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. 14, No. 9, 1980
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■ Synthesis of 5-Amino-2-pyrrolidinone and Its Derivatives
Yoshiyuki Kosugi,* Humiko Hamaguchi, Tatsuo Nagasaka, Naganori Ozawa, and Sadao Ohki
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Two routes to a new type of 2-pyrrolidinones having various nitrogen functions at the 5-position were described. The modified Curtius reaction of pyroglutamic acid derivatives (1 and 4) with diphenylphosphoryl azide (DPPA) gave 5-alkoxycarbonylamino-2-pyrrolidinones (5 and 14a) in one step. Furthermore, the substitution reaction of 5-ethoxy-2-pyrrolidinone (12) with nucleophiles (amines, carbamates, amide, indole, and diethylaniline) was found to be a preferable synthetic method to 5-substituted-2-pyrrolidinones (13, 14, 15, and 16). The synthesis of 5-amino-2-pyrrolidinone (8), a simple one, was also mentioned.
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■ Synthesis of a Novel β-Lactam Containing Nucleus: 1-Carboxy-2-aza-tricyclo[4.2.2.02,5]decan-3-one
G. Michael Bright, Michael F. Dee, and Michael S. Kellogg*
*Central Research Division, Pfizer Inc., Eastern Point Road, Groton, Connecticut 06340, U.S.A.
Abstract
The synthesis of 1-carboxy-2-aza-tricyclo[4.2.2.02,5]decane-3-one 1, a novel β-lactam carboxylate, from bicyclic amide carboxylate 4 via an efficient triplet sensitized photochemical diazo insertion reaction to produce β-lacram 12 has been described.
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■ Photocyclization of N-Aminoalkylphthalamides. Syntheses of Multicyclic Fused Hexahydropyrazines and Hexahydro-1,4-diazepines
Minoru Machida, Haruko Takechi, and Yuichi Kanaoka*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Photolysis of a series of N-aminoalkylphthalimides (3) afforded fused hexahydropyrazines (4a, 6a,b) and hexahydro-1,4-diazepines (4b, 6c,d).
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■ Cyclohexadienones. 3. Preparation and Thermal Decomposition of 4-Azido-2,4,6-tri-t-butyl-2,5-cyclohexadien-1-one
Gouki Fukata, Naoya Sakamoto, and Masashi Tashiro*
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Reaction of 4-bromo-2,4,6-tri-tert-butyl-2,5-cyclohexadien-1-one (1) with sodium azide was carried out in DMF to afford 4-azido-2,4,6-tri-tert-butyl-2,5-cyclohexadien-1-one (4) in 85% yield. Thermal decomposition of 4 in boiling toluene gives 6-amino-2,4-di-tert-butylphenol (5), 2,4,6,8-tetra-tert-butylphenoxazin-1-one (7) and 2,4,6,8a-tetra-tert-butyl-7-cyano-8-oxo-5a,8a-dihydrocyclopenteno[2,3-b]benzoxazine (8). However, the thermal decomposition of 4 was carried out under highly diluted conditions to afford 5 and 2,4-di-tert-butyl-5-cyano-2,4-cyclopentadien-1-one (9) in 48 and 50% yields, respectively. It was also found that the thermal decomposition of 4 in boiling toluene in the presence of acetic anhydride afforded 6-acetoamido-2,4-di-tert-butylphenol (6) and 9 in 47 and 50% yields, respectively. The reaction pathways of the formation of 5, 8 and 9 were proposed in the present paper.
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■ The Fries Rearrangement of Benzoates of 3-Hydroxy-6,7-dimethoxycoumarin
Vernon G. S. Box* and Yvette A. Jackson
*Department of Chemistry, Mona Campus, University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
The Fries rearrangement of benzoates of 3-hydroxy-6,7-dimethoxycoumarin lead to intermediates suitable for [1]benzopyran[3,4-b][1]benzopyran syntheses. The synthesis of a 11-chloro-6a,12a-dehydro-[1]benzopyran[3,4-b][1]benzopyran-6,12-dione is described.
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■ Methyl 2,3-Dideoxy-α-D-glycero-hex-2-eno-pyranosid-4-ulose
Lynda L. Box, Vernon G. S. Box,* and Earle V. E. Roberts
*Department of Chemistry, Mona Campus, University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
An efficient synthesis of the title compounds from methyl 4,6-O-benzylidene-α-D-glucopyranoside is described, thus making available a versatile group of intermediates for the syntheses of branched-chain sugars.
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■ Syntheses and Some Chemical Properties of Sulfoxides, Sulfilimines and Sufoximines Containing Pyridine Nuclei
Naomichi Furukawa, Fujio Takahashi, Keiko Kishimoto, Hiroyuki Morita, and Shigeru Oae*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Several 2-pyridyl sulfides, sulfoxides and N-(p-toluenesulfonyl)-sulfilimines were prepared by the usual methods. Hydrolysis of N-(p-toluenesulfonyl)-2-pyridyl-o-tolylsulfilimine with conc. sulfuric acid gave the corresponding N-unsubstituted (free) sulfilimine in a moderate yield. Sulfoximines were obtained by oxidation of the corresponding free sulfilimines derived from the aminosulfonium salts. These free sulfilimines and sulfoximines thus prepared were found to give adducts with few Cu-salts. Methyl 2-pyridyl sulfoxide was found to be a good phase transfer catalyst for some typical nucleophilic reactions.
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■ Synthesis of Heterocycles: Part 1. N-Iodosuccinimide, a Convenient Oxidative Cyclising Agent in the Synthesis of Oxazole, Isoxazole, Benzofuran, Furoxan and 1,2,3-Triazole-1-oxide Derivatives
Sunil K. Talapatra,* Prabir Chaudhuri, and Bani Talapatra
*Chemistry Department, University College of Science, 92 Acharya Prafulla Chandra Road, Calcutta-700009, India
Abstract
N-Iodosuccinimide has been successfully employed as an oxidative cyclising agent for the synthesis of oxazole, isoxazole, benzofuran, furoxan and 1,2,3-triazole-1-oxide derivatives. Synthesis of compounds (II) , (IV) , (VI), (VIII) and (X) having these basic skeletons respectively are reported.
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■ The Synthesis of 5’,5’-Dihydroxy-7,2’,4’-trimethoxyisoflavone and Its Isomer: A Revised Structure of Derrugenin
Masao Tsukayama, Tokunaru Horie, Yoshiro Yamashita, Mitsuo Masumura, and Mitsuru Nakayama*
*Department of Chemical Science and Technology, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-8506, Japan
Abstract
5,5’-Dihydroxy-7,2’,4’-trimethoxyisoflavone (1) and 5,4’-dihydroxy-7,2’,5’-trimethoxyisoflavone (2) were unambiguously synthesized from the corresponding chalcones using the oxidative rearrangement with TTN. It was found that the structure of derrugenin was not the proposed structure (1), but its isomer (2).
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■ Structure of Moracenin A, a Hypotensive Principle of Morus Root Barks
Yoshiteru Ohshima, Chohachi Konno, Hiroshi Hikino,* and Kazuhiro Matsushita
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
From the crude drug “sohakuhi”, the root barks of Morus plants, a novel isoprenoid flavone derivative, moracenin A, showing hypotensive activity has been isolated. The structure has been determined, as indicated by formula I, on the basis of chemical and physical evidence.
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■ A Mesomeric Betain Pyrazolo-Oxydotriazinium Ring System. 6-Alkyl-2-methylpyrazolo[1,5-d][1,2,4]triazin-6-ium-4-olates, Synthesis and Ring Cleavege
Endre Tihanyi,* Pál Sohár, Ödön Fehér, and Melinda Gál
*Institute for Drug Research Ltd., H-1325 Budapest, POB 82, Hungary
Abstract
A novel type of the mesomeric betain ring system was synthesized from pyrazolecarboxylic acid N’-alkylhydrazides by a simple method. The structure of the compounds was proved by spectroscopic methods and synthetic routes. The oxydotriazinium ring was opened with ethanol to yield the corresponding starting materials or with water to yield substituted pyrazolecarboxylic acid N’-acyl hydrazides.
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■ A Novel Synthesis of 6-Azapurines by the Oxidative Cyclization of Azahexatrienes with Diethyl Azodicarboxylate
Tetsuji Kametani,* Masatsugu Higuchi, Mitsuko Noguchi, Yuko Hashiguchi, and Fumio Yoneda
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Treatment of 6-benzylidenehydrazino-3-methyl-5-nitrosouracils with ethanolic potassium hydroxide caused a benzylic acid-type rearrangement accompanied with decarboxylation and dehydration to give 4,5-diimino-3-methylimidazolidin-2(1H)one 5-arylidenehydrazones. Alkylation of the latter with alkyl iodides gave the corresponding 1,3-dialkyl-4,5-diiminoimidazolidin-2(1H)one 5-arylidenehydrazones. Treatment of these azahexatriene-type imidazolidinones with diethyl azodicarboxylate gave the respective 3-aryl-5,7-dialkyl-5H-imidazo[4,5-e]-as-triazin-6(7H)ones (2-aryl-7,9-dialkyl-6-azapurine-8-ones) by the intramolecular cycloaddition through valence isomerization and then aromatization with diethyl azodicarboxylate.
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■ A Novel Route to a 16-Substituted Nine-membered Indole Alkaloid Related to Quebrachamine and Cleavamine
Seiichi Takano,* Chikara Murakata, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A novel route to a quebrachamine-cleavamine type alkaloid bearing C-16 carboxyl equivalent has been developed.
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■ An Alternative Total Synthesis of (±)-Thienamycin
Tetsuji Kametani,* Shyh-Pyng Huang, Takayasu Nagahara, and Masataka Ihara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
(±)-4β-(2’,2’-Dimethoxyethyl)-3α- (1’R*)-p-nitrobenzyloxycarbonyloxyethyl)-2-azetidinone (4) was converted into the thienamycin derivative (2) protected with p-nitobenzyl group, utilizing the carbene insertion reaction and subsequent introduction of the cysteamine moiety developed by the Merck group.
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■ Raucubaine, a New Type of Indole Alkaloid from Rauwolfia salicifolia Griseb
James P. Kutney,* James Trotter,* Richard A. Pauptit, Brian R. Worth, and Patricia Sierra
*Department of Chemistry, The University of British Columbia, 2036 Main Mall, Vancouver, B.C., V6T 1Z1, Canada
Abstract
Raucubaine (2), a new indole alkaloid with a novel carbon skeleton was isolated from the leaves of Rauwolfia salicifolia griseb. The structure was determined by X-ray diffraction analysis.
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■ Ring-Chain Tautomerism of Imidazolidine System
Stanislaw Witek,* Alicja Bielawska, and Jacek Bielawski
*Institute of Organic and Polymer Technology, Technical University of Wroclow, 50-370 Wroclaw, Poland
Abstract
The existance of the tautomeric equilibrium of imidazolidine system 3→←4 has heen established. Due to a higher reactivity of NH group in 4, the reaction of the system /3→←4/ with PhNCO unbalances the tautomeric equilibrium, and causes an increase in the content of the open-chain urea derivative 6 in the reaction mixture. The use of isocyanates or other similar reagents, e.g., isothiocyanates, seems to be a convenient method for studies of the tautomerism in similar systems.
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■ Chalcone Oximes. Part VI. Novel Rearrangement of 2,3-Dihydrobenzo-γ-pyrone Oximes into Δ2-Isoxazoline Derivatives
Zbigniew Witczak*
*Department of Organic Chemistry, Institute of Fundamental Chemical Sceince, Fuculty of Pharmacy, School of Medisine, 90-145 Lódz, Poland
Abstract
The (E) 2,3-dihydro-2-(R-phenyl)-4H-benzopyran-4-one oximes (1a - f) have been transformed into corresponding isomeric Δ2-isoxazolines (2a - f) by treatment with trifluoroacetic acid.
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■ Synthesis of the Basic Structure of Corynoline Alkaloid
Hideo Iida,* Iwao Endo, Mamoru Narimiya, and Toyohiko Kikuchi
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Synthesis of the compound having the basic structure of corynoline from homophthalimide derivative is described.
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■ A Novel Synthesis of 4-Phenylcoumarins Having a Free Hydroxyl Group in the Phenyl Ring: Synthesis of Melanettin and Stevenin
V. K. Ahluwalia* and Sunita Dhingra
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
Melanettin (1) and stevenin (2), two naturally occurring 4-phenyl coumarins have been synthesised in good yield using a novel method.
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■ Formation of [1,3]Benzoxazino[3,4-c]benzoxazines[1,3]
Shoji Morimura*
*Central Research Laboratories, Sankyo Co.,Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140 Japan
Abstract
The reaction of 1,1-bis(2-hydroxy-3-alkyl substituted-5-methylphenyl)methylamines with aldehyde gave [1,3]benzoxazino [3,4-c]benzoxazines[1,3], and with ketones gave oxazines.
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■ Recent Advances in the Chemistry of 1,3-Oxazines
Tetsuzo Kato,* Nobuya Katagiri, and Yutaka Yamamoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
This review describes the advances reported since 1963 in the chemistry of single ring 1,3-oxazines, especially the syntheses and reactions of oxo-derivatives of 3,4-dihydro-2H-1,3-oxazine and 4H-1,3-oxazine.