Yamaguchi-shi, Japan
Yamaguchi-shi, Japan

Time filter

Source Type

Kino T.,Sagami Chemical Research Center | Kino T.,Tokai University | Nagase Y.,Tokai University | Ohtsuka Y.,Sagami Chemical Research Center | And 4 more authors.
Journal of Fluorine Chemistry | Year: 2010

Trifluoromethylation of aromatic and hetero-aromatic compounds by CF3I in the presence of Fe(II) compound, H2O2 and dimethylsulfoxide was investigated. Various trifluoromethylated benzene derivatives, six-membered nitrogen-containing aromatic compounds and five-membered hetero-aromatic compounds were obtained under mild conditions. General orientation of electrophilic substitution of aromatic compounds was observed similarly as reported in other radical trifluoromethylation previously. © 2009 Elsevier B.V. All rights reserved.


Boschet F.,National Graduate School of Chemistry, Montpellier | Kostov G.,National Graduate School of Chemistry, Montpellier | Kostov G.,University Professor Dr. Assen Zlatarov Burgas | Ameduri B.,National Graduate School of Chemistry, Montpellier | And 2 more authors.
Journal of Polymer Science, Part A: Polymer Chemistry | Year: 2010

The radical copolymerlzation of two different meth-acrylate monomers, 2,2,2-trifluoroethyl methacrylate (TFEMA) and tert-butyl α- trifluoromethacrylate (TBTFMA) In solution was investigated. The resulting statistic poly(TFEMA-co-TBTFMA) copolymers were characterized by NMR spectroscopy to assess their compositions. The kinetics of copolymerization enabled one to determine the reactivity ratios of both comonomers according to the methods of Fineman-Ross, Kelen-Tüdos, and extended Kelen-Tüdos. Excellent correlations were found between these methods leading to the following reactivity ratios: rTFEMA = 4.87 ± 1.50 and r TBTFMA = 0.10 ± 0.02 at 74 °C. These values indicated that the structure of the copolymers was composed of poly(TFEMA) micro-blocks separated by one TBTFMA unit. Both yields and molecular weights (ranging between 1,000 and 12,000 g/mol) increased with the TFEMA content. The thermal stability of these (co)polymers showed that the decomposition temperature at 10% weight loss increased both with TFEMA content and increasing molecular weights of the poly(TFEMA-co-TBTFMA) copolymers. © 2010 Wiley Periodicals, Inc.


Shibata N.,Nagoya Institute of Technology | Nishimine T.,Nagoya Institute of Technology | Tokunaga E.,Nagoya Institute of Technology | Kawada K.,TOSOH F Technology Inc. | And 7 more authors.
Organic and Biomolecular Chemistry | Year: 2014

Inorganic as well as organic base catalysis was found to be effective for diastereoselective Mannich additions of malonic acid derivatives to (S S)-N-(tert-butanesulfinyl)-3,3,3-trifluoroacetaldimine. In the presence of catalytic amounts of inorganic bases, n-BuLi or DMAP, the reaction gives the corresponding (R,SS)-β-aminomalonates in good yield and with diastereoselectivity up to 9/1 dr. In contrast, phosphazene bases favour the formation of the (S,SS)-diastereomer with selectivities as high as 99/1. Simple choosing of an appropriate base catalyst for the Mannich addition reaction allowed us to obtain enantiomerically pure (R)- or (S)-configured 3-amino-4,4,4-trifluorobutanoic acids after hydrolysis and decarboxylation of the corresponding β-aminomalonates. © 2014 The Royal Society of Chemistry.


Milcent T.,University Paris - Sud | Hao J.,University Paris - Sud | Kawada K.,TOSOH F Technology Inc. | Soloshonok V.A.,University of the Basque Country | And 3 more authors.
European Journal of Organic Chemistry | Year: 2014

1,4-Diazabicyclo[2.2.2]octane-catalyzed asymmetric aza-Baylis-Hillman (ABH) reaction of (R)-N-tert-butanesulfinyl-(3,3,3)-trifluoroacetaldimine with various Michael acceptors proceeds with exceptionally high rates and stereochemical outcome. This ABH approach provides convenient and practical access to previously unknown enantiomerically pure α-methylene β-CF3 β-amino esters/acids, forthright useable for peptide synthesis. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


Shibata N.,Nagoya Institute of Technology | Nishimine T.,Nagoya Institute of Technology | Tokunaga E.,Nagoya Institute of Technology | Kawada K.,TOSOH F Technology Inc. | And 6 more authors.
Chemical Communications | Year: 2012

Organic base-catalyzed reaction of (S)-N-tert-butanesulfinyl (3,3,3)-trifluoroacetaldimine with dialkyl malonates was found to be effective for synthesis of both (S,S S) and (R,S S) β-aminomalonates in high yield with good to excellent diastereoselectivity (76-98% de). The products of this Mannich reaction provide direct access to β-trifluoromethyl-β-alanine of either (R) or (S) absolute configuration. © 2012 The Royal Society of Chemistry.


Shevchuk M.V.,Ukrainian Academy of Sciences | Kukhar V.P.,Ukrainian Academy of Sciences | Roschenthaler G.-V.,Jacobs University Bremen | Bassil B.S.,Jacobs University Bremen | And 6 more authors.
RSC Advances | Year: 2013

Enantiomerically pure N,O-protected β-trifluoromethyl isoserine derivatives of (2S,3S)- and (2R,3S)-absolute configurations have been easily prepared by diastereoselective addition of the enolates, derived from O-protected α-hydroxyacetates, to (S)-N-tert-butanesulfinyl (3,3,3)-trifluoroacetaldimine with high combined yield and good syn/anti stereoselectivity. To explain the unusual stereochemical outcome in these reactions a mechanistic rationale involving the addition of Z-enolates to (S)-imines via open transition states was proposed on the basis of the experimental data. Elaboration of these products via chemoselective manipulation of the protecting groups has been demonstrated. © 2013 The Royal Society of Chemistry.


Kagawa T.,TOSOH F Technology Inc. | Shigehiro D.,TOSOH F Technology Inc. | Kawada K.,TOSOH F Technology Inc.
Journal of Fluorine Chemistry | Year: 2015

Highly regioselective substitution reaction of 2,4-bis(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)pyrimidine (TFEFP) with aniline derivatives smoothly proceeded firstly at the 2-postion. For the subsequent nucleophilic substitution at the 4-position with alkoxides, trifluoroethoxy group at the 4-position serves as a practically efficient leaving group. © 2015 Elsevier B.V.


Ohtsuka Y.,Sagami Chemical Research Institute | Uraguchi D.,Sagami Chemical Research Institute | Uraguchi D.,Nagoya University | Yamamoto K.,Sagami Chemical Research Institute | And 2 more authors.
Tetrahedron | Year: 2012

Direct trifluoromethylation of 1,3-dicarbonyl compounds with CF 3I in the presence of a Fenton reagent in dimethylsulfoxide was investigated. 1,3-Diketones, 3-oxocarboxylates and 3-oxocarboxamides were readily trifluoromethylated at the methylene carbon between two oxo groups. Cycloaddition of hydrazine derivatives to the obtained 2-(trifluoromethyl)-1,3- dicarbonyl compounds provided fluorinated pyrazoles. 4-(Trifluoromethyl)pyrazole derivatives were formed from 2-(trifluoromethyl)-1,3-diketones, while 3-oxo-2-(trifluoromethyl)carboxylates or carboxamides gave 5-fluoropyrazole-4- carboxylates or carboxamides, respectively, via 3-hydrazono-2-(trifluoromethyl) carboxylates or carboxamides as an intermediate. © 2012 Elsevier Ltd. All rights reserved.


Mimura H.,TOSOH F Technology Inc. | Kawada K.,TOSOH F Technology Inc. | Yamashita T.,Josai University | Sakamoto T.,Josai University | Kikugawa Y.,Josai University
Journal of Fluorine Chemistry | Year: 2010

The synthesis of various trifluoromethylated amino compounds was studied using trifluoroacetaldehyde, an industrial bulk material, as a starting compound. One general application of trifluoroacetaldehyde is the preparation of trifluoroethylamino derivatives via reductive amination reaction. This synthesis includes the formation of the corresponding N,O-acetal intermediates followed by their reduction using NaBH4 or 2-picoline borane complex, affording the target trifluoroethylamino compounds in moderate to good yields (47-87%). Another general application of trifluoroacetaldehyde is the synthesis of chiral α-substituted trifluoroethylamino compounds. In this synthesis, trifluoroacetaldehyde was first converted into the chiral trifluoromethyl tert-butyl sulfinimine, which was subjected to 1,2-nucleophilic addition reactions across its C{double bond, long}N double bond. The addition of phenyllithium afforded α-(phenyl)trifluoroethylamino derivative in 83% yield and with 96% de. Allylation and Reformatsky reactions produced the corresponding α-substituted trifluoroethylamino derivatives in 82 and 58% yields and with 90 and 91% de, respectively. © 2010 Elsevier B.V. All rights reserved.


Kagawa T.,TOSOH F Technology Inc. | Fujita K.,TOSOH F Technology Inc. | Kawada K.,TOSOH F Technology Inc.
Journal of Fluorine Chemistry | Year: 2013

Optically active trifluoromethyl 2-ethoxy-1-phenylethyl-1-imine can react with various carbanions diastereoselectively, and in hetero Diels-Alder addition and in Mannich reaction, it can be derived to the corresponding products with high optical purity. © 2013 Elsevier B.V. All rights reserved.

Loading Tosoh F Technology Inc. collaborators
Loading Tosoh F Technology Inc. collaborators