HETEROCYCLES

■ Preparation of Indoloquinolizidine Derivatives through Pyridine Pseudobases

Mauri Lounasmaa and Tarja Ranta

*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, P.O. Box 6100, FIN-02150 HUT, Espoo 15, Finland

Abstract

The pseudobase formation from appropriate pyridinium salts with a convenient leaving group on the C-3 side-chain can be exploited for the preparation of indoloquinolizidine derivatives.

■ 7α-Methoxylation of Cephalosporins

Katsuyoshi Iwamatsu, Koichi Shudo, and Toshihiko Okamoto

*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan

Abstract

A method for 7α-methoxylation of cephalosporins is described. Treatment of the imidoyl chlorides of cephalosporins (2) with 4-methoxypyridine N-oxide afforded (4-pyrido-1-yl)oxyimino compounds (3), which were transformed to 7α-methoxycephalosporins (4) via thermal 1,4-elimination followed by addition of methanol.

■ A New and Simple Synthesis of 1,2-Diazaazulene

Kimiaki Imafuku and Akiko Shimazu

*Department of Chemistry, Faculty of Science, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan

Abstract

3-Methyl-8-methylamino-1,2-diazaazulene was synthesized in 24% yield from 3-acetyltropolone via 2-acetyl-7-methylaminotropone and its hydrazone.

■ An Entry into and Oxatwistane System: Invenstigations of Crosswise Ring Closures in Bicyclo[2.2.2]octene or Bicyclo[2.2.2]octane Systems

Shun Inokuma, Shigenari Katayama, Kikuo Ishizumi, and Junki Katsube

*Sumitomo Pharmaceuticals Research Center, 1-98, Kasugadenaka 3-chome, Konohana-ku, Osaka 554-0022, Japan

Abstract

Crosswise ring closures in bicyclo[2.2.2]octene or bicyclo[2.2.2]octane systems were studied in order to construct an oxatwistane frame. An entry into the oxatwistane system could be achieved by either crosswise etherization of a methylbicyclooctene-methanol(20) with 12N-HCl/EtOH or intramolecular dehydration of a hydroxy-methylbicyclooctane-methanol(25).

■ Molecular Structure of 2,5-Bis(ethylsulfonyl)-1,3,4-thiadiazole

Kazunobu Harano, Masami Yasuda, and Ken Kanematsu

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

Abstract

An X-ray crystallographic analysis was carried out to elucidate the molecular structure of the oxidized compound of 2,5-bis(ethylthio)-1,3,4-thiadiazole.

■ Synthesis and Structure of 4,5,6-Trimethyl-1-oxo-1H-1,2,4-triazolo[1,2-a]pyrazol-4-ium-3-olate. A New Mesoionic 4nπ-Heterocycle

Willy Friedrichsen, Andreas Böttcher, and Tony Debaerdemaeker

*Institut für Organische Chemie, Universität Kiel, Olshausenstrasse. 40, D-24098 Kiel, Germany

Abstract

Synthesis, structure, and reactions of the title compound are described.

■ Kanagawamicin, a New Aminonucleoside Analog Antibiotic from Actinoplanes kanagawaensis

Shunsuke Naruto, Hitoshi Uno, Akira Tanaka, Hirotada Kotani, and Yoshiyuki Takase

*Technical Research Laboratory, Dainippon Pharmaceutical Co., LTD., Ebie 1-5-51, Fukushima-ku, Osaka 553, Japan

Abstract

A new aminonucleoside, kanagawamicin (Ia), is produced by a strain belonging to Actinoplanes kanagawaensis. The structure of Ia has been deduced from physico-chemical data obtained using the natural compound and its acetates (Ib, Ic and Id).

■ Tetracyclic Phenothiazines. X. Lithiation of Pyrrolo[3,2,1-kl]phenothiazine

Torsten Dahlgren, Anders Hallberg, and Arnold R. Martin

*Department of Pharmaceutical Sciences, College of Pharmacy, The University of Arizona, Tucson, AZ 85721, U.S.A.

Abstract

The lithiation of pyrrolo [3,2,1-kl] phenothiazine and subsequent reactions of the lithio intermediates giving 1- and 10-mono- and 1,10-disubstituted derivatives are reported. The reaction sites were determined from decoupled ¹H and ¹³C NMR spectra.

■ Dragon’s Blood from Dracaena draco, Structure of Novel Homoisoflavanoids

Lorenzo Camarda, Lucio Merlini, and Gianluca Nasini

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

Abstract

Two novel homoisoflavans, 4’,7-dihydroxy- (4) and 4’,7-dihydroxy-8-methoxy- (5), were isolated from the resin “Dragon’s blood”, which is produced by Dracaena draco (Liliaceae). In the same resin were also identified 4’,7-dihydroxy- and 4’,5,7-trihydroxy-6-methylhomoisoflavanones (1) and (3), together with (2S)-4’,7-dihydroxy-3’-methoxy-8-methylflavan (8), (2S)-4’,5-dihydroxy-7-methoxy-8-methylflavan (9) and 3,4’-dihydroxy-7-methoxyflavone (10). Their structures were established on the basis of spectroscopic analysis and by synthesis.

■ Synthesis of Azoloyl Ketone and Azoloylacetic Acid Derivatives: Reactions of 4-Arylazo-2-oxazolin-5-ones with Active Methylene Compounds

Mohamed Ali Elsayed Khalifa, Gamal H. Tammam, Ramadan M. Abdel-Motaleb, and Mohamed H. Elnagdi

*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt

Abstract

The rearrangement of 4-arylazo-2-oxazolin-5-ones (1) with active methylene compounds was investigated. The 1,2,4-triazolyl derivatives (11) could be obtained on treatment of with 2-pyrazolin-5-one derivatives. The behaviour of the synthesised derivatives toward an aromatic diazonium salt was also investigated.

■ Rearrangement and Alkylation of Some 1,2,4-Triazine Derivatives

Said A. El-Bahaie, Mohamed A. Badawy, Sayed A. Abdel-Hady, and Yehia A. Ibrahim

*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt

Abstract

4-Aryl-5-oxo-3-alkylmercapto-1,2,4-triazine derivatives undergo interesting reaction with ammonia to give mainly, instead of the expected corresponding 3-amino derivatives, the 3-arylamino-2,5-dihydro-5-oxo-1,2,4-triazines. In this reaction 4-aryl-3,5-dioxo-2,3,4,5-tetrahydro-1,2,4-triazines were obtained as a minor product. Alkylation of 3-arylamino-4,5-dihydro-5-oxo-1,2,4-triazines with methyl iodide in alkaline medium gives the corresponding 2-methyl derivatives. Independent synthesis of 2- and 4-methyl-3-arylamino-1,2,4-triazine derivatives is alao described.

■ Facile Synthesis of 2’-Deoxy-2’-arylthiouridines

Akira Matsuda and Tadashi Miyasaka

*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan

Abstract

Cleavage of the anhydro linkage of O²,2’-cyclouridine(1a) with o-,m-, and p-substituted thiophenols and β-naphthalenethiol was carried out in dimethylformamide to give the corresponding 2’-deoxy-2’-arylthiouridines(6a-g) in good yields.

■ A Remarkable Oxidative Fragmentation of 16-Epi-19-S-vindolinine

Atta-ur-Rahman and Mohammad Bashir

*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan

Abstract

An interesting oxidative fragmentation of the hexacyclic 16-epi-19-S-vindolinine (1) to the tricyclic product (6) is reported.

■ An Entry to 5,6,7,8-Tetrahydro-4-cinnolones from 4,5,6,7-Tetrahydrobenzo-3(2H)-furanone Derivatives

Suzanne Gelin and René Dolmazon

*Département de Biochimie, Laboratoire de Chimie Organique, Institut National des Sciences Appliquées, 20 Avenue Albert Einstein 69621 Villeurbanne Cedex, France

Abstract

Synthesis of 3-methyl-5,6,7,8-tetrahydro-4-cinnolone and its N-1 and N-2 methylated derivatives, starting from 2-acetoxy- or -2-methoxy-2-methyl-4,5,6,7-tetrahydrobenzo-3(2H)-furanone is described.

■ The Stereochemistry and Conformation of the Diastereomers of Tetrahydrothiamin

Finian J. Leeper and Peter N. Lowe

*University Chemical Laboratory, Lensfield Road, Cambridge, CB2 1EW, U.K.

Abstract

The major isomer of tetrahydrothiamin produced by NaBH₄ reduction of thiamin is shown by ¹H n.m.r. to be cis (5) and its conformation is predominantly (5a) which should be a major factor in the strong inhibition shown by its pyrophosphate (2) towards the pyruvate dehydrogenase complex af E.coli.

■ The Isolation and Structure of “Harappamine” — A New Alkaloid from Buxus papilosa

Atta-ur-Rahman and Mehrun Nisa

*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan

Abstract

A new alkaloid “harappamine” has been isolated from the leaves of Buxus papilosa which has been assigned structure (1).

■ Fused 1,2,5-Thiadiazoles and Selemadiazoles

Wanda Sliwa and Antoni Thomas

*Department of Organic Chemistry, Pedagogical University, Al. Armii Krajowej 13/15, 42-201 Czestochowa, Poland

Abstract

Syntheses of aromatic and azaaromatic fused 1,2,5-thia- and selenadiazoles are described as well as the examples of their chemical reactivity are given.

■ Synthesis of Azaphenalenes

Shieu-Jeing Lee and James M. Cook

*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.

Abstract

The syntheses and properties of the tricyclic azaphenalenes are reviewed.

■ Ring Transformations of Heterocycles

Henk C. van der Plas

*Laboratory of Organic Chemistry, Agricultural University, De Dreijen 5, 6703 BC Wageningen, The Netherlands

■ Reactions of Pyridyl, Quinolyl, and Isoquinolyl Azides: Introduction of Halogeno, Alkoxy, and Alkylthio Groups

Hiroyuki Sawanishi, Toyoko Hirai, and Takashi Tsuchiya

*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan

■ Chemiluminescence of Monocyclic 3,6-Disubstituted Pyridazines

Nobutaka Suzuki, Mamoru Kato, Takeshi Ueyama, Kaniti Sano, and Yasuji Izawa

*Faculty of Engineering, Mie University, 1515 Uehama-cho, Tsu, Mie 514-5807, Japan

■ New Syntheses of Phthalocyanines

Haruhiko Tomoda, Kenichi Yoshioka, Shigeki Orita, Shojiro Saito, and Shinsaku Shiraishi

*Shibaura Institute of Technology, 307 Tamarigahara, Hukasaku, Omiya, Saitama 330-0003, Japan

■ Preparation of Bridged Thionin, Bridged Thiecinone, and Related Compounds

Hiroshi Kato, Yukihiro Arikawa, and Mayumi Masuzawa

*Department of Chemistry, Faculty of Science, Shinshu University, Asahi, Matsumoto 390-8621, Japan

■ The Ring Transformation of Substituted Isoxazoline N-Oxides by Lewis Acids

Kiyobumi Takahashi, Eisuke Kaji, Shonosuke Zen, Hikaru Nakamura, and Yoichi Iitaka

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

■ Novel Reactions of Xathiene Derivatives

Mikio Hori, Tadashi Kataoka, Hiroshi Shimizu, Eiji Imai, Yukiharu Mastumoto, and Masanori Kawachi

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

■ Reactions of 3-Methoxycarbonylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxaline and Its Derivative Hydrazide with Electrophilic Reagents

Yoshihisa Kurasawa and Atsushi Takada

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

■ Synthesis of 3-Spiro- and 3,6-Bridged 2,5-Piperazinediones

Chung-gi Shin, Yoshiaki Sato, Akira Ohtsuka, and Juji Yoshimura

*Department of Chemistry, Faculty of Science, Tokyo Instituteof Technology, Meguro-ku, Tokyo 152-8552, Japan

■ Synthsis and Reducing Abilities of 1-Substituted Dihydropyrimidines

Choji Kashima, Akira Katoh, Masao Shimizu, and Yoshimori Omote

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

■ Functionalized Crown Ethers as an Approach to Enzyme Models for the Synthesis of Peptides

Shigeki Sasaki, Mitsuhiko Shionoya, and Kenji Koga

*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan

■ Flash Vacuum Pyrolysis of Some Heterozromatic N-Oxides

Takayuki Kawaguchi, Akio Ohsawa, and Hiroshi Igeta

*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan