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. 4, 1983
Published online:
■ Competitive Formation of Pyrrole and Pyridazine Ring: Stable Tetrahydropyridazine Carbinolamine as Common Precursor
Leopoldo Ceraulo, Liliana Lamartina, Onofrio Migliara, Salvatore Petruso, and Vincenzo Spiro
*Instituto di Chimica Farmaceutica e Tossicologica, Università digli Studi di Palermo, Via Archirafi 32, 90123 Palermo, Italy
Abstract
It is demonstrated, by 13C-nmr analysis, that the precursors of both imidazo[1,5-b]pyridazines 3a-c and 1-ureidopyrroles 4d-f have the tetrahydropyridazine structure 2a-f, rather than the previously reported semicarbazone one 1a-f.
Published online:
■ NMR Spectroacopic Studies of Tryptophan Derivatives
Ari Koskinen, Pekka Somersalo, and Mauri Lounasmaa
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
Proton and carbon-13 nuclear magnetic resonance spectra of some tryptophan derivatives are reported along with their analysis. The spectral parameters reveal new sensitive probes for structure elucidation of indole alkaloids.
Published online:
■ 13C NMR Spectral Analysis of α-Aminonitriles
Ari Koskinen and Mauri Lounasmaa*
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
A carbon-13 NMR spectroscopic study of α-aminonitriles derived from piperidines has been conducted. The substituent effects for cyano group in the nitrogen heterocycles is shown to obey strict regularities. The preferred conformation of a lone cyano group located to the nitrogen is found to be equatorial.
Published online:
■ Reinvestigation of a Recent 1,3,4-Benzotriazepine Synthesis, Formation of 1,3,4-Oxadiazoles
Endre Tihanyi, Melinda Gál, and Péter Dvoetsák
*Institute for Drug Research Ltd., H-1325 Budapest, POB 82, Hungary
Abstract
It was shown by spectrosopic and synthetic methods that the reaction of anthranilic acid hydrazides with 1,1’-carbonylbisimidazole (CO/Im/2) afforded, in contrast with earlier literature data, no 1,3,4-benzotriazepines or quinazolines but 1,3,4-oxadiazole derivatives.
Published online:
■ Photochemical Synthesis of 2-Azetidinone Derivatives
Sang Chul Shim and Dae-Whang Kim
*Department of Applied Chemistry, Korea Advanced Institute of Science and Technology, P.O.Box 150 Chong-Yang-ni, Seoul 131, Korea
Abstract
Irradiation of N-Pyruvoyl-N-benzyl phenylglycine methyl ester (1) yields 1-(α-methoxycarbonyl)benzyl-3-hydroxy-4-phenyl-2-azetidinone (4) in 85% yield.
Published online:
■ Nitrogen Bridgehead Compounds Part 22. Reaction of 2,3a,6a-Triazaphenalenium Salts with Nucleophiles
István Bitter, Béla Pete, István Hermecz, Kálmán Simon, Gábor Tóth, and Zoltán Mészáros
*Department of Organic Chemical Technology, Technical University of Budapest, H-1521 Budapest, Gellért tér 4, Hungary
Abstract
Novel 2,3a,6a-triazaphenalenium chlorides were allowed to react with different nucleophiles. Beside anion exchange Michael addition took place with GN-and HSO3- anions affording tricyclic betaines.
Published online:
■ Synthesis of Setoclavine
Julius Rebek, Jr. and Dar-Fu Tai
*Department of Chemistry, University of Pittsburgh, Parkman Avenue & University Drive, Pittsburgh, PA 15260 , U.S.A.
Abstract
The first total synthesis of the ergot alkaloid setoclavine is described. Tryptophan is the starting material and methods used are of some generality for the synthesis of other ergot alkaloids.
Published online:
■ Kuwanon M, a New Diels-Alder Adduct from the Root Barks of the Cultivated Mulberry Tree (Morus lhou(ser.) Koidz.)
Taro Nomura, Toshio Fukai, Yoshio Hano, and Hisato Ikuta
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Kuwanon M (I), a new Diels-Alder adduct of two prenylflavone derivatives, has been isolated from the cultivated mulberry tree (Morus Lhou(ser.) Koidz.). The structure was shown to be I on the basis of spectral data. The compound (I) produced a hypotensive effect to spontaneously hypertensive rat (2 mg/Kg, i.v.).
Published online:
■ One-Pot Synthesis of Furan Systems Bearing 2-Pyridyl Substituent
Otohiko Tsuge, Koyo Matsuda, and Shuji Kanemasa
*Graduate School of Engineering Sciences, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The reaction of an anionic intermediate, generated in situ from the lithio derivative of 2-(trimethylsilylmethyl)pyridine and an aromatic nitrile, with α-haloketones such as phenacyl bromide, desyl chloride and 2-bromocyclohexanone provided a route to a one-pot synthesis of rare 2-pyridyl substituted furans. The reaction pathway is also described.
Published online:
■ Studies on Ketene and Its Derivatives 114. 1,4-Cycloaddition of Ketene to Ethyl N-(2-Pyridyl)formimidates
Nobuya Katagiri, Ryuji Niwa, and Tetsuzo Kato
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Reaction of ketene with ethyl N-(2-pyridyl)formimidate (1a) in acetone at room temperature gave 3-acetylpyrido[1,2-a]pyrimidin-4(4H)-one (2) whereas excess ketene gas was passed over the imidate 1a without solvent at 75 °C to give pyrido[1,2-a]pyrimidin-4(4H)-one (3a) and 2-formamidopyridine (4a), both of which would be formed by 1,4-cycloaddition of ketene. Similarly, reactions of ketene with the methyl analogs 1b-e were also carried out to give pyridopyrimidines (3b-e) and 2-formamidopyridines (4b,c,e).
Published online:
■ Application of the Oxygenative Nucleophile Introduction Reaction to 1-Alkoxycarbonyl-2-alkynyl-1,2-dihydropyridines. A Facile Synthesis of (±)-Sedacryptine
Mitsutaka Natsume and Masashi Ogawa
*Research Foundation Itsuu Laboratory, 2-28-10 Tamagawa, Setagaya-ku, Tokyo 158, Japan
Abstract
A Sedum alkaloid, (±)-sedacryptine (17) was effectively synthesized from the compound (3g), one of the products (3a-31) derived from 2-alkynyl-1,2-dihydropyridine derivatives (2) by application of our oxygenative nucleophile introduction reaction.
Published online:
■ Absolute Configuration and Grignard Reaction of Chiral 4-Isopropyl-3-methyloxazolidines
Hiroshi Takahashi, Yuji Suzuki, and Tetsuji Kametani
*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A new chiral 4-isopropyl-3-methyloxazolidines were synthesized by the condensation of N-methylvalinol with some aldehydes. The absolute configuration and asymmetric reactions of these compounds were discussed.
Published online:
■ Structure of Sanggenon G, a New Diels-Alder Adduct from the Chinese Crude Drug “Sang-Bai-Pi” (Morus Root Barks)
Toshio Fukai, Yoshio Hano, Tomoko Fujimoto, and Taro Nomura
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
From the methanol extract of the Chinese crude drug “Sang-Bai-Pi” (Japanese name Sohakuhi), root barks of Morus sp. (Moraceae), a new flavanone derivative with a fused dihydrochalcone partial moiety was isolated and named sanggenon G. The structure was shown to be I on the basis of spectral data. Sanggenon G (I) is regarded biogenetically as a Diels-Alder adduct of a chalcone derivative and dehydrogeranylflavanone derivative.
Published online:
■ Reactions of Amidines with Diphenylamine-2,2’-dicarbonyl Chloride
Avijit Banerji and Alpana Sahu
*Chemistry Department, College of Science, Culcutta University, 92 Acharya Prafulla Chandra Road, Calcutta-700009, India
Abstract
Amidines react with diphenylamine-2,2’-dicarbonyl chloride to yield polyheterocycles. Reactions of some of the latter with reducing agents are also reported.
Published online:
■ Preparation and Reactions of 1-Cyanomethyl-2,4,6-trisubstituted Pyridinium Ylids
Alan R. Katritzky, Wing Kai Yeung, Ranjan C. Patel, and Kevin Burgess
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
Aminoacetonitrile with pyrylium forms pyridiniums which are acylated to solvatochromic ylids. Pyrolysis of ylid (10a) (R = p-toluoyl) gives 3-cyano-2,4,6-triphenylpyridine. 1-Cyanomethyl-pyridinium (6) gives tetrahydroindolizines with α,β-unsaturated carbonyl compounds.
Published online:
■ Reaction of 2,2’-Diamino-4,4’-di-tert-butyldiphenyl with Excess SO2Cl2 Affording 1,3,4,6,8-Pentachloro-2,7-di-tert-butylcarbazole
Masashi Tashiro, Yasuhisa Fukuda, and Gouki Fukata
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Treatment of 2,2’-diamino-4,4’-di-tert-butyldiphenyl with excess SO2CI2 in a boiling CCI4 solution afforded 1,3,4,6,8-pentachloro-2,7-di-tert-butylcarbazole in 80% yield. The pathway of the above reaction is also described.
Published online:
■ Activated Nitriles in Heterocyclic Synthesis: Novel Synthesis of Thiopyrano[2,3-d]thiazoles
Sanna O. Abd Allah, Hamed A. Ead, Nazmi A. Kassab, and Nadia H. Metwali
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
A novel synthesis of thiopyrano[2,3-d]thiazoles is reported via the reaction of arylmethylenemalononitriles with thiazolidin-2-one-4-thione and thiazolidin-2,4-dithione.
Published online:
■ Pentacyclic Phenothiazines I. Construction of the Pyrido[3’,4’:4,5]pyrrolo[3,2,1-kl]phenothiazine Ring System via Selective Metallation of a 2-Substituted Pyrrolo[3,2,1-kl]phenothiazine
Torsten Dahlgren, Donald R. Deardorff, and Arnold R. Martin
*Department of Pharmaceutical Sciences, College of Pharmacy, The University of Arizona, Tucson, AZ 85721, U.S.A.
Abstract
A new pentacyclic heterocycle, 3-benzyl-1,2,3,4-tetrahydro-4H-pyrido[3’,4’:4,5]pyrrolo[3,2,1-kl]phenotiazin-4-one (2), the first known example of the pyrido[3’,4’:4,5]pyrrolo[3,2,1-kl]phenothiazine ring system (1) has been prepared in seven steps beginning with pyrrolo[3,2,1-kl]phenothiazine (3). Key to the success of the synthesis is the selective metallation, and subsequent alkylation with ethylene oxide, of 2-[2-pyrrolo-[3,2,1-kl]phenothiazinyl]-4,4-dimethyl-2-oxazoline (10).
Published online:
■ Regio- and Periselective Cycloaddition Reactions of a Biperifunctional Compound, 1,3,6-Triphenylimidazo[1,2-c]thiaIVzole
Otohiko Tsuge, Shuji Kanemasa, and Takayoshi Hamamoto
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
In the cycloaddition reactions of a biperifunctional compound, 1,3,6-triphenylimidazo[1,2-c]thiaIVzole, to a variety of unsymmetrically substituted olefinic dipolarophiles, one of the two peripheral thiocarbonyl ylides has exclusively contributed affording good yields of the regioselective [3 + 2] cycloadducts.
Published online:
■ Oxidative Coupling Reaction of 2-Halophenols with K3Fe(CN)6 in Benzene Solution
Masashi Tashiro and Haruo Yoshiya
*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The oxidative coupling of twelve 2-halophenols (1a-1l) was carried out with K3Fe(CN)6 in benzene solution to obtain the corresponding dibenzofuran derivatives. However, only a small amount of the desired dibenzofurans such as 2,6-di-tert-butyl-8-methoxydibenzofuran-1,4-quinone (9) and 4,8-di-tert-butyl-2,6-di-isopropyl-1-hydroxydibenzofuran (11) were obtained from 2-bromo-6-tert-butyl-4-methoxy- (1d) and 2-bromo-4-tert-butyl-6-isopropylphenol (1g), respectively. In the other cases, alternative type of products or tarry materials were formed.
Published online:
■ Constituent of the Chinese Crude Drug “Sang-Bai-Pi” (Morus Root Barks) III. Structure of a New Flavanone Derivative, Sanggenon F.
Taro Nomura, Toshio Fukai, Yoshio Hano, and Koji Tsukamoto
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
From the benzene extract of the Chinese crude drug “Sang-Bai-pi” (Japanese name “Sohakuhi”), the root barks of Morus sp. (Moraceae), an isoprene substituted flavanone derivative, named sanggenon F, was isolated, for which structure (I) was proposed on the basis of its spectral and chemical evidence.
Published online:
■ The Structures of Serratenone and Serratoline, Two Alkaloids from Aristotelia serrata
I. Ralph C. Bick, Mohammad A. Hai, and Nigel W. Preston
*Department of Chemistry, University of Tasmania, GPO Box 252C Hobart, Tasmania, 7001, Australia
Abstract
Serratenone, a new indole alkaloid from A. serrata, is shown to have structure 1, and the amended structure 3 is established for the indolenine alkaloid serratoline.
Published online:
■ Novel Applications of the Modified Polonovski Reaction—VI. Preparation of (±)-Hygrine and (±)-N-Methylruspolinone
Tord Langenskiöld and Mauri Lounasmaa
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
Preparation of (±)-hygrine 5 and (±)-N-methylruspolinone 6 via N-methyl-2-cyanopyrrolidine 1 is described.
Published online:
■ The Role of Lone Pair Interactions in the Selective Functionalisation of Some 4,6-O-Benzylidene-hexopyranosides by Both the Phase Transfer Esterification Reactions and the Tin-mediated Esterification and Alkylation Reactions
Vernon G. S. Box
*Department of Chemistry, Mona Campus, University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
The esterifications of some 4,6-O-benzylidene-hexo-pyranosides by the phase transfer method are reviewed and a mechanism for these reactions is proposed which takes into account the differential nucleophilicities of the oxygens, O-2 and O-3, as predicted by the β-effect and the γ-effect. The similarities between the tin mediated esterification and alkylation reactions of these monosaccharides and the corresponding phase transfer reactions lead to the proposal of a mechanism for the path of the tin mediated processes. The alkylation of diols by diazoalkanes in the presence of catalytic amounts of tin salts is reviewed and a mechanism is proposed for these reactions, which rationalises the apparently inverse reactivity of the ‘hydroxyl groups’.