JPS5921648A - Methacrylic acid ester containing fluorine - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (Rf is 1-20C polyfluoroalkyl or polyfluoroaryl; R is lower alkyl, H or Rf; n is an integer 0-5). EXAMPLE:4,4,4-Trifluorobutyl trifluoromethacrylate. USE:Capable of giving polymethacrylates, containing fluorine, and useful as resists for preparing large scale integrated circuits (LSI) by the polymerization thereof. PROCESS:Trifluoromethacrylic acid chloride is reacted with an alcohol having a perfluoroalkyl group of formula II, e.g. 2,2,2-trifluoroethanol, in the presence of a tertiary amine, e.g. triethylamine or pyridine, to give the aimed compound of formula I .

Description

[Detailed description of the invention] □ (In the formula, f is a polyfluor having 1 to 20 carbon atoms.
, 11 o. A2YA YV, 51Gdl IJ
y:szo. Ah, -8k, 1. □ is a lower alkyl group, a hydrogen atom, or an f group, and n is an integer of 0 to 5. The present invention relates to a novel 7-containing methacrylic acid ester represented by '). 1:, :1
*Yes□. Alff1e Type 8 (I) “e”i! By polymerizing tacrylic acid ester Fi, a fluorine-containing polymethacrylate can be obtained.Fluorine-containing polymethacrylate is useful as a resist for LSIM manufacturing.

The fluorine-containing methacrylic acid ester to be agitated with the general formula (I) of the present invention has the general formula
(,.

(In the formula, I(, f is a polyfluoroalkyl group or a polyfluoroalkyl group having 1 to 20 carbon atoms, □ is a lower alkyl group, a hydrogen atom, or an Rf group, and □n is 0 to 5
is an integer. ) can be produced by reacting an alcohol having a perfluoro group represented by (See Reference Example 6). In addition, trifluoromethacrylic acid is 2-promotrifluoropropene (see Reference Example 1), and alcohols having a catalytic carbopolyfluoro group include 2゜2.2-)lifluoroethanol, 11
-1, IH-pentafluoro-1-propanol, 1l-1, IH-heptafluoro-1-butanol,
3.3,4,4,5,5゜5-hebutafluoro-2-pentanol, hexafluoroisopropanol, 1H,
IH-pentadecafluoro-1-octacyl, 3,3
,4,4.4-pentafluoro-2-butanol, i,
1. i-tri'7-o-2-globanol, 1-chloro-1,1゜:・13jql:s=...friendtafluoro-2-7'-o/-/l/, 1) 1. , IH,
7f, 1-dodecafluoro-1-heptatool, IH
, I H, 11H-eicosafluoro-1-undecanol, I H, 1) (, 5H-octafluoro-1-pentanol, 1 H, 1) 1, 3 H-tetrafluoro-1-propanol, 4, 4.4-trifluoro-1
-butanol, 2-methyl-6゜6.5-1-lifluoromethyl-1-glopanol, 2-pentaflated orophenyl-1-glopanol, 3-pentafluorophenyl-
1-Globanol, IH, 1n-2-triflated leolotatiltetrafluoro-1-glopanol, 1f-1,
I H, 3H-2-IJ fluoromethyl-trifluoro-1-7' lovanol, i H, 111,, iI
-hexafluoro-1-butanol, 1 f-1, 11
4,20-2-Methyl-tridecafluoro-1-octatool, 1H21H,211,2)j, 3Fl, 3H=
) Ridecafluoro-1-nonanol, etc. can be used.

The reaction between FJjiF+16 is carried out in the presence of a tertiary amine. As the 6th class amine, for example, triethylamine, pyridine, N-methylmokuphorine, >-methylpiperidine, N,N-dimethylaniline, etc. can be used.

・A solvent is not necessarily required for K in producing the 7-containing methacrylic ester represented by the general formula (I) of the present invention, but hydrocarbonized water ice such as hexane and benzene, chloroform, and chloride that do not participate in the reaction are used. The use of halides such as methylene, ethers such as diethyl ether and tetrahydrofuran, nitriles such as acetonitrile, etc. will not make any difference. The reaction proceeds at room temperature, but may be cooled or heated as necessary.

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

Example 1 2-7' Romo 3.3.3-) Combination of lifluoropropene CF3＼Eyu + B' r 2 →
□To a mixture of bromine (500p, 3.13mo+) and methylene chloride (100me) 3. ,．． 3.3
L) Lifluoropropene (30;#, ro.20mo
+) was slowly blown in, and then the isobaric mercury lamp was turned on. After the reaction was completed, the mixture was washed with an aqueous thiosulfate-rthorium solution, and the Ariiso layer was dried over anhydrous calcium chloride. Boiling point 114-1□16 by distilling off the chloride
2,3-dibromo-1,1,1,=i with ゛0
+ Noflu □ Olopropane 790.9 (yield 99%) was obtained.

'HNMR (CDCI:TMS): δ 3゜5
6 (aa.

J the 1-. 5. ,．． 8. ,OHz,1fri,' 3
．． 84' (dd, J=11.5, 5.5Hz, 1
[1).

4, 51 (m, j H).

"F NMR (CDC13: CFCl2): δ -
71,1 (d, J =71-1z).

Next, grind well and 6ξ potassium hydroxide (70g, 1
．． 25m01) to 2,6-dibromo1,1.1-1. )
Lifluoropropane (256 g, l, Qmol) was slowly added dropwise. After the addition is complete, the reaction mixture is distilled to give 2-bromo-3,3 having a boiling point of 33-34°C.
, 172 g (yield 98%) of trifluoropropene was obtained.
TAi, 8): δ 6.00 (m.

IH), 6.45 (rn, IH).

19F NMR (CDCI3: CFIC13): δ
-69.5 (bs).

Reference example 2 17 fangs - Tokrei? tidichlorobisctriphenylphosph:renin) palladium (""5L6'1 g,'
8'mmol), 2-pulmo3.3.5-trifluorotetrapropene (14°C'0.80mol), water (2o
'y11.11mol), triethylamine (101,
! 7.1゜0[1mol and tetrahydrofuran (50
0mj), and the carbon monoxide pressure was 80°0.
The mixture was heated and stirred for 60 minutes. After cooling, the pressure was returned to normal, hydrolyzed with dilute hydrochloric acid, and extracted with ether.

Dry the extract over anhydrous magnesium sulfate.1. , the ether was distilled off. Melting point 52.5 by dividing IA trade goods
Trifluorometac IJ A with −53°0.

Acid 6'21I (yield 55%) was obtained.

'HNMR (CDCl 3: 'T'MS):
6.52 (m, 1H).

6.80 (m, IH).

19Ii"NM1't (CDC13: CFCl2)
: -66,5 (bs).

IR(neat),: 1715 鞞(ν(=0),
1655crn'(ν):.

-C Mass spectrum 2 M・+'14o.

Reference □Example 6 Thionyl chloride (Og, □59 mmol) and σ trifluoromethacrylic acid (7,3,!il, 52 mmol)
The mixture was heated under reflux for 5 hours and then distilled to obtain 4.5 g (yield 55%) of trifluoromethacrylic acid chloride having a boiling point of 88-92°C. Also, as a by-product, 2.1 g of trifluoromethacrylic anhydride (yield: 81 yen) has a boiling point of 106°C/3'1 mmHg.
was obtained, which can also be used for ester synthesis.

Trifluoromethacrylic acid chloride IHNMR (CDCI 3:, TMS): δ 6.8
9 (m.

1H), entering 06 (m, 1H).

9 PNMR (CDC,!,:CFe): δ -65,9
Trifluoromethacrylic anhydride' HNMR (CDC13:TMS): δ 66-6
9(,2H).

6.8 F3 (m s' 2f1).

p Nhcrc (c'Dct 3 :C'FC
1a): a-66,.

(bs).

Example 1 4.4.4-) Lifluorobutanol (,1821%,
Trifluoromethacrylic acid chloride (2
9.1-42 mmol of 251n was added dropwise in O''O, followed by dropwise addition of a mixture of triethylamine (217 mmol, 2.15 mmol) and ether (0.7 mmol).
After stirring for a minute, it was hydrolyzed and extracted with ether.

The extracted residue was dried over anhydrous sodium sulfate and then distilled to obtain 4,4.4-)trifluoromethacrylic acid having a boiling point of 75°O/30mmHg.
A yield of 85% was obtained.

'HNM)(, (CDCI 3:TM8):δ 1..
8-2.5 (rn.

4H), 4.3.0 (t, J = 6Hz, 2H
).

6゜44 (m, IH), 6.72 (rn, I
H).

19F' NMIL, (CDCj 3: C, FCl
3. ), ; δ -66,2(bs, 3F),
,,-6'7.1 (t,J,,-10,,%.

Hz, 3FJ.

IR (neat): 1745 (m (VCx:,
0), 1650cIIL (v. YuC), Accounts Payable Spectrum, M 250 Elemental Analysis C (%) H (%).

Calculated value 38.41 3.22 Actual value 5'8.6'7'''3.16 Example 2 2-Methyl-3,3,3-) fluoropro-hel(2,56,!9. 20 mmol), trifluoromethacrylic acid chloride (2,777,1
Triethylamine (4°04,9,40m
Mori was added dropwise. After stirring for 1 hour, the mixture was hydrolyzed and extracted with ether. The extract was dried over anhydrous sodium sulfate and then distilled to give a boiling point of 64°O/21+nmH.
g f trifluorometa, clyl rR2-methyl-3,6゜6-trifluoroprovir 6.69<I or 4
8296) was obtained.

・HNMR (CDC13MS): δ1.22 (d
, J=7.0Hz, 3H), 2.64 (m, IH
).

4. 33. (ABX, JAp-12Hz, JA
X=JeX: 6Hz, , 2H), 6.44 (m,
IH).

6.72 (m, 1) 1).

"F NMIL (CDC13:CFCl2): δ, -
66,4 (bs.

3F), -72,5((1, J=8.5Hz, 3F).

IR(neat): 1745clIL(ν.=
. ), 16501 cm,
(ν).

C2C hell"bt spectrum, M 250° elemental analysis
C (%) H・(chi) Calculation 1st shift 68!4
1 3゜22 Actual value 6B, 56 3.35 Example 6 Lophenylpropanol (3,39,
□g1150>rno, I),, trifluoromethacrylic acid chloride synthesized in Reference Example 6 (1°, 59g,
10 mm 1. ) and etire, (10, me
) to a mixture of triethylamine (6°0 filter 9., 3.,
OrnmOl) was added dropwise at 0°C. After stirring at room temperature for 71 hours, the mixture was hydrolyzed and extracted with ether.

The extract was dried over sodium bisulfate and distilled to obtain trifluoromethane with a boiling point of 85°C/3 nmml-1g. 2-pentafluorophenyl acrylate to propyl 2°901. (yield rate: 86).

'HNMR (CDC13: Wheat (S): δ1゜41(
bd, J Near 11, Z, 5ki), 6", 6
4' (a ext, J=7Hz.

1mu1) ,4,43 Qn,,2H) ,6.56
(rn.

1H), 6.62 (m, IH).

19I” NMR, (CDCI 3: (J'CI 3
); δ-66,2(bs.

3F), -143,1 (m, 2F), -156°7 (t
, J=21Hz, IF), -162,9(m.

2F).

II too (neat) + 17454m
(' .=(1) , 1655C1n
'(ν.-0)・Mass spectrum: M+ 348° Elemental analysis C (%) 1■ (%) Calculated value 44,84 2.52 Fruit 41 Iroshi f 44. 96 2.1
8 Example 4 Trifluoromethacrylic acid chloride synthesized in Reference Example 6 (1,59,9,10 mmol/l/o
Triethylamine (1,0
1, il, i.

mmol) was lowered for t1M at 0°0. The mixture was stirred at room temperature for 1 hour, hydrolyzed, and then extracted with ether. By drying the extract over anhydrous sodium sulfate and distilling it, the boiling point is 80°0-1.
Crude product 2 of 2,2,2-trifluoroethyl trifluoromethacrylate was obtained by collecting the fractions of []O'O.
1 g (yield 95%) was obtained. Purely isolated by fractionation by gas chromatography.

'HNM 几(CI)CI3: TMS):
δ4゜59 (quart.

J=8Hz, 2H), 6.52 (m, 1)4).

6.78 (m, 11().

19F NMR (CI) C1:CFCl3): δ-66
, 6 (b.s.

3F'), -74,6(t, J=81-1z,
3F).

IR (neat): 1745cm (νc = o),
1650cqa'(ν.-6)・IRζ21-1: Pi″″ Ruyul monument C(φ) H(%) Calculated value 32.45. 1.81 actual value 3
2.14 1.61 Example 5 Trifluoromethacrylic acid chloride (225+11s 1
゜42mmol) and 3,3.3-)refluoro-
2-propanol (260+11p, 2.28mmo
I) By carrying out the same operation as in Example 1 using fc and dyeing the fraction with a boiling point of 80 to 100°C, p-trifluoromethacrylic acid 2°2.2-)! A crude product of j-fluoroinpropyl, 285In9 (yield: 85%), was obtained. A pure product was obtained by fractionation using gas chromatography.

IHNMl also (CD(13:'1”MS): δ
1.48(d, J=7Hz, 61-wa *5.40(
sept, J Near 1-1z, IH), 6.51
(m, 1B), 6.76 (m, IH).

"F NM4 also (CDCI 3: CFCl
3) : δ −66,5(ba, 3F), −
79°4 (d, J = 7klz.

5F).

” (neat) '1750'm (v c
:o) 1655cnt (ν.=.).

Mass spectrum; M236 Elemental analysis: C (%) as C7H6F602 11 (%) Increased value 35,61 2.56 Actual value 35
．． 56 2.40 Implementation 1/16 Trifluoroacrylic acid (225 hiro1゜42 mmol)
The same operation as in Example 1 was carried out using
By collecting the fractions of trifluoromethacrylic acid 2
．． A crude product of 2', 2', 2'-hexafluoroimprovir (yield: 85%) was obtained.

A pure product was obtained by fractionation using gas chromatography.

+1-I NMIL (C1)C13:TMS) :δ
5.83 (sept.

J = 6 Hz, IH), 6.69 (
m, IH).

6.91 (m, 111).

19F'NMR (CI) C1:CFCl2): δ-66
,6(bs,3F),-73,9(d, J=6Hz
.

6F).

■几(Hg cell 1 nccl 4): 1780 Cfn (ν.-8) 1650 Confucian (ν.-6) Mass spectrum: M 290 Procedural amendment (spontaneous) August 19, 1980 Commissioner of the Japan Patent Office Kazu Wakasugi failure 1o Display of Case 1982 Can Patent Application No. 131162 2゜ Name of Invention Containing Heptagonal Meccrylic Acid ester 3゜ Relationship with the case of the person making the amendment Introduction to Patent Application +1111, ``Detailed Description of the Invention'' of 'i Column 5,
Contents of the amendment (1) "Trifluoroacrylic acid" on page 19, line 2 of the present specification is corrected to "trifluoromethacrylic acid chloride."

that's all

Claims (1)

[Claims] (1) Fluorine-containing methacrylic acid ester represented by the general formula (in the formula, 1
(, f is a difluoroalkyl group or a polyfluoroarylated group having 1 to 20 carbon atoms, IL is a lower alkyl group 1. hydrogen atom or Rf group, n is an integer of 0 to 5, and ).