JP2002003429A - Alicyclic vinyl ether compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl ether compound widely usable as a monomer constituting a resist using far-infrared rays as a light source and a method for producing the above compound. SOLUTION: The alicyclic vinyl ether compounds are 3, 4-bis (2- vinyloxyethyloxy) tricyclo[5,2,1,02,6] decane represented by formula [1] and 3(4)-hydroxy-4(3)-(2-vinyloxy)ethyloxytricyclo-[5,2,1,02,6] decane represented by formula [2]. The method for producing the above compounds represented by formulas [1] and [2] is characterized by reacting 3,4-dihydroxytricyclo-[5,2,1,02,6] decane represented by formula [3] with 2-halogenoethyl-vinyl ether represented by formula [4] (wherein X is a halogen atom) in the presence of a base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 3,4-bis (2
-Vinyloxyethyloxy) tricyclo [5.2.
1.0 ^2,6 ] decane and 3 (4) -hydroxy-4
(3) An alicyclic vinyl ether compound of-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 ^2,6 ] decane and a method for producing the same.

These vinyl ether derivatives are useful as monomers for photopolymers, that is, as monomers for resist resins for KrF and ArF, and as monomers for general ultraviolet curable resins. In particular, the alicyclic vinyl ether as in the present invention has no absorption in the ultraviolet region when polymerized, and can be widely used as a resist constituent monomer using ultraviolet light as a light source.

[0003]

2. Description of the Related Art Conventional vinyl ether derivatives include 2,2.
-Bis (4- (2-vinyloxy) ethoxy) phenyl) propane

[0004]

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Aromatic derivatives such as bis (2-vinyloxyethyl) ether and aliphatic vinyl ether derivatives such as 1,2 bis (2-vinyloxy) ethoxy) ethane are well known (Chemistry of Materials, 6 No. 10, pp. 1854-1860 (1994)
Year)).

Tricyclo [5.2.1.0 ^2,6 ] deca
An alicyclic derivative having a vinyloxyethyloxymethyl group at the 8,9-position of 3-ene or tricyclo [5.2.1.0 ^2,6 ] decane has not been known.

[0007]

In the field of ultraviolet curable resins and resist resins, it is desired to reduce water absorption and improve heat resistance (glass transition point), transparency of ultraviolet parts, and dry etching resistance. . That is, an object of the present invention is to provide a novel vinyl ether derivative which can be widely used as a resist constituent monomer using ultraviolet light as a light source without absorbing any ultraviolet portion, and a method for producing the same.

[0008]

SUMMARY OF THE INVENTION In the molecular design of a monomer, the fact that the number of alicyclic groups is increased and the presence of a vinyl ether substituent at the same position (1,2-position) next to the alicyclic group is not limited to glass. It is expected that the dislocation point will be improved.

That is, the present invention relates to the formula [1]

[0010]

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3,4-bis (2-vinyloxyethyloxy) tricyclo [5.2.1.0 ^2,6 ] decane represented by the formula:

Further, the present invention relates to the formula [2]

[0013]

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3 (4) -Hydroxy-4 represented by
(3) It relates to (2-vinyloxy) ethyloxytricyclo [5.2.1.0 ^2,6 ] decane.

Further, the present invention provides a compound of the formula [3]

[0016]

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3,4-dihydroxytricyclo [5.2.1.0 ^2,6 ] decane of the formula [4]

[0018]

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(Wherein X represents a halogen atom), wherein 2-halogenoethyl vinyl ether represented by the formula (1) is reacted in the presence of a base. Bis (2-vinyloxyethyloxy) tricyclo [5.2.1.0 ^2,6 ] decane and the formula [2]
3 (4) -Hydroxy-4 (3)-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 represented by
^2,6 ] a method for producing decane.

Further, the formula [2]

[0021]

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3 (4) -Hydroxy-4 represented by
(3)-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 ^2,6 ] decane and formula [4]

[0023]

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Wherein X represents a halogen atom, wherein 2-halogenoethyl vinyl ether represented by the formula (1) is reacted in the presence of a base. The present invention relates to a method for producing bis (2-vinyloxyethyloxy) tricyclo [5.2.1.0 ^2,6 ] decane.

Hereinafter, the present invention will be described in detail.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing each compound of the present invention is represented by the following reaction scheme.

[0027]

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(X represents a halogen atom.) That is, in the scheme (1), 3,4-dihydroxytricy
Black [5.2.1.0 ^2,6] Decane (hereinafter abbreviated as DHTC)
And 2 equivalents of 2-halogenoethyl vinyl ether
(HVE) in the presence of a base to give a compound of the formula
3,4-bis (2-vinyloxyethyl) represented by [1]
Ruoxy) tricyclo [5.2.1.0^{2, 6}] Decane
(Hereinafter abbreviated as BVTC).

[0029] Furthermore, scheme (2) is 3,4-dihydroxy tricyclo [5.2.1.0 ^{2, 6]} decane (hereinafter D
HTC) and an equivalent amount of 2-halogenoethyl vinyl ether (HVE) in the presence of a base to give 3 (4) -hydroxy-4 represented by the formula [2].
(3)-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 ^2,6 ] decane (hereinafter abbreviated as HVTC) is obtained.

In Scheme (3), BVTC is obtained by reacting HVTC with an equivalent amount of 2-halogenoethyl vinyl ether (HVE) in the presence of a base.

DHTC as a starting material can be obtained by the following production method described in Japanese Patent Application No. 11-213257 filed by the present inventors.

[0032]

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That is, 8,9-dihydrotricyclo [5.
2.1.0 ^2,6 ] dec-3-ene (hereinafter DH-DCPD
) Is oxidized with an oxidizing agent to obtain an epoxy compound thereof (hereinafter abbreviated as ETC). Subsequently, DHTC is obtained by hydrating ETC with an aqueous acid solution.

Next, the other raw material represented by the general formula [4]

[0035]

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Specific examples of 2-haloethyl vinyl ether represented by (X represents a halogen atom) include 2-fluoroethyl vinyl ether, 2-chloroethyl vinyl ether, 2-bromoethyl vinyl ether and 2-iodoethyl vinyl ether. Yes, and economically, 2-chloroethyl vinyl ether is used. The amount used is preferably 1 to 10 moles, more preferably 2 to 5 moles per mole of the substrate.

In this reaction, the presence of a base is essential. So
The types of alkali metal and alkaline earth metal water
Oxides or hydrides can be used. Specifically, LiO
H, NaOH, KOH, RbOH, CsOH, Mg (O
H)_Two, Ca (OH)_Two, Sr (OH)_Two, Ba (O
H)_Two, LiH, NaH, KH, MgH_Two, CaH_Two, S
rH _TwoAnd Ba (OH)_TwoAnd the like. In particular
Is NaOH, KOH, Ca (OH)_Two, Ba (O
H)_Two, NaH and KH are preferred. Its usage is
The molar ratio is preferably 1 to 10 times, especially 2 to 5 times the molar amount of the substrate.
Good.

This reaction preferably uses an organic solvent. The types include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA
c), amide solvents such as N-methylpyrrolidone, sulfoxide solvents such as dimethyl sulfoxide (DMSO) and sulfolane, aliphatic hydrocarbon solvents such as hexane, heptane and cyclohexane, and aromatic hydrocarbons such as toluene, xylene and ethylbenzene. Hydrogen solvents, dioxane, tetrahydrofuran (THF), 1,2-dimethoxyethane (DME), ether solvents such as diethylene glycol dimethyl ether, and water. One or more of these may be used in a homogeneous or two-phase system. it can. The amount used is economically 1 to 20 times by weight, especially 2 to 5 times by weight of the substrate.

In this reaction, it is also effective to use a phase transfer catalyst. For example, when an alkali metal or an alkaline earth metal is used in an amide solvent, or when an alkali metal or an alkaline earth metal is used in a binary solvent system of a hydrocarbon solvent and water, a phase transfer catalyst is effective. is there. Examples thereof include tetrabutylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetramethylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium hydrogen sulfate, and a methanol solution of trimethylbenzylammonium hydroxide. And tetra-n
-Butylammonium hydroxide aqueous solution and the like. The amount used is 0.1 to 20 wt.
%, Preferably 0.5 to 10% by weight.

The reaction is carried out at a temperature of 0 to 150 ° C.
Preferably, it is carried out at a temperature of from 40 to 120 ° C. to improve the yield of the desired product. The reaction can be carried out under normal pressure or under pressure.

The reaction time depends on the type, amount, reaction temperature,
Although it varies depending on the solvent and the like, it is usually carried out in 1 to 50 hours, preferably in 2 to 20 hours. Also,
The reaction can be carried out batchwise or continuously.

For tracking the reaction, the reaction solution was sampled,
The analysis can be performed by gas chromatography.
The product is isolated by adding water, isopropyl ether, ethyl acetate, methyl ethyl ketone (MIBK) and the like to the reaction solution, dehydrating and concentrating the organic layer, and purifying the target substance by distillation and / or column chromatography. be able to.

[0043]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. Example 1 A 500 ml four-necked reaction flask was charged with 50 g (0.3 g) of DHTC.
0 mol) was dissolved in 150 ml of DMSO, and 85% KO was dissolved.
H119g (1.8 mol) was added at 60-70 ° C.
Stirred for hours. Subsequently, after adding 7.0 g (0.03 mol) of benzyltriethylammonium chloride, 2-chloroethyl vinyl ether (CVE) 128 was added.
g (1.2 mol) was added dropwise while refluxing over 4 hours. Thereafter, the mixture was stirred under reflux at 57 ° C. for 15 hours. continue,
After adding 79 g (1.2 mol) of 85% KOH, C
VE 128 g (1.2 mol) was added dropwise while refluxing over 4 hours. Furthermore, 26 g of 85% KOH (0.4 m
ol), 43 g (0.4 mol) of CVE was added dropwise with reflux over 30 minutes, and the mixture was refluxed and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into ice water, and the product was extracted with isopropyl ether and concentrated to obtain 105 g of a residue.

The residue was purified by silica gel column chromatography. As a first fraction, 65 g (0.21 mol) of a colorless and transparent oily substance (BVTC) (yield: 7)
0%) and a colorless transparent oily substance (HVT) as a second fraction.
C) 15 g (0.063 mol) (21% yield) were obtained. The structures of these products were confirmed from the following analysis results.

First fraction (BVTC) MASS (FD +): 308 (M +). ¹ H-NMR (CDCl ₃ , δ ppm): 1.31-1.47 (m, 3H), 1.49 (s, 2H), 1.5
2-1.62 (m, 2H), 1.83-1.88 (m, 1H) 2.09-2.12 (m, 2H), 2.23-
2.28 (m, 2H), 3.64 (t, J = 7.94Hz, 1H), 3.71-3.91 (m, 9H), 3.9
8-4.00 (m, 2H), 4.18 (d, J = 2.44Hz, 2H), 6.47-6.53 (m, 2H) 13 C-NMR (CDCl 3, δppm):. 22.18,23.36,28.49,38.88,39.4
8,39.61,43.13,47.79,67.51,67.57,68.09,68.52,84.15,
86.47 (for 2), 87.59, 151.7 (for 2). Second fraction (HVTC) MASS (FD +): 238 (M +). ¹ H-NMR (CDCl ₃ , δppm): 1.31-1.47 (m, 3H), 1.49 (s, 2H), 1.5
2-1.62 (m, 2H), 1.83-1.88 (m, 1H) 2.09-2.12 (m, 2H), 2.23-
2.28 (m, 2H), 3.64 (t, J = 7.94Hz, 1H), 3.71-3.91 (m, 5H), 3.9
8-4.00 (m, 1H), 4.18 (d, J = 2.44Hz, 1H), 6.47-6.53 (m, 1H).

Example 2 DHTC (2 g, 12 mm) was placed in a 50 ml four-necked reaction flask.
1) was dissolved in 20 ml of DMF, and 60% NaH1.43 was added.
g (36 mmol) was added and stirred at 20 ° C. for 4 hours. Subsequently, the mixture was cooled to 5 ° C., and 3.81 g (36 mmol) of 2-chloroethyl vinyl ether (CVE) was added dropwise.
Stirred at 0 ° C. for 18 hours. After completion of the reaction, the reaction solution was poured into ice water, and the product was extracted with isopropyl ether, washed with water, and then concentrated to obtain 1.97 g of a crude product.

The residue was purified by silica gel column chromatography. As a first fraction, 0.59 g (1.9 mmol) of a colorless and transparent oily substance (BVTC) (1.9 mmol) (16% yield) and a second fraction as a colorless (H
(VTC) 0.74 g (3.1 mmol) (26% yield)
was gotten.

Claims (6)

[Claims] [Claim 1] Formula [1] 3,4-bis (2-vinyloxyethyloxy) tricyclo [5.2.1.0 ^2,6 ] decane represented by the formula: 2. Formula [2] 3 (4) -Hydroxy-4 (3)-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 represented by
^2,6 ] Decane. 3. Formula [3] 3,4-dihydroxytricyclo [5.2.
1.0 ^2,6 ] decane and formula [4] Wherein X represents a halogen atom, wherein 2-halogenoethyl vinyl ether is reacted in the presence of a base. 3,4-bis (2-vinyloxyethyloxy) tricyclo [5.2.1.0 ^2,6 ] decane represented by the formula: and the formula [2] 3 (4) -Hydroxy-4 (3)-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 represented by
^2,6 ] Method for producing decane. 4. The formula [2] 3 (4) -Hydroxy-4 (3)-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 represented by
^2,6 ] decane and formula [4] Wherein X represents a halogen atom, wherein 2-halogenoethyl vinyl ether represented by the formula (1) is reacted in the presence of a base: A method for producing 3,4-bis (2-vinyloxyethyloxy) tricyclo [5.2.1.0 ^2,6 ] decane represented by the formula: 5. The 3,4-bis (2-vinyloxyethyloxy) tricyclo [5.2.1.] According to claim 3, wherein the base is a hydroxide or hydride of an alkali metal or an alkaline earth metal. 0 ^2,6 ] decane and 3 (4) -hydroxy-4 (3)-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 ^2,6 ] decane. 6. The production method according to claim 3, wherein a phase transfer catalyst is used, and 3,4-bis (2-vinyloxyethyloxy) tricyclo [5.2.1] is used. 0.0 ^2,6 ] decane and 3 (4) -hydroxy-4 (3)-(2-vinyloxy) ethyloxytricyclo [5.2.1.0 ^2,6 ] decane.