HETEROCYCLES

■ Cyanoketenes. Cycloadditions of tert-Butylcyano- and Chlorocyanoketene to Sulfer Diimides

Dorothy M. Goldish, Barry W. Axon, and Harold W. Moore

*Department of Chemsitry, California State University, Long Beach, U.S.A.

Abstract

A number of unusual transformations were observed when di-t-butyl and diphenylsulfur diimide were treated with t-butylcyano- and chlorocyanoketene. These include the fomation of reactive thione-s-imines, which subsequently lead to 3-isothiazolidinones and benzisothiazoles. Other products include a cyclic thioimidate and a β-lactam.

■ The Reaction of 3-Bromo-4-methoxyquinoline 1-Oxide with Dimethyl Acetylenedicarboxylate

Yasuhisa Ishiguro, Mitsutaka Yoshida, Kazuhisa Funakoshi, Seitaro Saeki, Masatomo Hamana, Ikuhiko Ueda, and Shigeaki Kawano

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

Abstract

3-Bromo-4-methoxyquinoline 1-oxide (1) reacts with dimethyl acetylenedicarboxylate (DMAD) at room temperature in dioxane, CH₂Cl₂, MeCN or DMF to give α-[N-(3-bromo-4-methoxyquinolinium)]-α,β-bismethoxycarbonyl-β-oxo-ethylide (2) and methyl 2-(3-bromo-4-methoxyquinoline)acetate (4). On the other hand, heating 1 with DMAD in dioxane or DMF affords dimethyl α-[N-(3-bromo-4-oxo-1,4-dihydroquinolyl)]-β-methoxyfumalate (3) as the predominant product, which is proved to be formed by thermal rearrangement of 2.

■ Reactions of o-Quinoid Compounds with Quadricyclanes III. Competitive [σ2+σ2+π4] and [σ2+σ2+π2]Cycloadditions of Tetrachloro-o-benzoquinone with Quadricyclanol

Willy Friedrichsen and Eggert Büldt

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

Abstract

Quadricyclanol (1) reacts with tetrachloro-o-benzoquinone (2) to give both [σ2 + σ2 +π4] (3,4,5,6) and [σ2 +σ2 +π2] (7) cycloadducts.

■ Intramolecuar 1,3-Dipolar Cycloaddition of 3-Phenylpropioloyloxyalkylpyridinium N-Imines

Yasuyoshi Miki, Michiko Konishi, Noriko Nishikubo, Toshihiko Yoshimaru, and Shoji Takemura

*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan

Abstract

Treatment of N-aminopyridinium salt (3a) with base in methanol gave unexpected product (4) but the salts (3b,c) in acetonitrile yielded normal adducts with 7- or 8-membered lactone (6b,c).

■ 1-(3-Diazo-2-oxopropyl)-4-thio-substituted Azetidine-2-ones. Versatile Intermediates for the Preparation of Bicyclic β-Lactams: Synthesis of Novel Cephem Derivatives

Hans Fliri, Ching-Pong Mak, Kapa Prasad, Gerhard Schulz, and Peter Stütz

*Sandoz Forschungsinstitut, 1235 Wien, Brunnerstraße 59, Austria

Abstract

Metal-catalyzed thermal decomposition of diazoketones 3c-3f afforded different substituted cephems, whose formation can be rationalized by assuming different reaction pathways. Possible mechanisms are proposed, and the effect of various 4-thio-substituents on the decomposition of these diazoketones are summarised.

■ Three New Isoprenylated Xanthones, Cudraxanthone A, B, and C, from the Root Barks of Cudrania tricuspidata (Carr.) Bur

Taro Nomura, Yoshio Hano, and Tomoko Fujimoto

*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan

Abstract

From the hexane extract of the root barks of Cudrania tricuspidata(Carr.) Bur. (Japanese name “Hariguwa”, Moraceae), these new isoprenylated xanthones were isolated and named cudraxanthone A, B and C. The structures of cudraxanthone A, B and C were shown to be I~III, respectively, on the basis of spectral data.

■ 1,2-Oxaphosphol-3-ene Derivatives by Cyclohalogenation of 2-(1,2-Alkadienyl)-2-oxo-1,3,2-dioxaphosphaolanes

Christo M. Angelov and Christo Zh. Christov

*Department of Chemistry, Higher Pedagogical Institute, 9700 Shoumen, Bulgaria

Abstract

In our investigations of reactions of electrophilic addition to allene organophosphorus compounds we have shown that in the halogenation of 2-(1,2-alkadienyl)-2-oxo-1,3,2-dioxaphospholanes in inert solvents, the 1,2-dienylphosphonate system of bonds (O=P-C=C=C) is involved in the reaction with the halogen. As a result the cycloaddition of reagent takes place followed by opening of the dioxaphospholane ring and formation of 1,2-oxaphosphol-3-ene derivatives. The structure of the compounds 2a-e and 3a-d was established by analyses of the ir and ¹H- and ³¹P-nmr spectra.

■ A New Synthesis of Phenanthridine Derivatives

Hideo Iida, Toshiyuki Takahashi, Mamoru Narimiya, Hiroshi Takayanagi, and Toyohiko Kikuchi

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

Abstract

Reduction of 4-(3-oxobutyl)isocarbostyril derivatives gave 4-(3-oxobutyl)-1,2-dihydroisoquinolines which were treated with 12 N hydrochloric acid to give cis-phenanthridine derivatives.

■ Synthesis and Molecular-biological Activity of the Pyridine Analogue of Cardiotonic Steroids

Jerzy Wicha, Marek Mansnyk, Werner Schönfeld, and Kurt R. H. Repke

*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland

Abstract

Pyridylandrostane derivative 1 was synthesized from compound 4 and shown to exert remarkably high molecular-biological activity in the Na,K-ATPase test for cardiotonic steroids.

■ The Synthesis of (1R,2S,8S)- and (1S,2S,8S)-1-Hydroxymethyl-2-hydroxypyrrolizidine: Petasinecine and Its C-1 Epimer

Heinrich Rüeger and Michael Benn

*Department of Chemistry, The University of Alberta, Calgary, Alberta, T2N, 1N4, Canada

Abstract

The hydrogenation of (8S)-1-ethoxycarbonylpyrrolizidin-2-one in aqueous acetic acid, over Adam’s catalyst, afforded a separable mixture of (1R,2S,8S)- and (1S,2S,8S)-1-ethoxycarbonylpyrrolizidin-2-ol. Reduction of the individual epimers with lithium aluminium hydride gave the corresponding diols, the (1R,2S,8S)-compound being petasinecine.

■ ¹³C-NMR Quanternisation Shift Increments for 3-Substituted Pyridines in N-Banzyl- and N-2,4-Dinitrophenyl-pyridinium Salts

Roger Dommisse, Eddy Freyne, Josef Lepoivre, and Frank Alderweireldt

*Labratory of Organic Chemistryn University of Antwerp (RUCA), Groenenborgerlaan 171, B-2020 Antwerp, Belgium

Abstract

The ¹³C-NMR spectra of a series of 3-substituted and 3,5-disubstituted pyridinium salts are examined. It appears that quaternisation shift increments have to be used with care because of their dependence on the pyridine substituents present, the N-alkyl- or N-aryl group and the experimental conditions (e. g. solvent, concentration, counter ion . . . ) .

■ Novel Conformational Effects of the N-Benzyloxycarbonyl-cis-3a-aryl-octahydroindole Nucleus. Formal Total Synthesis of Racemic Elwesine and Epielwesine

Ignacio H. Sánchez, Francisco J. López, Humberto J. Flores, and María Isabel Larraza

*Facultad de Química, Universidad Nacional Autónama de México, Circuito Exterior, Ciudad Universitaria, Coyoacán 04510, Mexico

Abstract

The formal total synthesis of racemic elwesine (I) and epielwesine (II) is described. The preferred ground-state conformation of the cis-3a-aryl-octahydroindole precursors is shown to be dependant on the substituent on nitrogen.

■ Polycondensed Nitrogen Heterocycles. Part XIV. Reactivity of 3-Diazopyrroles: Pyrrolo[3,4-c]pyridazine

Gaetano Dattolo, Girolamo Cirrincione, Anna Maria Almerico, and Enrico Aiello

*Dipartimento di Chimica e Tecnologie Farmaceutiche, Università degli Studi di Palermo , Via Archirafi n 32 90123 Palermo, Italy

Abstract

3-Diazopyrroles 2a,b were prepared in excellent yields by diazotization of the corresponding amines 1a,b. Compounds 2a,b, by acid catalyzed intramolecular coupling reaction led to the new ring system pyrrolo[3,4-c]pyridazine 3a,b.

■ The Preparation of Coumaric Acids via Styrylisoxazoles

Stefano Chimichi, Francesco De Sio, Donato Donati, Giuseppe Fina, Roberto Pepino, and Piero Sarti-Fantoni

*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e loro Applicazioni, c/o Dipartimento di Chimica Organica “Ugo Schiff”, Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy

Abstract

The preparation of coumaric acids (2a-f) by hydrolysis of the requisite 3-methyl-4-nitro-5-styrylisoxazoles (1a-f) is reported.

■ A Convenient and Simplified Method for Synthesis of 1,4-Dioxo-1,2,4,5-tetrahydroimidazo[1,5-a]quinoxalines

Yoshihisa Kurasawa, Mitsugu Ichikawa, and Atsushi Takada

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

Abstract

1,4-Dioxo-1,2,4,5-tetrahydroimidazo[1,5-a]quinoxalines were prepared via 3-azidocarbonylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxaline from 3-hydrazinocarbonylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxaline.

■ Study on the Coupling Reactions of Benzylisoqunolines with Lead Tetraacetate

Gábor Blaskó, Gábor Dörnyei, Marietta Bárczai-Beke, Péter Péchy, and Csaba Szántay

*Institute for Organic Chemistry, Technical University Budapest, H-1521 Budapest, P.O. Box 91Gellért tér 4, Hungary

Abstract

Lead tetraacetate (LTA) oxidation of different mono- or non-phenolic tetrahydrobenzylisoquinolines containing secondary amino group leads to dibenzopyrrocoline derivative or oxoaporphine, respectively. The substrate selectivity of LTA has been discussed.

■ Stereospecific Synthesis of Racemic Intermadiates of the Penems and the Carbapenems from trans-Crotonic Acid

Masao Shiozaki, Noboru Ishida, Hiroshi Maruyama, and Tetsuo Hiraoka

*Chemical Research Laboratories and Analytical & Metabolic Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan

Abstract

Stereocontrolled syntheses of two (±)-3-(1-t-butyldimethylsilyloxyethyl)-4-acetoxy-2-azetidinones (cis-10 and trans-10), which are key intermediates for the penems and the carbapenems, from trans-crotonic acid are reported.

■ Infrared Spectra of Phenothiazines

Sayeed Saraf, Mohammad Akram Khan, and Saleh Al-Mousawi

*Department of Chemistry, Faculty of Science, University of Kuwait, Safat 13060, P.O. Box 5969, Kuwait

Abstract

Infrared spectra of phenothiazine including N-alkylated derivatives, sulphoxides and sulphones are reviewed with particular reference to their structural determination.

■ Reactivity of Pyridines and Pyridiniums

Alan R. Katritzky

*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.

■ Manufacture and Use of Pyridine and Its Derivatives

Gerald L. Goe

*Reilly Tar & Chemicak Corporation, 1500 South Tibbs Avenue, P. O. Box 41076, Indianapolis, Indiana 46241, U.S.A.

■ Synthesis and Selected Applications of Polymers Containing Pyridine Moieties

Jean M. L. Fréchet

*Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, K1N 6N5, Canada

■ Regioselective Cyanation of Pyridine-1-oxides

Wilmer K. Fife

*Department of Chemistry, Indiana-Purdue University, PO Box 647, Indianapolis, IN 46223, U.S.A.

■ Rearrangements in the Pyridine Series

Rudolph A. Abramovitch

*Department of Chemistry, Clemson University, Clemson, SC 29631, U.S.A.

■ Pyridine Chemistry in the Preparation of Two Medical Agents: Rosoxacin and Amrinone

George Y. Lesher

*Sterling Winthrop Pharmaceuticals Research Division, Rensselaer, New York, 12144, U.S.A.

■ Halogenated Pyridines: Their Synthesis and Applications to Several Areas of Crop Protection

Howard Johnston

*Agricultural Products Research, Dow Chemical U. S. A., P. O. Box 9002, Walnut Creek, CA 94598, U.S.A.

■ Polyactivated Polychlorinated Pyridines

Basil J. Wakefield

*Department of Chemistry and Applied Chemistry, The Ramage Laboratories, University of Salford, Salford M5 4WT, U.K.

■ Pyridine with Polyfunctionalized Appendages

George R. Newkome

*Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803-1804, U.S.A.

■ Anodic Monofluorination of Pyridine

James R. Ballinger, Fred W. Teare, Barry M. Bowen, and E. Stephen Garnett

*Medical Science Building, Department of Pharmacology, University of Toronto, Toronto, Ont. M5S1A8, Canada

■ Aplication of Klopman’s Polyelectronic Perturbation Approch to Electrophilic Substitution on Pyridines and Their N-Oxides

Gerritt P. Bean

*Chemistry Department, Western Illinois University, Macomb, IL 61455, U.S.A.

■ Fused Ring 3-(3-Pyridyl)sydnones

Steven J. Hodson, Kenneth Turnbull, and Geoffrey Waldo

*Department of Chemistry, Wright State Univerity, Dayton, OH 45435, U.S.A.