JPS6225654B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula (wherein, Rf is a perfluoroalkyl group or a pentafluorophenyl group having 1 to 4 carbon atoms).

The fluorine-containing methacrylic acid ester of the present invention represented by the above general formula () can be made into a fluorine-containing polymethacrylate by polymerizing it. Fluorine-containing polymethacrylate is useful as a resist for LSI manufacturing.

The present inventors have studied fluorine-containing methacrylic acid esters that can lead to fluorine-containing polymers that are effective as new LSI fabrication resists, and have discovered the present invention.

The fluorine-containing methacrylic ester of the present invention represented by the general formula () is methacrylic acid chloride and the general formula (In the formula, Rf is a perfluoroalkyl group or a pentafluorophenyl group having 1 to 4 carbon atoms.) It can be produced by reacting it with an alcohol having a perfluoro group represented by the following formula.

Methacrylic acid chloride is a compound that is easily available as an industrial raw material. Also, the general formula ()
The perfluoro group-containing alcohol represented by is a compound that can be easily produced by hydroformylating the corresponding perfluoro group-containing olefin and then reducing it (see Reference Examples below).

The reaction between methacrylic acid chloride and the alcohol having a perfluoro group represented by the general formula () is preferably carried out in the presence of a base. As the base, for example, amines such as triethylamine, N,N-dimethylaniline, and pyridine, metal salts such as sodium carbonate, sodium bicarbonate, and potassium acetate, and metals such as magnesium can be used, but depending on the yield. Preferably, tertiary amines are used.

In producing the methacrylic ester represented by the above general formula () of the present invention, a solvent is not necessarily required, but hydrocarbons such as hexane and benzene that do not participate in the reaction, halides such as chloroform and methylene chloride, diethyl ether,
There is no problem in using ethers such as tetrahydrofuran, nitriles such as acetonitrile, etc. The reaction proceeds at room temperature, but may be cooled or heated if necessary.

Hereinafter, the present invention will be further explained in detail with reference to Reference Examples and Examples.

Reference Example 1 92.5 mg (0.10 mmol) of chlorotris(triphenylphosphine)rhodium, 1.12 mg (0.10 mmol) of 3,3,3-trifluoro-1-propene (gas volume 50 mmol), and 10 ml of toluene as a solvent were placed in a 200 ml autoclave. The reaction was completed by heating and stirring at 100° C. for 44 hours under a carbon monoxide pressure of 50 atm and a hydrogen pressure of 50 atm. 5.67 g of 2-trifluoromethylpropanal was obtained by distilling the reaction mixture.
(yield 90%).

Reference example 2 Chlorocarbonylbis(triphenylphosphine)rhodium 20.7mg (3.00×10 ^-2 mmol),
3,3,3-trifluoro-1-propene 224ml
(Gas volume, 10.0 mmol) and 2 ml of toluene as a solvent were placed in a 200 ml autoclave, and heated at 110°C under 40 atm carbon monoxide pressure and 40 atm hydrogen pressure.
After stirring for an hour, the reaction was completed. By distilling the reaction mixture, 1.20 g (yield 95%) of a crude product of 2-trifluoromethylpropanal was obtained.

Reference Example 3 Put 28 mg (3.04 x 10 ^-2 mmol) of chlorotris(triphenylphosphine)rhodium, 5.86 g (30.2 mmol) of pentafluorostyrene, and 20 ml of benzene as a solvent into a 200 ml autoclave, and
Atmospheric carbon monoxide pressure and 40 atm hydrogen pressure, 90℃
The reaction was completed after stirring for 20 hours. After removing the solvent from the reaction mixture, it is distilled to a boiling point of 96℃/
6.43 g (95% yield) of 2-pentafluorophenylpropanal having a pressure of 21 mmHg was obtained.

n ²⁰ _D : 1.4428 ¹ H NMR (CDCl ₃ :TMS): δ1.56 (double line,
J=7.4Hz, 3H), 3.95 (multiplet, 1H), 9.75
(Triple line, J=2.2Hz, 1H)・^19F NMR (CDCl ₃ :CF ₃ COOH): δ−63.28
(Multiplet, 2F), -75.95 (Triplet, J=20.9
Hz, 1F), −82.91 (multiplet, 2F) IR (neat): 2820, 2720cm ^-1 (ν _CH ), 1740cm
^-1 (ν _C=0 )・Mass spectrum: M ⁺ 224 Elemental analysis value Actual value: C, 48.00; H, 2.21. Calculated value: C, 48.23; H, 2.25. Reference example 4 Lithium aluminum hydride 600 mg (15.8 2-trifluoromethylpropanal) was suspended in 15 ml of ether and cooled to 0°C.
A solution of 6.00 g (47.6 mmol) in 15 ml ether was added dropwise. After heating under reflux for 1 hour, the mixture was hydrolyzed with dilute hydrochloric acid, extracted with ether, and the extract was dried over anhydrous sodium sulfate. By distilling this ether solution, 5.94 g (96%) of 2-trifluoromethylpropanol was obtained.

Reference Example 5 1.00 g (26.3 mmol) of lithium aluminum hydride was suspended in 50 ml of ether, cooled to 0°C, and 2-pentafluorophenylpropanal was added.
A solution of 19.0 g (85.0 mmol) in 15 ml ether was added dropwise. After heating under reflux for an hour, it was hydrolyzed with dilute hydrochloric acid, extracted with ether, and the extract was dried over anhydrous sodium sulfate. By distilling this ether solution, 18.2 g (yield: 95%) of 2-pentafluorophenyl-1-propanol was obtained.

n ²⁰ _D : 1.4449 Boiling point: 115℃/21mmHg ¹ H NMR (CDCl ₃ :TMS): δ1.31 (broad doublet, J=7Hz, 3H), 1.83 (broad singlet,
1H), 3.37 (sextet, J=7Hz, 1H), 3.79
(Wide doublet, J=7Hz, 2H)・^19F NMR (CDCl ₃ : CFCl ₃ ): δ−143.28 (multiplet, 2F), −157.88 (triplet, J=21Hz,
1F), −163.30 (multiplet, 2F) IR (neat): 3350cm ^-1 (ν _CH ) Mass spectrum: M ⁺ 226 Elemental analysis value Actual value: C, 47.54; H, 3.19. Calculated value: C, 47.80 ; H, 3.12. Example 1 2.99 g (13.2 mmol) of 2-pentafluorophenyl-1-propanol was dissolved in triethylamine 10
ml, cooled to 0°C, and 1.50 g (14.3 mmol) of methacrylic acid chloride was added dropwise. After stirring for 2 hours and adding 10 ml of ether, hydrolysis was carried out.
After extraction with ether, it was dried over anhydrous sodium sulfate. 5 mg of hydroquinone was added and distilled to obtain 3.25 g of 2-pentafluorophenylpropyl methacrylate (yield: 84%).

n ²⁰ _D : 1.4489 Boiling point: 97-98°C/3 mmHg ¹ H NMR (CDCl ₃ :TMS): δ1.43 (broad doublet, J=7Hz, 3H), 1.89 (broad singlet,
3H), 3.65 (sextet, J=7Hz, 1H), 4.37
(Wide doublet, J=7Hz, 2H), 5.55 (Wide singlet, 1H), 6.02 (Wide singlet, 1H)・^19F NMR (CDCl ₃ : CFCl ₃ ): δ−143.03 (Multiplet, 2F ), −157.11 (triple line, 1F), −
163.00 (multiplet, 2F)・IR (neat): 1725cm ^-1 (ν _C=O ), 1640cm ^-1
(ν _C=C ) Mass spectrum: M ⁺ 294 Elemental analysis value Actual value: C, 53.04; H, 3.77. Calculated value: C, 53.07; H, 3.77. Example 2 2-trifluoromethylpropanol 1.68 g
(13.1 mmol) was dissolved in 8 ml of triethylamine, cooled to 0°C, and 1.45 mmol of methacrylic acid chloride was added.
g (13.9 mmol) was added dropwise. Stir for 2 hours,
Hydrolysis was carried out after adding 10 ml of ether. After extraction with ether, it was dried over anhydrous sodium sulfate. Add 5 mg of hydroquinone and distill to obtain 2.03 g of 2-trifluoromethylpropyl methacrylate.
(yield 79%).

^n20D : _1.3863 Boiling point: 70-71℃/37mmHg ^1H NMR ( _CDCl3 :TMS): δ1.18 (double line,
J=7.2Hz, 3H), 1.91 (wide singlet, 3H),
2.6 (multiplet, 1H), 4.14 (multiple doublet, J=
12, 5.9Hz, 1H), 4.26 (double double line, J=12,
6.1Hz, 1H), 5.54 (wide singlet, 1H), 6.09
(Broad singlet, 1H)・^19F NMR (CDCl ₃ :CFCl ₃ ): δ−72.20 (doublet, J=8.7Hz)・IR (neat): 1735cm ^-1 (ν _C=O ), 1640cm ^{- 1}
(ν _C=C )・Mass spectrum: M ⁺ 196 Elemental analysis value Actual value: C, 48.98; H, 5.81. Calculated value: C, 48.98; H, 5.65. Example 3 2-pentafluorophenyl-1- 61 g (270 mmol) of propanol and 200 ml of triethylamine
The mixture was cooled to 0° C., and 30 g (287 mmol) of methacrylic acid chloride was added dropwise. After stirring for 2 hours and adding 150 ml of ether, hydrolysis was carried out.
After extraction with ether, it was dried over anhydrous sodium sulfate. By adding 10 ml of hydroquinone and distilling it, 75.5 g (yield 95%) of 2-pentafluorophenylpropyl methacrylate was obtained.

Reference Example 6 Chlorotris(triphenylphosphine)rhodium 92.5 mg (0.1 mmol), pentafluorostyrene 19.4 g (100 mmol) and solvent benzene
30 ml was placed in a 200 ml autoclave and heated at 90°C under a carbon monoxide partial pressure of 50 atm and a hydrogen partial pressure of 50 atm.
The reaction was completed after stirring for 22 hours. After removing the solvent from the reaction mixture, it is distilled to a boiling point of 96℃/21
20.6 g (92% yield) of 2-pentafluorophenylpropanal with mmHg was obtained.

Claims (1)

[Claims] 1. General formula A fluorine-containing methacrylic acid ester represented by (wherein Rf is a perfluoroalkyl group or a pentafluorophenyl group having 1 to 4 carbon atoms).