HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Tetsuji Kametani's Special Issues, Vol. 15, No. 2, 1981
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■ Heterocycles from 2-Alkyl- or Arylthio-1-chloroenamines
Léon Ghosez,* Patrick Notté, Christiane Bernard-Henriet, and Robert Maurin
*Laboratoire de Chimie Organique de Synthése, Université de Louvain, Place Louis Pasteur 1, B-1348 Louvain-la-Neuve, Belgium
Abstract
2-alkyl-or arylthio-1-chloroenamines are readily prepared from tertiary amides or from ynamines. The 2-arylthio derivatives are readily cyclized to 3-dialkylaminobenzothiophenes in the presence of Lewis acids. With sodium azide they give 2-amino-1-azirines bearing a thioether group at position 3. These highly functionalized azirines are potential precursors of the 2-amino-1-azirinyl-cations.
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■ Propellanes. LVII. Reaction of an Optically Active Tetraenic Propellane Imide with an Optically Active Substituted Triazolinedione
Michael Peled and David Ginsburg*
*Department of Chemistry, Israel Institute of Technology, Haifa 32000, Israel
Abstract
Optically active components were reacted in a Diels-Alder reaction in order to obtain additional infomation with respect to secondary orbital interactions in such systems. Separation of diastereomeric adducts failed when racemic imide was employed.
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■ Ultraviolet Absorption Spectra of 4-Amino-and 4-Dimethylaminopyridines: Effects of Concentration and Solvent
Chikara Kaneko,* Kazuhiro Shiba, and Harue Fujii
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The effect of concentration on the UV spectra of 4-aminopyridine and its derivatives in various solvents was studied in the concentration range from 10-6 to 10-3 M/l. At high concentration, 4-aminopyridines were found to form molecular aggregates (loosely bonded dimers) showing the maxima around 245-260 nm, whose position corresponded to those previously assigned as the 1La-band of the monomer. The monomeric form of these pyridines showed a single absorption maximum around 265-280 nm, which had been previously assigned as the 1Lb-band of the monomer.
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■ Synthesis of Uroporphyrin-III, and Related Hepta- and Penta-carboxylic Porphyrins by Modifications of the MacDonald Method
M. Charkrabarty, S. A. Ali, G. Philip, and A. H. Jackson*
*Department of Chemistry, University College, Cardiff, Wales, U.K.
Abstract
A modification of the McDonald route has been developed in which all four pyrrole units of uroporphyrin-III have been derived from the same conveniently prepared starting pyrrole. Related hepta- and penta- carboxylic porphyrins have also been synthesised by condensation of appropriate α-fomyl pyrromethae-α’-carboxylic acids; in each case other porphyrins with different numbers of acidic side-chains were also produced but the desired products were easily separated (as their methyl esters) by h.p.l.c.
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■ The Conversion of L-Glutamate to L-Tyrosine
Samuel Danishefsky,* Joel Morris, and Lane A. Clizbe
*Department of Chemistry, University of Pittsburgh, Pittsburgh,15260, Pakistan
Abstract
The Diels Alder reaction of a glutamate derived dienophile with trans-1-methoxy-3-trimethylsilyloxy-1,3-butadiene affords a spirodienone. This, upon treatment with aqueous base leads to N-CBz-tyrosine. Optical activity is substantially maintained throughout the process.
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■ The Synthesis of Regiospecifically 13C-Labeled α-Tocopheryl Acetate
M. Kajiwara,* O. Sakamoto, H. Katsura, and S. Ohta
*Shiseido Laboratories, 1050 Nippa-cho, Kohoku-ku, Yokohama 223, Japan
Abstract
A convenient procedure for the synthesis of regiospecifically 13C-labeled α-tocopheryl acetate of high enrichment is described.
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■ Benzo- and Indoloquinolizine Derivatives XX. Synthesis and Conformation of 5,6,8,9-Tetrahydro-13b-H -dibenzo[a,h]quinolizine and 5,6,8,9,14,14b-Hexahydrobenzo[a]indolo[3,2-h ]quinolizine
F. Vlaeminck, E. De Cock, D. Tourwé, and G.Van Binst*
*Laboratoium voor organische Chemie, Vrije Universiteit Brussel, Pleinlaan 2, B-1050 Brussel, Belgium
Abstract
Dibenzo[a,h]quinolizidines are prepared by an imminium cyclization or by PPA cyclization of the ethyleneoxide adduct of 1,2,3,4-tetrahydro-1-phenylisoquinoline. The conformational equilibrium in the title compounds is studied by 13C NMR.
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■ Anodic Oxidation of the Bridged Ether Derivative of (±)-Reticuline
Masayuki Murase and Seisho Tobinaga*
*Showa College of Pharmaceutical Sciences, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Anodic oxidation of the bridged ether derivative (7) of (±)-reticuline (1b), synthesized from the N-carbethoxy-1-benzyl-tetrahydroisoquinoline (1a), afforded the proerythrinadienone type coupling product (8) and the morphinadienone type coupling product (9).
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■ 1,3-Dipolar Cycloaddition Reaction of Trifluoroacetonitrile with Heterocyclic Ylides
Yoshiro Kobayashi,* Itsumaro Kumadaki, and Emi Kobayashi
*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Trifluoroacetonitrile is found to be a good dipolarophile and reacts with heterocyclic N-ylides to give (trifluoromethyl)imidazolopyridine compounds.
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■ New Heterocycles-Acces to Thieno[3,2-b][f ]- and Thieno[2,3-b][f ]benzazepine Derivatives
Jacques Guillaume, Lucien Nédélec,* Michel Cariou, and André Allais
*Centre de Recherche ROUSSEL-UCLAF, 102-111, route de Noisy, 93230 Romainville, France
Abstract
The synthesis of the new heterocycles in the title is described. From these, the thieno analogues of imipramine and clomipramine were prepared.
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■ Studies on the Structure-Activity Relationship of Thiepin and Oxepin Derivatives to Anti-inflammatory Activities
Yoshio Suzuki,* Tohru Yamanaka, Yoshihiro Tanaka, Kiyosato Niu, Masakastu Mizushima, Sigeo Ikeda, Yasuo Fujimoto, and Shigeru Yamabe
*Research Institute, Nippoon Chemiphar Co., Ltd., Hikokawato 1-22-1, Misato-shi, Saitama 341-0005, Japan
Abstract
A series of dibenzo[b,f]thiepincarboxylic acid derivatives has been synthesized and it’s anti-inflammatory activity was examined by the method of carrageenan edema.
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■ Hypotensive Principles from Plants
Shinji Funayama and Hiroshi Hikino*
*Pharmaceutical Institute, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
This review article summarizes our knowledge regarding the structure, occurence and activity of known substances showing hypotensive activity in the plant kingdom.
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■ Indole Alkaloid Biosynthesis
A. Ian Scott,* Siu-Leung Lee, Michael G. Culver, Winnie Wan, Toshifumi Hirata, Francoise Guéritte, Rober L. Baxter, Hans Nordlöv, Craig A. Dorschel, Hajime Mizukami, and Neil E. Mackenzie
*Department of Chemistry, Texas A & M University, College Station, Texas 77843-3255, U.S.A.
Abstract
The early and late stages of indole alkaloid biosynthesis in Catharanthus roseus were studied by cell-free enzymes isolated from the plant and its tissue culture. The intermediacy of strictosidine (isovincoside), geissoschizine and other compounds in the formation of ajmalicine is discussed. Vinblastine, the antineoplastic dimeric alkaloid, was synthesized enzymically from a semi-synthetic precursor, anhydrovinblastine.
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■ The N-O-O Triangulation Hypothesis-An Assessment After One Decade
C. C. Cheng* and Robert K. Y. Zee-Cheng
*Drug Development Laboratory, The University of Kansas Cancer Center and Department of Pharmacology, Toxicology & Therapeutics, The University of Kansas Medical Center, Kansas City, Kansas 66160-7419, U.S.A.
Abstract
A triangular atomic arrangement composed of three electronegative atoms (one nitrogen and two oxygen) was observed among many antineoplastic compounds in 1970. Today, the extent of the application of this hypothesis is assessed with affirmative and nonconfirmative examples provided from the literature. The hypothesis has been used for the design and synthesis of several interesting antineoplastic agents, including DHAQ.
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■ A Correlation of the Chemistries of Two Thienopyridines with Those of Benzo[b]thiophene and Quinoline
L. H. Klemm*
*Department of Chemistry, University of Oregon, Eugene, OR 97403, U.S.A.
Abstract
All of the presently known chemistries (including SE and SN reactions, heteroatomic oxidations, reactions of ring substituents, and reactions of N- and S-oxides) of the thieno[2,3-b]pyridine and thieno[3,2-b]pyridine (TP) systems are shown to be interpretable as amalgamations of the chemistries of the reference compounds benzo[b]thiophene (BT) and quinoline (Q). Three general relationships are noted, viz. (a) cases where all systems (TP, BT, and Q) give reactions which are consistent with one another, (b) cases where the TP system gives reaction analogous to that of the BT or Q system only, and (c) cases where the TP system gives dual reactions as if it were a mixture of the BT and Q systems. In particular, isosteric relationships are commonly observed. Electronic interactions between the rings in TP are considered.
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■ Recent Chemistry of Some Indian Piper Species
Balawant S. Joshi*
*CIBA-GEIGY Research Centre, Goregaon Bombay 400063, India
Abstract
This review summarises some of our work on the chemistry of six Indian Piper species.
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■ Tannis of Medicinal Plants and Drugs
Takuo Okuda,* Takashi Yoshida, Kazuo Mori, and Tsutomu Hatano
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
This review summarizes the research carried out in recent years at the author’s laboratory on tannins in several medicinal plants and drugs, most of which have been presumed to contain tannin as the main active principle.
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■ The Novel Dihydrothiazolo[3,2-a]pyridinium-8-olate and Closely Related Systems: Syntheses and Reactions
Kjell Undheim*
*Department of Chemistry, University of Oslo, P.O.Box 1033, Blindern, N-0315 Oslo, Norway
Abstract
This review covers the chemistry of the dihydrothiazolo[3,2-a]pyridinium-8-olate system, of its quinoline homologues, of amino- and nitro-dihydrothiazolo[3,2-a]pyridinium derivatives, of the dihydrothiazolo[3,2-c]pyrimidinium-8-olate system, and of the thiazolo[3,2-a]pyridinium-8- and -3-olate systems as developed in the author’s laboratories. The dihydrothiazoles are formed by cyclisations over thio-azines. Asymmetric induction has been achieved in Michael adducts with thiolactams. Stereochemistry and mechanisms in adduct and cyclisation reactions have been elucidated; anchimeric involvement of the sulfur has been demonstrated. Optically active 3-carboxydihydrothiazoles are available from (R)-cysteine and oxidized furfurals; other α-pyridino acids are similarly prepared. Syntheses of thiazoles are described. Electrophilic substitution occurs readily in azinium-olates. Regiospecific deuteriations are described. N-Vinylpyridine-2-thiones are conveniently prepared from dihydrothiazoles. Photolysis of pyridinium-olates yielded the valence isomeric aziridines which are rearranged to α-pyridinones. Anchimeric assistance in oxidation of 3-carboxydihydrothiazoles yielded mainly the 1,3-cis oxide; ready decarboxylation of optically active reactant yielded the sulfoxide enantiomer. The N-chloroacetyl protecting group in peptides is removed by reaction with 3-nitropyridine-2-thione and cyclisation in cold TFA to the thiazolo[3,2-a]pyridinium-3-olate. Relevant X-ray data from structure analyses, pKa values, NMR data, and ionisation potentials in structure analyses in the gas phase, are discussed.
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■ Relative Reactivity of the Aromatic Ring in Benzo-1,3-dioxole, Its Cyclohomologues and Veratrole
V. K. Dauksas,* G. V. Purvaneckas, E. B. Udrenaite, V. L. Gineityte, and A. V. Barauskaite
*Kapsukas State University, U.S.S.R.
Abstract
A study of the reactivities of benzo-1,3dioxole (1, n=1), benzo-1,4-dioxane (1, n=2), benzo-1,5-dioxepane (1, n=3) and veratrole (2) is of great interest, since those 1,2-dialkoxybenzenes are essential structural fragments of many natural and synthetic biologically active substances1,2 and the synthesis of their derivatives often results in the formation of new compounds of practical interest.2 However, many aspects of reactivity and other properties of compounds 1 and 2 have received insufficient study and the standpoints referred to in publications are of contradictory nature and need additional experimental verification.2-13
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■ Studies on Plant Tissue Cultures
James P. Kutney*
*Department of Chemisry, University of British Columbia, Vancouver 8, V5T 1W5, Canada
Abstract
A summary of recent experiments with various plant tissue cultures at the University of British Columbia and at the Prairie Regional Laboratory, National Research Council of Canada, Saskatoon, is provided. The main emphasis of the research program is to propagate tissue cultures from plant species known to produce active agents of interest in the cancer area.
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■ Enamide Photocyclization and Its Application to the Synthesis of Heterocycles
Ichiya Ninomiya* and Takeaki Naito
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Enamides are class of the conjugated systems which contain two C=C double bonds, irrespective of their olefinic or aromatic nature, on both sides of an amide group, thus forming six π-electron conjugated systems capable of undergoing smooth cyclization under irradiation. The application of enamide photocyclization to the synthesis of a variety of six-membered lactams as exemplified by a number of alkaloid and heterocycle syntheses proved this reaction as of a useful general synthetic tool for the construction of various heterocyclic compounds.
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■ Studies in Protoberberine Aikaloids XVII — Neooxyberberine Acetone
Tuticorin R. Govindachari,* Bantwal R. Pai, Sundaramurthy Rajeswari, Sankaran Natarajan, Sundaram Chandrasekaran, Manakkal S. Premila, and Ramamurthy Charubala Kailasam venkatesan and Mohan madhav Bhadbhade Kuppuswamy Nagrajan W.J. richter
*Department of Chemistry, Presidency College, Madras 600005, India
Abstract
Structure and Stereochemistry of Neooxyberberine acetone, 8,13a-(2’-Oxopropano)-13-hydroxy-2,3-methylenedioxy-9,10-dimethoxydibenzo-(a,g)-quinolizine 4. Chemical, spectroscopic and X-ray crystallographic studies are presented.
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■ The Diterpenoids of Teucrium Species
Franco Piozzi*
*Institute of Organic Chemistry, Palermo University, Archirafi 20,Palermo, Italy
Abstract
This review describes the major advances reported during the last five years on the chemistry of these terpenoids.
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■ Alkaloids from Plants of the Subfamily Wurmbaeoideae
Frantisek Santavy*
*Institute of Medical Chemistry, Medical Faculty, Palacky University, 775 15 Olomouc, Czech Republic
Abstract
This review gives a survey of the most important papers on the isolation and chemistry of alkaloids (i.e. the tropolone alkaloids, their precursors, and the minor alkaloids) from plants of the subfamily Wurmbaeoideae, and of those of the biosynthesis of these compounds.
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■ Prenylflavonoids from the Root Bark of the Cultivated Mulberry Tree
Taro Nomura* and Toshio Fukai
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Our present knowledge is reviewed of the chemistry of prenylflavonoid derivatives isolated from the root bark of the Japanese cultivated mulberry tree by our group. The oxidative cyclization is also discussed on the flavone derivatives having a free hydroxyl group at C-2’ position and γ,γ-dimethylallyl group at C-3 position.
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■ Cyclization and Cycloaddition Reactions of Heteroepins, Conjugated Seven-membered Heterocyclic Compounds
Toshio Mukai,* Tsutomu Kumagai, and Yoshiro Yamashita
*Department of Chemistry, Faculty of Science, Tohoku University, Aoba-ku, Ssendai 980-8578, Japan
Abstract
This review describes the recent advances in the chemistry of heteroepins, especially the thermally and photochemically induced reactions of 1H-azepine, 1H-1,2-diazepines and 1,3-oxazepine derivatives as well as the synthesis of these heterocyclic compounds.
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■ 13C-NMR Spectral Correlation for Simplified Structure Determination of Curamycins and Related Oligosaccharide Antibiotics
Nicholas F. Cappuccino, Ajay K. Bose,* James B. Morton, and Ashit K.Ganguly*
*Department of Chemistry and Chemical Engineering, Stevens Institute of Technology, Castle Point on the Hudson, Hoboken, NJ 07030, U.S.A.
Abstract
13C NMR spectral analysis for structure determination of oligosaccharide antibiotics is discussed. The details of the structure of a pentasaccharide segment (pseudo-olgose A) of curamycin A is deduced on the basis of 13C NMR data.
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■ The Role of Cyclic Peroxides in the Reactions of 1,2-Diphenylcyclopropenes and Cyclobutenes with Singlet Oxygen
Caetan Vaz, Gary Griffin,* Siegfried Christensen, and David Lankin
*Department of Chemistry, University of New Orleans, New Orleans, LA 70148, U.S.A.
Abstract
An array of cyclic peroxy intermediates, including dioxetanes, endo-peroxides and 1,2-dioxoles, are advanced as intermediates in the reactions of 1O2 with 1,2-diphenylcyclopropenes and cyclobutenes.