JP2003064073A - Alicyclic oxygen-containing compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a monomer containing a polar group such as a lactone group or an ether group in its aliphatic structure and having excellent dry etching resistance and good adhesiveness to substrates among industrially profitable new photoresist monomers, and to provide a new lubricant and a new solvent. SOLUTION: The aliphatic oxygen-containing compound represented by formula [1] (Y is carbonyl or methylene; the broken line is a single bond or a double bond; R is H or a 1 to 10C alkyl) is produced by reducing a compound of formula [2] or by reacting a compound of formula [4] with an acid or further by catalytically reducing the compound of formula [6]. And methods for producing the compound of formula [1] are provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a formula [1].

[0002]

[Chemical 8]

(Where Y Represents a carbonyl group or a methylene group, and the broken line represents a single bond or a double bond. ) And an alicyclic oxygen-containing compound represented by

The alicyclic lactone compound and alicyclic ether compound having a double bond produced in the present invention are aimed at improving the insulating property, heat resistance and adhesion of a photoresist monomer used in a semiconductor manufacturing process. The alicyclic lactone compound and alicyclic ether compound having a single bond which can be used as a monomer for the field of optical materials can be used for fields such as lubricating oil and solvent.

[0005]

2. Description of the Related Art The introduction of a functional group having a polar group into the alicyclic structure of its monomer has been studied in order to improve the adhesion of a photoresist to a substrate. The hyperlactone of the following formula is
It is said to be a monomer with excellent dry etching resistance and good adhesion. However, the fact that it is expensive due to the manufacturing method is regarded as a practical problem. [2000-2 Proceedings of the Society for Optical and Electronic Materials Research, 9-12 (2000-1
1-21); Chemistry and Industry, 53 (10) 1181-11.
86 (2000)]

[0006]

[Chemical 9]

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to provide a novel photoresist monomer industrially economically advantageous by introducing a polar group such as a lactone group or an ether group into its alicyclic structure and drying it. It is to provide a monomer having excellent etching resistance and good substrate adhesion. Another object of the present invention is to provide a novel alicyclic oxygen-containing compound which can be used in fields such as lubricating oils and solvents.

[0008]

The present inventors have found the present invention as a result of earnest research to solve the above problems. That is, the present invention is

[0009]

[Chemical 10]

(Where Y Represents a carbonyl group or a methylene group, and the broken line represents a single bond or a double bond. ) Relates to an alicyclic oxygen-containing compound.

The present invention also provides the formula [2].

[0012]

[Chemical 11]

(Wherein the broken line represents a double bond or a single bond), tricyclo [5.2.1.0 ^2,6 ].
Dece-3-ene-8,9-dicarboxylic acid anhydride (TCD
Abbreviated as A. ) Or tricyclo [5.2.1.
0 ^2,6 ] decane-8,9-dicarboxylic acid anhydride (DH-
Abbreviated as TCDA. ) By reducing or by the formula [4]

[0014]

[Chemical 12]

(In the formula, the broken line has the same meaning as above.)
8,9-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] dec-3-ene (abbreviated as DOL) and 8,9-bis (hydroxymethyl) tricyclo By reacting [5.2.1.0 ^2,6 ] decane (abbreviated as DH-DOL) with an acid, the compound of formula [6] is further added.

[0016]

[Chemical 13]

(In the formula, R represents a hydrogen atom or a carbon number of 1 to 10)
Represents an alkyl group. ) Catalytic reduction of 8,9-bis (alkoxycarbonyl) tricyclo [5.2.1.0 ^2,6 ] decane or 8,9-dicarboxytricyclo [5.2.1.0 ^2,6 ] decane And a method for producing an alicyclic oxygen-containing compound represented by the above formula [1]. Hereinafter, the present invention will be described in detail.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The production method of the compound of the present invention is as follows.
It is represented by one reaction scheme.

[0019]

[Chemical 14]

(In the formula, R represents a hydrogen atom or a carbon number of 1 to 10)
Represents an alkyl group and the broken line represents a single bond or a double bond. ) The manufacturing method of each raw material of (1) to (3) is represented by the following reaction scheme.

[0021]

[Chemical 15]

[0022]

[Chemical 16]

(In the formula, R'represents an alkyl group having 1 to 10 carbon atoms.) That is, dicyclopentadiene (DCPD), carbon monoxide and an alcohol compound are reacted with palladium catalyst in the presence of cupric chloride. This gives 8,9-bis (alkoxycarbonyl) tricyclo [5.2.1.0 ^2,6 ] dec-3-ene (TCDE). TCDA can be obtained by using a tertiary alcohol in this reaction. DH-TCDE and DH-T are obtained by reducing these by a catalytic reduction method or the like.
CDA is obtained.

Further, DOL and D are obtained by reducing the TCDE and DH-TCDE with a metal hydride complex or the like.
H-DOL can be obtained. When R is a hydrogen atom, TC
Obtained by hydrolyzing DE and DH-TCDE.

The reduction method of the reaction schemes (1) and (2) will be described. Various general reduction methods for converting a carbonyl group into a methylene group can be applied.

For example, (1) reduction with metals and metal salts (2) reduction with metal hydrides (3) reduction with metal hydride complexes (4) reduction with diborane and substituted boranes (5) reduction with hydrazine (6) diimide Reduction (7)
Examples include reduction with a phosphorus compound (8) electrolytic reduction (9) catalytic reduction and the like.

Regarding the reaction scheme (1), a reduction method using a metal, a metal hydride and a metal hydride complex is simple.

As the metal, an alkali metal of Group 1 and an alkaline earth metal of Group 2 of the Periodic Table can be applied, and specific examples thereof include lithium, sodium, potassium, magnesium and calcium. Furthermore, as a metal hydride and a metal hydride complex, lithium hydride, sodium hydride,
Potassium hydride, lithium aluminum hydride, sodium aluminum hydride, potassium aluminum hydride, lithium borohydride, sodium borohydride,
Examples thereof include potassium borohydride.

The reaction is carried out using the substrates TCDA and DH-TCD.
It is preferable to use a metal, a metal hydride or a metal hydride complex with respect to A in a theoretical equivalent amount.

In this reaction, it is preferable to use a solvent,
Tetrahydrofuran (THF), 1,4-dioxane,
Examples include ethers such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether. The amount of the solvent used is 1 to 20 times by weight, more preferably 1 to 20 times the weight of the substrate.
6 times the weight. The reaction temperature is −20 to 100 ° C., more preferably 0 to 50 ° C. The target product can be purified by distillation or column chromatography.

Next, the method for producing the reaction scheme (2) will be described. A catalytic reduction method is practical for this reaction. The catalytic reduction method that can be used in the present invention is as follows. As the catalyst metal, palladium, ruthenium, rhodium, platinum, nickel, cobalt and iron of Group 8 of the periodic table, or copper of Group 1 can be used. These metals are used alone or in a multi-element system in which they are compounded with other elements. Examples of the usage form thereof include individual metals, Raney-type catalysts, diatomaceous earth, alumina, zeolite, catalysts supported on carbon and other carriers, and complex catalysts.

Specifically, palladium / carbon, ruthenium / carbon, rhodium / carbon, platinum / carbon, palladium /
Alumina, ruthenium / alumina, rhodium / alumina, platinum / alumina, reduced nickel, reduced cobalt, Raney nickel, Raney cobalt, Raney copper, copper oxide, copper chromatograph, chlorotris (triphenylphosphine) rhodium, chlorohydridotris (triphenylphosphine) Examples thereof include ruthenium, dichlorotris (triphenylphosphine) ruthenium and hydridocarbonyltris (triphenylphosphine) iridium. Among these, Raney copper, copper oxide, copper chromite and the like are particularly preferable.

The amount of the catalyst used is preferably 1 to 50% by weight, more preferably 5 to 20% by weight, based on the substrate. Although the solvent can be used without any solvent, when used, alcohols represented by methanol, ethanol and propanol, 1,4-dioxane, tetrahydrofuran and 1,
Ethers typified by 2-dimethoxyethane, hydrocarbons typified by cyclohexane and methylcyclohexane, and esters typified by ethyl acetate and propyl acetate can be used.

The amount used is preferably in the range of 1 to 50 times by weight, particularly 3 to 10 times by weight of the raw material. The hydrogen pressure is in the range of atmospheric pressure to 30 MPa (300 kg / cm ² ), especially 2 MPa (20 kg / cm ² ) to 25 M.
The range of Pa (250 kg / cm ² ) is preferable. The reaction temperature is in the range of 0 to 300 ° C, particularly 100 to 250 ° C.
Is preferred.

The reaction can be traced by the amount of absorbed hydrogen, and can be confirmed by sampling after absorption of the theoretical amount of hydrogen and analyzing by gas chromatography. This reaction can be carried out batchwise or continuously. After the reaction, the catalyst can be removed by filtration, followed by concentration and further recrystallization or purification by column chromatography.

Next, a method for producing the reaction scheme (3) will be described. This reaction proceeds with an acid catalyst. As the acid catalyst, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid can be used, and sulfuric acid is particularly preferable. In addition, fatty acids such as formic acid, acetic acid, and propionic acid, and organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and trifluoroacetic acid can also be used, and particularly benzenesulfonic acid, p -Toluenesulfonic acid is preferred.

Furthermore, tungstic acid, molybdic acid or heteropolyacids thereof can be mentioned. Specific examples of the heteropoly acid include H ₃ PW ₁₂ O ₄₀ , H ₄ SiW ₁₂ O ₄₀ , and H.
₄ TiW ₁₂ O ₄₀ , H ₅ CoW ₁₂ O ₄₀ , H ₅ FeW ₁₂ O ₄₀ ,
_{H 6 P 2 W 18 O 62} , H 7 PW 11 O 33, H 4 TiMo
₁₂ O ₄₀ , H ₃ PMo ₁₂ O ₄₀ , H ₇ PMo ₁₁ O ₃₉ , H ₆ P ₂ M
o ₁₈ O ₆₂ , H ₄ PMoW ₁₁ O ₄₀ , H ₄ PVMo ₁₁ O ₄₀ , H
₄ SiMo ₁₂ O ₄₀ , H ₅ PV ₂ Mo ₁₀ O ₄₀ , H ₃ PMo ₆ W ₆
Typical examples include O ₄₀ , H _0.5 Cs _2.5 PW ₁₂ O _40, and hydrates thereof. Further, a catalyst in which these are supported on carbon or silica can be used. Among these heteropolyacids, H ₃ PW ₁₃ O ₄₀ , H ₃ PMo ₁₂ O ₄₀ and hydrates thereof are particularly preferable.

Further, a cation exchange resin such as Amberlyst IR120 and an H-type zeolite such as H-ZSM-5 can be used. The amount of these catalysts used is
0.001 to 1% by weight can be used with respect to the reaction substrate, and economically 0.01 to 0.1% by weight is preferable.

Although it can be carried out without using a solvent,
Usually, it is preferable to use a solvent. The types of solvents include 1,2-dichloroethane (EDC) and 1,1,
Halogenated hydrocarbons such as 1-trichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, 1,
Examples thereof include 2-dimethoxyethane, ethers such as 1,4-dioxane and diethylene glycol dimethyl ether.

The amount of the solvent used is 1 to 20 with respect to the reaction substrate.
It is 1 times by weight, more preferably 1 to 6 times by weight. The reaction temperature is 0 to 200 ° C, more preferably 10 to 150 ° C. The reaction can be carried out at normal pressure or under pressure. The reaction time can be 1 to 50 hours, and usually 2 to 12 hours is practical.

After the reaction, the desired product can be obtained by removing the acid catalyst, distilling off the solvent and purifying by distillation or column chromatography. The above-mentioned reaction and purification of the present invention can be performed in a batch system or a continuous system.

[0042]

[Example] Example 1

[0043]

[Chemical 17]

A 200 ml four-neck reaction flask was charged with 45 ml of tetrahydrofuran (THF), and under cooling with ice, 4.54 g (120%) of sodium borohydride (NaBH ₄ ).
mmol) is added. Then, with stirring under ice cooling, 20.4 g (100 mmo) of tricyclo [5.2.1.0 ^2,6 ] dec-3-ene-8,9-dicarboxylic acid anhydride (TCDA) was obtained.
A solution prepared by dissolving l) in 60 g of THF was added dropwise over 1 hour. After gradually returning to room temperature (25 ° C.) and stirring for 1 hour, a gel was formed and 40 g of THF was added. It was stirred again for 2 hours. Subsequently, 48 g of 3N-hydrochloric acid was added dropwise under ice-cooling stirring to make the solution acidic. After THF was distilled off by concentration, 1,2-dichloroethane was added to separate the aqueous layer, and the organic layer was concentrated to obtain 19.0 g (100%) of an oily substance. The structure of this material from the following analysis results 4-oxa-3-oxo-tetracyclo [5.5.1.0 ^2,6 .0 ^{8, 12]} tridec -9
-Ene and 4-oxa-3-oxotetracyclo [5.
5.1.0 ^2,6 .0 ^8,12] tridec-10-ene (OOT
It was confirmed to be a mixture of E). The isomer ratio was 62:38 by gas chromatography (GC).

MASS (FAB ⁺ , m / e (%)): 191 ([M + H] ⁺ , 100),
145 (13), 105 (9), 91 (13). Main component: ¹ H-NMR (CDCl ₃ , δppm): 1.47-1.50 (m, 3H), 2.
17-2.24 (m, 3H), 2.43-2.52 (m, 3H), 3.15-3.19 (m, 1
H), 3.83 (dd, J ₁ = 3.66Hz, J ₂ = 9.16Hz, 1H), 4.44 (t, J =
9.16Hz, 1H), 5.57 (dd, J ₁ = 2.44Hz, J ₂ = 5.51Hz, 1H),
5.71 (dd, J ₁ = 1.83Hz, J ₂ = 5.49Hz, 1H) .Subcomponent: 1H-NMR (CDCl ₃ , δppm): 1.43-1.46 (m, 3H), 2.
26-2.37 (m, 3H), 2.54-2.59 (m, 3H), 3.09-3.14 (m, 1
H), 3.86 (dd, J ₁ = 2.66Hz, J ₂ = 10.61Hz, 1H), 4.37 (dd,
J ₁ = 2.05H, J ₂ = 8.16H, 1H), 5.53 (dd, J ₁ = 2.44Hz, J ₂ = 4.
49Hz, 1H), 5.68 (dd, J ₁ = 3.66Hz, J ₂ = 5.39Hz, 1H) .Main component: ¹³ C-NMR (CDCl ₃ , δppm): 31.88, 34.32, 36.0
3, 40.79, 43.74, 44.35, 47.18, 51.98, 73.05, 131.4,
(2), 180.84. (2) represents two lines. Secondary component: ¹³ C-NMR (CDCl ₃ , δppm): 32.21, 35.96, 37.2
6, 41.42, 41.64, 45.38, 45.44, 51.74, 72.39 131.8,
(2), 180.54. (2) represents two lines.

Example 2

[0047]

[Chemical 18]

Tetrahydrofuran (THF) (20 ml) was charged into a 100 ml four-neck reaction flask, and sodium borohydride (NaBH ₄ ) 1.25 g (33 mmo) was added under ice cooling.
l) is added. Then, tricyclo [5.
2.1.0 ^2,6 ] decane-8,9-dicarboxylic acid anhydride (DH-TCDA) 6.18 g (30 mmol) was added to TH.
The solution dissolved in F20 ml was added dropwise over 30 minutes. The temperature was gradually returned to room temperature (25 ° C.), and the mixture was stirred for 3 hours. Again, 10 g of 4N-hydrochloric acid was added dropwise under ice-cooling stirring to make the solution acidic. After the THF was distilled off by concentration, 1,2-dichloroethane was added to separate the aqueous layer and the organic layer was concentrated to give an oil (solidified).
5.1 g (89.2%) were obtained. The structure of this material, analysis results from 4-oxa-3-oxo tetracyclo below [5.5.1.0 ^2,6 .0 ^8,12] tridecane (OO
It was confirmed to be TA).

MASS (FAB ⁺ , m / e (%)): 193 ([M + H] ⁺ , 90), 1
47 (73), 105 (70), 91 (100), 79 (83), 66 (65). ¹ H-NMR (CDCl ₃ , δppm): 1.18 (d, J = 10.0Hz, 1H), 1.33-
1.42 (m, 2H), 1.46-1.58 (m, 4H), 1.69 (d, J = 10.0Hz, 1
H), 1.90 (dd, J ₁ = 1.20Hz, J ₂ = 3.2Hz, 2H), 2.25-2.27
(m, 4H), 3.30-3.33 (m, 2H), 3.74-3.78 (m, 2H). ¹³ C-NMR (CDCl ₃ , δppm): 27.11 (2), 29.36, 37.93, 41.
88 (2), 45.58 (2), 46.20 (2), 74.43 (2). (2) represent two lines. mp. (° C): 20-22.

Example 3

[0051]

[Chemical 19]

In a 300 ml four-neck reaction flask, 3,4-
Bis (hydroxymethyl) tricyclo [5.2.1.0]
^2,6 ] Dece-8-ene (DOL) 0.97 g (5 mmo
1), 10 ml of toluene and 50 mg of 95% sulfuric acid were charged, and the mixture was stirred at 95 ° C. for 3 hours. Then, after cooling to room temperature, washing with water three times and concentrating the organic layer, an oily substance was obtained.
0 g (yield 90.9%) was obtained. This oily substance was analyzed by the following analysis results, and 4-oxatetracyclo [5.5.
1.0 ^2,6 .0 ^8,12] was confirmed to be a tridec 9-ene (DTTE).

MASS (FAB⁺, m / e (%)): 177 ([M + H]⁺, 53), 1
75 (100), 109 (45), 105 (55), 95 (68). ¹H-NMR (CDCl₃, δp
pm): 1.18 (d, J = 10.0Hz, 1H), 1.69 (d, J = 10.0Hz, 1
H), 1.92 (d, J = 4.58Hz, 1H), 2.07-2.18 (m, 5H), 2.41-
2.45 (m, 1H), 2.93-2.98 (m, 1H), 3.33-3.38 (m, 2H), 3.
68 (t, J = 8.25Hz, 1H), 3.74 (t, J = 8.24Hz, 1H), 5.44-
5.47 (m, 1H), 5.57-5.59 (m, 1H).¹³ C-NMR (CDCl₃, δppm): 31.85, 35.99, 40.13, 41.54,
 43.30, 43.60, 45.30, 52.53, 73.33, 74.03, 76.75, 1
30.89, 131.77.

Example 4

[0055]

[Chemical 20]

In a 300 ml four-neck reaction flask, 3,4-
Bis (hydroxymethyl) tricyclo [5.2.1.0]
^2,6 ] Decane (DH-DOL) 15.0 g (76.5 mm)
ol), 150 ml of toluene and 0.5 ml of 95% sulfuric acid.
Was charged, and the mixture was stirred under reflux for 1.5 hours. Then, after cooling to room temperature, washing with water three times, and concentration of the organic layer, an oily substance was obtained. When this residue was purified by distillation, the fraction 11
3-115 ° C. / 1.33 kPa of a colorless transparent oil 4-oxa tetracyclo [5.5.1.0 ^2,6 .0 ^8,12]
Tridecane (OTTA) 9.05 g (yield 66.5%)
was gotten. The structure of OTTA was confirmed from the following analysis results.

[0057] ^{MASS (FAB -, m / e} (%)): 177 ([MH] +, 66), 1
61 (59), 147 (49), 131 (54), 117 (58), 105 (61), 91 (10
0). ¹ H-NMR (CDCl ₃ , δppm): 1.18 (d, J = 10.0Hz, 1H), 1.33-
1.42 (m, 2H), 1.46-1.58 (m, 4H), 1.69 (d, J = 10.0Hz, 1
H), 1.90 (dd, J ₁ = 1.20Hz, J ₂ = 3.2Hz, 2H), 2.25-2.27
(m, 4H), 3.30-3.33 (m, 2H), 3.74-3.78 (m, 2H). ¹³ C-NMR (CDCl ₃ , δppm): 27.11 (2), 29.36, 37.93, 41.
88 (2), 45.58 (2), 46.20 (2), 74.43 (2). (2) represent two lines.

Example 5

[0059]

[Chemical 21]

8.9 in a 500 ml SUS autoclave
-Bis (methoxycarbonyl) tricyclo [5.2.
1.0 ^2,6 ] decane (DH-TCDME) 100 g
(0.397 mol), 50 g of ethanol and 20 g of copper chromite were charged, and the mixture was stirred at a hydrogen pressure of 25 MPa and 250 ° C. for 5 hours. After the reaction was completed, the reaction solution was cooled and then analyzed by gas chromatography. As a result, OOTA59.8 was obtained.
%, OTTE 27.9% was obtained, DH-TCDME1
0.2% was recovered.

Example 6

[0062]

[Chemical formula 22]

The reaction was carried out in the same manner as in Example 5 except that the solvent was changed to 1,4-dioxane. After completion of the reaction and cooling, the reaction solution was analyzed by gas chromatography, and as a result, OTTE of 99.7% was obtained.

Claims (6)

[Claims] 1. A formula [1] (In the formula, Y Represents a carbonyl group or a methylene group, and the broken line represents a single bond or a double bond. ) An alicyclic oxygen-containing compound represented by: 2. A formula [2] (In the formula, the broken line represents a double bond or a single bond.) Tricyclo [5.2.1.0 ^2,6 ] dece-3-ene-
8,9-Dicarboxylic acid anhydride or tricyclo [5.2.
1.0 ^2,6 ] decane-8,9-dicarboxylic acid anhydride is reduced to give a compound of the formula [1] (In the formula, Y Represents a carbonyl group or a methylene group, and the broken line represents a single bond or a double bond. The manufacturing method of the alicyclic oxygen-containing compound represented by these. 3. The method for producing an alicyclic oxygen-containing compound according to claim 2, wherein the reduction reaction is carried out using a metal hydride complex. 4. The formula [4]: (In the formula, the broken line represents a single bond or a double bond.) 8,9-bis (hydroxymethyl) tricyclo [5.
2.1.0 ^2,6 ] Dec-3-ene and 8,9-bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane are reacted with an acid. [5] embedded image (In the formula, the broken line has the same meaning as described above.) A method for producing an alicyclic oxygen-containing compound. 5. The formula [6] [Chemical 6] (In the formula, R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Represents ) 8,9-bis (alkoxycarbo)
Nyl) tricyclo [5.2.1.0] ^2,6] Decane or
8,9-Dicarboxytricyclo [5.2.1.
0^2,6] It is characterized by reducing decane by a catalytic reduction method
Formula [7] [Chemical 7] A method for producing an alicyclic oxygen-containing compound represented by: 6. The method for producing an alicyclic oxygen-containing compound according to claim 5, wherein the catalytic reduction catalyst is copper chromite.