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. 8, 1980
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■ Ring Transformation of 2-Furylcarbamates to 5-Hydroxy-3-pyrrolin-2-ones. Revised Structure of Jatropham
Kenichi Yakushijin, Masamichi Kozuka, Yoko Ito, Rika Suzuki, and Hiroshi Furukawa*
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
2-Furylcarbamates 1-7 react with oxygen under stirring or irradiation in benzene at room temperature to give the corresponding N-substituted 5-hydroxy-3-pyrrolin-2-ones 8-14. In the syntheses and NMR experiments of these pyrrolinone derivatives, the structure of jatropham 27, one of pyrrolinone derivatives proposed by Cole et al., is revised to the formula 11 (R1=H).
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■ Synthetic Studies on Optically Active β-Lactams. Chiral Synthesis of Carbapenam Ring System Starting from L-Aspartic Acid
Nobuo Ikota, Hisanari Shibata, and Kenji Koga*
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
Benzyl (3R,5R)-1-carba-2-oxopenam-3-carboxylate (12), a useful synthon for β-lactams having carbapenem ring system, was synthesized in optically pure state starting from L-aspartic acid.
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■ Synthesis of Some Hexahydro-2,7-benzoxazacycloundecine-7(1H)-carbonitrile Derivatives from Tetrahydroisoquinoline Precursors
John B. Bremner,* Charles Drager, and Narumol Thirasasana
*Department of Chemistry, University of Tasmania, GPO Box 252C Hobart, Tasmania, 7001, Australia
Abstract
Treatment of 2-(4-hydroxybutyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (3a) with cyanogen bromide in chloroform/potassium carbonate gave the novel heterocyclic product, 11,12-dimethoxy-3,4,5,6,8,9-hexahydro-2,7-benzoxazacycloundecine-7(1H)-carbonitrile (5a) in low yield. The 1-methyl (5b) and 1-phenyl (5c) derivatives of (5a) were prepared in a similar fashion.
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■ Synthesis of the 3,4,6,7-Tetrahydro-1H-1,5-methano-2,5-benzoxazonine Ring System by Cyanogen Bromide-Mediated Rearrangement of a 10b-Methyl-5H-oxazolo[2,3-a]isoquinoline Derivative
John B. Bremner* and Kevin N. Winzenberg
*Department of Chemistry, University of Tasmania, GPO Box 252C Hobart, Tasmania, 7001, Australia
Abstract
The new heterocyclic derivatives, 1,9,10-trimethoxy-3,4,6,7-tetrahydro-1H-1,5-methano-2,5-benzoxazonine (2a) and 9,10-dimethoxy-3,4,6,7- tetrahydro-1H-1,5-methano-2,5-benzoxazonine-1-carbonitrile (2b), were prepared in 76% and 4% yield respectively by the reaction of 8,9-dimethoxy-10b-methyl-2,3,6,10b-tetrahydro-5H-oxazolo[2,3-a]isoquinoline (1b) with cyanogen bromide in the presence of methanol and potassium carbonate. Acid hydrolysis of (2a), followed by reduction with lithium tetrahydroaluminate, afforded 3-(2-hydroxy)ethyl-7,8-dimethoxy-2,3,4,5-tetrahydro-1H-3-benzazepin-1-ol (4) in good yield. A mechanism of formation of (2a) and (2b) is outlined.
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■ A New Synthesis of Bicyclo[1,3]oxazine Derivatives
Makoto Okita, Takeshi Wakamatsu, Miwako Mori, and Yoshio Ban*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
There has been described a new synthesis of bicyclo-tetrahydro-[1,3]-oxazine derivatives from five- and six-membered lactams by anodic oxidation, followed by simultaneous cyclization.
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■ On Acetylation of 4-(N-Hydroxy-N-methylamino)quinoline 1-Oxide
Yutaka Kawazoe* and Osamu Ogawa
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Treatment of carcinogenic and mutagenic 4-(N-hydroxy-N-methylamino)quinoline 1-oxide with acetic anhydride gave 4-(N-acetoxy-N-acetoxymethylamino)quinoline and 4-(N-acetoxy-N-methylamino)quinoline as the main products with evolution of methane and carbon dioxide. Discussion is made in connection with the carcinogenicity and mutagenicity.
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■ A Modified Total Synthesis of (±)-Lycorine
T. Sano,* N. Kashiwaba, J. Toda, Y. Tsuda, and H. Irie
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
A modified total synthesis of lycorine was accomplished starting from the lactam-ester (5). Selective reduction of the lactam carbonyl of 5, followed by cyclization gave 5-oxolycorene (4). Epoxidation of 4 gave stereoselectively the α-epoxide (9). Repeated application of Sharpless method to convert epoxide into allylic alcohol and acetylation of the product gave diacetyl 5-oxolycorine (19). Lithium aluminium hydride reduction of 19 gave (±)-lycorine.
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■ Total Synthesis of (±)-6,7-Secoagroclavine
Mitsutaka Natsume and Hideaki Muratake*
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
An ergot alkaloid, 6,7-secoagroclavine was synthesized in racemic form from 1-methoxycarbonylpyrrole in 15 steps.
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■ Synthesis of a New Azacyclazine, Indolizino[3,4,5,6-cde]quinoxaline
Shuji Kanemasa,* Seigo Kobira, and Shoji Kajigaeshi
*Department of Industrial Chemsitry, Faculty of Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Abstract
A new peripheral azomethine ylid 1,3-dipole, anhydro 3H-pyrido[1,2,3-de]quinoxalin-4-ium hydroxide, was generated from the pyridoquinoxalinium bromide and reacted with dimethyl acetylenedicarboxylate giving the indolizino[3,4,5,6-cde]quinoxaline in quantitative yield. With electron-deficient olefins such as diethyl fumarate and N-benzylmaleimide, the corresponding [4+2] cycloadducts were formed, which were then dehydrogenated with p-chloranil into the similar heterocycles in fair yields.
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■ Facile α,β’-Annelation of 1,6-Dihydro-3(2H)-pyridinones with 1,3-Dicarbonyl Compounds. A New Synthetic Method for 2-Azabicyclo[2.2.2]octan-6-ones
Takeshi Imanishi, Hiroaki Shin, Miyoji Hanaoka,* Takefumi Momose, and Ichiro Imanishi
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
On treatment of N-substituted 1,6-dihydro-3(2H)-pyridinones with 1,3-dicarbonyl compounds proceeded a facile α,β’-annelation to give the 2-azabicyclo[2.2.2]octan-6-ones under a basic condition, while the reaction with dimethyl acetonedicarboxylate afforded a 3-azabicyclo[3.3.1]nonanone.
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■ Ene Reaction of 1-Pyrazoline Derivatives with Tetracyanoethylene
Alma Calatroni and Remo Gandolfi*
*Dipartamento di Chimica Organica, Università di Pavia, V. le Taramelli 10, 27100 Pavia, Italy
Abstract
1-Pyrazoline derivatives 4 and 5 reacted with tetracyanoethylene to give, through a formal ene reaction followed by a loss of hydrogen cyanide, 1-tricyanovinyl-2-pyrazoline derivatives 6 and 7 as dominant products. By contrast, tetracyanoethylene played only a catalytic role in the reaction with 1-pyrazolines 11 promoting their tautomerization to 2-pyrazolines 13. The possible mechanisms of such reactions are discussed.
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■ A Simple Enantioselective Inversion in Chiral 2-Oxabicyclo[3.3.0]octa-6-en-3-one, a Key Intermediate for Chiral Prostaglandin Syntheses
Naoyasu Ishizuka,* Souji Miyamura, Tadashi Takeuchi, and Kazuo Achiwa
*Fuji Chemical Industries, Ltd., 530 Chokeiji, Takaoka, Toyama 933- 0951, Japan
Abstract
A simple and effective inversion of (1R,5S)-2-oxabicyclo[3.3.0]octa-6-en-3-one into its enantiomer was described.
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■ Studies on Heterocyclic Compounds XXXV. Facile Synthesis of 3-Methylamino-1,2,4-triazolo[4,3-a]pyridine with Nickel Peroxide
Haruo Ogura,* Satoshi Mineo, and Kunio Nakagawa
*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
3-Methylamino-1,2,4-triazolo[4,3-a]pyridine (II) was obtained from the reaction of 1-(2-pyridyl)-4-methylthiosemicarbazide (I) and Nickel Peroxide (Ni-PO) in a good yield.
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■ Studies Aiming at the Synthesis of Morphine I. Separation and Characterization of the Amide Rotamers of 6’-Halogeno-N-formyl-norreticulines
Csaba Szántay,* Gábor Blaskó, Marietta Bárczai-Beke, Gábor Dörnyei, and Lajos Radics
*Institute for Organic Chemistry, Technical University Budapest, H-1521 Budapest, P.O. Box 91Gellért tér 4, Hungary
Abstract
Via direct halogenation of N-substituted norreticulines, number of 6’-halogeno derivatives were prepared. The physical and spectroscopic properties of the successfully separated crystalline rotamers of both 6’-bromo- and 6’-chloro-N-formyl-norreticuline were studied.
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■ On the Structure of Glauvine: Synthesis of Oxolirioferine, Norlirioferine and N,O-Diacetylnorlirioferine
Luis Castedo,* José M. Saá, Rafael Suau, and Carmen Villaverde
*Departamento de Química Orgánica e Unidade Asociada al CSIC, Facultad de Quimica, Universidad de Santiago de Compostela, E-15706, Santiago de Compostela, Spain
Abstract
Further support for structure (2) of glauvine by proving that its reduction product and norlirioferine (3c) were distinct compounds is described. Norlirioferine (3c) and its N,O-diacetylderivative (3d) were obtained via oxolirioferine (4a), which was synthetized by two independent routes.
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■ The Demethylation of Aporphines with Sulfuric Acid
Luis Castedo,* Angel Rodriguez de Lera, José M. Saá, Rafael Suau, and Carmen Villaverde
*Departamento de Química Orgánica e Unidade Asociada al CSIC, Facultad de Quimica, Universidad de Santiago de Compostela, E-15706, Santiago de Compostela, Spain
Abstract
Sulfuric acid at room temperature has been found a useful reagent for interconverting aporphine alkaloids by selective O-demethylation. This was controlled by electronic or steric effects.
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■ Synthesis and Alkylation of 6,7-Dimethyl-5H-1,2,4-triazino[5,6-b]indole-3(2H)-thione
William A. Romanchick and Madeleine M. Joullié*
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
The synthesis and alkylation of 6,7-dimethyl-5H-1,2,4-triazino[5,6-b]indole-3(2H)-thione (5) are described.
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■ A Convenient and Single Step Synthesis of Substituted 4H[1,4]-Benzothiazines
R. R. Gupta,* K. G. Ojha, G. S. Kalwania, and M. Kumar
*Department of Chemistry, University of Rajasthan, Jaipur 302 004, India
Abstract
A simple one step synthesis is reported for substituted 4H[1,4]-benzothiazines involving the condensation of 5-(chloro, bromo, methyl, methoxy, ethoxy)-, 4-methyl- and 3-(chloro and methoxy)-2-aminobenzenethiols with acetylacetone/ethyl acetoacetate/dibenzoylmethane in DMSO.
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■ A One-pot Isoquinoline Synthesis by Cyclodehydrogenation of Benzylaminoacetals with Chlorosulfonic Acid
Kazuko Kido and Yasuo Watanabe*
*Daiichi College of Pharmaceutical Sciences, 22-1 Tamagawa-cho, Minami-ku, Fukuoka 815-0037
Abstract
A direct preparation of the fully aromatized isoquinolines (3a-l) by the cyclodehydrogenation of benzylaminoacetals (2a-l) with chlorosulfonic acid is described.
Comparing the behavior of chlorosulfonic acid with that of sulfuric acid toward 1,2-dihydroisoquinoline, it is able to be suggested that benzylaminoacetals were cyclized first to 1,2-dihydroisoquinolines, subsequently, dehydrogenated to the fully aromatized isoquinolines by the hydride abstraction with ClSO3H. Substitution by a larger R3 group than isopropyl in the acetal ArCH(R3)NHCH2CH(OEt)2, interfered this second step, so the corresponding isoquinolines could not be obtained.
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■ Formation of the Oxazolidine Ring in C20-Dieterpenoid Alkaloids by Oxidative Cyclization with Silver Oxide
S. William Pelletier,* Abdel-Monem M. Ateya, Naresh V. Mody, and Lee C. Schramm
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
Treatment of the N-CH2-CH2OH group-containing alkaloids with silver oxide in alcohol affords the “iso-type” oxazolidine ring-containing alkaloids in yields of 72 to 90% via oxidative cyclization. This method affords higher yields than earlier reported methods for this type of transformation.
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■ The Effect of Hydroxy, Methoxy and Mehtylenedioxy Groups on the Ultraviolet Spectra of Aromatic and Heterocyclic Compounds — Alkaloids
Frantisek Santavy*
*Institute of Medical Chemistry, Palacky University, 3, Hnevotínská, 775 15 Olomouc, Czech Republic
Abstract
This review describes the work done in the field of electron spectroscopy (ultraviolet spectra) of aromatic and heterocyclic compounds with or without electron accepting groups substituted by hydroxy, methoxy or methylenedioxy groups in different positions of the aromatic nucleus.
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■ Synthesis and Biosynthesis of Phytoxanthones
M. Afzal* and J. M. Al-Hassan
*Biochemistry Department, Kuwait University, Safat 13060, P.O. Box 5969, Kuwait
Abstract
Chemotherapeutic and taxonomic values of natural xanthones are appraised. Synthesis and biosynthesis of phytoxanthones is reviewed.