JP2002020353A - New cyclopentenone compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclopentenone compound which is an important intermediate for the production of polymers used for photoresists in photolithography process for processing of semiconductors. SOLUTION: This cyclopentenone compound represented by the general formula (1) (R1 and R2 are each independently H or a 1 to 5C alkyl; R3 is H or a 1 to 4C alkyl), and a method for producing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclopentenone compound which is a useful intermediate in producing a photopolymer for a photoresist used in a photolithography step of semiconductor processing, and a method for producing the same.

[0002]

2. Description of the Related Art A copolymer having adamantyl methacrylate units, which is an alicyclic polymer, is used as a photoresist photopolymer having transparency to a wavelength of 193 nm and dry etching resistance [S. Takechi et al., Journal of Photopolymer Science and Technology
d Technology), 5 (3), 439-446 (19
92); and JP-A-5-265212], a copolymer having a poly (isobornyl methacrylate) unit [GM
GMWallraff et al., Journal of Vacuum Science and Technology (Jour)
nal of Vacuum Science and Technology), B11 (No. 6), pp. 2783-2788 (1993)] and a copolymer having a poly (menthyl methacrylate) unit [JP-A-8-8].
No. 2925] is known.

[0003]

However, the above-mentioned photoresist photopolymer has the required properties,
It is not always sufficient in terms of dry etching resistance, substrate adhesion, solubility in an alkaline aqueous solution, and the like.

There are also compounds that are problematic in terms of cost, and more practical photopolymers for photoresists have been demanded.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a cyclopentenone compound can be a useful intermediate of a photoresist photopolymer capable of overcoming the above-mentioned problems. Thus, the present invention has been completed.

That is, the compound of the present invention has the formula (1)

[0007]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom or a C _1-5 alkyl group, and R ³ represents a hydrogen atom or a C _1-4 alkyl group). A cyclopentenone compound represented by the formula (2):

[0009]

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(Wherein R ¹ and R ² each independently represent a hydrogen atom or a C _1-5 alkyl group);

[0011]

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Wherein R ³ represents a hydrogen atom or a C _1-4 alkyl group, and R ⁴ represents a C _1-5 alkyl group.

[0013]

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Wherein R ³ and R ⁴ have the same meanings as described above, and carbon monoxide is reacted with a ruthenium catalyst in the presence of a base. Equation (1)

[0015]

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(Wherein, R ¹ , R ² and R ³ have the same meanings as described above).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

First, each substituent of the compound (1) of the present invention will be described specifically.

In this specification, "n" means normal, "i" means iso, "s" means secondary, and "t" means tertiary.

The C _1-4 alkyl group includes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-
Butyl and t-butyl and the like, and as the C _1-5 alkyl group, in addition to the above, 1-pentyl, 2-pentyl, 3-pentyl, i-pentyl, neopentyl and 2,2-dimethylpropyl and the like Can be

Specific examples of R ¹ and R ² include a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 1-pentyl, 2-pentyl, 3-pentyl, i-pentyl, neopentyl and 2,
2-dimethylpropyl and the like, preferably methyl and ethyl.

Specific examples of R ³ include a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl and t-butyl. Examples include a hydrogen atom and methyl.

Specifically, R ⁴ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-
Examples thereof include butyl, t-butyl, 1-pentyl, 2-pentyl, 3-pentyl, i-pentyl, neopentyl, and 2,2-dimethylpropyl, and preferably include methyl and ethyl.

Preferred compounds used in the present invention include the following compounds.

R ¹ and R ² are each independently methyl or ethyl, and R ³ is a hydrogen atom or methyl;
A cyclopentenone compound represented by the formula (1).

Next, a method for producing the cyclopentenone compound represented by the formula (1) will be described.

The cyclopentenone compound represented by the formula (1) comprises a norbornene compound represented by the formula (2), an allyl compound represented by the formula (3) or (4), and carbon monoxide. And a reaction with a ruthenium catalyst in the presence of a base.

The charge ratio of the norbornene compound represented by the formula (2) to the allyl compound represented by the formula (3) or (4) is not particularly limited, but is preferably 1:10 to 1
0: 1, more preferably 1: 1 to 4: 1.
Range. From the economical viewpoint, it is preferable to use an inexpensive excess.

Specific examples of the allyl compound represented by the formula (3) or (4) include, for example, allyl methyl carbonate,
-Methyl allyl carbonate, 3-methyl allyl carbonate, 1-ethyl allyl carbonate, 3-ethyl allyl carbonate, 1-n-propyl allyl carbonate, 3-n
-Methyl propylallyl carbonate, 1-i-propylallyl methyl carbonate, 3-i-propylallyl methyl carbonate, 3-
Methyl n-butyl allyl carbonate, methyl 3-i-butyl allyl carbonate, ethyl allyl carbonate, ethyl 1-methyl allyl carbonate, ethyl 3-methyl allyl carbonate, ethyl 1-ethyl allyl carbonate, ethyl 3-ethyl allyl carbonate, ethyl 1-n-propyl allyl carbonate , 3-n-propyl allyl carbonate, 1-i-propyl allyl carbonate, 3-i-
Ethyl propyl allyl carbonate, 3-n-butyl allyl carbonate, 3-i-butyl allyl carbonate, n-propyl allyl carbonate, i-propyl allyl carbonate, n-allyl carbonate
-Butyl, i-butyl allyl carbonate, s-butyl allyl carbonate, t-butyl allyl carbonate, n-pentyl allyl carbonate and the like, preferably methyl allyl carbonate, methyl 1-methylallyl carbonate, methyl 3-methylallyl carbonate,
Ethyl allyl carbonate, 1-methylallyl ethyl carbonate and 3
-Ethyl allyl carbonate; more preferably, methyl allyl carbonate and ethyl allyl carbonate.

As carbon monoxide, a commercially available product can be used as it is, or a mixed gas composed of a gas inert to carbon monoxide and a reaction may be used.

The pressure of carbon monoxide is usually 10 to 10 ⁴ k
Pa, but a preferred range is 10 ² to 10 ³ kP.
a.

As the form of the ruthenium catalyst, a ruthenium complex, a ruthenium metal salt, a ruthenium metal alone, a supported ruthenium metal, a ruthenium oxide and the like can be used.

As the ruthenium complex, for example, [Ru
Cl ₂ (CO) ₃ ] ₂ , (η ³ -allyl) RuCl (C
O) ₃ , (η ³ -allyl) RuBr (CO) ₃ , (η ³ -allyl)
l) RuI (CO) ₃ , [(p-cymene) RuCl ₂ ] ₂ , Cp ^*
RuCl (cod) [cod = 1,5-cyclooctadiene, Cp ^* = pentamethylcyclopentadiene] and [(η ⁶ -C ₆ H ₆ ) RuCl ₂ ] ₂ .

As the ruthenium metal salt, RuCl _3.
nH ₂ O, RuBr ₃ .nH ₂ O and RuI ₃ .nH ₂ O.

The ruthenium metal alone includes metal ruthenium and ruthenium black.

Examples of the supported ruthenium metal include those in which the above-mentioned ruthenium metal alone is supported on a carrier such as carbon, silica, alumina and zeolite.

Examples of the ruthenium oxide include ruthenium oxide (IV) and ruthenium oxide (VIII).

Preferred examples of the ruthenium catalyst include a ruthenium complex, and particularly preferred is [Ru
Cl ₂ (CO) ₃ ] ₂ , (η ³ -allyl) RuCl (C
O) ₃ , (η ³ -allyl) RuBr (CO) ₃ , (η ³ -allyl)
l) RuI (CO) ₃ and [(p-cymene) RuCl ₂ ] _{2 and the} like.

The amount of the ruthenium catalyst used is usually 0.1 to 0.1% based on the allyl compound represented by the formula (3) or (4).
-30 mol%, preferably 0.5-10 mol%.

As the base, an organic base and an inorganic base can be used, and specific examples of the organic base include, for example, triethylamine, tri (n-propyl) amine and tri (n-butyl) amine. Aliphatic amines, cyclic amines such as N-methylpiperidine and quinuclidine, and the like. Specific examples of the inorganic base include, for example, alkali metal carbonates such as sodium carbonate and potassium carbonate, magnesium hydroxide and hydroxide. Alkaline earth metal hydroxides such as calcium can be exemplified, preferably an organic base, more preferably an aliphatic amine, and particularly preferably triethylamine.

The amount of the base to be used is generally in the range of 0.1 to 30 mol%, preferably 0.5 to 10 mol%, based on the allyl compound represented by the formula (3) or (4). Range.

This reaction can be carried out without solvent, but it is preferable to use a solvent. Specific examples of the solvent include ethers such as tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, and diethylene glycol dimethyl ether (diglyme);
Benzene, and aromatic hydrocarbons such as toluene and xylene, and the like, preferably ethers,
More preferred are THF and diglyme.

The amount of the solvent used is 1 to 30 times by weight, more preferably 2 to 10 times by weight, based on the allyl compound represented by the formula (3) or (4).

The reaction can be carried out usually at a temperature of 50 to 250 ° C., preferably 100 to 200 ° C.

The reaction time can be monitored and determined by collecting the reaction solution and analyzing it by gas chromatography.

This reaction can be carried out either batchwise or continuously.

After the reaction, by concentrating and purifying by distillation or column chromatography, a highly purified cyclopentenone compound represented by the formula (1) can be obtained.

Next, a method for synthesizing a norbornene compound represented by the formula (2), which is a starting material, will be described.

The norbornene compounds are available from Journal of the American Chemical Society (Journa
l of the American Chemical Society), 88, 42
It can be synthesized by the method described on page 73 (1966).

The reaction scheme is shown below.

[0051]

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That is, by heating quadricyclane (5) and dimethyl acetylenedicarboxylate (6),
Desired tricyclo [4.2.1.0 ^2,5 ] nona-3,7
-Diene-3,4-dicarboxylic acid dimethyl (7) can be obtained.

Similarly, by using another dialkyl acetylenedicarboxylate, the corresponding diester derivative can be obtained.

Further, the diester derivative (7) is hydrolyzed to obtain tricyclo [4.2.1.0 ^2,5 ] nona-3,7-diene-3,4-dicarboxylic acid (8). Can be.

[0055]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

[Example 1]

[0057]

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In a 50 ml stainless steel autoclave equipped with a magnetic rotor and a glass liner, 116 mg (1.0 mmol) of allyl methyl carbonate and 3,4-bis (ethoxycarbonyl) tricyclo [4.2.1. 0 ^2,5 ] nona-3,7-diene 500 mg (2 mmol), (η ³
-Allyl) Ru (CO) ₃ Br 15.3 mg (5 mol
%), 10.1 mg (10 mol%) of triethylamine
And 8.0 mL of tetrahydrofuran (THF), followed by purging with argon and then filling with 303 kPa of carbon monoxide. The temperature was raised while stirring was started.
Allowed to react for hours. After completion, the mixture was cooled to room temperature, the remaining carbon monoxide was exhausted, and the atmosphere was replaced with argon, and then the reaction solution was taken out. After concentration, the obtained residue was purified by silica gel column chromatography to obtain a colorless transparent oily substance, 4-
Methyl-9,10-bis (ethoxycarbonyl) tetracyclo [5.4.1.0 ^2,5 . 0 ^8,11 ] Dodeca-4,9
241 mg (73 mmol) of -dien-3-one (73% yield) were obtained. This structure was confirmed from the following analysis results.

MASS (EI, m / z): 330 (M ⁺ ). ¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.86 (d, J = 11.72 Hz, 1
H), 1.12 (d, J = 11.72Hz, 1H), 1.24 (t, J = 7.08Hz, 3H),
1.25 (t, J = 7.08Hz, 3H), 1.71 (s, 3H), 2.11 (d, J = 4.89H
z, 1H), 2.19 (s, 1H), 2.43 (s, 1H), 2.53 (br, 1H),
2.76 (s, 1H), 2.78 (s, 1H), 4.15 (q, J = 7.08Hz, 2H),
4.16 (q, J = 7.08Hz, 2H), 7.09 (s, 1H) 13 C-NMR (100MHz, CDCl 3, δppm):. 10.0, 14.0, 14.1, 2
3.7, 35.9, 36.1, 46.6, 46.7, 47.2, 51.9, 60.8, 60.
9, 142.2 (for 2), 145.0, 158.5, 160.7, 161.0, 209.
^{9. IR (neat, cm -1)} : 1731, 1705. Elemental analysis: C ₁₉ H ₂₂ O ₅ measurements (%); H 6.71, C 69.07
[Theoretical (%); H 6.98, C68.98]. bp. (Kugelrohr): 160-170 (℃ / 133Pa).

[0060]

The cyclopentenone compound of the present invention is useful as an intermediate for synthesizing a photoresist photopolymer having excellent properties.

Claims (4)

[Claims] (1) Formula (1) (Wherein, R ¹ and R ² each independently represent a hydrogen atom or a C _1-5 alkyl group, and R ³ represents a hydrogen atom or a C _1-4 alkyl group.) Tenone compounds. 2. The cyclopentenone compound according to claim 1, wherein R ¹ and R ² are each independently methyl or ethyl, and R ³ is a hydrogen atom or methyl. 3. Formula (2) (Wherein R ¹ and R ² each independently represent a hydrogen atom or a C _1-5 alkyl group) and a norbornene compound represented by the formula (3): (Wherein, R ³ represents a hydrogen atom or a C _1-4 alkyl group;
R ⁴ represents a C _1-5 alkyl group. ) Or formula (4) (Wherein R ³ and R ⁴ represent the same meaning as described above) and carbon monoxide in the presence of a base.
Formula (1) characterized in that the reaction is carried out with a ruthenium catalyst. (Wherein, R ¹ , R ² and R ³ represent the same meaning as described above). 4. A ruthenium catalyst comprising [RuCl ₂ (C
O) ₃ ] ₂ , (η ³ -allyl) RuCl (CO) ₃ , (η ³ -al
lyl) RuBr (CO) ₃ , (η ³ -allyl) RuI (C
O) ₃ or _{[(p-cymene) RuCl 2} ] The process according to claim 3 cyclopentenone compound according _2.