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. 32, No. 5, 1991
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■ Fischer Reaction of 1-Acetyl-3-oxo-2,3-dihydroindole and 1-(p-Toluenesulfonyloxy)-3-oxo-2,3-dihydroindole
Jean-Yves Mérour* and Laurence Savelon
*Laboratoire de Chimie Bioorganique et Analytique, URA-CNRS N° 499, Université d‘Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
1-(p-toluenesulfonyloxy)-3-oxo-2,3-dihydroindole reacted with phenylhydrazine in acetic acid affording 5-(p-toluenesulfonyloxy)indolo[3,2-b]indole. By contrast 1-acetyl-3-oxo-2,3-dihydroindole in the same experimental conditions afforded 12-aminoindolo[1,2-c]quinazoline.
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■ Radical Carbamoylation of 1,2,3-Triazinium 2-Dicyanomethylides
Kazuhiro Nagata, Takashi Itoh, Mamiko Okada, Hiroyuki Takahashi, and Akio Ohsawa*
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
The nucleophilic radical carbamoylation of 4,6-disubstituted 1,2,3-triazinium 2-dicyanomethylides occurred at their 5-positions followed by the elimination of dicyanomethylene to form 5-substituted 1,2,3-triazines. The reaction did not proceed when parent triazines were adopted as the substrates.
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■ Synthesis of Dehydrodeoxypodophyllotoxin Cyclic Ether via Allene Intramolecular Cycloaddition Strategy and Evaluation of Its Cytotoxicity
Ken Kanematsu,* Michiko Tsuruoka, Yumiko Takaoka, and Takuma Sasaki
*Institute of Synthetic Organic Chemistry, Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
The new route to dehydrodeoxypodophyllotoxin cyclic ether (10) has been realized via allene intramolecular Diels-Alder reaction of the propargyl ether (8).
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■ A Novel Approach to Quaternary Substituted Chiral Cyclobutanes. A Formal Enantioselective Total Synthesis of 1,3-Dioxole Pheromone, (-)-Frontalin
Hideo Nemoto, Toshie Yamada, Hiroki Ishibashi, Junko Takazawa, and Keiichiro Fukumoto*
*Faculty Institute Sciences, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
A novel synthesis of the quaternary substituted chiral cyclobutanone (9) was achieved by the concerted ring expansion of the chiral cyclopropyl epoxide (8) which lead to a formal total synthesis of (-)-frontalin (14).
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■ Synthesis of Carbocyclic Oxetanocin Analogues as Potential Anti-HIV Agents. Part 3
Hassane Boumchita, Michel Legraverend,* Jean Guilhem, and Emile Bisagni
*URA 1387, CNRS, Institut Curie, Section de Biologie, Centne Universitaire, Bât. 110-112, Institut Curie, 15 Rue Georges Clemenceau 91405 Orsay, France
Abstract
Two new carbocyclic oxetanocin analogues have been prepared from 1-amino-3-methylenecyclobutane. The results of biological testing against HIV-12 invitro are presented.
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■ Ergot Alkaloids: The First and Five Step Total Syntheses of (—)- and (+)-6,7-Secoagroclavines, and the Syntheses of (—)- and (+)-6-Nor-6-propyl-6,7-secoagroclavines ((—)- and (+)-KSU 1415)
Kyoko Nakagawa and Masanori Somei*
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Simple synthetic method for optically active 4,5-trans-((—)- and (+)-6) and 4,5-cis-5-(2-methyl-1-propen-1-yl)-4-nitro-1,3,4,5-tetrahydrobenz[cd]indoles ((—)- and (+)-7) was developed. Using these chiral common synthetic intermediates, the first total syntheses of (—)- and (+)-6,7-secoagroclavines were achieved in only five steps. Preparations of (—)- and (+)-6-nor-6-propyl-6,7-secoagroclavines ((—)- and (+)-KSU 1415) are also described.
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■ Asymmetric Synthesis XXV. Diastereoselective Synthesis of Indolizidinediol Alkaloid Analogs
Virginie Ratovelomanana, Laurent Vidal, Jacques Royer, and Henri-Philippe Husson*
*Institut de Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
The asymmetric synthesis of 3-methylindolizidine-1,2-diol, analog of indolizidine-1,2-diol alkaloids, has been achieved from the chiral 2-cyano-6-oxazolopiperidine synthon (1). The synthesis commenced with 1,2 addition of the anion of 1 on crotonaldehyde leading to 8 with enantioselective formation of the firtst hydroxyl group. Epoxidation of the double bond followed by hydrogenolysis of the benzyl appendage led to the amino epoxides (13). Finally the five membered ring construction was accomplished by employing cyclization of 13.
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■ A Facile Synthesis of dl-Sedamine and dl-Allosedamine
Naganori Ozawa,* Setsuko Nakajima, Kyoko Zaoya, Fumiko Hamaguchi, and Tatsuo Nagasaka
*School of Pharmacy, Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Racemic sedamine and dl-allosedamine were easily synthesized from the intermediate (3) using a cyclic acyliminium salt by the addition-elimination reaction sequence.
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■ Pyridazine Derivatives and Related Compounds Part 5. Pyrazolo[3,4-c]pyridazine: Synthesis and Some Reactions
Ali Deeb,* Besher Bayoumy, Abd El-Naby Essawy, and Rida Fikry
*Department of Chemistry, Faculty of Science, University of Zagazig, Zagazig, Egypt
Abstract
This paper describes the synthesis of three pyrimido[1’,2’: 1,5]pyrazolo[3,4-c]pyridazines (6, 7 and 9) starting from 3-amino[3,4-c]pyridazine (1). Pyrimido[5’,4’:5,6]pyrimido[1’,2’:1,5]pyrazolo[3,4-c]pyridazine derivatives (8) was obtained by condensing 7a with formamide. Reactions of 1 with acetic anhydride, benzoyl chloride, phenacyl bromide and 4-chlorophenacyl bromide gave 3-substituted amino derivatives.
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■ Pyridazine Derivatives and Related Compound Part 6. Synthesis of Triazolo[3’,4’:5,1]pyrazolo[3,4-c]pyridazine, Pyrido[2’,1’:3,2][1,2,4]triazolo[5’,1’:5,1]pyrazolo[3,4-c]pyridazine and Naphtho[2,1-e]pyridazino[3’,4’:3,4]pyrazolo[5,1-c][1,2,4]triazine Derivatives
Ali Deeb,* Besher Bayoumy, Ahmed Hataba, and Rida Fikry
*Department of Chemistry, Faculty of Science, University of Zagazig, Zagazig, Egypt
Abstract
1,2,4-Triazolo[3’,4’:5,1]pyrazolo[3,4-c]pyridazine, pyrido[2’,1’:3,2][1,2,4]triazolo[5’,1’:5,1]pyrazolo[3,4-c]pyridazine, naphtho[2,1-e]pyridazino[3’,4’:3,4]pyrazolo[5,1-c][1,2,4]triazine and pyridazino[3’,4’:3,4]pyrazolo[5,1-c][1,2,4]triazin-4(1H)-one were synthesized from 3-amino-1H-pyrazolo[3,4-c]pyridazine.
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■ Synthesis of 1,3-Diaryl-1,3-dihydro-4,5-dioxo-2-thioxofuro[2,3-d]pyrimidines and 1,3-Diaryl-1,3-dihydro-2-thioxo-5-(thiazol-4-l)-2H,5H-pyrimidine-4,6-diones
Vinod Kumar Ahluwalia,* Rashmi Sharma, Chandra Has Khanduri, M. Kaur, and Charu Gupta
*Department of Chemistry, University of Delhi, Delhi-110 007, India
Abstract
The reaction of thiobarbituric acids with chloroacetyl chloride in presence of triethylamine afforded 5-chloroacetyl derivatives which on cyclisation with ethanolic sodium acetate gave the corresponding furo[2,3-d]pyrimidines. Further the 5-chloroacetyl derivative on reaction with ammonium dithiocarbamate and thioacetamide gave 1,3-diaryl-1,3-dihydro-2-thioxo-5-(thiazol-4-yl)-2H,5H-pyrimidine-4,6-diones.
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■ Regiochemical Study in the Diels-Alder Reaction of 2-Azaanthraquinon-3-ones
Boufelja Bouammali, Félix Pautet, and Houda Fillion*
*Laboratoire de Chimie Organique Institut des Sciences, Pharmaceutiques et Biologiques, Université Claude Bernard, Lyon I, 8 avenue Rockfeller, 69373 Lyon Cedex 08, France
Abstract
The regiochemistry of the Diels-Alder reaction between 2-aza-1,3-butadienes (1) and naphthoquinones (2) (R = OH or OAc) is investigated.
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■ First Synthesis of (+)-Septorine
Akihiro Ohta,* Akihiko Kojima, Terumi Saito, Kayoko Kobayashi, Hideo Saito, Koichi Wakabayashi, Susumu Honma, Chiseko Sakuma, and Yutaka Aoyagi
*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
(+)-Septorine, a metabolite of Septoria nodorum, was synthesized via alanyl-isoleucyl anhydride (2) from L-isoleucine at the first time. Compound (2) was led to a pyrazine-carboxaldehyde (13), which was treated with p-methoxymethoxyphenylmagnesium bromide to afford an alcohol (14) in a quantative yield. The alcohol (14) was oxidized to ketone (16), which was subjected to the Pummerer reacton and the following hydrolysis to give (+)-septorine.
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■ Reactions of Cyclohexyl and Aryl Pyrazinyl Sulfoxides with Trifluoroacetic Anhydride
Makoto Shimazaki, Miyuki Hikita, Tomoko Hosoda, and Akihiro Ohta*
*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Cyclohexy pyrazinyl sulfoxides reacted with trifluoroacetic anhydride to give 1-cyclohexenyl pyrazinyl sulfides and/or cyclohexyl hydroxypyrazinyl sulfides. The presence of alkyl groups on the pyrazine ring is essential to obtain the latter compounds.
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■ Cobalt-mediated Alkylation of Siloxy Furans
John G. Stuart and Kenneth M. Nicholas*
*Department of Chemistry and Biochemistry, University of Oklahoma, Nrman, Oklahoma 73019, U.S.A.
Abstract
Dicobalt hexacarbonyl complexes of propargylium and α-vinylpropargylium cations couple efficiently with 2-trimethylsilyloxyfuran (5), 4-trimethylsilyloxy-2-benzyloxymethylfuran (15) and 2-trimethylsilyl-3-trimethylsilyloxy-4-ethylbenzo[b]furan (20) to produce the corresponding complexed furan derivatives in good yields. A convenient procedure for introducing the 2,4-enyne moiety regio- and stereoselectively into the above heterocycles using this methodology is described.
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■ Stereoselective Syntheses of Spicy Components in Peppers
Akihiro Ohta,* Yoshiko Tonomura, Junko Sawaki, Naohito Sato, Hitomi Akiike, Mizue Ikuta, and Makoto Shimazaki
*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The Syntheses of (E)-α,β-unsaturated amides were accomplished from chloroacetamides and alkyl halides via β-elimination of the pyrazinylsulfinyl group, and some of the products are spicy components of piperaceous plants.
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■ Electron Impact Mass Spectra of Some 2’-,3’- and 4’-Substituted Thiophene-2- and 3-Carboxanilides
Cristina Lea Barbieri,* Leopoldo Ceraulo, Paolo De Maria, Antonella Fontana, Domenico Spinelli, and Luca Zuppiroli
*Dipartimento di Chimica Organica "A Mangini", Università degli Studi di Bologna, Via S.Donato 15, 40127 Bologna, Italy
Abstract
The electron impact mass spectra (EI/MS) of 2- and 3-carboxanilides are dominated by the peak due to the corresponding thenoyl cations formed by cleavage of the C-N amide bond. This reaction is not affected by the polar effect of the substituents present in the phenyl ring. Most of the 2’-substituted derivatives undergo a cyclisation reaction with ejection of the substituent. In addition, for 2’-methyl and 2’-ethyl derivatives of both series of thiophene anilides a cryptic "ortho"-effect was suggested as responsible of the charge retention in the aniline moiety.
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■ Structure and Stereochemistry of Divaricine, a New Bisindole Alkaloid from Strychnos divaricans Ducke.
Rabindranath Mukherjee,* Bagnolia A. da Silva, Bhupesh C. Das, Paul A. Keifer, and James N. Shoolery
*Institut de Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
The complete stereostructure of divaricine, a new bisindole alkaloid from Srychnos divaricans Ducke., has been determined mainly by the use of one - and two-dimensional nmr techniques.
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■ Preparation of a Series of Oligo[thiophene-2,5-diyl]vinylenes
Juzo Nakayama* and Toru Fujimori
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
Preparation of a series of oligo[thiophene-2,5-diyl]vinylenes (3) is reported. Compounds containing an even number of thiopehene rings were synthesized by the carbonyl coupling of thiophenecarbaldehydes with a low-valent titanium reagent and those carrying an odd number of thiophene rings by the coupling of thiophenecarbaldehydes with Wittig-Horner (Wittig) reagents. Uv-vis spectral feature of these compounds is also reported.
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■ Fused Imidazophenothiazines: Studies on the Bernthsen Thionation of 1-Methyl-6-(p-tolylamino)benzimidazole and 2-Methyl-1-phenylbenezimidazole
Pilar López-Alvarado, Carmen Avendaño,* and J. Carlos Menéndez
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
Thionation of 1-methyl-6-(p-tolylamino)benzimidazole (obtained from 1-methyl-6-aminobenzomidazole and p-tolyllead triacetate) afforded a 7:3 mixture of two isomeric imidazophenothiazines, by inclusion of sulphur into the C7 and C2 ’ or C5 and C2’ positions, respectively. The capability of 1-arylbenzimidazoles to cyclize to a fused imidazophenothiazine was also shown. These results are discussed in comparison to those previously obtained on 2-methyl-1-phenyl-5-phenylaminobenzimidazole, a more complex system where both diarylamine units are present.
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■ Effective Synthesis of 7-Benzylidenefuro[3,4-b]pyridin-5-one
Nagatoshi Nishiwaki, Mitsuo Komatsu, and Yoshiki Ohshiro*
*Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565, Japan
Abstract
The title compound (5) was synthesized by silica gel assisted cyclization of 2-phenylethynylpyridine-3-carboxylic acid (3). Its was also synthesized from 3-cyano-2-phenylethynylpyridine (6) in good yield by basic cyclization and dehydration processes.