JP2003040842A - beta-ALKYLCARBOXYLATES AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new β-alkylcarboxylate which has two functional groups in the identical molecule and is useful as resist materials having excellent etching resistance, an acid releasing property and adhesivity, or as medicines, agrochemicals, and polymers, and to provide a method for producing the β- alkylcarboxylate. SOLUTION: This β-alkylcarboxylate represented by formula (1) (R<1> and R<2> are each H, an alkyl, or an aryl, or R<1> and R<2> may form an alicyclic hydrocarbon group together with the adjacent carbon atom; R<3> is an alkyl; R<4> is an alkyl, an alkenyl or an aryl), and the method for producing the β- alkylcarboxylate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to novel β-alkylcarboxylic acid esters and a method for producing the same.

[0002]

2. Description of the Related Art Acrylic acid or methacrylic acid ester of a tertiary alcohol having a bulky aliphatic or alicyclic substituent as a new type of resist material necessary for producing a highly integrated next generation LSI (Large Scale Integrated Circuit) Was noticed,
Many trial resists have been synthesized. Among them, 2-alkyl-2-adamantyl methacrylate is regarded as an indispensable material for next-generation resists because of its excellent performance.

[0003]

However, for example, a copolymer resist material of 2-alkyl-2-adamantyl methacrylate and a 5- or 6-membered ring lactone has insufficient etching resistance and acid sensitivity, and has higher performance. Resist materials are desired. From such a viewpoint, a compound having a lactone ring in the adamantyl mother nucleus has been developed. But it is less realistic than very expensive.

An object of the present invention is to provide a novel ester having two functional groups in the same molecule and having excellent etching resistance, acid desorption property and adhesiveness, and a method for producing the same. Another object of the present invention is to provide a novel ester and a method for producing the same, which has great potential demand as a raw material also in the field of synthetic chemical industry related to pharmaceuticals, agricultural chemicals, polymers and the like.

[0005]

The present invention relates to β-alkylcarboxylic acid esters represented by the formula (1).

[0006]

[Chemical 6]

(In the formula, R ¹ and R ² each represent hydrogen, an alkyl group or an aryl group, or may form a cycloaliphatic hydrocarbon group together with both of them. R ³ represents an alkyl group or R ⁴ represents an alkyl group, an alkenyl group, or an aryl group.)

Since the above ester of the present invention has two functional groups of adamantyl type and lactone type in the same molecule,
It has its respective characteristics. As a result, it has excellent advantages over conventional resist materials such as excellent etching resistance, acid desorption and adhesion.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The ester (1) of the present invention is obtained, for example, by reacting the following carbonyl compound (2) with a lithium derivative (3) to obtain a lithium alkoxide (4), which is converted into an acid halide (6). ) And can be manufactured. R ¹ R ² C═O (2) (In the formula, R ¹ and R ² each represent hydrogen, an alkyl group, or an aryl group, or may form a cycloaliphatic hydrocarbon group together with carbon atoms. ^{_{) Li-CH 2 CO 2 R}} 3 (3) ( wherein, ^{R 3} represents an alkyl group.)

[0010]

[Chemical 7]

(In the formula, R ¹ , R ² and R ³ are the same as above.) R ⁴ COX (6) (In the formula, R ⁴ represents an alkyl group, an alkenyl group or an aryl group.)

[0012]

[Chemical 8] (In the formula, R ^1, R ² , R ³ and R ⁴ are the same as above.)

Examples of the alkyl group in the carbonyl compound (2) include methyl, ethyl, propyl and butyl having 1 to 4 carbon atoms. Examples of the aryl group include phenyl, tolyl, naphthyl and the like. Examples of the alicyclic hydrocarbon group include (1) adamantane and its derivatives, (2) norbornane and its derivatives, (3) perhydroanthracene and its derivatives, (4) perhydronaphthalene and its derivatives, (5). Tricyclo [5.2.1.0 ^2,5 ] decane and its derivatives, (6) Bicyclohexane and its derivatives, (7) Spiro [4,
Examples thereof include alicyclic hydrocarbon groups derived from 4] nonane and its derivative, and (8) spiro [4,5] decane and its derivative.

Typical examples of these carbonyl compounds include formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Examples thereof include benzaldehyde, benzophenone, 2-adamantanone and camphor.

In the present invention, the lithium derivative (3) is
For example, it can be produced by reacting an acetic acid ester (7) with an aminolithium compound (8). ^{_{CH 3 CO 2 R 3 (7}} ) ( wherein, ^{R 3} represents an alkyl group.) Li-Y (8) ( in the formula, Y represents an amino group which may have a substituent.)

Examples of the alkyl group represented by R ³ include methyl, ethyl, propyl, isopropyl, butyl and t-butyl having 1 to 4 carbon atoms. Examples of the amino group which may have a substituent of Y include methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, diisopropylamino, t-butylamino, dit-butylamino, cyclohexylamino and cyclohexylmethyl. Amino etc. can be illustrated.

The carbonyl compound (2) is preferably used in an amount of about 1 to 1.5 equivalents based on the lithium derivative (3). The reaction is preferably carried out at about -50 ° to 25 ° C for about 1 to 5 hours. The obtained lithium alkoxide can be isolated by filtering and then concentrating it, but usually it is directly used for the next reaction.

Examples of the alkyl group of R ⁴ of the acid halide (6) include methyl, ethyl, propyl having 1 to 4 carbon atoms,
Butyl etc. can be illustrated. 2 carbon atoms as alkenyl group
Examples thereof include vinyl, allyl, propenyl and the like. Examples of the aryl group include phenyl, tolyl, naphthyl and the like. Examples of the halogen atom of X include chlorine, bromine, iodine and the like. Representative examples of the acid halide (6) include acetyl chloride, propionyl chloride, acryloyl chloride, methacryloyl chloride, benzoyl chloride, and their corresponding bromides and iodides. The acid halide (6) is 1 to the lithium alkoxide (4).
It is recommended to use about 1.5 equivalents. The reaction is about -50 °
It is preferable to perform the treatment at 25 ° C. for about 1 to 8 hours.

A solvent may be used in the above reaction of the present invention. As the solvent, for example, tetrahydrofuran (THF) and butyl ether are preferable, but isopropyl ether, methyl-t-butyl ether, dioxane and the like can also be used, and the solvent is not particularly limited.

Isolation of the ester can be carried out by adding water to the reaction mixture, subsequently adding an aqueous solution of NaHCO ₃ , Na ₂ CO _{3 ,} NaOH, etc., extracting with a suitable organic solvent, drying and then concentrating. it can.

The obtained ester (1) is, for example, methoxycarbonylethyl acetate, 2-ethoxycarbonylpropyl acetate, 2-sec-butoxycarbonylpropyl acetate, 2-t-butoxycarbonylbutyl acetate, methoxycarbonylethyl propionate. , 2-ethoxycarbonylpropyl propionate, 2-ethoxycarbonylmethyl-2-adamantyl methacrylate, 2-t-butoxycarbonylmethyl-2-adamantyl methacrylate, 2-ethoxycarbonylmethyl-2-adamantyl acrylate,
Examples thereof include 2-t-butoxycarbonylmethyl-2-adamantyl acrylate, methoxycarbonylethyl benzoate, ethoxycarbonylpropyl benzoate.

In the present invention, for example, when the lithium alkoxide (4) is reacted with water, a corresponding alcohol (5) is obtained.

[0023]

[Chemical 9] (In the formula, R ¹ , R ² and R ³ are the same as above.)

Water is 1 to 1 with respect to the lithium alkoxide.
It is recommended to use about 10 equivalents. The reaction is about 0-25 ° C
Then, it is good to carry out in about 30 minutes to 3 hours. The alcohol can be isolated by treating with water, extracting with an appropriate organic solvent, drying and concentrating and removing the solvent.

[0025]

EXAMPLES The present invention will be described below with reference to examples, but the invention is not limited thereto.

Example 1 A four-necked flask was charged with 300 ml of THF and 111 ml of diisopropylamine (1.2 equivalents), and n-
Butyl lithium (460 ml, 1.56 mole / l) was added dropwise over 0.5 hours while maintaining the reaction temperature at -20 ° C. After stirring for 2 hours, 91 ml of t-butyl acetate (1.0 equivalent) was added to the reaction temperature of -2 for 1 hour.
Add dropwise while maintaining at 0 ° C. Then after stirring for 3 hours,
2-adamantanone 100 dissolved in 300 ml of THF
g (0.67 mole) is added. After stirring for 3 hours,
76 ml (1.2 equivalents) of methacrylic acid chloride is added dropwise over 1 hour. During this time, the reaction temperature was kept at -20 ° C. The reaction mixture was treated with brine, the organic layer was dried over magnesium sulfate, and concentrated to give 2-t-butoxycarbonylmethyl-2-adamantyl methacrylate. The NMR spectrum of the obtained 2-t-butoxycarbonylmethyl-2-adamantyl methacrylate is shown in FIG. The yield was 35%.

Example 2 A reaction was carried out in the same manner as in Example 1 except that water (10 equivalents) was used instead of methacrylic acid chloride. As a result, 2-t-butoxycarbonylmethyl-2-
Adamantanol was obtained. The NMR spectrum of the obtained 2-t-butoxycarbonylmethyl-2-adamantanol is shown in FIG. The yield was 48%.

[0028]

INDUSTRIAL APPLICABILITY According to the present invention, a resist material having two functional groups in the same molecule and having excellent etching resistance, acid desorption property, and adhesion property, or a drug, an agricultural chemical, a polymer, etc. It is possible to obtain novel β-alkylcarboxylic acid esters useful in the field of synthetic chemical industry.

[Brief description of drawings]

FIG. 1 is an NMR spectrum of 2-t-butoxycarbonylmethyl-2-adamantyl methacrylate.

FIG. 2 is an NMR spectrum of 2-t-butoxycarbonylmethyl-2-adamantanol.

Claims (5)

[Claims] 1. A β-alkylcarboxylic acid ester represented by the formula (1). [Chemical 1] (In the formula, R ¹ and R ² each represent hydrogen, an alkyl group, or an aryl group, or may form a cycloaliphatic hydrocarbon group together with carbon atoms. R ³ is an alkyl group, and R ⁴ is an alkyl group. Group, alkenyl group, aryl group.) 2. A carbonyl compound (2) is reacted with a lithium derivative (3) to obtain a lithium alkoxide (4), which is reacted with water to obtain an alcohol (5). Manufacturing method. R ¹ R ² C═O (2) (In the formula, R ¹ and R ² each represent hydrogen, an alkyl group, or an aryl group, or may form a cycloaliphatic hydrocarbon group together with carbon atoms. ^{_{) Li-CH 2 CO 2 R}} 3 (3) ( wherein, ^{R 3} represents an alkyl group.) embedded image (In the formula, R ¹ , R ² and R ³ are the same as above.) (In the formula, R ¹ , R ² and R ³ are the same as above.) 3. A carbonyl compound (2) is reacted with a lithium derivative (3) to obtain a lithium alkoxide (4), which is reacted with an acid halide (6) to obtain an ester (1). A process for producing a β-alkylcarboxylic acid ester, which is characterized. R ¹ R ² C═O (2) (In the formula, R ¹ and R ² each represent hydrogen, an alkyl group, or an aryl group, or may form a cycloaliphatic hydrocarbon group together with carbon atoms. ^{_{) Li-CH 2 CO 2 R}} 3 (3) ( wherein, ^{R 3} represents an alkyl group.) embedded image (In the formula, R ¹ , R ² and R ³ are the same as above.) R ⁴ COX (6) (In the formula, R ⁴ represents an alkyl group, an alkenyl group or an aryl group.) (In the formula, R ^1, R ² , R ³ and R ⁴ are the same as above.) 4. An alicyclic hydrocarbon group is (1) adamantane and its derivative (2) norbornane and its derivative (3) perhydroanthracene and its derivative (4) perhydronaphthalene and its derivative (5) tricyclo [5]. .2.1.0 ^2,5 ] decane and its derivative (6) Bicyclohexane and its derivative (7) Spiro [4,4] nonane and its derivative (8) Derived from spiro [4,5] decane and its derivative The method according to claim 1, which is one of the groups described below. 5. The production method according to claim 2, wherein the carbonyl compound (2) is 2-adamantanone.