- Method for synthesizing adamantyl (meth) acrylate
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The invention discloses a method for synthesizing adamantyl (meth) acrylate, and relates to the field of organic synthesis. The method for synthesizing adamantyl (meth) acrylate comprises the steps: 1, reacting (methyl) acrylic acid with alkyl sulfonyl chloride to generate mixed anhydride S1; 2, reacting 2-adamantanone with halogenated alkane under the action of a lithium reagent or a Grignard reagent to generate an intermediate S2; and 3, reacting the mixed anhydride S1 with the intermediate S2 to generate the adamantyl (meth) acrylate. The invention provides a synthetic method of adamantyl (meth) acrylate, and provides more selectivity for synthesis of adamantyl (meth) acrylate. The synthesis method disclosed by the invention is high in yield, high in product purity and low in synthesis cost.
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Paragraph 0038-0039; 0041-0042
(2021/05/19)
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- Process for Producing 2-Methyladamantan-2-Yl (Meth)Acrylate and 2-Methyladamantan-2-Yl (Meth)Acrylate
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An object of the present invention is to provide a process for purifying 2-methyladamantan-2-yl(meth)acrylate with high separation efficiency and an industrially advantageous preparation process of 2-methyladamantan-2-yl(meth)acrylate. The present invention pertains to a preparation process of 2-methyladamantan-2-yl(meth)acrylate which comprises reacting 2-methyleneadamantane and (meth)acrylic acid by an acid catalyst to obtain a reaction mixture, and then separating 2-methyleneadamantane from the reaction mixture to obtain 2-methyladamantan-2-yl(meth)acrylate, wherein the reaction mixture is distilled in the presence of an organic compound having a boiling point, under atmospheric pressure, of 150° C. or greater but not greater than 260° C.
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Page/Page column 4-5
(2008/06/13)
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- Adamantyl ester monomer composition
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The present invention discloses an adamantyl ester monomer composition characterized by containing at least an adamantyl ester monomer having at least one polymerizable unsaturated bond in the molecule, and a compound represented by the following general formula (1): (in the formula, R1 is an alkyl group of 1 to 5 carbon atoms, R2 is an alkyl group of 1 to 5 carbon atoms, R3 is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, and R4 is a hydrogen atom or a methyl group). The composition has high storage stability and, by subjecting it to distillation, an adamantyl ester monomer of high purity can be obtained easily.
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- Process of the preparation of high-purity alkyladamantyl esters
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There is provided a method for obtaining an alkyladamantyl ester efficiently by distilling and purifying a crude alkyladamantyl ester containing impurities which decompose the alkyladamantyl ester without decomposing the alkyladamantyl ester. The crude alkyladamantyl ester such as crude 2-methyl-2-adamantyl methacrylate is distilled in the presence of a heterocyclic compound and/or a basic compound such as 3-ethyl-3-hydroxymethyloxetane or diglycidyl bisphenol A.
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- Processes for preparation of 2-alkyl-2adamantyl esters
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A magnesium halide salt of a 2-alkyl-2-adamantanol is reacted with a carboxylic acid halide such as acrylic chloride or the like in the presence of a tertiary amine to produce a 2-alkyl-2-adamantyl ester (the first invention). A 2-alkyl-2-adamantanol is reacted with a carboxylic acid such as acrylic acid or the like in the presence of an acid catalyst such as concentrated sulfuric acid or the like and a drying agent composed of an acidic or neutral inorganic compound (e.g. magnesium sulfate) which is a solid at ordinary temperature in a dried state or of a water-absorbing high-molecular compound, to produce a 2-alkyl-2-admantyl ester (the second invention). The above ester is important as a raw material for a resist for semiconductor production.
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- Process for the preparation of alicyclic ketones and an alkyl-substituted alicyclic esters
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A high-purity alicyclic ketone which is a raw material for an alkyl-substituted alicyclic ester such as an alkyl adamantyl ester compound which is useful as a resist raw material can be obtained by a simple operation such as extraction without a special purification step such as distillation or recrystallization. In this process, when an alicyclic hydrocarbon is oxidized with concentrated sulfuric acid or fuming sulfuric acid, the reaction solution after oxidation is poured into water and a solid is extracted with an organic solvent, the concentration of sulfuric acid in the water layer at the time of extraction is adjusted to 60 to 90 wt % to carry out extraction so as to obtain an alicyclic ketone.
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- ADAMANTYL ESTER MONOMER COMPOSITION
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The present invention discloses an adamantyl ester monomer composition characterized by containing at least an adamantyl ester monomer having at least one polymerizable unsaturated bond in the molecule, and a compound represented by the following general formula (1): (in the formula, R1 is an alkyl group of 1 to 5 carbon atoms, R2 is an alkyl group of 1 to 5 carbon atoms, R3 is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, and R4 is a hydrogen atom or a methyl group). The composition has high storage stability and, by subjecting it to distillation, an adamantyl ester monomer of high purity can be obtained easily.
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- Process for preparing acrylate compound
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An acrylate compound of formula (4): 1is produced by allowing an acrylic acid compound of formula (1): 2to react with an unsaturated compound of formula (2) or (3): 3In formulae (1) through (4), R1 and R2 are H or F, R3 is H, F, or an alkyl, alkenyl, fluoroalkyl or fluoroalkenyl group, R4 and R5 are H, halogen, or an alkyl, alkenyl, halogenated alkyl or halogenated alkenyl group; and X and Y are an unsubstituted or substituted hydrocarbon group, and dashed line - - - - - means that X and Y may be bonded together to form a cyclic structure.
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- PROCESS FOR PRODUCING (METH)ACRYLIC ANHYDRIDE AND PROCESS FOR PRODUCING (METH) ACRYLIC ESTER
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(Meth)acrylic acid is reacted with a fatty acid anhydride and the resultant reaction mixture is neutralized and washed with an aqueous alkaline solution having a pH of 7.5 to 13.5. Thus, high-purity (meth)acrylic anhydride can be industrially advantageously produced while avoiding polymerization. This (meth)acrylic anhydride is reacted with a secondary or tertiary alcohol in the presence of a basic compound which in 25° C. water has an acidity (pKa) of 11 or lower. Thus, a high-purity (meth)acrylic ester can be produced in high yield.
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- Process for producing a 2-adamantyl (meth>acrylate
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An efficient process for producing a high quality 2-adamantyl (meth)acrylate of the formula (I): wherein R1is hydrogen or methyl and R2is hydrogen of lower alkyl, by using very common facilities and procedures, which reacting a (meth)acryloyl halide of the formula (II) wherein R1is as defined above and X is halogen with a 2-adamantanol of the formula (III): wherein R2is as defined above to form the 2-adamantyl (meth)acrylate of the formula (I), then treating a solution of this product in an organic solvent with active carbon, subsequently removing the active carbon, and thereafter separating a purified 2-adamantyl (meth)acrylate, is provided.
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- Production of 2-hydrocarbyl-2-adamantyl acrylate compounds
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A 2-hydrocarbyl-2-adamantyl acrylate compound represented by the following Formula 6: is produced easily and stably with high yields by reacting a 2-adamantanone compound represented by the following Formula 1: with at least one organometallic compound represented by the following Formula 2 or 3: R1MgX??(2) R1Li??(3) and at least one acrylic compound represented by the following Formula 4 or 5: wherein, R1, R2, R3, X, Y and n in the above formulae being as defined in the disclosure.
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- Production of 2-hydrocarbyl-2-adamantyl acrylate compounds
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A 2-hydrocarbyl-2-adamantyl acrylate compound represented by the following Formula 6: is produced easily and stably with high yields by reacting a 2-adamantanone compound represented by the following Formula 1: with at least one organometallic compound represented by the following Formula 2 or 3:R1MgXR1Li and at least one acrylic compound represented by the following Formula 4 or 5: wherein, R1, R2, R3, X, Y and n in the above formulae being as defined in the disclosure.
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- Preparation process for esters and resist materials
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Process for the quantitative preparation of esters, with a high yield, which comprises reacting an aldehyde or ketone compound and an acid halide compound in a one pot reaction in the presence of at least one compound represented by the following formulae: RMgX ??(I); RMgX/CuX ??(II); and RLi or R(CuLi)???(III); in which R represents a hydrocarbon group, and X represents a halogen atom. Production processes of a resist material and a semiconductor device are also disclosed.
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- Chemical amplification type positive resist
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A chemical amplification type positive resist composition which is good in resolution, provide a good pattern profile under exposure using light of wavelength of 220 nm or shorter even when applied on a basic substrate or a low reflectance substrate and which comprises an acid generator comprising an aliphatic sulfonium salt represented by the following formula (I): wherein Q1 represents an alkyl group, Q2 represents an alkyl group or a residue of an alicyclic hydrocarbon and m represents an integer of 1 to 8; and at least one onium salt selected from triphenylsulfonium salts represented by the following formula (IIa) and diphenyiodonium salts represented by the following formula (IIb): wherein Q3, Q4, Q5, Q6 and Q7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and q and p represent a integer of 4 to 8; and (2) a resin which has a polymerization unit with a group unstable to an acid, and is insoluble or barely soluble in alkali by itself but changes to become soluble in alkali by the action of the acid, is provided.
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