HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Regular Issue
Vol. 4, No. 7, 1976
Published online:
■ Stevens Rearrangement of Berbine Methiodides by Sodium Bis-(2-methoxyethoxy)aluminium Hydride
Tetsuji Kametani,* Shyh-Pyng Huang, Akira Ujiie, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Stevens rearrangement of several berbine methiodides (1, 2, 6, 9 and 11) to the spirobenzylisoquinolines (3, 7, 10 and 12) and the 8-methylberbines (4, 8 and 13) with sodium bis-(2-methoxyethoxy)aluminium hydride is reported. The stereochemistry at the migrating carbon and the relation between the comformation of the quinolizidinium salts and products are also described.
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■ Photochemical Cycloaddition of 2-Phenyl-3-ethoxycarbonyl-Δ2-pyrroline-4,5-dione with Olefins
Takehiro Sano and Yoshisuke Tsuda*
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Photocycloaddition of 2-phenyl-3-ethoxycarbonyl-Δ2-pyrroline-4,5-dione with olefins carrying electron rich group proceeds in highly regio- and stereoselective manner to give [2+2] cycloadducts, while olefins substituted by electron withdrawing group gave no cycloadduct, suggesting that donor-acceptor interaction between two reactants may play an important role in this reaction.
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■ Crystal Structure of the Photocycloaddition of 1-(4’-Bromophenyl)-2-phenyl-3-ethoxycarbonyl-Δ2-pyrroline-4,5-dione with Styrene
Takehiro Sano, Yoshisuke Tsuda,* Haruo Ogura,* Kimio Furuhata, and Yoichi Iidaka
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
The structure of the cycloadduct of 1-[4’-bromophenyl]-2-phenyl-3-ethoxycarbonyl-Δ2-pyrroline-4,5-dione with styrene was determined by X-ray analysis using a heavy atom method.
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■ Thermal Reaction of 1-Phenyl-2-ethoxycarbonyl-3-benzoyl-Δ2-pyrroline-4,5-dione with Olefins
Yoshisuke Tsuda,* Yoshie Horiguchi, and Takehiro Sano
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Olefins carrying electron rich substituents thermally cycloadded to 1-phenyl-2-ethoxycarbonyl-3-benzoyl-Δ2-pyrroline-4,5-dione in regio- and stereospecific manner to give [4+2] cycloadducts, while olefins with electron deficient substituents did not react at all. These facts indicated that the donor-acceptor interaction played an important role in this reaction.
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■ Reactions of N4S4 with Benzil Mono- and Bishydrazone
Masashi Tashiro* and Shuntaro Mataka
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The reactions of N4S4 with benzil mono- (1) and bishydrazone (2) were carried out in refluxing toluene. In the reaction with 1, 2-benzoyl-2,4,5-triphenylisoimidazole (3), which was assumed to be the intermediate for the lophine formation in the reaction of benzil with ammonia, was isolated together with 3,4-diphenyl-1,2,5-thiadiazole (4), benzilazine (5) and diphenylacetamide (6), however, the compound (3) was not the intermediate. In the reaction with 2, 4 was isolated in a modest yield with a trace of a novel compound, 5,6-diphenyl-1,3,2,4-dithiadiazine (7).
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■ 13C-NMR of 1,3-Disubstituted 1,2,3,4-Tetrahydro-β-carbolines
Joseph Sandrin, Dave Soerens, and James M. Cook*
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
The stereochemistry of cis and trans-l,3-disubstituted-1,2,3,4-tetrahydro-β-carbolines has been determined by 13C-NMR for a variety of 1-phenyl- and 1-cyclohexyl-β-carboline derivatives. The signals due to carbon atoms 1 and 3 in the trans isomers appear consistently at higher field in the 13C-NMR spectra than the analogous carbons of the cis isomers. This is presumably due to the 1, 3 interactions present in the trans bases which do not occur in the cis compounds.
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■ The Mechanism in the Colorimetry of Caffeine and Theobromine by Hypochlorous Acid-Pyridine Method
Kazuo Kigasawa, Kazumi Ohkubo, Toshitaka Kohagisawa, Hiroaki Shimizu, Setsu Saitoh, and Tetsuji Kametani*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Caffeine (1) and theobromine (2) reacted with pyridine in the presence of hypochlorous acid to give 8-(N-pyridinium)xanthine salts, which were characterised as the triiodides (3 and 5) and monoiodides (4 and 6). Treatment of 8-(N-pyridinium)caffeine iodide (3) with sodium hydroxide afforded sodium 5-(caffeine-8-yl)imino-1,3-pentadienoxide (7). This experiment made clear the mechanism in the colorimetry of caffeine by hypochlorous acid-pyridine method.
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■ The Structure and the Synthesis of Sevanine
Vilím Simánek, Vladimír Preininger,* Antonín Klásek, and Jan Jurina
*Department of Organic Chemistry, Palacky University, Trida Svobody 8 ,77146 Olomouc, Czech Republic
Abstract
7-Hydroxy-6-methoxy-l-(3,4-methylenedioxybenzy)isoquinoline (II), which is identical with the alkaloid sevanine, was synthesized via two pathways.
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■ Studies on the Synthesis of Bisindole Alkaloids. IV. Novel Oxygenated Catharanthine Derivatives
James P. Kutney,* Gordon H. Bokelman, Masahiro Ichikawa, Edwin Jahngen, Alummoottil V. Joshua, Ping-huang Liao, and Brian R. Worth
*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5
, Canada
Abstract
Electrophilic attack of various reagents on the 3,4-double bond of catharanthine derivatives (e.g. II, R = O) furnished novel intermediates, potentially useful in syntheses of naturally occurring bisindole alkaloids.
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■ Photosensitized Oxygenation of 2,3-Diphenylindole Derivatives
Masako Nakagawa,* Noriko Ohyoshi, and Tohru Hino
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
Photosensitized oxygenation of 2,3-diphenylindole (1a) gave 3-hydroxyindolenine (5) as a major product. N-Acelyl-2,3-diphenyIindole (1b) yielded 2,3-dihydroxy derivative (10a) whereas N-methylderivative (1c) gave 2,3-bond cleavage product (8c) and 2,3-dihydro-1,4-benzoxazine (11).
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■ Azafulvenes 4. Cycloaddition Reaction of 6-Amino-1-azafulvene to Isocyanate, Ketene and Sulfene
Takashi Kobayahsi, Shoji Kajigaeshi, and Shuji Kanemasa*
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
6-Amino-1-azafulvene and its benzo analog, generated from the iminium perchlorate by deprotonation, reacted with isocyanate, ketene and sulfene affording the corresponding [6+2] cycloadducts.