium trifluoromethanesulfonate, n-heptafluoropropylphenyl iodonium trifluoromethanesulfonate, Pentafluoroethyl phenyl iodonium trifluoromethanesulfonate, trifluoromethyl phenyl iodonium trifluoromethanesulfonate, pentafluoroethyl phenyl iodonium chloride, n-heptafluoropropyl-p-tolyliodonium chloride, n
-heptadecafluorooctyl tolyliodonium chloride, n-heptafluoropropyl tolyliodonium trifluoroacetate, n-heptadecafluorooctyl phenyl iodonium methanesulfonate, n-heptadecafluorooctyl phenyl iodonium trichloromethane sulfonate, n-heptafluoropropyl -p-tolyliodonium methanesulfonate, n-heptadecafluorooctyltolyliodonium methanesulfonate, n-heptafluoropropyl-
p-tolyliodonium benzenesulfonate,
Mono(pentafluoroethyl phenyl iodonium) sulfate, mono(n-heptafluoropropylphenyl iodonium) sulfate, mono(i-heptafluoropropylphenyl iodonium) sulfate, mono(n-tridecafluorohexylphenyl iodonium) sulfate , mono(n-heptadecafluorooctyl phenyl iodonium) sulfate, mono(n-heneicosafluorodecyl phenyl iodonium) sulfate, bis(n-heptafluoropropylphenyl iodonium) sulfate, n
-heptafluoropropylphenyl iodonium fluorosulfonate, n-heptadecafluorooctyl phenyl iodonium chlorosulfonate, n-heptafluoropropylphenyl iodonium methyl sulfate, n-heptadecafluorooctyl phenyl iodonium pyridinium sulfate, n -heptafluoropropylphenyl iodonium sodium sulfate, n-
Examples include heptafluoropropylphenyliodonium potassium sulfate and n-tridecafluorohexylphenyliodonium tetrafluoroborate. In addition, examples of the ene compound represented by the general formula () include ethylene, styrene, p-methylstyrene, p-chlorostyrene, propene, hexene, cyclohexene, cycloheptene, allylbenzene, 1-phenyl-1-propene, and allylbenzene. enyl ether, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-
Butadiene, 1-phenyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3
Examples include -pentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, 5,6-dihydro-2H-pyran, 1,4-dihydronaphthalene, and 1,4-cyclohexadiene. Examples of the amide compound represented by the general formula () include N,N-dimethylformaldehyde, N-methylformaldehyde, formaldehyde, and N,N-dimethylacetamide. Hydrolysis is accomplished by contacting the reaction mixture with water. Further, there is no problem in causing water to be present in the reaction solution from the beginning so that hydrolysis can be carried out simultaneously within the reaction system. In carrying out the reaction, an excess amount of the amide compound represented by the above general formula () can be used as a solvent, but other solvents such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, , halides such as 1,2-trichlorotrifluoroethane, polar solvents such as acetone, acetonitrile, dimethyl sulfoxide (DMSO), nitromethane, ethyl acetate, diethyl ether, tetrahydrofuran,
Ethers such as dioxane, benzene, toluene,
Hydrocarbon solvents such as hexane, cyclohexane, octane, and decalin can also be used. The reaction temperature is -30°C to 120°C, but preferably -20°C to 100°C for the reaction to proceed efficiently. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 n-heptadecafluorooctyl phenyl iodonium trifluoromethanesulfonate 193mg
(0.25 mmol) was placed in a reaction vessel, and after degassing with a vacuum pump, 2 ml of N,N-dimethylformamide was added and dissolved. 1,3-butadiene was introduced and stirred at room temperature for 2 hours. Ether extraction was performed by adding 2 ml of water. The drained liquid was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was applied to a silica gel column (developed with 5% ether/n-pentane) to obtain 81 mg of formic acid (4-(n-heptadecafluorooctyl)-2-butenyl ester).
Yield 36%. The physical property values are shown in Table 2. Examples 2 to 8 Reactions were carried out in the same manner as in Example 1 under the conditions shown in Table 1. The results are shown in Table 1. The physical property values are shown in Table 2. [Table] [Table] The physical property values are shown in Table 2.
[Table] Reference example 1 n-C ₈ F ₁₇ CH ₂ CH=CHCH ₂ OCHO→ n-C ₈ F ₁₇ CH ₂ CH=CHCH ₂ OH Formic acid 4-(n-heptadecafluorooctyl)-
2-butenyl ester 150mg (0.29mmol), ethanol 4ml, water 1ml and 1N sodium hydroxide solution
0.35 ml (0.35 mmol) of the mixture was refluxed for 3 hours.
Thereafter, brine was added and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and subjected to silica gel column chromatography to collect 120 mg of 4
-(n-heptadecafluorooctyl)-2-buten-1-ol was obtained. Yield 85%. The physical property values were as follows. Melting point: 32-33℃ ¹ H-NMR (δ, in deuterated chloroform): 1.80
(s, 1H), 2.81 (td, J=18.4, 6.0Hz,
2H), 4.12 (d, J = 4.4Hz, 2H), 5.62 (dt,
J=16.0, 6.0Hz, 1H), 5.88(dt, J=
16.0, 4, 4Hz, 1H). ¹⁹ F-NMR (ppm, CCl ₃ F internal standard in deuterated chloroform); 81.36 (t, J = 10 Hz, CF ₃ ), 113.5 (m,
α−CF ₂ ). IR (cm ^-1 , neat); 3400 (OH), 1680 (c=c),
1150, 1200 (c-F). Mass spectrum (m/e); 490 (M ⁺ ). Reference example 2 n-C ₈ F ₁₇ CH ₂ CH=CHCH ₂ OCOCHO ₃ → n-C ₈ F ₁₇ CH ₂ CH=CHCH ₂ OH Formic acid 4-(n-heptadecafluorooctyl)-
The reaction was carried out under the same conditions as in Reference Example 1 in terms of molar ratio, except that 290 mg (0.38 mmol) of 4-(n-heptadecafluorooctyl)-2-butenyl acetate was used instead of 2-butenyl ester. , 190
mg of 4-(n-heptadecafluorooctyl)-2
-Buten-1-ol was obtained as an oil. yield
75%. Reference example 3 n-C ₈ F ₁₇ CH ₂ CH=CHCH ₂ OHP ₂ O ₅ ---→ n-C ₈ F ₁₇ CH=CHCH=CH ₂ 4-(n-heptadecafluorooctyl)-2-
Mix 490 mg (1 mmol) of buten-1-ol and 852 mg (6 mmol) of phosphorus pentoxide, and reduce the pressure with a vacuum pump equipped with a liquid nitrogen trap until 80 ~
Heated to 100°C for 4 hours. The mixture was extracted with methylene chloride to obtain 144 mg of 1-(n-heptadecafluorooctyl)-1,3-butadiene. 47 mg of product was also obtained from the trap under liquid nitrogen cooling.
A total of 191 mg (40% yield) was obtained. Colorless oil ^1H -NMR (ppm, in deuterated chloroform); 5.36~
5.87 (m, 3H), 6.16-6.88 (m, 2H). ¹⁹ F-NMR (ppm, in deuterated chloroform, CCl ₃ F internal standard); 81.40 (t, J = 10 Hz, CF ₃ ), 111.9 (m,
α−CF ² ). IR (cm ^-1 , neat); 1155, 1210, 1250 (CF), 1615,
1665 (c=c). Mass spectrum (m/e); 472 (M ⁺ ). Elemental analysis: Actual value: C, 30.49%; H, 1.06% Calculated value: C, 30.53%; H, 1.07%. Reference example 4 n-C ₆ F ₁₃ CH ₂ CH=CHCH ₂ OH+CH ₂ =CHCOCl→n-C ₆ F ₁₃ CH ₂ CH =CHCH ₂ OCOCH=CH ₂ 4-(n-tridecafluorohexyl)-2-butene -1-ol 222 mg (0.57 mmol) and triethylamine 138 mg (1.36 mmol) were dissolved in 4 ml of ether, and 124 mg of acrylic acid chloride was dissolved in 2 ml of ether with stirring at room temperature.
(1.36 mmol) was added dropwise. After stirring for an additional hour and a half, the precipitate was removed by filtration. The solvent of the filtrate was distilled off under reduced pressure, and the residue was passed through a silica gel column (5
% ether/n-pentane development) to obtain 138 mg of acrylic acid 4-(n-tridecafluorohexyl)-2-butenyl ester. Yield 55%. Colorless oil ^1H -NMR (ppm, in deuterochloroform); 2.83 (td,
J=17.8, 6.0Hz, 2H), 4.42(d, J=4.0
Hz, 2H), 5.54-6.00 (m, 2H), 5.77 (dd,
J=9.8, 2.4Hz, 1H), 6.07(dd, J=
17.6, 9.8Hz, 1H), 6.39(dd, J=17.6,
2.4Hz, 1H). ¹⁹ F-NMR (ppm, in deuterated chloroform, CCl ₃ F internal standard); 81.28 (t, J = 10 Hz, CF ₃ ), 113.4 (m,
α−CF ₂ ). IR (cm ^-1 , neat; 1145, 1190, 1240 (CF), 1620,
1635 (c=c), 1735 (c=o). Mass spectrum (m/e); 444 (M ⁺ ).

Claims (1)

[Claims] 1. General formula A perfluoroalkylaryl iodonium compound represented by the general formula R ¹ R ² C (= CR ³ − CR ⁴ =) _o CR ⁵ R ⁶ and an ene compound represented by the general formula The general formula consists of reacting with an amide compound represented by and then hydrolyzing A method for producing a perfluoroalkyl-substituted ester represented by (wherein Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, Ar is _a substituted or unsubstituted phenyl group, and , a group represented by -OCOZ, a halogen atom, BF ₄ , ClO ₄ , PF ₄ , PF ₆ , AsF ₄ , AsF ₆ ,
SbF ₆ or SbF ₄ . However, Y is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a halogen atom, an OM group, an alkoxy group,
is a phenoxy group or a perhaloalkyl group, and Z
is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a perhaloalkyl group. M is a hydrogen atom, an alkali metal atom, an ammonium residue, a pyridinium residue, or a group represented by the formula; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and
R ⁶ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or an aryl group, and R ⁷ , R ⁸ and R ⁹ are a hydrogen atom, an alkyl group or an aryl group. n is 0 or 1. R ¹ and R ⁵ can be combined to form a cyclic structure. ).