Central Glass Company, Limited

Kenjin Inomiya

Akihiro Ishii

Manabu Yasumoto

Koji Ueda

Takashi Ootsuka

Yokusu Kuriyama

Masatomi Kanai

Takashi Mori

Haruhiko Komoriya

Shinichi Sumida

Takamasa Kitamoto

Hideyuki Tsuruta

Yusuke Kanto

Kaori Mogi

Katsuhide Suto

Disclosed is a polymerizable fluoromonomer represented by the following general formula (1). In the formula, Rrepresents a hydrogen atom, methyl group, fluorine atom, or trifluoromethyl group. n is an integer of 0 or 1, and m is that of from 1 to (3+n). Rand Reach independently represents a hydrogen atom or a protective group. A resist containing a fluoropolymer obtained by polymerizing or copolymerizing the monomer is suitable for use in microfabrication by immersion exposure or by a double patterning process based on immersion exposure. 

Polymerizable fluoromonomer, fluoropolymer, resist material, and method of pattern formation

Disclosed is a top coat composition for photoresist, which is characterized by containing a fluorinated polymer having a repeating unit represented by general formula (5). In the formula, Rrepresents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group; n represents 0 or 1; m represents an integer of 1 to (3+n); and Ror Rrepresents a hydrogen atom or a protecting group. The top coat composition has a proper degree of solubility in a developing solution.

Top coat composition

There is provided a novel, useful dehydroxyfluorination agent containing sulfuryl fluoride (SOF) and an organic base that is free from a free hydroxyl group in the molecule. According to the present dehydroxyfluorination agent, it is not necessary to use perfluoroalkanesulfonyl fluoride, which is not preferable in large-scale use, and it is possible to advantageously produce optically-active fluoro derivatives, which are important intermediates of medicines, agricultural chemicals and optical materials, for example, 4-fluoroproline derivatives, 2'-deoxy-2&#x2032;-fluorouridine derivatives, optically-active &#x3b1;-fluorocarboxylate derivatives, and monofluoromethyl derivatives, even in large scale.

Dehydroxyfluorination agent

There is provided a method for producing an optically active 1-(fluoro-, trifluoromethyl- or trifluoromethoxy-substituted phenyl)alkylamine N-monoalkyl derivative, which includes the steps of conducting reductive alkylation of an optically active secondary amine and a formaldehyde (including an equivalent thereof) or lower aldehyde in the presence of a transition metal catalyst under a hydrogen gas atmosphere, thereby converting the secondary amine to an optically active tertiary amine of the formula, and subjecting the tertiary amine to hydrogenolysis. The target optically active compound can be produced efficiently by this production method.

Method for producing optically active 1-(fluoro-, trifluoromethyl- or trifluoromethoxy-substituted phenyl) alkylamine N-monoalkyl derivative

It was found that a fluoro derivative can be produced by reacting a hydroxy derivative with sulfuryl fluoride (SOF) in the presence of an organic base or in the presence of an organic base and 'a salt or complex comprising an organic base and hydrogen fluoride'. According to the present production process, it is not necessary to use perfluoroalkanesulfonyl fluoride, which is not preferable in industrial use, and it is possible to advantageously produce optically-active fluoro derivatives, which are important intermediates of medicines, agricultural chemicals and optical materials, specifically 4-fluoroproline derivatives, 2'-deoxy-2&#x2032;-fluorouridine derivatives, optically-active &#x3b1;-fluorocarboxylate derivatives, and the like, even in a large scale.

Process for production of fluoro derivative

The present invention relates to a process for producing an optically active &#x3b1;-fluorocarboxylate derivative represented by the formula [2], by reacting an optically active &#x3b1;-hydroxycarboxylate derivative with trifluoromethanesulfonyl fluoride (CFSOF) in the presence of an organic base, in the formula [2], R represents a straight-chain or branched-chain alkyl group of a carbon number of 1 to 12; one of or two by any combination of aromatic hydrocarbon groups, unsaturated hydrocarbon groups, straight-chain or branched alkoxy groups of a carbon number of 1 to 6, aryloxy groups, halogen atoms (fluorine, chlorine, bromine and iodine), protected carboxyl groups, protected amino groups or protected hydroxyl group can be substituted on any carbon atoms of the alkyl group; Rrepresents a straight-chain or branched-chain alkyl group of a carbon number of 1 to 8; any carbon atoms of the alkyl groups of R and Rmay form a covalent bond; and * represents an asymmetric carbon.

Process for production of optically active &#x3b1;-fluoro-carboxylic ester derivatives

The present invention relates to a method of producing an optically active 1-aryl-2-fluoro-substituted ethylamine compound of the formula [2] or a salt thereof by hydrogenolysis of an optically active secondary amine compound of the formula [1] or a salt thereof in the presence of a transition metal catalyst of Group VIII [Chem. 59] [where Ar represents an aryl group; n represents an integer of 1 or 2; and * represents an asymmetric carbon][Chem. 60] [where Ar represents an aryl group; n represents an integer of 1 or 2; and * represents an asymmetric carbon].

Optically active 1-aryl-2-fluoro-substituted ethylamine and method for producing same

The present invention relates to a process for producing an optically active 1-alkyl-substituted 2,2,2-trifluoroethylamine, which is an important intermediate of medicines and agricultural chemicals, and which is represented by the formula [3] [in the formula R represents a lower alkyl group of a carbon and * represents an asymmetric carbon], or its salt by subjecting an optically active imine represented by the formula [1] to an asymmetric reduction under hydrogen atmosphere using a metal catalyst of Group VIII to convert it into an optically active secondary amine represented by the formula [2] and then by subjecting the secondary amine or its salt to hydrogenolysis. [Chem. 23] 

Process for producing optically active 1-alkyl-substituted 2,2,2-trifluoroethylamine

1-&#x3b2;-D-Arabinofuranosyluracil in 3',5&#x2032;-hydroxyl-protected form is reacted with a trifluoromethanesulfonylating agent in the presence of an organic base to convert it into a 2&#x2032;-triflate form, and then it is reacted with a fluorinating agent containing 'a salt or complex formed by an organic base and hydrofluoric acid' to produce 2&#x2032;-deoxy-2&#x2032;-fluorouridine in 3&#x2032;,5&#x2032;-hydroxyl-protected form. A deprotecting agent is further caused to act thereon to obtain 2&#x2032;-deoxy-2&#x2032;-fluorouridine. The 2&#x2032;-deoxy-2&#x2032;-fluorouridine obtained can efficiently be purified by temporarily converting it into a 3&#x2032;,5&#x2032;-diacetyl form, recrystallizing the 3&#x2032;,5&#x2032;-diacetyl form, and then deacetylating it. Thus, high-purity 2&#x2032;-deoxy-2&#x2032;-fluorouridine can be produced.

Processing for producing 2'-deoxy-2&#x2032;-fluorouridine

An optically active 1-(fluoro-, trifluoromethyl- or trifluoromethoxy-substituted phenyl)alkylamine N-monoalkyl derivative represented by the formula 4 is produced by a process including (a) reacting an optically active secondary amine, represented by the formula 1, with an alkylation agent R&#x2014;X, in the presence of a base, thereby converting the secondary amine into an optically active tertiary amine represented by the formula 3; and (b) subjecting the tertiary amine to a hydrogenolysis, thereby producing the N-monoalkyl derivative,  wherein R represents a fluorine atom, trifluoromethyl group or trifluoromethoxy group, n represents an integer of from 1 to 5, each of Rand Rindependently represents an alkyl group having a carbon atom number of from 1 to 6, Me represents a methyl group, Ar represents a phenyl group or 1- or 2-naphthyl group, * represents a chiral carbon, and X represents a leaving group.

Optically active 1-(fluoro-, trifluoromethyl- or trifluoromethoxy- substituted phenyl)alkylamine N-monoalkyl derivatives and process for producing same

A process for producing a brominated acetal (represented by the formula 3) includes (a) brominating a trifluoromethyl-substituted acetophenone by Brin the presence of an alkylene diol. It is optional to produce a trifluoromethyl-substituted 2-alkoxyacetophenone derivative (represented by the formula 9) by (b) reacting the brominated acetal with a metal alkoxide, thereby converting the brominated acetal into an ether; and (c) hydrolyzing the ether in the presence of an acid catalyst to remove an acetal group from the ether, thereby producing the 2-alkoxyacetophenone derivative. Alternatively, the 2-alkoxyacetophenone can be produced by (a) reacting a trifluoromethyl-substituted phenacyl halide with an acetalization agent, thereby converting the phenacyl halide into an acetal; (b) reacting the acetal with a metal alkoxide, thereby converting the acetal into an ether; and (c) hydrolyzing the ether in the presence of an acid catalyst to remove the acetal group from the ether 

Process for producing trifluoromethyl-substituted 2-alkoxyacetophenone derivatives

An optically active 1-(fluoro-, trifluoromethyl- or trifluoromethoxy-substituted phenyl)alkylamine N-monoalkyl derivative represented by the formula 4 is produced by a process including (a) reacting an optically active secondary amine, represented by the formula 1, with an alkylation agent R&#x2014;X, in the presence of a base, thereby converting the secondary amine into an optically active tertiary amine represented by the formula 3; and (b) subjecting the tertiary amine to a hydrogenolysis, thereby producing the N-monoalkyl derivative, 

Optically active 1-(fluoro-, trifluoromethyl-or trifluoromethoxy-substituted phenyl) alkylamine n-monoalkyl derivatives and process for producing same

A process for producing a brominated acetal (represented by the formula 3) includes (a) brominating a trifluoromethyl-substituted acetophenone by Brin the presence of an alkylene diol. It is optional to produce a trifluoromethyl-substituted 2-alkoxyacetophenone derivative (represented by the formula 9) by (b) reacting the brominated acetal with a metal alkoxide, thereby converting the brominated acetal into an ether; and (c) hydrolyzing the ether in the presence of an acid catalyst to remove an acetal group from the ether, thereby producing the 2-alkoxyacetophenone derivative. Alternatively, the 2-alkoxyacetophenone can be produced by (a) reacting a trifluoromethyl-substituted phenacyl halide with an acetalization agent, thereby converting the phenacyl halide into an acetal; (b) reacting the acetal with a metal alkoxide, thereby converting the acetal into an ether; and (c) hydrolyzing the ether in the presence of an acid catalyst to remove the acetal group from the ether. 

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Fujimino, Japan

Kenjin Inomiya