HETEROCYCLES

■ Abnormal Displacement Reaction of 2-(Chloromethyl)furan with Cyanide Ion

Fumio Yamamoto, Hiroyuki Morita, and Shigeru Oae*

*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan

Abstract

Among similar chloromethyl aromatics, only 2-(chloromethyl)furan (I) gives abnormal displacement product, i.e., 5-methyl-2-cyanofuran (V) in the reaction with cyanide ion in aqueous media. The remarkably high rate of solvolysis of (I), the negligible or small kinetic isotope effect due both to α- or 5-deuterium substitution and other pertinent data suggest the mechanism involving the rate-determining proton transfer in the intermediate, i.e., 5-methylene-2,5-dihydro-2-furonitrile(IV).

■ Antimicrobial Agents from Higher Plants. Synthesis in the Canthin-6-one (6H-Indolo[3,2,1-de][1,5]naphthyridin-6-one) Series

Lester A. Mitscher,* Mohammed Shipchandler, H. D. Hollis Showalter, and Mohinder S. Bathala

*Division of Natural Products Chemistry, The Ohio State University, Columbus, Ohio 43210, U.S.A.

Abstract

A practical synthetic route has been developed by which canthin-6-one and a variety of naturally occurring and synthetic analogs have been prepared for evaluation as antimicrobial agents. Less successful and unsuccessful routes are also briefly described.

■ Studies on Medium-membered Heterocyclic Compounds. I. The Formation of 2,5-Diphenyl-3,4-diaza-2,4-norcaradiene from 4,6-Dihydro-3,7-diphenyl-1,2-diazepine

Otohiko Tsuge* and Kichinosuke Kamata

*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan

Abstract

Treatment of 4,6-dihydro-3,7-diphenyl-1,2-diazepine (2) with NBS or bromine afforded 4-methyl-3,6-diphenylpyridazine (3) which is formed from 2,5-diphenyl-3,4-diaza-2,4-norcaradiene (1) and hydrogen bromide. The dihydrodiazepine 2, reacted with chlorine or sulfuryl chloride, giving 1 and 4,5,5,6-tetrachloro- 4,6-dihydro-3,7-diphenyl-1,2-diazepine (4).

■ Reactions of Aromatic N-Oxides with O-Benzoyl Aromatic Aldehyde Cyanohydrins in Acetic Anhydride

Toshiyasu Endo, Seitaro Saeki, and Masatomo Hamana*

*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan

Abstract

Quinoline N-oxide (I) readily reacts in hot acetic anhydride with some O-benzoyl aromatic aldehyde cyanohydrins (Va-d) to produce O-benzoylcyanohydrins (VIa-d) of 2-quinolyl aryl ketones which are easily convertible to the corresponding ketones (VIIa-d) by alkaline hydrolysis. Similar reactions occur also with N-oxides of isoquinoline, pyridine and phenanthridine (II, III and IV). The derivatives of benzaldehyde and p-chloro- benzaldehyde resist the reaction.

■ Selective Reduction of 12-Oxa[4.4.3]propella-2,4,7,9-Tetraene Catalyzed by an Arenechromium Tricarbonyl

Chaim Amith, Michael Cais,* Dan Fraenkel, and David Ginsburg*

*Department of Chemistry, Israel Institute of Technology, Haifa, Israel

Abstract

Hydrogenation of the title compound afforded chiefly 1,4-addition of hydrogen from the “top” face of each cyclohexadiene ring.

■ Total Synthesis of Certain Isoquinoline and Indole Alkaloids by Theromolysis

Tetsuji Kametani* and Keiichiro Fukumoto

*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan

Abstract

The total syntheses of some isoquinoline and indole alkaloids were achieved by inter-and intramolecular cycloaddition of o-quinodimethanes by thermolysis.

■ Desulufurisation of Epidithia-2,5-piperazinedione Derivative

Tadao Sato and Tohru Hino*

*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan

■ Reaction of 3-Substituted 2-Nitrosoimino-2,3-dihydrobenzothiazoles with Grignard Reagents and Organolithiums

Motoyuki Hisaoka, Kin-ya Akiba, and Naoki Inamoto*

*Department of Chemistry, Scool of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033

■ Syntheses and Reactions of Benzothiazolines

Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, and Yutaka Imai

*Department of Pharmacognosy, Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan

■ Syntheses of Phosphorus Containing Heterocycles by the Ozonolyses of Alkenylphosphoramidates (2). Syntheses of the Suggested Active Metabolite of Isophosphamide and Some Related Compounds

Akira Takamizawa,* Saichi Matsumoto, Tsuyoshi Iwata, and Itsuo Makino

*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan

■ Syntheses and Reactions of (Trifluoromethyl)benzofurans

Yoshiro Kobayashi,* Itsumaro Kumadaki, Yuji Hanazawa, and Noriaki Fujii

*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan

■ Photochemical and Thermal Decompositions of 5-Substituted 4,6-Dihydro-3,7-diaryl-1,2,5-triazepines

Otohiko Tsuge* and Seiichi Yogi

*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan

■ Synthesis of N-Heteropolycyclic Aromatics from 3-Aryl-1-azirines by Thermal Ring Expansion

Hiroshi Taguchi, Matsuki Yamano, Kazuaki Isomura, and Hiroshi Taniguchi*

*Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, 1-1 Sensuicho, Tobata, Kitakyushu, 804-8550, Japan

■ Intramolecular Reactions of Enaminonitriles. A Novel Synthesis of New β-Aminopyrroles and Related Heterocycles

Tadakazu Murata,* Tohru Sugawara, and Kiyoshi Ukawa

*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan

■ Syntheses of Δ²-Pyrrolin-4,5-diones and Their Reaction with Butadiene

Takehiro Sano,* Yoshie Horiguchi, and Yoshisuke Tsuda

*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan

■ Photochemical Addition of Acrylonitrile to Imidazoles and Indoles

Teruo Matsuura, Yoshikatsu Ito, Kazuyuki Yamasaki, and Isao Saito*

*Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan

■ Synthesis of Furo[3,4-d]imidazoles

Yasuhiko Aoki,* Hiroyuki Suzuki, and Hisao Akiyama

*Research Department, Sumitomo Chemical Co. Ltd., 4-2-1, Takatsukasa, Takarazuka, Hyogo, Japan

■ The Reaction of 3,5-Dimethylisoxazole with Electrophiles

Choji Kashima,* Yoshihiko Tsuda, Yasuhiro Yamamoto, and Yoshimori Omote

*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan

■ Photochemical Rearrangements of Isothiazoles

Mamoru Ohashi,* Akira Iio, Atsushi Ezaki, and Teijiro Yonezawa

*Department of Maerial Science, The University of Electro-Communications, 1-5-1, Chofugaoka, Chofu, Tokyo 182-0021, Japan

■ New HeterocyclieSyntheses by Metal Isonitrile Complexes — Preparation of 2-Unsubstituted Oxazoline, Oxazine, Imidazoline and Imidazolone

Yoshihiko Ito,* Yoshinori Inubushi, and Takeo Saegusa

*Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan

■ On the Effect of the Steric Environment of the Starting Phenylhydrazone to the Fischer Indolization

Hisashi Ishii,* Takao Hagiwara, Tsutomu Ishikawa, Nisaburo Ikeda, and Yasuoki Murakami

*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan

■ Reaction of N-Ylides with Diketene

Tetsuzo Kato,* Takuo Chiba, Shinichi Masuda, and Shigeru Tanaka

*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan

■ Syntheses of Heterocyclic Compounds by the Use of Ylides Stabilized by Diketovinyl Groups

Yasumitsu Tamura,* Yoshio Sumida, Yasuyoshi Miki, Tomohisa Miyamoto, Hiroshi Taniguchi, Masayoshi Tsunekawa, Shin-ichi Haruki, and Masazumi Ikeda

*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan

■ Synthesis of Carbazole Alkaloids by Cyclization of β-Ketosulfoxides

Yuji Oikawa,* Shigenori Unno, Takao Kurosawa, and Osamu Yonemitsu

*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan

■ Synteheses of Heterocyclic Systems by Photo-reactions of Phthalimides: Photocyclization of N-Alkylphthalimides

Yuichi Kanaoka,* Koichi Koyama, Yoshihiro Migita, Yasuhiko Sato, Hideo Nakai, Hiroshi Ogiwara, and Tomishige Mizoguchi

*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan

■ Molecular Design by Cycloaddition Reactions with Oxabenzonorbornadiene

Tadashi Sasaki,* Ken Kanematsu, Masayuki Uchide, Kenji Hayakawa, and Kinji Iizuka

*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan

■ The Reactions of O-Alkylated Imides

Katsuhide Matoba,* Suguki Imoto, and Takao Yamazaki

*Faculty of Pharmaceutical Sciences, ToyamaUniversity, Gofuku 3190, Toyama 930-8555, Japan

■ A New Method for the Synthesis of Substituted Enaminoketones

Tsunetoshi Honma* and Yukio Tada

*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan

■ Thermal and Photochemical Reactions of Bicyclo[3.2.0]heptadienes Containing C=N-O Group

Osamu Seshimoto, Takahiro Tezuka, and Toshio Mukai*

*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan

■ The Friedel-Crafts Reaction of 1-Methyl-2(1H)-pyridone and Its Derivatives

Hiroshi Tomisawa,* Reiko Fujita, Hiroshi Hongo, Hideki Kato, and Masao Watanabe

*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan