著者

熊懐 稜丸

出版者

公益社団法人 日本薬学会

雑誌

YAKUGAKU ZASSHI (ISSN:00316903)

巻号頁・発行日

vol.105, no.8, pp.713-723, 1985-08-25 (Released:2008-05-30)

参考文献数

26

被引用文献数

4 3

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New reactions developed for the synthesis of medicinally useful trifluoromethyl compounds are discussed. First, the trifluoromethylation of aromatic halogen compounds with CF3I and Cu powder is presented. This method is applicable to a wide range of aromatic halides, while aliphatic halides cannot be converted to trifluoromethyl compounds. This difficulty was removed by two-step procedure. CF3I and Cu powder were shaken in a stainless steel tube, and the excess of Cu powder was removed by filtration. The solution of [CF3-Cu] was treated with halogen compounds to give trifluoromethyl compounds. Next, the Friedel-Crafts reaction of trifluoropropene was presented, which gave trifluoropropyl compounds. It was very difficult to obtain these products by other routes. Attempted application of the trifluoropropyl compounds are included. Finally, some reactions useful for the synthesis of special types of trifluoromethyl compounds were summarized, where photoreaction, 1, 3-dipolar reaction, and ene reaction of trifluoromethyl compounds are included.

著者

小林 義郎 熊懐 稜丸 大沢 昭緒 山田 猛

出版者

The Pharmaceutical Society of Japan

雑誌

Chemical and Pharmaceutical Bulletin (ISSN:00092363)

巻号頁・発行日

vol.20, no.8, pp.1839, 1972-08-25 (Released:2008-03-31)

被引用文献数

15 20

著者

熊懐 稜丸

出版者

公益社団法人 日本薬学会

雑誌

YAKUGAKU ZASSHI (ISSN:00316903)

巻号頁・発行日

vol.126, no.11, pp.1059-1085, 2006-11-01 (Released:2006-11-01)

参考文献数

66

被引用文献数

2 2

---

This review describes new syntheses of organofluorine compounds taking advantage of the special properties of fluorine compounds as synthones. The main reactions presented are as follows: 1) Trifluoromethylation of aryl or alkyl halides. Application of this reaction for the synthesis of fluorine analogues of nucleic acid bases is discussed. 2) Some syntheses of trifluoromethyl compounds using the Diels-Alder or the 1,3-dipolar reaction, trifluoromethylated carbene, and photoreaction. 3) The Friedel-Crafts reaction of 3,3,3-trifluoropropene, where linear alkylation occurs due to electronic effect of the trifluoromethyl group in good contrast with the Friedel-Crafts reaction of propene. 4) The ene reaction of trifluoromethylated carbonyl compounds, which work as good enophiles. Application of this reaction to the synthesis of trifluoro analogues of terpenes is discussed. 5) The ene reaction of trifluoromethylated imines. 6) Reaction of halothane, which has a highly acidic hydrogen and two halogens adjacent to the trifluoromethyl group and shows interesting reactivities with various bases and metals to give products with unexpected structures. 7) Reaction of 2-bromo-2,2-difluoroacetate with Cu, where the cross-coupling reaction, Michael-type reaction, and radical reaction for different types of difluoroacetates are presented. 8) Reaction of 2-bromo-2,2-difluoroacetate in the presence of Rh catalyst. This reaction provided a new methodology for the introduction of fluoroalkyl substituents to the α-position of α,β-unsaturated ketones. The Rh catalyst solved some difficulties in the introduction of difluoroacetate to carbonyl compounds (Reformatsky reaction). Application of this reaction to imines provided easy access to β,β-difluoro-β-lactams.

著者

小林 義郎 熊懐 稜丸 大沢 昭緒 村上 慎一 中野 隆治

出版者

The Pharmaceutical Society of Japan

雑誌

Chemical and Pharmaceutical Bulletin (ISSN:00092363)

巻号頁・発行日

vol.26, no.4, pp.1247-1249, 1978-04-25 (Released:2008-03-31)

被引用文献数

31 45

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Photochemical trifluoromethylation of pyridine gave a mixture of three (trifluoromethyl) pyridines. Pyrrole and N-methylpyrrole were trifluoromethylated in α-position. Benzene gave very low yield of benzotrifluoride.

著者

小林 義郎 熊懐 稜丸 佐藤 進 原 伸祀 近見 永一

出版者

The Pharmaceutical Society of Japan

雑誌

Chemical and Pharmaceutical Bulletin (ISSN:00092363)

巻号頁・発行日

vol.18, no.11, pp.2334-2339, 1970-11-25 (Released:2008-03-31)

被引用文献数

39 65

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Trifluoromethyl iodide reacts with aryl halide in the presence of copper powder to give aryltrifluoromethane derivatives in a fairly good yield. This newly observed reaction is applicable to heterocyclic halides as well as benzene derivatives. Activities of halides are in the following order of readiness : iodide>bromide>chloride. Effects of solvents and natures of copper were examined.

著者

小林 義郎 熊懐 稜丸 榛沢 雄二

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.37, no.3, pp.183-196, 1979-03-01 (Released:2009-11-13)

参考文献数

50

被引用文献数

2 2

---

Trifluoromethyl group shows a stabilizing effect on the compounds which would be unstable if they had no trifluoromethyl group. This review is concerned with two faces of the chemistry of trifluoromethylated valence bond isomers of aromatic compounds : Diels-Alder and 1, 3-dipolar reactions planned for the conversion of hexakis (trifluoromethyl) benzvalene to the corresponding tetrahedrane and the synthesis of new valence bond isomers of heteroaromatic compounds. In the former, the tetrahedrane itself could not yet be isolated, but the formation of tetrakis (trifluoromethyl) cyclobutadiene and new valence isomers of oxepin was confirmed. In the latter, Dewar thiopene, Dewar pyrrole, Dewar pyridine, and diphosphabenzvalene with trifluoromethyl groups were synthesized and their reactions were discussed. The effect of trifluoromethyl group is not limited to the strained compound. Thus, tetrakis (trifluoromethyl) -1, 4-diphosphabenzene, the first example of diphosphabenzenes, was synthesized.

著者

熊懐 稜丸

出版者

九州大学

巻号頁・発行日

1967

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博士論文

著者

小林 義郎 熊懐 稜丸 田口 武夫

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.38, no.11, pp.1119-1129, 1980-11-01 (Released:2010-01-22)

参考文献数

36

被引用文献数

3 4

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First, characteristics of a carbon-fluorine bond from the biological point of view are summarized with some examples : mimic effect, protective fluorination, irreversible conjugation with enzyme, increased lipophilicity and so on are presented. Secondly, some approaches to biologically active compounds utilizing the above characteristics are shown by the examples of trifluoromethylated nucleoside derivatives and fluorinated vitamin D3 analogues.