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. 11, 1979
Published online:
■ A Study of the Binding of Methylene Blue, Thionin, Azure A, Azure B, and Azure C to DNA
Scott A. Burton and Raymond N. Castle*
*Department of Chemistry, Brigham Young University, Provo, UT 84602, U.S.A.
Abstract
Methylene Blue, Thionin, Azure A, Azure B, and Azure C were found to bind strongly to DNA probably via intercalation. Binding affinity is the result of several factors including π moment along the long axis and dipoIe-dipoIe coupling both constrained by steric effects.
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■ A Simple Synthesis of Cardenolides and Their Less Toxic Isomers via Furyl Intermediates
Thomas Y. R. Tsai, Akwasi Minta, and Karel Wiesner*
*Natural Products Research Center, Department of Chemistry, University of New Brunswick, Bag Service #45222, Fredericton, New Brunswick, E3b 5A3, Canada
Abstract
A novel efficient and stereospecific synthesis of digitoxigenine (19) and its isomer (23) via the common intermediate (15) is described.
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■ New Complexing Surfactants. Syntheses of 4-Alkoxypyridines and Bipyridines
Jacek Skarzewski* and Jacek Mlochowski
*Institute of Organic and Polymer Technology, Technical University of Wroclow, 50-370 Wroclaw, Poland
Abstract
Some of the long chain 4-alkoxypyridines 2, 4-alkoxy- 3 and 4,4’-dialkoxy-2,2’-bipyridines 1 were synthesized as the new complexing surfactants.
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■ Novel Ring Transformation of a 4H-Pyrido[1,2-a]pyrimidine into a 1,8-Naphthyridine
István Hermecz* and Zoltán Mészáros
*CHINOIN Pharmaceutical and Chemical Works Ltd., P. O. Box 110, H-1325 Budapest, Hungary
Abstract
Ethyl 4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidine-3-carboxylates (1) can be converted into ethyl 4-oxo-1,4,5,6,7,8-hexahydro-1,8-naphthyridine-3-carboxylates (2) under basic conditions.
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■ Partial Synthesis of Tchibangensine and Derivatives
Catherine Mirand-Richard, Louisette Le Men-Olivier, Jean Lévy, and Jean Le Men*
*Facluté de Pharmacie, UPRES-A/CNRS 6013, Insitut des Biomoleculés, 51, rue Cognacq-Jay, F-51096 Reims Cedex, France
Abstract
The alkaloid tchibangensine 1 and two of its derivatives 6a and 6b were synthesised. Catalytic hydrogenation of 6a,b and acetylation of 1 were described.
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■ Bis-(Tetrahydroxy-dibenz[b,g]indolizine) by Air Oxidation of Tetrahydropapaveroline
Ching-Pong Mak and Arnold Brossi*
*Section of Medicinal Chemistry, Laboratory of Bioorganic Chrmistry, NIDDK, National Institute of Health, Bethesda, MD 20892, U.S.A.
Abstract
THP was oxidized in aqueous alkaline milieu into a mixture of compounds. Two of them were dihydrodibenzoindolizines, isolated as their O-acetates. One was identical with a known monomer, the second proved to be a dimer.
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■ Stereochemistry of 9-Arylthioxanthene 10-Oxides and 10,10-Dioxides
Mikio Hori,* Tadashi Kataoka, Hiroshi Shimizu, and Sachio Ohno
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
The stereochemistry of 9-arylthioxanthene 10-oxides and 10,10-dioxides were studied by the nmr spectroscopy. The conformation was elucidated.
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■ Establishment of the Structures of Azatropolones and Their Rearrangement Products by X-Ray Analysis
Yoshisuke Tsuda,* Miyuki Kaneda, Takehiro Sano,* Yoshie Horiguchi, and Yoichi Iitaka
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The structure of the azatropolone methyl ether [7-(4’-bromophenyl)-4-ethoxycarbonyl-3-methoxy-6-phenyl-2H-azepin-2-one] was determined by X-ray analysis using the heavy atom method. The result indicated that the azatropolone nucleus is not planar and has a chirality. The structures of solvolytic rearrangement products of azatropolones were also established by X-ray analyses as pyridine-2-carboxylates.
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■ Base Catalysed Ring Expansion of an 2-Azabicyclo[3.2.0]heptane-3,4-dione to a Dihydroazatropolone: A New Azatropolones
Takehiro Sano,* Yoshie Horiguchi, and Yoshisuke Tsuda*
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
The syntheses of azatropolones, new nonbenzenoid aromatic compounds, are described. Base catalysed ring expansion of an 2-azabicyclo[3.2.0]heptane-3,4-dione gave a dihydroazatropolone, which was dehydrogenated with DDQ oxidation to give an azatropolone.
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■ Quinazolinocarboline Alkaloids Chemistry: Thermal Rearrangement of 14-Alkylindole[2’,3’:3,4]pyrido[2,1-b]quinazolin-5-one. Part II
Bruno Danieli, Giordano Lesma, and Giovanni Palmisano*
*Instituto Chimica Industriale, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy
Abstract
The thermal rearrangement of 14-alkylindolo[2’,3’:3,4]pyrido[2,1-b]quinazolin-5-ones (1a-h) in boiling DMSO has been studied. (1a-d,f,g) give hydrogen migration products (2a,c,e,g,h) and alkyl migration products (2b,d,f,k,l) respectively, whereas (1e,h) give only (2g). Crossover experiments support the intramolecular character of these processes. The formation of hydrogen migration products is interpreted through an α-elimination induced by N13 atom and α-bond cleavage. A radical fragmentation-recombination mechanism is suggested for alkyl migration.
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■ The C(7) Stereochemistry of the Chloroindolenines of Cleavamines and Quebrachamines
Ernest Wenkert,* Edward W. Hagaman, Nai-yi Wang, and Nicole Kunesch
*Department of Chemistry, Rice University, Houston, Texas 77251, U.S.A.
Abstract
A 13C analysis of the 7-chloroindolenine derivatives of representative cleavamines and quebrachamines reveals these products of indole chlorination to possess a 7β-chloro configuration.
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■ Elaeodendrogenin, Elaeodendroside B and C: New Cardiac Steroids from Elaeodendron glaucum
Kazutake Shimada, Toshio Nambara,* Itsuo Uchida, and S. Morris Kupchan (deceased)
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A new cardiac steroid named elaeodendrogenin and two new cardiac glycosides named elaeodendroside B and C having an unusual sugar linkage were isolated from seeds of Elaeodendron glaucum Pers. The structure of elaeodendrogenin was elucidated to be Ia on the basis of chemical and spectral data. A newly developed procedure for cleavage of a glycoside having a doubly linked sugar was applied to characterization of elaeodendroside B and C. In consequence, the probable structures of these two stereoisomers were deduced to be VI.
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■ N-Alkylation of Lactams with Phase Transfer Catalyst
Hiroki Takahata,* Torahiko Hashizume, and Takao Yamazaki
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
N-Alkylation of lactams (1a,b,c) with alkyl halides (2) with phase transfer catalyst afforded various N-alkyl lactams (3,4, and 5) in good yields.
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■ Thermal Rearrangements of 4- and 6-Vinyl-1,2,5,6-tetrahydropyridine and 2-Vinylpiperidine N-Imides
Takashi Tsuchiya* and Haruki Sashida
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
The thermolysis of the 4-vinyl-1,2,5,6-tetrahydropyridine N-imide (3) resulted in both [1,2]- and [2,3]-sigmatropic rearrangement to give the diazepine (4) and the pyrazole (5), respectively. This reaction mechanism was confirmed by a deuterium-labelling experiment. Whereas, in the thermolysis of the 2-vinyl derivatives (7 and 12), the [2,3]-rearrangement took place preferentially with the vinyl group to give the ring-expansion products (8 and 13).
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■ Synthesis of Pimprinine and Related Oxazolylindole Alkaloids from N-Acyl Derivatives of Tryptamine and Tryptophan Methyl Ester by DDQ Oxidation
Yuji Oikawa, Tadao Yoshioka, Kunihiko Mohri, and Osamu Yonemitsu*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
N-Acyl derivatives of tryptamine and L-tryptophan methyl ester were treated with DDQ under anhydrous conditions directly to give pimprinine and related oxazolylindole alkaloids. Under aqueous conditions, the N-acyl derivatives were readily oxidized to the corresponding β-keto compounds, which were also converted to the oxazolylindoles by the treatment with POCl3.
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■ Synthesis of (±)-9-Demethylpsychotrine and (±)-10-Demethylpsychotrine
Tozo Fujii,* Masashi Ohba, Satyesh C. Pakrashi, and Esahak Ali
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The synthesis of (±)-9-demethylpsychotrine (I) has been achieved by an initial condensation of 3-benzyloxy-4-methoxyphenacyl bromide (Xa) with the lactim ether IX, derived from the lactam ester VIII, and the subsequent steps proceeding through the intermediates XIa, XIIa, XIIIc, XIIIa, XIVa, XVa, XVIa, XVIIa, and XVIIIa. A parallel synthesis starting with 4-benzyloxy-3-methoxyphenacyl bromide (Xb) and IX afforded (±)-10-demethylpsychotrine (II).
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■ A General Method for the Preparation of Polysubstituted Furans. A New Synthesis of dl-Menthofuran
Katsuhiko Inomata, Yukiharu Nakayama, Masumi Tsutsumi, and Hiroshi Kotake*
*Department of Chemistry, Faculty of Siencce, Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192, Japan
Abstract
Various types of polysubstituted furans were prepared via γ-hydroxy-β-tosylacetals starting from α,β-unsaturated carbonyl compounds in fairly good yields. dl-Menthofuran was synthesized by the present method.
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■ Photolysis of Thieno[2,3-c]pyridine N-Imides: Formation of Novel 1,3- and 2,3-Thienodiazepines
Takashi Tsuchiya,* Michiko Enkaku, and Hiroyuki Sawanishi
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Photolysis of the 7-methyl-thieno[2,3-c]pyridine N-imides (3) resulted in rearrangements with ring-expansion to give 1H-1,3- (4) and 3H-2,3- (5) thieno[2,3-d]diazepines, which are previously unknown heterocyclic ring systems.
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■ A Formal Synthesis of (±)-Lycorine
Bunsuke Umezawa,* Osamu Hoshino, Shohei Sawaki, Haruki Sashida, and Kazuhiko Mori
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Since the title compound has been known to be derivable from (±)-α-Δ2-lycorene-7-one (14), its alternative synthesis is described briefly.
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■ New Synthesis of Thieno[3,2-c]pyridines
Jean-Pierre Maffrand* and Robert Boigegrain
*Department Recherche et Developpement, Linge Hèmobiologie, Parcor, 195, route d‘Espagne 31024 Toulouse Cedex, France
Abstract
A new synthesis of thieno[3,2-c]pyridines by thermal rearrangement of 5-(2-thienyl)oxazolidines is described.
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■ Synthesis of Heterocycles via Lactones. Part XI. A New Route to Yohimbane Skeleton-Synthesis of 17,18-Dimethoxy-15,16,17,18,19,20-hexadehydroyohimbane
Ganesh D. Pandey* and Kamla P. Tiwari
*Department of Chemistry, University of Allahabad, Allahabad, 211002, India
Abstract
A new synthesis of the yohimbane skeleton has been described. Condensation of the bromo ester (I) with tryptamine (II) gave the lactam (III) which was cyclized and reduced to get the title compound (V).