Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-12-06
2003-02-18
Rotman, Alan L. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S205000, C560S120000, C525S337000
Reexamination Certificate
active
06521781
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing a 2-hydrocarbyl-2-adamantyl acrylate compound which gains industrial attention as a material for ArF excimer laser resists and high performance polymers.
2. Description of the Prior Art
In the known production of a 2-alkyl-2-adamantyl (meth)acrylate compound from a 2-adamantanone compound corresponding to its ester moiety, the 2-adamantanone compound is converted into a corresponding 2-alkyl-2-adamantanol compound, and then the 2-alkyl-2-adamantanol compound is reacted with (meth)acrylic acid or a (meth)acryloyl halide.
K. Nozaki et al., Jpn. J. Appl. Phys., 35,528(1996) report to synthesize 2-methyl-2-adamantyl methacrylate by the esterification reaction between 2-methyl-2-adamantanol and methacryloyl chloride. Japanese Patent Application Laid-Open No. 2000-229911 propose to synthesize a 2-alkyl-2-adamantyl (meth)acrylate by the reaction of a corresponding 2-alkyl-2-adamantanol compound with (meth)acryloyl chloride. Japanese Patent Application Laid-Open No. 2000-309558 discloses a reaction of a corresponding 2-alkyl-2-adamantanol compound or its metal salt with a (meth)acryloyl halide.
Japanese Patent Application Laid-Open No. 10-182552 discloses a process for producing an ester of tertiary alcohol without separating and purifying a tertiary alcohol, in which a starting ketone compound is reacted with a carboxylic acid halide in the presence of an organometallic compound to directly obtain the ester of tertiary alcohol. However, a (meth)acryloyl halide used as the esterification reagent is expensive and intractable, and contains various by-products which are difficult to remove. In addition, the (meth)acryloyl halide by-produces an alkyladamantyl halide which generates acid during distillation to decompose the target 2-alkyl-2-adamantyl (meth)acrylate compound, thereby significantly reducing the yield.
Japanese Patent Application Laid-Open No. 2000-97924 proposes to convert the alkyladamantyl halide to a compound which does not generate acid during distillation by contacting a 2-alkyl-2-adamantyl (meth)acrylate compound containing the alkyladamantyl halide with an alkali compound, thereby preventing the yield from being lowered. Japanese Patent Application Laid-Open No. 2000-229911 proposes a method for producing the 2-alkyl-2-adamantyl (meth)acrylate compound in high yields by using an acid halide prepared by reacting (meth)acrylic acid with benzoyl chloride or phosphorus trichloride.
However, since a production method using an acid halide should be carried out in a specific manner, it has been demanded to develop a production method which is easily operated in industrial scale and produces a 2-hydrocarbyl-2-adamantyl acrylate compound with high yields without using acid halide.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a process for producing a 2-hydrocarbyl-2-adamantyl acrylate compound easily and stably with high yields from a 2-adamantanone compound without using a (meth)acryloyl halide.
As a result of extensive study in view of attaining the above object, the inventors have found that the 2-hydrocarbyl-2-adamantyl acrylate compound is efficiently produced from a 2-adamantanone compound by using a (meth)acrylic ester and/or an acrylic anhydride compound in place of the (meth)acryloyl halide. On the basis of this finding, the present invention has been accomplished.
Thus, the present invention provides a process for producing a 2-hydrocarbyl-2-adamantyl acrylate compound represented by the following
Formula 6:
wherein R
1
is a hydrocarbyl group, R
2
is a hydrogen atom or an alkyl group, and Y is a hydrogen atom, an alkyl group, a hydroxyl group, or a halogen atom, and n is an integer of 1 to 14;
the process comprising a step of reacting a 2-adamantanone compound represented by the following Formula 1:
wherein Y and n are the same as defined above;
with at least one organometallic compound and at least one acrylic compound, the organometallic compound being represented by the following Formula 2 or 3:
R
1
MgX (2)
R
1
Li (3)
wherein R
1
is the same as defined above, and X is a halogen atom;
and the acrylic compound being represented by the following Formula 4 or 5:
wherein R
2
is the same as defined above, and R
3
is an alkyl group.
DETAILED DESCRIPTION OF THE INVENTION
The 2-adamantanone compound (2-adamantanone and its derivatives) used as a starting material is represented by the following Formula 1:
In Formula 1, Y is a hydrogen atom, an alkyl group, a hydroxyl group, or a halogen atom. The alkyl group is preferably a C1-C10 alkyl such as methyl group, ethyl group, isopropyl group and amyl group. Examples of halogen atom is chlorine atom, bromine atom and iodine atom. The suffix “n” is an integer of 1 to 14, preferably 1 to 4. If n is 2 or more, two or more Y substituents may be the same as or different from each other. Particularly preferred 2-adamantanone compound is 2-adamantanone.
In the process of the present invention, a Grignard reagent represented by Formula 2 and/or an organolithium compound represented by Formula 3 is used as the organometallic compound.
R
1
MgX (2)
R
1
Li (3)
In Formulas 2 and 3, R
1
is a hydrocarbyl group, preferably an aliphatic, alicyclic or aromatic hydrocarbyl group having 1 to 10 carbon atoms, more preferably methyl group, ethyl group, propyl group, butyl group or phenyl group. X is a halogen such as chlorine, bromine and iodine. Specific Grignard reagent may be CH
3
MgBr, C
2
H
5
MgBr, or C
4
H
9
MgBr, and a specific organolithium compound may be CH
3
Li, C
2
H
5
Li or C
4
H
9
Li.
The Grignard reagent and the organolithium compound is added to the reaction system in the form of solution. As the solvent, usable are ether compounds such as tetrahydrofuran and diethyl ether; hydrocarbon compounds such as hexane, heptane and cyclohexane; and halogen compounds such as carbon tetrachloride and dichloromethane, although not limited thereto and another solvent is usable as far as inert to the reaction.
The Grignard reagent or the organolithium compound is used in an amount of 1 to 10 equivalents, preferably 1 to 2 equivalents based on the starting 2-adamantanone compound. Although the Grignard reagent or the organolithium compound may be added to the reaction system in any manner and at any addition speed, but preferably added at a speed so as to avoid the abnormal rise of the reaction temperature.
In the process of the present invention, the acrylic ester compound represented by the following Formula 4 and/or the acrylic anhydride compound represented by the following Formula 5 is used as the acrylic compound:
In Formulas 4 and 5, R
2
is a hydrogen atom or an alkyl group. The alkyl group is preferably a C1-C4 alkyl group such as methyl group and ethyl group. Preferred R
2
is a hydrogen atom or methyl group. R
3
is an alkyl group, preferably a C1-C6 alkyl group such as methyl group and ethyl group. The specific acrylic compound of Formula 4 is methyl ester, ethyl ester or isopropyl ester of acrylic acid or methacrylic acid; and the specific acrylic anhydride compound of Formula 5 is acrylic anhydride or methacrylic anhydride.
The addition amount of the acrylic compound is 1 to 100 equivalents, preferably 1 to 20 equivalents, more preferably 1 to 5 equivalents based on the starting 2-adamantanone compound. If less than one equivalent, the yield of the 2-hydrocarbyl-2-adamantyl acrylate compound is reduced. If more than 100 equivalents, the batch efficiency is lowered and the purification of the product becomes difficult.
The acrylic compound is added to the reaction system in any manner and in any addition speed. For example, the acrylic compound may be added to the reaction system prior to the addition of the Grignard reagent and/or the organolithium compound. Alternatively, the acrylic compound may be added simultaneously with the Grignard reagent and/or the organolithium compound. Preferably, the acrylic compound is added after the addition of
Arai Yoshihisa
Furukawa Kikuo
Isobe Takehiko
Kakuda Minoru
Antonelli Terry Stout & Kraus LLP
Mitsubishi Gas Chemical Company Inc.
Reys Hector
Rotman Alan L.
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