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. 20, No. 8, 1983
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■ Reaction of 4-Acetoxy-1,4-benzoxazin-3-one with Amino Acid Derivatives
Takayoshi Ishizaki, Yuichi Hashimoto, Koichi Shudo, and Toshihiko Okamoto
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
A reaction of 4-acetoxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one (2) with t-butoxycarbonyl-L-tyrosine ethyl ester (Boc-L-Tyr-OEt), t-butoxycarbonyl-L-histidine methyl ester (Boc-L-His-OMe) and t-butoxycarbonyl-L-tryptophan methyl ester (Boc-L-Trp-OMe) was described. The 4 and 6 positions in the benzozaxinone ring were attacked by the amino acids. The reaction with Boc-L-Trp-OMe gave hexahydropyrroloindoles.
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■ Surprising Absence of Reactivity towards Borane of a Cyclic Phenylamine in Two Heterocycles 1,3-Dioxa-2-phosphaIII-6-aza-2-R-6-phenyloctane
Apolonioa Murillo, Rosalinda Contreras, Alain Klaébé, and Robert Wolf
*Centro de Investigación y de Estudios Avanzados, Departmento de Química , I.P.N, Apartado 14-740, México, D.F., 07000, Mexico
Abstract
The title compound was reacted with an excess of BH3·SMe2 and only one BH3 molecule was added. This phenomenon is discussed.
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■ Synthesis of New Orally Absorbed Penem Esters, Structurally Related to Thienamycin and Cephamycins
Maurizio Foglio, Carlo Battistini, Franco Zarini, Cosimo Scarafile, and Giovanni Franceschi
*Ricerca&Sviluppo Chimico, Farmitalia Carlo Erba SpA, Via dei Gracchi 35, 20146 Milano, Italy
Abstract
The synthesis of two new 6α-hydroxyethyl penem esters, with the relevant feature of a carbamoyloxymethyl moiety in position 2, is described.
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■ New Condensed Tri- and Tetracyclic 1,2,4-Triazole Ring Systems
Jan Svetlík
*Drug Research Institute, Palárikova 31, 811 04 Bratislava, Slovakia
Abstract
A facile two step synthesis of 7,8-dihydroimidazo[1,2-e]-1,2,4-triazolo[1,5-a]-1,3,5-triazine and 1,2,4-triazolo[1’,5’:1,2]-1,3,5-triazino [5,6-a]benzimidazole is described. Heterocyclic hydrazines react easily with ethyl N-cyanoformimidate to form 1,2,4-triazole derivatives, which are then cyclized with ortho esters into hitherto unknown polyazaheterocycles.
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■ Structure and Conformation of a New Helenanolide, Pulchelloid C
Seiichi Inayama, Kenzo Harimaya, Hitoshi Hori, Takeshi Kawamata, Tamiko Ohkura, Iwao Miura, and Yoichi Iitaka
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
The stereostructure, conformation and absolute configuration of pulchelloid C, a new minor component, helenanolide isolated from the methanol extract of Gaillardia pulchella, were deduced by combination of chemical and spectroscopic methods as well as X-ray crystallography.
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■ Concurrent Formation of Two Isomeric Dipyridazino[4,5-b:4’,5’-e][1,4]thiazines Attended with Occurrence of a Unique Dipyridazino[4,5-b:4’,5’-d]pyrrole
Kenji Kaji, Hiromu Nagashima, Katsushi Yamaguchi, and Hirohisa Oda
*Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Interaction of 4-amino-5-mercapto-2-methyl-3(2H)-pyridazinone (1) and 4,5-dichloro-2-methyl-3(2H)-pyridazinone (3) in a basic medium, followed by benzylation, yielded concurrently 10-benzyl-2,7-dimethyl-dipyridazino[4,5-b:4’,5’-e][1,4]thiazine-1,6(2H,7H)-dione (I) and the 2,8-dimethyl-1,9-dione isomer (II). An analogous result leading to a mixture of products, (I) and the alternative 3,7-dimethyl-4,6-dione isomer (III), was also observed in the case of reaction between the 4,5-substituents of counterpart of 1, (2) and (3). Under somewhat more vigorous condition, the condensation reaction of either combination of the reactants added a consecutive formation of a unique 9-benzyl-2,6-dimethyldipyridazino(4,5-b: 4’, 5’-d]pyrrole-1,5(2H,6H)-dione (IV) to that of the mixtures of the respective dipyridazino[1,4]thiazine products (I+II or I+III).
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■ Norisohaplophytine and Haplocidiphytine — New Bisindole Alkaloids from Haplophyton cimicidum (Apocynaceae)
Akinbo A. Adesomoju, M. V. Lakshmikantham, and M. P. Cava
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
Norisohaplophytine and haplocidiphytine, two new bisindole alkaloids from Haplophyton cimicidum (Apocynaceae) have been assigned the aspidosperma-canthinone structures 1 and 2 respectively.
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■ Investigations on Intramolecular Cycloaddition Reactions of Photochemically Generated Carbonyl Ylides
Jürgen Brokatzky-Geiger and Wolfgang Eberbach
*Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, D-7800, Germany
Abstract
Upon photoexcitation of appropriately substituted oxiranes ring opening leads to carbonyl ylides which undergo intramolecular cycloaddition reactions affording annelated and/or bridged tetrahydrofurans.
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■ Syntheses and Cycloadditions of 1,2-Aromatic Ring-fuseed 3-Cyanoindolizines
Kiyoshi Matsumoto, Takane Uchida, Takazumi Sugi, and Takako Kobayashi
*College of Liberal Arts and Science, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan
Abstract
The syntheses and 1,3-dipolar and Michael type cycloaddition reactions of 1,2-aromatic ring-fused 3-cyanoindolizines such as benzo[c]pyrrolo[1,2-a]pyridines, 1,3-diphenylthieno[3’,4’:3,4]pyrrolo[1,2-a]pyridines, and 1,4-diphenylpyrido[1’,2’:1, 2]pyrrolo[3,4-d]pyridazines are described.
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■ A New Sulfonating Agent on Hetero Atoms
Masayuki Shibuya, Yoshikazu Jinbo, and Seiju Kubota
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi 1, Tokushima 770-8505, Japan
Abstract
The novel amidine-N-sulfonic acid (2) was prepared from 3,3,6,9,9-pentamethyl-2,10-diazabicyclo[4.4.0]-1-decene (1) and chlorosulfonic acid. Reaction of 2 with the azetidinone (4) and different hydroxy compounds under rather mild conditions yielded corresponding N- and O-sulfonic acid PDBD salts, which could be purified by the usual column chromatography on silica gel and/or recrystallization.
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■ The Pyrolysis and Photolysis of the Protopine Type Alkaloid N-Oxides. The Synthesis of the Secoberbines and Benzo[c]phenanthridines
Kinuko Iwasa and Narao Takao
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, kobe, Hyogo 658, Japan
Abstract
The pyrolysis of the N-oxides of the protopine-type alkaloids afforded three products, one of which was converted to the naturally occurring secoberbines. The photolysis of the N-oxides of the protopines supplied the benzo[c]phenanthridines as well as the one of the pyrolysis products.
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■ Influence of Heteroaromatic Amines to Knoevenagel Condensation
Hiroshi Yamanaka, Masaaki Yokoyama, Takao Sakamoto, Takayuki Shiraishi, Mataichi Sagi, and Michinao Mizugaki
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
In the Knoevenagel condensation of hexanal and malonic acid, the ratio of α,β- and β,γ-unsaturated acids was remarkably affected by the nature of tertiary amines used as a catalyst. That is, the condensation in pyridine or isoquinoline gave 2-octenoic acid selectively, whereas the condensation in 2-methylpyridine, 2,6-dimethylpyridine, or quinoline gave 3-octenoic acid as a main product.
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■ The Reaction of 2-Substituted Quinoline 1-Oxides with Dimethyl Acetylenedicarboxylate: Formation of 1-Benzazepine Derivatives
Yasuhisa Ishiguro, Kazuhisa Funakoshi, Seitaro Saeki, Masatomo Hamana, Ikuhiko Ueda, and Shigeaki Kawano
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
The 1,3-dipolar cycloaddition of 2-phenylquinoline 1-oxide (1) and quinaldine 1-oxide (3) with dimethyl acetylenedicarboxylate gives ring expanded products, 2-phenyl- (2) and 2-methyl-3H-3-methoxalyl-3-methoxycarbonyl-1-benzazepines (5), respectively. The reaction of quinaldonitrile 1-oxide (4) yields 1H-2-cyano-3-methoxycarbonyl-1-benzazepine (6) accompanied by further demethoxalylation.
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■ A Novel One Pot Synthesis of 7,9-Disubstituted 5H-Thiazolo[2,3-b]quinazoline-3,5 [2H]-diones
Munnu Ram Chaurasia and Ajay Kumar Sharma
*Department of Chemistry, D. A. V. (P. G.) College, Dehra Dun, India
Abstract
Various 7,9-disubstituted 5H-thiazolo[2,3-b]quinazoline-3,5(2H)-diones and 7,9-disubstituted 2-benzylidene-5H-thiazolo[2,3-b]quinazoline-3,5(2H)-diones have been synthesized and screened for various biological activities. Some of the compounds checked fungal growth and also showed significant antibacterial activity.
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■ Intramolecular Cyclization Reaction of Some 2-Alkenylphenols with Tl(III) Nitrate
Maria Luigia Forcellese, Carlo Alfonsi, Settimia Calvitti, and Enrico Mincione
*del C. N. R., c/o Istituto do Chimica Organica, Università degli Studi di Roma “La Sapienza”, Piazzale Aldo Moro 2 - 00185 Roma, Italy
Abstract
Some 2-allylphenols give an intramolecular cyclization by reaction with Tl(III) nitrate (TTN) leading to 2-substituted 2,3-dihydrobenzofurans; 2-substituted 2,3-dihydrobenzopyran is obtained from 2-(3-butenyl)phenol with the same reagent.
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■ Access to a Chirally Substituted Furan. Synthesis of 5-(D-Glycero-1,2-dihydroxyethyl)-2-furaldehyde from a Natural Heptulose
Catherine Fayet and Jacques Gelas
*Laboratoire de Chomie Organique 2, Ecole Nationale Supérieure de Chimie de Clermont-Ferrand, Université de Clermont II, B. P. 45, 63170 Aubière, France
Abstract
A simple preparative one-step access to a chiral furan [5-(1’,2’(R)-dihydroxyethyl)-2-furaldehyde] from a natural sugar (sedoheptulosan) is described.
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■ Synthesis of 9-Hexadecen-5-olides; Hypothetical Intermediates in the Biosynthesis of Brefeldin A
Tomihisa Ohta, Masayuki Sunagawa, Kazuko Nishimaki, and Shigeo Nozoe
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Four types of lactones 1-4 which might be biosynthetic intermediates of brefeldin A have been synthesized. In the course of their synthesis, it was found that coupling of a hydroxy phosphonium salt and a carbomethoxy-aldehyde gave a macrocyclic lactone in onepot probably by a sequential reaction in which intramolecular Wittig condensation followed transesterification.
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■ Studies on the Syntheses of Heterocyclic Compounds and Natural Products. Part 1007. Synthetic Studies on Cephalosporin Derivatives: An Efrfective Amide Formation Reaction
Tetsuji Kametani, Hiroyasu Sekine, and Toshio Honda
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
An effective amide formation reaction at the C7-position of 7-aminocephalosporanic acid benzhydryl ester has been achieved by the adoption of Mukaiyama’s procedure with a slight modification.
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■ Synthesis of Some 1H- or 2H,4H-Benzo[4,5]cyclohepta[1,2-c]pyrazol-4-one Derivatives
Christian Deshayes, Michel Chabannet, and Suzanne Gelin
*Département de Biochimie, Laboratoire de Chimie Organique, Institut National des Sciences Appliquées, 20 Avenue Albert Einstein 69621 Villeurbanne Cedex, France
Abstract
Synthesis of some 1H- or -2H,4H-benzo[4,5]cyclohepta[1,2-c]pyrazol-4-one derivatives from 4-ethoxycarbonyl-1-substituted-5 or 3-styrylpyrazoles is described.
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■ Selective Ether-Cleavage of Thiocolchicoside and Thiocolchine: Characterization of 3- and 2-Demethylthiocolchicine and Catecholic Congeners
Padam N. Sharma and Arnold Brossi
*Medical Chemistry Section, Laboratory of Chemistry, NIDDK, National Institute of Health, Bethesda, MD 20892, U.S.A.
Abstract
Selective ether cleavage in the thiocolchicine series took a similar course as observed in the colchicine series. Thiocolchicoside (2) afforded with phosphoric acid, the known 3-demethylthiocolchicine (6), and thiocolchicine (1) gave with conc. sulfuric acid at 70 °C, a mixture of the 2-demethylthiocolchicine (3) and the catechols 4 and 5.
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■ Heterocyclic Amidines and Hydroxyamidines as Synthons for Bi- and Polycyclic Heterocycles
Miha Tisler
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
This review summarizes the synthetic utility of heterocyclic amidines, N-hydroxyamidines and their derivatives. From these precursors a new heterocyclic ring can be formed, the cyclization involving participation of either a ring nitrogen atom or an ortho functional group.
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■ Recent Developments in the Chemistry of Ylidene Azolones
Hamed A. Daboun and Sadek E. Abdou
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
The recent developments in the chemistry of ylidene azolones are reported and the literature data were critically discussed.
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■ The Role of Lone Pair Interactions in the Chemistry of Monosaccharides. The Selective Esterification of 4,6-O-Benzylidene-Hexopyranosides
Vernon G. S. Box
*Department of Chemistry, Mona Campus, University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
Mechanistic proposals are presented which seek to describe the course of the esterification of a 4,6-O-benzylidene-hexopyranoside by an acid chloride or an acid anhydride. These two proposals are then elaborated into a rationalisation of the selectivity observed in the esterification of the hydroxyl groups of some 4,6-O-benzylidene-hexopyranosides. Central to the rationalisations are the roles of the β- and γ-effects1,2 which determine the relative energies of the lone pair bearing orbitals of the oxygen atoms of the reacting molecules.