Central Glass Company, Limited

International Business Machines Corporation

Manabu Yasumoto

Akihiro Ishii

Yokusu Kuriyama

Masatomi Kanai

Koji Ueda

Kenjin Inomiya

Takashi Ootsuka

Takako Yamazaki

Daniel Sanders

James L Hedrick

Masaki Fujiwara

Hideyuki Tsuruta

Kaori Mogi

Takashi Hayami

Takashi Masuda

Kazumasa Funabiki

Masaki Matsui

Katsuyoshi Shibata

Yoshiharu Terui

Takehisa Ishimaru

Shunsuke Mimura

Takashi Kashiwaba

Masanori Fushimi

Ryuichi Okamoto

Haruki Kobayashi

Shoko Ishii

Rudy J Wojtecki

Ratnam Sooriyakumaran

Satoru Narizuka

Hoa D Truong

Kazunori Mori

Katsuhide Suto

Kanjin Inomiya

Ishii Akihiro

Akihiro Ishi

The present invention provides an industrially applicable method for production of a fluorine-containing cyclopropane carboxylic acid compound useful as an intermediate for pharmaceutical and agrichemical products. A fluorine-containing cyclopropane monoester is obtained by: forming a fluorine-containing cyclic sulfate with the use of a fluorine-containing diol compound and sulfuryl fluoride (as a cyclic sulfuric esterification step); reacting the fluorine-containing cyclic sulfate with a malonic diester, thereby forming a fluorine-containing cyclopropane diester (as a cyclopropanation step); and hydrolyzing the fluorine-containing cyclopropane diester (as a hydrolysis step). The fluorine-containing cyclopropane carboxylic acid compound, such as fluorine-containing cyclopropane monoester or its salt, can be obtained with high chemical and optical purity by mixing the fluorine-containing cyclopropane monoester with an amine and subjecting the resulting salt of the fluorine-containing cyclopropane monoester and amine to recrystallization purification.

Method for producing fluorine-containing cyclopropane carboxylic acid compound

The present invention provides an industrially applicable method for production of a fluorine-containing cyclopropane carboxylic acid compound useful as an intermediate for pharmaceutical and agrichemical products. A fluorine-containing cyclopropane monoester is obtained by: forming a fluorine-containing cyclic sulfate with the use of a fluorine-containing dial compound and sulfuryl fluoride (as a cyclic sulfuric esterification step); reacting the fluorine-containing cyclic sulfate with a malonic diester, thereby forming a fluorine-containing cyclopropane diester (as a cyclopropanation step); and hydrolyzing the fluorine-containing cyclopropane diester (as a hydrolysis step). The fluorine-containing cyclopropane carboxylic acid compound, such as fluorine-containing cyclopropane monoester or its salt, can be obtained with high chemical and optical purity by mixing the fluorine-containing cyclopropane monoester with an amine and subjecting the resulting salt of the fluorine-containing cyclopropane monoester and amine to recrystallization purification.

Photo-acid generating vinyl polymerizable monomers (PAG monomers) were prepared comprising sulfonate ester groups of N-hydroxide imides. The photo-acid generating portion of the PAG monomer is linked to a polymerizable portion of the monomer by an amide linking group. Photo-acid generating polymers (PAG polymers) of the PAG monomers show high sensitivity to extreme ultraviolet radiation (13.5 nm) and much less sensitivity to far ultraviolet wavelengths (193 nm, 248 nm). The PAG polymers also exhibit thermal and chemical amplification properties useful for forming high resolution positive tone or negative tone lithographic resist patterns.

Non-ionic photo-acid generating polymers for resist applications

A production process of a fluorosulfuric acid aromatic-ring ester according to the present invention includes reaction of an aromatic-ring hydroxyl compound with sulfuryl fluoride (SOF) in the presence of a tertiary amine except pyridine and methylpyridine. The sulfuryl fluoride, used as the reactant in the production process according to the present invention, is widely adapted as a fumigant and is easily available on a large scale. Further, the target compound can be obtained rapidly with a high yield under moderate reaction conditions in the production process according to the present invention. In this way, all of the prior art problems can be solved in the production process according to the present invention. The production process according to the present invention is thus particularly useful for industrial production of the fluorosulfuric acid aromatic-ring ester.

Process for producing fluorosulfuric acid aromatic-ring esters

Fluorosulfuric acid esters can be produced by reacting alcohols with sulfuryl fluoride (SOF) in the presence of a base and water. As a substrate thereof, optically active secondary alcohols are preferable, and optically active &#x3b1;-hydroxyesters and optically active 4-hydroxyprolines are particularly preferable. By performing the reaction in a two-phase system in the presence of a reaction solvent immiscible with water, a desired reaction proceeds particularly well. The present invention is a production method solving all the problems involved in conventional techniques while being industrially practicable.

Method for producing fluorosulfuric acid ester

An &#x3b1;-trifluoromethyl-&#x3b1;,&#x3b2;-unsaturated ester can be produced by reacting an &#x3b1;-trifluoromethyl-&#x3b1;-hydroxy ester with sulfuryl fluoride (SOF) in the presence of an organic base. It is preferable that the raw substrate has a hydrogen atom as one &#x3b2;-position substituent group and either an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aromatic ring group or a substituted aromatic ring group as the other &#x3b2;-position substituent group. It is more preferable that an ester moiety of the raw substrate is an alkyl ester. This raw substrate is readily available. Further, the desired reaction can proceed favorably with the use of this raw substrate. It is also preferable to use either 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the organic base. The desired reaction can proceed more favorably with the use of this organic base.

Process for producing &#x3b1;-trifluoromethyl-&#x3b1;,&#x3b2;-unsaturated ester

&#x3b1;-Trifluoromethyl-&#x3b2;-substituted-&#x3b2;-amino acids can be produced by allowing &#x3b1;-trifluoromethyl-&#x3b2;-substituted-&#x3b1;,&#x3b2;-unsaturated esters to react with hydroxylamine to convert &#x3b1;-trifluoromethyl-&#x3b2;-substituted-&#x3b1;,&#x3b2;-unsaturated esters into dehydrogenated closed-ring body of &#x3b1;-trifluoromethyl-&#x3b2;-substituted-&#x3b2;-amino acid, and by hydrogenolyzing the dehydrogenated closed-ring body. According to this production process, novel &#x3b1;-trifluoromethyl-&#x3b2;-substituted-&#x3b2;-amino acids which are free amino acids whose functional groups are not protected can be produced, in which &#x3b2;-position substituent is not limited to aromatic ring group or substituted aromatic ring group while the relative stereochemistry of &#x3b1;-position and &#x3b2;-position can be also controlled.

Process for production of &#x3b1;-trifluoromethyl-&#x3b2;-substituted-&#x3b2;-amino acid

A one pot method of preparing cyclic carbonyl compounds comprising an active pendant pentafluorophenyl ester group is disclosed. The cyclic carbonyl compounds can be polymerized by ring opening methods to form ROP polymers comprising repeat units comprising a side chain pentafluorophenyl ester group. Using a suitable nucleophile, the pendant pentafluorophenyl ester group can be selectively transformed into a variety of other functional groups before or after the ring opening polymerization.

Polymers bearing pendant pentafluorophenyl ester groups, and methods of synthesis and functionalization thereof

Disclosed is a process for producing a protected optically active fluoroamine, which comprises the step of reacting an imine-protected optically active hydroxyamine, an oxazolidine-protected optically active hydroxyamine, or a mixture of the imine-protected optically active hydroxyamine and the oxazolidine-protected optically active hydroxyamine, with sulfuryl fluoride (SOF) in the presence of a tertiary amine having a carbon number of 7 to 18 (produced by substituting all of three hydrogen atoms in ammonia by alkyl groups). The desired optically active fluoroamine can be produced by hydrolyzing the protected optically active fluoroamine under acidic conditions.

Process for production of optically active fluoroamine

A one pot method of preparing cyclic carbonyl compounds comprising an active pendant pentafluorophenyl carbonate group is disclosed. The cyclic carbonyl compounds can be polymerized by ring opening methods to form ROP polymers comprising repeat units comprising a side chain pentafluorophenyl carbonate group. Using a suitable nucleophile, the pendant pentafluorophenyl carbonate group can be selectively transformed into a variety of other functional groups before or after the ring opening polymerization.

Cyclic carbonyl compounds with pendant carbonate groups, preparations thereof, and polymers therefrom

Halogenated &#x3b1;-fluoroethers (or bis-derivatives thereof) can be produced by reacting a halogenated hemiacetal (or bis-derivative thereof) with sulfuryl fluoride (SOF) in the presence of an organic base. The reaction is conducted preferably in the presence of 'a salt or complex of an organic base with hydrogen fluoride', whereby the objective dehydroxyfluorination can proceed extremely favorably. It is still preferable to use as the starting substrate a halogenated hemiacetal prepared from fluoral or 3,3,3-trifluoropyruvic acid ester. Thus, industrially important halogenated &#x3b1;-fluoroethers can be industrially produced with high selectivity and in high yield.

Process for production of halogenated alpha-fluoroethers

There is provided a process for producing an &#x3b1;-substituted ester by reaction of a fluorosulfuric acid ester of &#x3b1;-hydroxyester with a Grignard reagent in the presence of a zinc catalyst. It is newly found that the reaction for production of &#x3b1;-substituted esters, in which the raw reaction substrate is limited to expensive trifluoromethanesulfonic acid esters, can proceed favorably with the use of fluorosulfuric acid esters suitable for mass-production uses. By the use of the fluorosulfuric acid ester high in optical purity, it is possible to obtain the &#x3b1;-substituted ester with high optical purity upon inversion of the asymmetric carbon configuration. The process of the present invention can solve all of the prior art problems and can be applied for industrial uses.

Process for producing &#x3b1;-substituted ester

By reacting a &#x3b2;-hydroxy-&#x3b1;-amino acid with sulfuryl fluoride (SOF) in the presence of an organic base, it is possible to produce an &#x3b1;-fluoro-&#x3b2;-amino acid of the formula [2]. By using a C8-12 tertiary amine having two or more alkyl groups of C3 or higher, and especially diisopropylethylamine, as the organic base, by-production of quantery ammonium salts is effectively suppressed. By applying the production process of the present invention, it is possible to very easily produce (2R)-3-(dibenzylamino)-2-fluoropropionic acid methyl ester, which is extremely important as a pharmaceutical intermediate, with high positional selectivity even on an industrial scale.

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Kawagoe, Japan

Manabu Yasumoto