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. 24, No. 7, 1986
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■ Studies on the Synthesis of Morphinan and Its Related Compounds: New Entry to the Construction of Benzomorphan Ring Skeleton
Tetsuji Kametani,* Masato Nishimura, Yukio Suzuki, and Toshio Honda
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Construction of a benzomorphan ring system was achieved by employing phenylselenenyl chloride mediated arene-alkene cyclization and subsequent C-ring formation via an amilynium ion intermediate, as key steps.
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■ Pyridocarbazole Alkaloids. Synthesis of Olivacine and Ellipticine Analogues
Willem F. A. Wijsmuller, Martin J. Wanner, Gerrit-Jan Koomen, and Upendra K. Pandit*
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
3,6-Dimethylellipticine and 1-demethyl-3,6-dimethylolivacine have been synthesized via the common intermediate 5-ethoxycarbonyl-3,5,6-trimethyl-11-oxo-5,11-dihydropyrido[4,3-b]carbazole.
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■ Synthesis and Reactions of (C3)-Propyn-1‘-ol Cephem
Douglas O. Spry* and Anita R. Bhala
*Lilly Reserach Laboratories, Lilly Corporate Center, Eli Lilly & Company, Indianapolis, IN 46285-4813, U.S.A.
Abstract
Cephalosporin-C(3)-allenes, propenes, acyl pyrazoles, pyrazoles and isoxazoles can be synthesized from the C(3)-propyn-1’-ol cephem 2.
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■ Structure of Mulberrofuran Q, a Novel 2-Arylbenzofuran Derivative from the Cultivated Mulberry Tree (Morus alba L.)
Yoshio Hano, Hiromi Tsubura, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A novel 2-arylbenzofuran derivative, mulberrofuran Q, was isolated from the reddish violet powder (lenticel) of the surface of the root bark of cultivated mulberry tree (Ichinose, a cultivated variety of Morus alba L.). Its structure was shown to be 1 on the basis of spectral and chemical evidence. Mulberrofuran Q is regarded biogenetically as a variation of a Diels-Alder type adduct of a chalcone derivative and a dehydroprenyl-2-arylbenzofuran derivative.
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■ The Syntehsis of the Cooked-beef Mutagen 2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine and Its 3-Methyl Isomer
Mark G. Knize and James S. Felton*
*Department of Chemistry and Biochemistry, University of Oklahoma, Nrman, Oklahoma 73019, U.S.A.
Abstract
2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine, a mutagenic compound newly isolated from cooked beef, and its 3-methyl isomer have been synthesized. The spectroscopic data and the mutagenicity of the isomers are compared.
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■ Synthesis of the Quinoline Alkaloids Buchapine and Ravesilone
Aurora Bellino* and Pietro Venturella
*Dipartimento di Chimica Organica, Università digli Studi di Palermo, Via Archirafi 20 90123 Palermo, Italy
Abstract
Buchapine (I) has been synthesized in one step by a Claisen rearrangement of 3-(γ,γ-dimethylallyl)-4-(γ,γ-dimethylallyloxy)-2-quinolone (III). The total synthesis of ravesilone (II) has been carried out from γ,γ-dimethylallylmalonic acid-2-methoxyanilide (V) in three steps.
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■ Asymmetric Synthesis of 1-Methyl-2-(2-hydroxyethyl)pyrrolidine
Theo Nikiforov,* Stephan Stanchev, Branimir Milenkov, and Vladimir Dimitrov
*Institut für Organische Chemie, Technische Universität Darmstadt, Petersenstr. 22, D-64287 Darmstadt, Germany
Abstract
An asymmetric synthesis of 1-methyl-2-(2-hydroxyethyl)pyrrolidine based on optically active 1-phenylethylamine is described.
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■ The Reaction of 1-Alkoxycarbonyl-1H-azepine with Palladium Acetane in Benzene
Katsuhiro Saito*
*Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
Heating of 1-alkoxycarbonyl-1H-azepines in benzene in the presence of palladium acetate followed by addition of water afforded 2-alkoxycarbonyl-7-phenyl-2-azabicyclo[4.1.0]hept-4-en-3-ols via reaction of the azepines with palladium salt coordinated by phenyl group, which is derived from palladium acetate and benzene.
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■ The High Pressure Mediated Reaction of π-Excessive Heterocycles with Maleic Anhydride Derivatives: A Synthetic Approach to Cantharidibn Analogues
Kiyoshi Matsumoto,* Shiro Hashimoto, Yukio Ikemi, Shinichi Otani, and Takane Uchida
*Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan
Abstract
High pressure mediated Diels-Alder reactions of 3,4-dimethoxyfuran with cyclohexene-1,2-dicarboxylic anhydrides and cyclopentene-1,2-dicarboxylic anhydride followed by catalytic hydrogenstion produced 11-oxatricyclo[6.2.1.02,7]undecane-endo-2,7dicarboxylic anhydrides and 10-oxatricyclo[5.2.1.02,6]decane-endo-2,6-dicarboxylic anhydride albeit in low yields. Reactions of N-methylpyrrole and pyrrole with dichloromaleic anhydride at high pressure resulted in Friedel-Crafts type of acylation.
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■ Biomimetic Synthesis of Elaeocarpusin
Takuo Okuda,* Takashi Yoshida, Tsutomu Hatano, and Yoshitaka Ikeda
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Elaeocarpusin, a tannin-ascorbic acid condensation product, isolated from Geranium thunbergii as one of the water-soluble forms of tannin, has been biomimetically synthesized from geraniin and ascorbic acid, and shown to occur widely in the geraniin-containing species of plants.
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■ Condensed Heteroaromatic Ring System. X. Synthesis of Benzindoles from o-Bromonaphthylamines
Takao Sakamoto, Yoshinori Kondo, and Hiroshi Yamanaka*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Benz[f]indole, of which few effective preparative methods are known, was easily synthesized by palladium-catalyzed reaction of ethyl 3-bromo-2-naphthylcarbamate with trimethylsilylacetylene and subsequent cyclization with sodium ethoxide in ethanol. By the same method, benz[g]indole and benz[e]indole were obtained from 2-bromo-1-naphthylcarbamate and 1-bromo-2-naphthylcarbamate, respectively.
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■ Synthesis of Macrobicyclic Peptides
Kazutaka Tanizawa, Kunio Okuyama, Yasumaru Hatanaka, and Yuichi Kanaoka*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
With a view to design a new type of host molecules, macrobicyclic peptides in which two lysyl ε-amino groups in cyclic peptides were intramolecularly bridged were synthesized.
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■ The Diterpenoid Alkaloids of Delphinium delavayi Franch var. pogonanthum (H. -M.) Wang
S. William Pelletier,* Fathalla M. Harraz, Mohamed M. Badawi, Sirirat Tantiraksachai, Feng-peng Wang, and Szu-ying Chen
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
Investigation of the alkaloids of Delphinium delavayi Franch var. pogonanthun (H-M) Wang has led to the isolation of nine known alkaloids and a new pair of regioisomeric alkaloids delavaine A (10A) and delavaine B (10B) whose structures have been determined based on spectroscopic evidence and two syntheses from methyllycaconitine (3). The known alkaloids that were isolated are the C19-diterpenoid alkaloids: deltaline (1), deltamine (2), methyllycaconitine (3), anthranoyllycaconitine (4), lycoctonine (5), delsemine (6), and the C20-diterpenoid alkaloids: hetisinone (7), hetisine (8), and ajaconine (9). Delsemine (6) has been synthesized from methyllycaconitine and chromatographically separated into its component regioisomers 6A and 6B.
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■ Preparation and Stereochemistry of Phenolic 1-Methyl-3-aryltetrahydroisoquinoline Derivatives
Dolores Badía, Esther Domínguez,* Carmen Iriondo, and Eduardo Martínez de Marigorta
*Departmento de Química, Facultad de Ciencias, Universidad del País Vasco, Apartado 450, 01080 Vitoria-Gasteiza, Spain
Abstract
The preparation of cis- and trans-1-methyl-3-(3,4-dimethoxyphenyl)-6-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline (5a) and (5b) , and the stereochemistry of the isoquinoline system of these compounds are reported.
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■ Behaviour of o-Phenylenediamine and o-Aminothiophenol with Aziactones. A New Synthesis of Some Benzimidazole and Benzothiazole Derivatives
Abdel-Fattah A. Harb, Salem E. Zayed, Awatef M. El-Maghraby, and Saoud A. Metwally*
*Chemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt
Abstract
A new route for the preparation of benzimidazoles (5) and benzothiazoles (10) is described. o-Phenylenediamine reacted with 2-aryl-4-arylidene-2-oxazolin-5-ones to give the corresponding benzimidazole derivatives (5) while o-aminothiophenol produced either benzothiazole (10) or intermediates (8) and (9) which could be cyclised to (10).
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■ Preparation and Properties of Methylenebispyridinium Derivatives
Shekhar Munavalli, Edward J. Poziomek,* and Wayne G. Landis
*Development & Engineering Center, U.S. Army Edgewood Research, Aberdeen Proving Ground, Maryland 21010-5423, U.S.A.
Abstract
A number of N,N’-methylenebispyridinium halides have been synthesized and characterized. The toxicological properties, mass spectra and NMR spectra of this unusual group of compounds containing a reactive methylene group flanked by two positively charged nitrogen atoms have been examined.
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■ Synthesis of Novel Azapyridocyanines
Shekhar Munavalli, Fu-Lian Hsu,* and Edward J. Poziomek
*Development & Engineering Center, U.S. Army Edgewood Research, Aberdeen Proving Ground, Maryland 21010-5423, U.S.A.
Abstract
A facile synthesis of azapyridocyanines from substituted 2-aminopyridines and dihalomethane is described. The influence of the substituents on the course of the reaction and the scope of the synthesis have been further explored.
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■ Transformation of 2,4,5-Trisubstituted Pyrimidines. The Syntheses and Transformations of Pyrimido[4,5-d]pyrimidine, 1,2,4-Triazolo[4,3-a]pyrimidine, Tetrazolo[1,5-a]pyrimidine, 1,2,4-Triazolo[3,4-b]purine and Tetrazolo[5,1-b]purine Derivatives
Uros Urleb, Branko Stanovnik,* Vekoslava Stibilj, and Miha Tisler
*Department of Chemistry, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
Some new approaches for the syntheses of pyrimido-[4,5-d]pyrimidines 3, 4, 9, and 10,5,6-disubstituted 1,2,4- triazolo[4,3-a]pyrimidines 13,15,16,17,19, and 20,5,6-disubstituted tetrazolo[5,1-a]pyrimidine 21,1,2,4-triazolo[3,4-b]purine 27 from 2,4,5-trisubstituted pyrimidines 2 and 12 are described.
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■ A Novel Intramolecular Acylation of unsym-Diacylaminoazetidinone Disulfides. The 3,8-Dioxo-5-thia-2,7-Diazabicyclo[4.2.0]octanes
Ronald G. Micetich and Rajeshwar Singh*
*Department of Chemistry, Faculty of Science, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada
Abstract
unsym-Diacylaminoazetidinone disulfides on treatment with triethylamine produce the 3,8-dioxo-5-thia-2,7-diazabicyclo[4.2.0]octanes.
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■ Synthesis of 2,3-Diphenyl-4H-benzofuro[3,2-g]furo[3,2-c][1]benzopyran-4-ones and 2,3-Diphenyl-4H-benzofuro[3,2-g]pyrrolo[3,2-c][1]benzopyran-4-ones
Vinod Kumar Ahluwalia,* Raju Adhikari, and Rishi Pal Singh
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
The synthesis of 2,3-diphenyl-4H-benzofuro[3,2-g]furo[3,2-c][1]benzopyran-4-ones (1,5,6) and 2,3-diphenyl-4H-benzofuro[3,2-g]pyrrolo[3,2-c][1]benzopyran-4-ones (15,18) is described.
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■ Cinnamoylation of Chromans: Formation of Flavonoids and Neoflavonoids
Raghava Venkataramanna Suresh, Chandrasekharapuram Subramonyam Rukmani Iyer, and Parameswaran Ramasubramonia Iyer*
*Department of Chemistry, Indian Institute of Technology, Powai, Bombay 400 076, India
Abstract
Cinnamoylation of chroman 1 with acid 4 in presence of fused zinc chloride and phosphorus oxychloride gave chalcone 8 and with acids 5-7, the chalcones 9-11 and dihydrocoumarins 15-17 respectively. A similar reaction of chroman 2 with acids 4 and 5 afforded the chalcones 12 and 13 and dihydrocoumarins 18 and 19 while chroman 3 reacted with acid 4 to yield the chalcone 14 and flavanone 20.
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■ Synthesis of 5-Oxo-5H-[1]benzopyrano[4,3-b]pyridine Derivatives
Kiyoshi Ukawa, Toshihiro Ishiguro,* Yoshikazu Wada, and Akira Nohara
*Central Research Division, Takeda Chemical Industries, Ltd., 17-85 Jusohonmachi 2-chome, Yodogawa-ku, Osaka 532-8686, Japan
Abstract
5-Oxo-5H-[1]benzopyrano[4,3-b]pyridine-3-carboxamides (2) were synthesized by the reaction of 4-oxo-4H-1-benzopyran-3-carbonitriles (1) with malonamide in the presence of sodium methoxide. Compounds (2) were also converted into carboxylic acids and tetrazole derivatives. The structures of 2 and their derivatives were confirmed by IR and NMR spectra and by X-ray crystallographic analysis.
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■ On the Leuckart Reaction of Deoxybenzoins. Isolation and Characterization of 2,3,4,5-Tetraarypyridine Derivatives
María Jesús Villa, Ester Domínguez,* and Ester Lete
*Departamento de Física Aplicada, Facultad de Ciencias, Universidad del País Vasco, Apartado 450, 01080 Vitoria-Gasteiza, Spain
Abstract
The Leuckart reaction of deoxybenzoins has been examined. The deoxybenzoins (1b-c) possessing a phenolic substituent in the ortho position to the carbonyl group react with formamide to afford, besides the known stilbene, pyrimidine and isoflavone derivatives, 2,3,4,5-tetraarylpyridines, whose structures and formation mechanism are discussed. In contrast, the Leuckart reaction of the alkoxy substituted deoxybenzoins (1d-f) leads to the expected formamides in high yields, though always accompanied by the corresponding stilbenes and pyrimidines as by-products.
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■ Spectroscopic Analysis of Iodinated Molecular Complexes of N-Methylimidazole and Other Imidazole and Imidazoline Derivatives of Pharmacological Importabce
Anne-Catherine Jambut-Absil, Jacques Buxeraud, Chiristian Moesch, Jean-François Lagorce, and Claude Raby*
*Department de Chimie Therapeutique, UFR de Pharmacie, 2, rue du Docteur Marcland, 87025 Limoges Cedex, France
Abstract
Molecular interactions between iodine and heterocyclic molecules such as N-methylimidazole, methimazole, clotrimazole, levamisole and tetrahydrozoline were investigated by UV/Vis spectroscopy. Iodine was found to form charge transfer complexes with these molecules of 1:1 stoichiometry of the n-o type. The values of the formation constants Kc of these iodinated complexes indicated a strong donor-acceptor interaction. These compounds can therefore be expected to have an action on thyroid metabolism.
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■ Synthesis of 4-Cyanoimdole from 4-Oxo-4,5,6,7-tetrahydroindole Derivatives
Naoto Hatanaka and Masakatsu Matsumoto*
*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan,
Abstract
4-Oxo-4,5,6,7-tetrahydroindoles are first converted to cyanohydrin silyl ethers and subsequent elimination and/or oxidation produced 4-cyanoindole.
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■ Hashish: Oxidation of Δ8-Tetrahydrocannabinol (THC); Synthesis of Δ8-THC-1,2-Dione and 2-Hydroxy-Δ8-THC
Hossein Hadjat-Kashani, Gali Lambert, Richard Duffley, and Raj Razdan*
*The SISA Institute for research Inc., 763D Concord Avenue, Cambridge, MA 02138, U.S.A.
Abstract
The title compounds were synthesized from δ8-THC in yields of 65% and 63% respectively. The structure of 3 as a 1,2-dione was supported by NOE data. structural re-assignment of a previously isolated quinonoid-THC 4 is proposed.
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■ Synthesis of 2-Substituted-6,7-dihydro-4H-pyrimido[6,1-a]thieno[2,3-c]- and [3,2-c]pyridin-4-ones
Bansi Lal,* Lalitha Krishnan, and Noel J. de Sauza
*Department of Chemistry, Research Centre, Hoechst India Limited, Mulund, Bombay 400 080, India
Abstract
1-(2-(3-Thienyl)ethyl)barbituric acid (7a) and 1-(2-(2-thienyl)ethyl)barbituric acid (7b) were cyclized to novel 2-chloro-6,7-dihydro-4H-pyrimido[6,1-a]thieno[2,3-c]pyridin-4-one (8a) and 2-chloro-6,7-dihydro-4H-pyrimido[6,1-a]thieno[3,2-c]pyridin-4-one (8b), respectively. The chloro group in both 8a and 8b was displaced by different amines to give the corresponding amino compounds 9a and 9b.
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■ Short Step Synthesis of 4-Formylindole and Derivatives from 4-Oxo-4,5,6,7-tetrahydroindole
Naoto Hatanaka, Nobuko Watanabe, and Masakatsu Matsumoto*
*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan
Abstract
The reaction of 4-oxo-4,5,6,7-tetrahydroindole with umpolung anions provides a new short efficient procedure for the synthesis of 4-formylindole derivatives.
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■ Polycyclic N-Hetero Compounds. XXVI. Synthesis of 4-Substituted 6,7-Duhydro-5H-pyrimido[5,4-d][1]benzazepine
Takashi Hirota,* Masami Fukumoto, and Kenji Sasaki
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
4-Substituted 6,7-dihydro-5H-pyrimido[5,4-d][1]benzazepines (IIIa-j) were synthesized by the reaction of 4-chloro-6,7-dihydro-5H-pyrimido[5,4-d][1]benzazepine (I) with amines (IIa-j) and their antidepressive activities were investigated.
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■ A Novel Synthetic Route to Oxazoles: One Pot Synthesis of 2-Arylthio-5-alkoxyoxazoles
Ricardo Bossio, Stefano Marcaccini,* and Roberto Pepino
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
Reaction between alkyl isocyanoacetates and arylsulfenyl chlorides afforded isothiocarbamoyl chlorides Ia-f which on treatment with triethylamine gave 2-arylthio-5-alkoxyoxazoles IIa-f in almost quantitative yields.