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. 3, No. 10, 1975
Published online:
■ Stereochemistry of 4-Hydroperoxyisophosphamide, a Potentially Active Antitumor Alkylating Agent
Akira Takamizawa,* Saichi Matsumoto, Tsuyoshi Iwata, and Itsuo Makino
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
An acid-catalyzed ismerization of 4-hydroperoxyisophosphamide, an antitumor alkylating agent having the 1,3,2-oxazaphosphorinane ring, gave an epimer with inversion of phosphorus configuration. The stereochemistry of the epimer was elucidated and found to be effective in promoting the antitumor activity.
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■ Reaction of 1-[2,2-Bis(methylthio)vinyl]pyridinium Iodines with Active Methylene Compounds
Yoshinori Tominaga, Kazumichi Mizuyama, Yoshinori Miyake, Hiroshi Fujito, Yoshiro Matsuda, and Goro Kobayashi*
*Faculty of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
The reaction of 1-[2,2-bis(methylthio)vinyl]pyridinium iodide derivatives (1b,c) with active methylene compounds in the presence of triethylmine as a base in EtOH gave pyridinium allylide derivatives (2a,b,c) in good yields.
When potassium hydroxide was used instead of triethylamine as a base in dimethyl sulfoxide, the reaction of la,b,c with active methylene compounds afforded cleaved compounds of pyridine ring, N-[2,2-bis(methylthio)vinyl]-N-(6,6-disubstituted 1,3,5-hexatrienyl)amine derivatives (3a, b,c,d,e,f,g,h,i) in excellent yields.
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■ Biomimetic Transformation of Indoloquinolizidine Derivative to 2-Acylindole
Masako Nakagawa,* Yoko Okajima, Kazumi Kobayashi, Toshifumi Asaka, and Tohru Hino
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
2-Acylindole 2 has been synthesised by photosensitised oxygenation of indoloquinolizidine 1a, while 1-methyl derivative 1b gave a quinolone 3.
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■ Oxidative Cyclization of Nb-Dimethyltryptamine, 3-Indolepropanol, and 3-Indolepropnethiol with N-Bromo- or N-Chlorosuccinimide
Tohru Hino,* Hidetoshi Miura, Toru Nakamura, Ryoichi Murata, and Masako Nakagawa
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
The reaction of Nb-dimethyltryptomine (5b) with NBS in carbon tetrachloride yielded a quaternary salt of pyrrolo[2,3-b]indole (7b). The similar oxidative cyclization of 3-indolepropanol (5c) and 3-indolepropanethiol (5e) with NBS in methylene chloride gave pyrano- and thiopyranoindoles (7c and 7e). Further halogenation of 7c with NCS yielded a spirooxindole (12, Y=O) and a dichloride (l3), whereas 7e with NBS gave 12 (Y=S) and bromothiopyranoindole (14).
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■ Formation of Protoberberines by Debenzylation and Photolysis of Tetrahydroisoquinolines
Tetsuji Kametani,* Keiichiro Fukumoto, Masataka Ihara, Makoto Takemura, Hiroo Matsumoto, Bantwal R. Pai, Kuppuswamy Nagarajan, Manakkal S. Premila, and Hosbett Suguna
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Treatment of 1-(3-benzyloxybenzyl)-1,2,3,4-tetra- hydroisoquinolines (1, 5 and 6) with hydrochloric acid in ethanol without formalin gave the corresponding phenolic isoquinolines (2, 8 and 9) and the tetrahydroprotoberberines (3, 11 and 12). The former products (2, 8 and 9) on photolysis also gave the tetrahydroprotoberberines (3, 11 and 12) together with the normal products, aporphines.
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■ Synthesis of Oxoaporphine by Photolysis: a Total Synthesis of Atheroline
Tetsuji Kametani,* Ryuko Nitadori, Hirofumi Terasawa, Keiichi Takahashi, and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Two-step oxidation of 1-(3-benzyloxy-4-methoxybenzyl)-8-bromo-3,4-dihydro-6,7-dimethoxyisoquinoline (4), followed by debenzylation, addorded 8-bromo-1-(3-hydroxy-4-methoxybenzoyl)-6,7-dimethoxyisoquinoline (8), the irradiation of which yielded atheroline (1) and its positional isomer (3).
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■ Intramolecular Effect of 1-(ω-Hydroxyalkyl) Groups on Alkali Degradation of 3-Methyl-1-(ω-hydroxyalkyl)uracils
Fumihiko Yoshizaki, Yoshikazu Kondo, and Tsunematsu Takemoto*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The alkali degradation of 3-methyl-1-(ω-hydroxyalkyl)uracils has been shown to involve the intramolecular acceleration by the ω-hydroxyl participation; in fact, the ω-hydroxypropyl group formed favorable six-membered intermediate 5 showed a rate enhancement. The degradation products were proved to be N-hydroxyalkyl-N’methylureas.
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■ Synthesis of Hexa-O-methyl-8,8”-binaringenin
Fa-ching Chen,* Yuh-meei Lin, Tong-ing Ho, and Tsong Ueng
*Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan 30013, Taiwan, R.O.C.
Abstract
The hitherto unknown title compound was synthesized and its structure was confirmed by spectral evidence and by conversion by means of NBS to cupressuflavone derivative.
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■ Some Recent Chemistry of Indian Rutaceae
Balawant S. Joshi*
*CIBA-GEIGY Research Centr, Goregaon Bombay 400063, India
Abstract
Chemistry of five plants of the Rutaceae family, namely Clausena heptaphylla Wt. & Arn., Clausena indica Oliv., Murraya exotica Linn., Murraya koenigii Spreng., and Vepris bilocularis Engler, has been reviewed. The structures of some new carbazole alkaloids, terpenes, flavonoids and coumarins have been discussed.