HETEROCYCLES

■ 2-Hydroxynethyl-3,4,5,6,7,8-hexahydro-2H-1-benzopyran-5-ones. An Unusual Case of Methylene Transfer Reaction from Sulfur Ylides

Pierfrancesco Bravo,* Calimero Ticozzi, and Domenico Maggi

*CNR, Centro Studio Sostanze Organiche Naturali, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy

Abstract

Reaction of dimethylsulfonium and -sulfoxonium methylides with 2-(3’-oxaalkyl)-1,3-cyclohexanediones (VII) or with 2-hydroxy-3,4,5,6,7,8-hexahydro-2H-1-benzopyran-5-ones (VIII) gives the 2-hydroxymethyl-3,4,5,6,7,8-hexahydro-2H-1-benzopyran-5-ones (XII).

■ Dehydrogenative Cyclization of 6-Amino-5-benzylideneaminopyrimidines to Purines with Diethyl Azodicarboxylate

Fumio Yoneda,* Masatsugu Higuchi, Keitaro Senga, Kayoko Shimizu, and Sadao Nishigaki

*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan

Abstract

The treatment of 6-amino-5-benzylideneaminopyrimidines with diethyl azodicarboxylate (DAD) gave the corresponding purines in essentially quantitative yields.

■ Reaction of 5-Nitrouracil Derivatives with Hydrazine and Potassium Cyanide

Shigeo Senda,* Kosaku Hirota, Tetsuji Asao, and Yoshihiro Yamada

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

Abstract

Treatment of 5-nitro-1,3,6-trimethyluracil (I) with potassium cyanide or hydrazines gave 6-cyano-5- nitro-1,3,6-trimethyl-5,6-dihydrouracil (III) or 5-methyl-4-nitropyrazol-3-ones (IV), respectively. A treatment of 6-bromomethyl-1,3-dimethyl-5-nitrouracil (II) with potassium cyanide gave 6-cyano-1,3-dimethyl-5-nitrocyclothymine (V). Hydrazinolysis of II gave 1,3-dimethyluracil-6-carboxaldehyde hydrazones (VII).

■ Reactions of1,2,3,3a,4,5-Hexahydro-N-(3,4-dimethoxyphenylacetyl)indol-6-one with Acids and Phosphoryl Chloride: A Synthesis of the Erythrinan-type Compound

Hideo Iida,* Sakae Aoyagi, Kensuke Kohno, Norio Sasaki, and Chihiro Kibayashi

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

Abstract

Some reactions of 1,2,3,3a,4,5-hexahydro-N-(3,4-dimethoxyphenylacetyl)indol-6-one (4), which was obtained from the iminoenol ether (5) and the acid chloride, with acids and electrophiles were investigated, and intramolecular cyclization to the erythrinan derivative (10) was achieved on treatment with phosphoryl chloride in acetonitrile.

■ Studies on the Synthesis of Bisindole Alkaloids. VII. Stereochemistry and Alternative Total Synthesis of Leurosine

James P. Kutney* and Brian R. Worth

*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5 , Canada

Abstract

Polonovski-type coupling between 3β,4β-epoxy-3,4-dihydrocatharanthine-N-oxide and vindoline provides an alternative route to the anti-tumor agent leurosine. The previously questioned stereochemistry of the oxirane function of this bisindole alkaloid is determined unambiguously.

■ 1,4-Substituted β-Carbolines from Carex brevicollis DC

Georgii Lazurjevski* and Ida Terentjeva

*Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishinev, U.S.S.R.

Abstract

The paper describes new natural heterocyclic compounds, alkaloids of Carex brevicollis DC., which are 1,4-substituted β-carbolines. There are discussed the results of studies of thier physical properties and chemical transformations which are used to determine the structure of the alkaloids and to put forward suggestions about their biogenesis.

■ The Systematic Classification of Bisbenzylisoquinolines

Maurice Shamma* and Jerome L. Moniot

*Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, U.S.A.

Abstract

Bisbenzylisoquinolines are classified into 26 types. Each benzylisoquinoline half is numbered as in expression 4 below, and is described in terms of its oxygenation pattern. The two sets of numbers denoting the oxygenated sites are separated by a hyphen. The more highly oxygenated benzylisoquinoline half constitutes the left hand side of the dimer, and is listed first. In the case of head to tail coupling, the more highly oxygenated benzylisoquinoline is placed on top, and is listed first. An asterisk (*) or other symbol († ‡) on the upper right of a number indicates the terminal of a diaryl ether. Numbers between parentheses, appearing directly after the listing of oxygenated sites, describe the positions of a biphenyl linkage. The stereochemistry of some of these alkaloids is also discussed.

■ Reactions of Benzofuran, Benzothiophene and Indoles with Photoexcited Dibromomaleic Anhydrides

Taku Matsuo,* Satoru Mihara, and Ikuhiko Ueda

*Faculty of Engineering, Kyushu University, 6-19-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan

■ Photochemistry of 2-Allylindoles

Kuniyuki Tomita,* Teiki Iwaoka, and Atsusuke Terada

*Biomedicinal Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan

■ Peroxidic Intermediates in Indole-Singlet Oxygen Reactions

Isao Saito,* Yoshiyuki Takahashi, Mitsuru Imuta, Seichi Matsugo, and Teruo Matsuura

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

■ Synthesis of Heterocyclic Systems by Photocyclization of Anilides

Yuichi Kanaoka,* Yasumaru Hatanaka, Kunio San-nohe, and Sadao Nakao

*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan

■ Photosensitized Oxygenation of Tryptophan and Melatonin Related Compounds

Masako Nakagawa,* Haruo Okajima, Jun Chiba, Hideyuki Watanabe, and Tohru Hino

*Graduate School of Pharmaceutical Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan

■ Synthesis Using the Reaction of the Singlet Oxygen with 1,2-Dihydropyridines

Mitsutaka Natsume,* Moritaka Wada, Yasuo Sekine, Masashi Ogawa, and Hiroe Soyagimi

*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan

■ Photochemistry of Pyridazine Betaines

Yoshifumi Maki,* Mikio Suzuki, Masao Kawamura, Hisanori Okamoto, and Masayuki Kuzuya

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

■ Photochemistry of 6-Azido-1,3-dimethyluracil Derivatives

Shigeo Senda,* Kosaku Hirota, Tetsuji Asao, and Kazuo Maruhashi

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

■ Reactions of Diphosphabarrelene

Yoshiro Kobayashi,* Itsumaro Kumadaki, Akio Ohsawa, Yuji Hanzawa, Hiroshi Hamana, and Shomi Fujino

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

■ Synthesis of Tetrathiofulvalenes

Yoshio Ueno* and Makoto Okawara

*Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501, Japan

■ Transannular Reactions on 6,11-Dihydrodibenzo[b,e]thiepins

Kazuhiro Onogi,* Masahiko Nagakura, and Mikio Hori

*Tokyo Research Laboratories, Kowa Co., Ltd., 2-17-43, Noguchi-cho, Higashimurayama 189, Japan

■ New Synthetic Entry into the Thiepin System benzo[d]- and Dibenzo[b,d]thiepins

Kazuhiro Nakasuji,* Koichi Kawamura, Toshio Ishihara, and Ichiro Murata

*Department of Chemistry, Faculty of Science, Osaka University, Toyonaka, Osaka 560-8531, Japan

■ Synthesis and Reactions of Thiaazulenium Salts

Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, and Mitsuhito Okitsu

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

■ Syntheses and Reactions of Thioxanthenesulfilimines

Kunihiro Sumoto,* Yasumitsu Tamura, Masazumi Ikeda, Masahiro Kise, and Masao Murase

*Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan

■ Syntheses and Rectivities of Sulfur-containing Heterocycles

Jun-ichi Ohishi,* Yasuo Shimizu, Tsuneyuki Murota, and Shiro Ikegami

*National Institute of radiological Sciences, 9-1, Anagawa-4-Chome, Inage-ku, Chiba 263-0024, Japan

■ The Structure and Reaction of 1:1 Adduct of Iminothiazolines and Nitriles Bond Switch on Hypervalent Sulfer

Tohru Tsuchiya,* Shin-ichi Arai, Yutaka Murata, 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 Stereochemistry of the Antitumor Alkylating Agents Related to 4-Hydroperoxyisophosphamide

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

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

■ Synthesis of 2-Pyridones by the Co-trimerization of Acetylenes and Isocyanates

Pangbu Hong and Hiroshi Yamazaki*

*The Institute of Physical and Chemical Research, Wako-shi, Saitama 351-0198, Japan

■ Rection of Schiff Bases with Metal Halide in Dimethyl Sulfoxide

Haruo Ogura,* Masakazu Sakaguchi, Toshihiko Okamoto, Kinji Gonda, and Shozo Koga

*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan

■ Synthesis of Some Mold Metabolites, Possessing a Pyrazine Ring

Akihiro Ohta,* Tokuhiro Watanabe, and Yasuo Akita

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

■ Studies on Homopiperazine Derivatives: Conformational Analysis of 2-(4-Acylhomopiperazin-1-yl)-4-amino-6,7-dimethoxyquinazolines by Nmr

Hachiro Sugimoto,* Sachiyuki Hamano, Tohru Takahashi, Takeshi Suzuki, Fukuko Kuriyagawa, and Kenya Sakaguchi

*Eisai Research Laboratories, Eisai Co., ltd., Koisikawa4-6-10, Bunkyo-ku, Tokyo 112, Japan

■ Synthesis of Some 5,6-Diamino-as-triazin-3(2H)-ones and Their Reactivity for the Cyclisation to the Derivatives in the Novel Rings, 6-Azapurine, 6,8-Diazapurine, and 4,7-Diazapteridine

Kenji Kaji,* Hiromu Nagashima, Hirohisa Oda, and Masami Kawase

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

■ Ring Transformations of 1,3-Oxazin-4-one Derivatives

Tetsuzo Kato,* Masatsugu Kondo, and Nobuya Katagiri

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