HETEROCYCLES

■ Studies in the Dihydropyridine Series IV. Bipiperidyl Synthons via Coupling of Dihydropyridinetricarbonylchromium (0) Complexes

James P. Kutney,* Thomas C. W. Mak, Danuta Mostwicz, James Trotter, and Brian R. Worth

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

Abstract

The reaction of 1,2-dihydro-3-ethyl-N-methylpyridinetricarbonylchromium (0) complex with various alkyllithiums provides a high yield of three novel bipiperidyl intermediates. X-ray structures of these isomers are provided.

■ Stereoselective Total Synthesis of Optically Active trans- and cis-Burseran. Determination of the Stereochemistry of Natural Antitumor Burseran

Kiyoshi Tomioka and Kenji Koga*

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

Abstract

Optically pure trans- and cis-burseran were synthesized stereoselectively from (R)-(+)-β-piperonyl-γ-butyrolactone (2). Both compounds gave satisfactory ¹³C NMR spectra. By comparing their behavior on gas chromatography, the naturally occurring burseran characterized as an antitumor agent was determined to be the trans-isomer.

■ The Photoreaction of Morusin Trimethyl Ether

Taro Nomura,* Toshio Fukai, and Masako Amagai

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

Abstract

The photoreaction of morusin trimethyl ether (Ia) afforded hydroperoxide (II), the structure of which was confirmed on the basis of spectral and chemical data. On the other hand, the photoreaction of morusin-2’,4’-dimethyl ether (Ib) did not occur. The possible mechanism of the photoreaction of Ia is discussed being based on the several experimental results obtained here.

■ Potential Carcinostatics VI. Biologically Active 5-Fluorouracil Derivatives of 2-Oxo-2,5-dihydrofuran

Gerrit-Jan Koomen, Frans van Alewijk, Direk Blok, and Upendra K. Pandit*

*Laboratory of Organic Chemistry, University of Amsterdam, Nieuwe Achtergracht 129,1018 WS Amsterdam, The Netherlands

Abstract

1-(2-Oxo-2,5-dihydro-5-furyl)-5-fluorouracil derivatives have been synthesized and shown to be active in the P-388 mouse leukemia test system.

■ The Structure of Lisetin: The Synthesis of Isolisetin Dimethyl Ether

Masao Tsukayama,* Tokunaru Horie, Mitsuo Masumura, Mitsuru Nakayama, and Shûichi Hayashi

*Department of Chemical Science and Technology, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-8506, Japan

Abstract

Isolisetin dimethyl ether (3) was prepared by oxidative cyclization of the isoflavone derivative (7) derived from 2-hydroxy-4,6-dimethoxyacetophenone and 5-benzyloxy-6-formyl-8-methoxy-2,2-dimethylchroman via three steps. The compound (3) was also obtained by the same reaction of 2’,4’-dihydroxy-5,7,5’-trimethoxy-3’-(3-methyl-2-butenyl)isoflavone (12), followed by cyclization of the resultant compound (13) Lisetin (1) was synthesized by way of piscerythrone (2) and converted into isolisetin dimethyl ether (3) in succession.

■ Syntheses of 9-Allyladenine 1-Oxide and 9-(Δ²-Isopentenyl)adenine 1-Oxide

Tozo Fujii,* Isao Inoue, Taisuke Itaya, and Tohru Saito

*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan

Abstract

An unequivocal synthesis of 9-allyladenine 1-oxide (III) has been accomplished by an initial alkylation of 1-ethoxyadenine (VI) with allyl bromide and the Et-O bond cleavage of the resulting 9-allyl-1-ethoxyadenine hydrobromide (VII) with pyridine. 9- (Δ²-Isopentenyl)adenine 1-oxide (IX) was also prepared in a similar manner.

■ Transformation of Tazettine to Pretazettine

Shigeru Kobayashi, Masaru Kihara, and Tetsuro Shingu

*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan

Abstract

Transformation of tazettine (2) to pretazettine (1) having antileukemic activity is described. This transformation confirmed the stereochemistry of pretazettine (1).

■ 2,5-Cyclohexadienones. 1. A Novel Formation of 1-(3,5-Di-t-butyl-1-hydroxyphenyl)pyridinium Bromide

Masashi Tashiro* and Gouki Fukata

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

Abstract

The reaction of 4-bromo-2,4,6-tri-t-butyl-2,5-cyclohexadien-1-one (1) with pyridine (3) afforded 1-(3,5-di-t-butyl-2-hydroxyphenyl)pyridinium bromide (4) in 20% yield, which gave easily 2,4-di-t-butyl-6-(1-pyridinio)phenolate (10) by the treatment with strong base such as DBU. It was also found in this reaction that addition of ethylene glycol increased the yield of 4 from 20% to 45%. The reduction of 4 and 10 with sodium borohydride afforded same product, 2,4-di-t-butyl-6-(1,2,3,6-tetrahydro-1-pyridyl)phenol (11). A tentative mechanistic interpretation for the formation of 4 is also proposed.

■ Stereochemistry of 1-Alkyl-9-arylthioxanthenium Salts

Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, and Sachio Ohno

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

Abstract

The stereochemistry of 10-alkyl-9-arylthioxanthenium salts was studied in detail by the nmr spectroscopy. The conformation was elucidated.

■ Calafatine, An Unusual Bisbenzylisoquinoline Alkaloid

Víctor Fajardo,* Alejandaro Urzúa, and Bruce K. Cassele

*Departmento de Química, Facultad de Ciencia, Universidad Técnica del Estado, Santiago 2, Chile

Abstract

Spectrometric and chemical evidence is presented that calafatine, an alkaloid from Berberis buxifolia, has structure 1. The substitution pattern on ring E is unique in isoquinoline alkaloids.

■ Biogenesis of Aristorotelia Alkaloids

I. Ralph C. Bick,* Mohammad A. Hai, and Nigel W. Preston

*Department of Chemistry, University of Tasmania, GPO Box 252C Hobart, Tasmania, 7001, Australia

Abstract

A possible biosynthetic scheme for the Aristotelia alkaloids is presented.

■ General Synthesis of Octaalkylporphyrins

K. S. Chamberlin and E. LeGoff*

*Department of Chemistry, Michigan State University, East Lansing, MI 48824, U.S.A.

Abstract

Reaction of the α,β-unsaturated ketone, 2a-f, with toluenesulfonyl methyl isocyanide give the 3-alkanoyl-4-alkyl pyrroles, 3a-f. Hydride reduction of 3a-f affords the 3,4-dialkylpyrroles 4a-f which condense with formaldehyde to give the 2,3,7,8,12,13,17,18-octaalkylporphyrins, 1a-f.

■ An Efficient Method for Synthesis of 1,1-Diarylhydrazines as an Intermediate for Indole Synthesis

Yasuoki Murakami* and Yuusaku Yokoyama

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

Abstract

The Hofmann reaction of 1,1-diarylureas (2) to afford the corresponding hydrazines (3) is described.
Diarylamines (1) were converted to 1,1-diarylureas (2) with sodium cyanate and trifluoroacetic acid, or chlorosulfonyl isocyanate. The Hofmann reaction of 2 with alkaline sodium hypochlorite in ethanol successfully gave the corresponding hydrazines (3) in good yields. This method is especially effective for the preparation of easily reducible 1,1-diarylhydrazine derivatives.

■ Electroreductive Synthesis of Nitrogen Heterocycles

Tatsuya Shono*

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

■ New Analysis of Reactivity and Reactions of Nitrogen-containing Heterocycles

Naoki Inamoto*

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

■ Syntheses and Reactions of the σ-Pyridyl Nickel(II) and Palladium(II) Complexes

Shinichi Kawaguchi*

*Faculty of Science, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan

■ Planning and Operation in the Multistep Alkaloid Synthesis

Yasuo Inubushi*

*Faculty of Pharmaceutical Sciences, Kyoto University, 46-29 Yoshida-shimoadachi-machi, Sakyo-ku, Kyoto 606-8501, Japan

■ Synthesis of fMet-tRNA from E. Coli

Morio Ikehara*

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

■ Chemical Reconstruction of Biological Functions of Porphyrin Containing Proteins

Iwao Tabushi*

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

■ Reaction of Anilenium Ion-related Species and Their Synthetic Application

Koichi Shudo*

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

■ Agricultural Antibiotics Blasticidin S and Its Selective Antagonist Detoxins

Hiroshi Yonehara*

*Institute of Applied Microbiology, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8567, Japan

■ Studies Directed toward the Total Synthesis of Calcimycin (A-23187)

Paul A. Grieco,* Ken-ichi Kanai, and Eric Williams

*Department of Chemistry, University of Pittsburgh, Parkman Avenue & University Drive, Pittsburgh, PA 15260 , U.S.A.

■ Estimation of Fundamental Properties of Nitrogen-containing Organic Compounds

Yukio Yoneda*

*Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan

■ Vinylcyclopropanes as Synthons for Macrocycles

Shalom Sarel*

*Department of Organic Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

■ Recent Progress in Alkaloid Synthesis

Ekkehard Winterfeldt*

*Institut für Organische Chemie, Universität Hannover, Schneiderberg 1b, D-30167 Hannover, Germany

■ Reactions of Sodium Diethyl Phosphite with Some Aryl Halides

Joseph F. Bunnett*

*University of California, Santa Cruz, U.S.A.

■ New Results of Organic Charge-transfer Compounds

H. A. Staab*

*Abteilung Organische Chemie, Max-Planck-Institut für Medizinische Forschung, Heidelberg, Germany