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. 12, No. 7, 1970
Published online:
■ Biomimetic Synthesis of Protoberberine Alkaloids and Aporphine Alkaloids through N-Oxide Intermediates
Tetsuji Kametani* and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reaction of (±)-reticuline N-oxide (3) with cuprous chloride in methanol, followed by treatment with sodium hydrosulphite, gave (±)-corytuberine (8) in excellent yield, while phenol oxidative coupling of (±)-orientaline N-oxide (4) was less effective under the same conditions. Treatment of 3 with ferrous sulphate in methanol afforded (±)-coreximine (5) and (±)-scoulerine (6), but formation of the protoberberine (7) from 4 with this reagent required acidic conditions.
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■ Syn Selectivity in the Reactions of Azomethiene Imines and Azomethine Oxides with cis-3,4-Disubstituted Cyclobutenes
Remo Gandolfi,* Missimo Ratti, Lucio Toma, and Carlo De Micheli
*Dipartamento di Chimica Organica, Università di Pavia, V. le Taramelli 10, 27100 Pavia, Italy
Abstract
3,4-Dihydroisoquinoline-N-phenylimine reacted with cis-3,4-dichloro, -dihydroxy and -diacetoxycyclobutenes to give the sterically disfavoured syn adducts as dominant products; with carbonyldioxy and dicarbomethoxycyclobutenes repulsive steric interactions led to the prevailence of the anti adducts. An increased syn selectivity was found for the reactions of 3,4-dihydroisoquinoline-N-oxide with diacetoxycyclobutene and of nitro substituted 3,4-dihydroisoquinoline-N-phenylimines with dichlorocyclobutene.
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■ Synthesis of 1,6-Diazaphenalene, a Vinylogous Imidazole
Jen-C. Chang, Mustafa I. El-Sheikh, and James M. Cook*
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
The simple synthesis of a new heterocycle,1,6-diazaphenalene (2), a vinylogous imidazole is described; the key step in the synthesis was conversion of 7 to 8 by cleavage of the N-O bond followed by hydrogen shifts under modified Semmler Wolff conditions [CF3COOH, (CF3CO)2O, HCl].
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■ Synthesis of Spirofluorenes via Ketene Adducts
Magid A. Abou-Gharbia and Madeleine M. Joullié*
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
New classes of spirofluorenes were prepared via simple transformations of ketene adducts.
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■ Synthesis of 1-Benzazocin-5-one Derivatives from a 1,2,3,4-Tetrahydrocyclopent[b]indole; a Synthetic Approach to Mitomycins
Tetsuji Kametani,* Tatsushi Ohsawa, and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Photo-oxygenation of 4-benzyl-1,2,3,4-tetrahydro-5,7-dimethoxy-6-methylcyclopent[b]indole (14), derived from 2,4-dimethoxy-3-methylacetanilide (6) in eight steps, gave, in excellent yield, 1-benzyl-1,2,3,4,5,6-hexahydro-2,5-diketo-8,10-dimethoxy-9-methyl-1-benzazocine (15), which was converted to 1-benzyl-1,2,3,4,5,6-hexahydro-2-keto-5,5,8,10-tetramethoxy-9-methyl-6-methylene-1-benzazocine (19).
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■ Thermal Decomposition of 2H-[1,2,4]Oxadiazolo[2,3-a]pyridine-2-thione and 2H-[1,2,4]Oxadiazolo[2,3-b]pyridazine-2-thione
Akio Ohsawa, Heihachiro Arai, and Hiroshi Igeta*
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
Pyrolysis of 2H-[1,2,4]oxadiazolo[2,3-a]pyridine-2-thione gave 3-(2-pyridyl)-2H-pyrido[1,2-a]-s-triazine-2,4(3H)-dione. 2-Isocyanatopyridine which is considered to be the intermediate in the reaction was utilized to the synthesis of N,N’-substituted ureas. Similar investigation was carried out on 2H-[1,2,4]oxadiazolo[2,3-b]pyridazine-2-thione.
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■ The Synthesis of Benzolactones by Palladium Catalyzed Carbonylation
Miwako Mori, Katsumi Chiba, Nobuo Inotsume, and Yoshio Ban*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Phthalide was easily prepared from o-bromobenzyl alcohol in the presence of a catalytic amount of Pd(OAC)2 and PPh3 under an atmospheric pressure of carbon monoxide in a good yield. When a large amount of PPh3 was used as a ligand, a better result was obtained. The six- and seven-membered benzolactones were synthesized by the same procedure.
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■ Synthesis of Benzo[g]indolizines. Reaction of Acid Anhydrides with Isoquinolinium Methylides
Tetsuzo Kato,* Takuo Chiba, and Toshiki Sasaki
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reaction of isoquinolinium bis(ethoxycarbonyl)methylide (1) with acid anhydrides, such as acetic anhydride, propionic anhydride, n-butyric anhydride, and phenylacetic anhydride, gives rise to the benzo[g]indolizines, ethyl 2-acyloxypyrrolo[2,1-a]isoquinoline-3-carboxylate (where acyl is acetyl (5), propionyl (6), n-butyryl (7), and phenylacetyl (8), respectively). Similar reaction of isoquinolinium cyano(ethoxycarbonyl)methylide (2) affords the same products (5, 6, 7, and 8).
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■ The Identity of Glycophymine and Glycosminie: An Alkaloid of Glycosmis arborea (Roxb.) DC
J. Bhattacharyya* and S. C. Pakrashi
*Department of Chemistry and Geology, Clemson University, Clemson, SC 29631, U.S.A.
Abstract
Glycophymine, a new alkaloid reported from Glycosmis pentaphylla is shown to be identical to glycosminine isolated from the same plant earlier.
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■ Synthesis of Seco-Mitosane Type Compounds as Key Intermediates to Mitomycins
Tetsuji Kametani,* Kimio Takahashi, Masataka Ihara, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
1,3,4,6-tetrahydro-6-methylene-1-benzazocin-5(2H)-ones (4 and 13) were prepared from 1,3,4,6-tetrahydro-1-benzazocin-5(2H)-ones (3 and 12) by treatment with N,N,N’,N’-tetramethyldiaminomethane and acetic anhydride. Functionallisation of the methylene groups of (4 and 13) and transannular cyclisation of the seco-mitosane type compounds (16 and 17) are also described.
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■ Kuwanon F, a New Flavanone Derivative from the Root Bark of the Cultivated Mulberry Tree (Morus alba L.)
Taro Nomura* and Toshio Fukai
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A new flavanone derivative containing 2-methyl-2-(4-methylpent-3-enyl)chromene ring named kuwanon F was isolated from the root bark of the cultivated mulberry tree (a variety of Morus alba L.). The structure was shown to be I on the basis of spectral and chemical data.
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■ Synthesis of (±)-Oxadethia-2,3-benzocephems
Masayuki Shibuya* and Seiju Kubota
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi 1, Tokushima 770-8505, Japan
Abstract
The new 1-oxadethia-2,3-benzocephem ring system has been obtained by a one step synthesis from the readily available 4-acetoxyazetidin-2-one (2).
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■ Synthesis of Nitrogen-containing Heterocycles by the Imino Diels-Alder Reaction
Steven M. Weinreb* and Jeremy I. Levin
*Department of Chemistry, The Pennsylvania State University, York Campus, P1031 Edgecomb Avenue, York, Pennsylvania 17403, U.S.A.
Abstract
This review describes the major advances reported during the past fifteen years on synthesis of heterocyclic compounds using imino dienophiles in the Diels Alder [4+2]-cycloaddition reaction.