Regular Issue

Vol. 36, No. 10, 1993

27 data found. 1 - 27 listed
Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2185 - 2190
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DOI: 10.3987/COM-93-6387
Synthesis of Highly Substituted Pyridines through Nucleophilic Substitution of Tetrachloro-3-cyanopyridine

Sergei V. Chapyshev and Toshikazu Ibata*

*Institute of Chemistry, College of General Educatin, Osaka University, Toyonaka, Osaka 560-8531, Japan


Tetrachloro-3-cyanopyridine reacts with anilines and/or sodium azide through replacement of three chlorine atoms at the 2-, 4-, and 6-positions, whereas with difunctional nucleophiles by replacement of chlorines at the 5- and 6-positions. Using these reactions synthesis of highly substituted pyridines has been developed.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2191 - 2194
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DOI: 10.3987/COM-93-6403
Isolation of Novel Meso-substituted Uroporphyrins from Cultures of Pseudomonas

Wen Lin, Robert S. Burkhalter, and Russell Timkovich*

*Department of Chemistry, University of Alabama, Box 870336, University, Tuscaloosa, Alabama 35478-0336, U. S. A.


Two novel and unusal porphyrins have been isolated from the pool of porphyrin metabolites in cultures of Pseudomonas. They correspond to substitution of a meso proton in uroporphyrin by a nitro group or a chlorine atom. The purified compounds have been characterized by 1H-nmr, mass spectrometry, and visible spectroscopy to establish their structure.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2195 - 2202
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DOI: 10.3987/COM-93-6432
Dicarbonyl(η5-cyclopentadienyl)iron-(II)-η1-complexes of Carbohydrates

Jozua F. Booysen, Martin W. Bredenkamp,* and Cedric W. Holzapfel

*Department o f Chemistry and Biochemistry, Rand Afrikaans University, P.O. Box 524, Auckland Park, 2006, Johanesberg, South Africa


Dicarbonl(η5-cyclopentadienyl)iron(II) η1-complexes of carbohydrates are prepared by reaction of 2-deoxy-2-halosugars with sodium dicarbonyl(η5-cyclopentadienyl)ferrate via a single-electron-transfer mechanism. Evidence for the in situ conversion of these compounds into the corresponding thermo-labile dicarbonyl(η5-cyclopentadienyl)iron(II) η2-complexes, is presented.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2203 - 2204
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DOI: 10.3987/COM-93-6444
Ring Expansion of Spirocyclic Dithioketals via 1,3-Sulfur Migration by the Mitsunobu Reaction

Seiichi Takano,* Hirokazu Iida, and Kunio Ogasawara

*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan


Treatment of the spirocyclic dithioketals of some β-hydroxy ketone derivatives with diisopropyl azodicarboxylate and triphenylphosphine furnished the ring-expanded products via 1,3-sulfur migration.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2205 - 2208
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DOI: 10.3987/COM-93-6445
(-)-Corydecumbine, a Novel Phthalideisoquinoline Alkaloid from Corydalis decumbens

Purusotam Basnet, Shigetoshi Kadota,* Jian Xin Li, Chun Zhen Wu, and Tsuneo Namba

*Research Institute for Wakan-Yaku, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan


A novel alkaloid, (-)-corydecumbine (1) was isolated from the cultivated tuber of Corydalis decumbens (Thunb.) Pers. (Papaveraceae) and the structure was determined by the use of 2D nmr.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2209 - 2213
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DOI: 10.3987/COM-93-6446
A New Synthesis of Streptomyces Lactones by 1,3-Dipolar Cycloaddition

Ugo Chiacchio, Maria R. Di Bella, Antonio Rescifina, Giovanni Romeo,* and Nicola Uccella

*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy


The cycloaddition of nitrones (4) to propene, followed by sequential treatment with methyl trifluoromethanesulfonate, H2-Pd/C, and m-chloroperbenzoic acid, is shown to provide a general method for the preparation of a variety of volatile streptomyces lactones.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2215 - 2219
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DOI: 10.3987/COM-93-6451
Mannich Reactions of Indoles with Dichloromethane and Secondary Amines under High Pressure

Kiyoshi Matsumoto,* Takane Uchida, Shiro Hashimoto, Yukie Yonezawa, Hirokazu Iida, Akikazu Kakehi, and Shinichi Otani

*Graduate School of Human and Environmental Studies, Kyoto University, Yoshida-Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, Japan


Mannich reactions of indole with dichloromethane and secondary amines gave the corresponding Mannich bases in moderate to good yield, while 2-methylindole afforded only low yields of the Mannich bases. Some limitations were observed in the cases of hindered amines and 2-phenylindole.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2221 - 2228
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DOI: 10.3987/COM-93-6452
Bullacin: A New Cytotoxic Annonaceous Acetogenin from Annona bullata

Zhe-ming Gu, Xin-ping Fang, Lu Zeng, Karl V. Wood, and Jerry L. McLaughlin*

*Department of Medicinal Chemistry and Pharmacology, School of Pharmacy and Pharmacal Sciences, Purdue University, West Lafayette IN 47907, Indiana 47907, U.S.A.


Using the brine shrimp lethality test (BST) to direct fractionation, two additional Annonaceous acetogenins, bullacin (1) and parviflorin (2), were isolated from the ethanol extract of the bark of Annona bullata Rich. Their absoulte stereochemistries were revealed by the use of Mosher’s methodology. Compound (1) is a new adjacent bis-tetrahydrofuran (THF) acetogenin possessing a relatively rare C35 skeleton and an unprecedented C-6 hydroxyl group. The absolute configuration of 1 was assigned as 6S, 13R, 14R, 17R, 18R, 21R, 22R, and 34S. Compound (2) is a known acetogenin but is new to this plant. The absolute configuration of 2 was concluded to be 4R, 13R, 14R, 17R, 18R, 21R, 22R,and 34S. This is the first paper in which the absolute stereochemistry of a new acetogenin is published with the new structure. 1 showed 10 to 1000 times the cytotoxic potency of adriamycin when tested in human tumor cell lines.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2229 - 2236
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DOI: 10.3987/COM-93-6454
The Regiospecific Synthesis of ortho Aminonaphthophenones via the Addition of Carbanions to Naphthoxazin-4-ones

Weijiang Zhang, Ruiyan Liu, and James M. Cook*

*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.


The conversion of nitronaphthalenes (see 4a and 4b) into the corresponding ortho aminonaphthylnitriles (5a and 5b) via the process of Tomioka, when combined with the addition of carbanions to the intermediate naphthoxazin-4-ones, provided a route to ortho aminonaphthophenones (7a) and (7b). These key intermediates were employed to synthesize the benzfused 2’-fluoro-1,4-benzodiazepines (1-3).

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2237 - 2240
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DOI: 10.3987/COM-93-6457
An Expeditiuos Total Synthesis of (+)-Blastmycinone

Kiyoharu Nishide, Atsunori Aramata, Teruki Kamanaka, and Manabu Node*

*Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8412, Japan


Asymmetric γ-methylation of tetronic acid using (S)-2-methoxymethylpyrrolidine as a chiral auxiliary and its application to the total synthesis (+)-blastmycinone (1) were described.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2241 - 2245
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DOI: 10.3987/COM-93-6458
A Synthesis of 3,4-Disubstituted Indoles

Géza Galambos, Csaba Szántay Jr., József Tamás, and Csaba Szántay*

*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, Pusztaszeri ut 59-67, P.O.Box 17, Hungary


3,4-Disubstituted indoles are prepared through palladium-catalyzed coupling.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2247 - 2254
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DOI: 10.3987/COM-93-6471
A New Route to 1-Azaazulene Ring System by the Reaction of 1-(Diphenylphosphinyl)azaallyl Anions with Tropone Derivatives

Koji Ito and Makoto Nitta*

*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan


The reaction of 1-(diphenylphosphinyl)azaallyl anions, derived from the corresponding imines, with tropones underwent enamine-type alkylation and mainly followed by aza-Wittig reaction to give 1-azaazulene derivatives, in addition to a trace amount of 4H-4-oxocyclohepta[b]pyrroles.

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Communication | Regular issue | Vol 36, No. 10, 1993, pp. 2255 - 2258
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DOI: 10.3987/COM-93-6489
Iminophosphorane-mediated Synthesis of Oxazole Alkaloids: One-Step Preparation of O-Methylhalfordinol and Annuloline

Pedro Molina,* Pilar M. Fresneda, and Pedro Almendros

*Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, E-30071, Murcia, Spain


The three-component reaction between triphenylphosphine, 4-methoxyphenacyl azide and nicotinoyl chloride or 3,4-dimethoxycinnamoyl chloride leads directly in good yields to O-methylhalfordinol or annuloline respectively.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2259 - 2265
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DOI: 10.3987/COM-92-6209
A Short Synthesis of Potential Juvenoids Based on the Isoxazole Chemistry

Lourdes Martin, Cecilia Polo, Vicente Ramos, Tomás Torroba,* and Stefano Marcaccini

*Departamento de Química Orgánica, Facultad de Veterinaria, Universidad de Extremadura, E-10071 Cáceres, Spain


3,4,5-Trisubstituted isoxazoles (1) and (4) afforded, after chromic oxidation and borohydride reduction, (±)-3-methyl-6-(3-methyl-5-phenylisoxazol-4-yl)-6-hydroxyhexanoic acid (2) or (±)-1-(3-methyl-5-phenylisoxazol-4-yl)-3,4-dihydro-1H-2-benzopyran-3-ona (5) which were reduced to (±)-(Z/E)-3-methyl-7-benzoyl-8-oxonon-6-enoic acid (3) and (E)-2-(2-[2-benzoyl-3-oxobut-1-enyl]phenyl)acetic acid (6) with molybdenum hexacarbonyl. Lactone (5) afforded a single E-diastereoisomer of acid (6). Catalytic hydrogenation of 5 afforded selectively isoxazole (7) which was reduced with molybdenum hexacarbonyl to 2-(2-[2-benzoyl-3-oxobutyl]phenyl)acetic acid (8). Structures of products are related with those of some juvenoids.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2267 - 2272
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DOI: 10.3987/COM-93-6396
Synthesis of Pyrazolidin-3-ones from α,β-Unsaturated Sugar Lactones and Hydrazine

Irma Panfil and Marek Chmielewski*

*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland


Conjugate addition - cyclization of hydrazine to δ-lactones (2, 3, and 6) provides the respective pyrazolidin-3-ones as single products. The addition proceeds anti to the terminal carbon atom of the sugar lactone.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2273 - 2280
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DOI: 10.3987/COM-93-6412
Synthesis of 4-Amino-8-cyanoquinazolines from Enones and Enals

Pedro J. Victory,* José I. Borrell, Anton Vidal-Ferran, Elvira Montenegro, and M. Luisa Jimeno

*Departament de Química Organica, CETS Institut Químic de Sarria, Universitat Ramon Llull, Via Augusta 390, E-08017 Barcelona, Spain


The treatement in a sodium methoxide/methanol solution of α,β-unsaturated enones or aldehydes with propanedinitrile in a 1:2 molar ratio led to 2-aminobenzene-1,3-dicarbonitriles. These compounds afforded 4-amino-8-cyanoquinazolines by reaction with formamide or guanidine.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2281 - 2290
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DOI: 10.3987/COM-93-6416
Synthesis with Nitriles: 92. Synthesis of 5-Formylcytosine Derivatives

Madhukar Jachak,* Martin Mittelbach, and Hans Junek

*Institute for Organic Chemistry,University Graz, Heinrichstrbe. 28, A-8010 Graz, Austria


The reactivity of 3-dimethylamino-2-formylpropenenitrile (1) with various amino compounds is studied. Thus, condensation of 1 with anilines gives the corresponding azomethines (2a-c). Reaction of 1 with thiourea and guanidine resp., leads to 5-formylthiocytosine (3) and 2-amino-5-cyanopyrimidine (4). The 2-formyl-3-ureidopropenenitriles (5a-i) can be obtained by reaction of 1with urea and substituted ureas. 5a-i can easily be cyclized to 3-substituted 5-formylcytosines (6a-e). Condensation of 6 with aniline, benzylamine and phenylhydrazine leads to the azomethines (7a-i). Pyrido[2,3-d]pyrimidine-6-carbonitriles (8a, 8b, 8d and 8e) are obtained by reaction of 6 with malononitrile.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2291 - 2301
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DOI: 10.3987/COM-93-6421
An Efficient Procedure for the Synthesis of Pyrazolo]3,4-d][1,3]thiazine-4-ones

Chiara B. Vicentini, Augusto C. Veronese, Salvatore Guccione, Mario Guarneri, Maurizio Manfrini, and Paolo Giori*

*Dipartimento di Scienze Farmaceutiche, Università di Ferrara, via Fossato di Mortara 17, I-44100, Ferrara, Italy


Trichloromethyl chloroformate reacts with N-(1-alkyl/aryl-5-pyrazolyl)thiocarboxamides (2a-j) to give pyrazolo[3,4-d][1,3]thiazin-4-ones (3) while it reacts with N-(3-methyl-5-pyrazolyl)thiobenzamide (2m) to give the pyrazolo[1,5-c][1,3,5]thiadiazine-4-one (4). Heating under reflux in formic acid of homologues (3g-i) bearing a tert-butyl group linked to pyrazole N-1 atom afforded the dealkylated derivatives (3k-m).

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2303 - 2314
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DOI: 10.3987/COM-93-6437
Heterocyclic Systems: Synthesis and Reactivity of Thieno[2,3(3,2)-b]indolizidin-9-ones

Dominique Lebosquain and Bernard Decroix*

*Laboratoire de Chimie, UER des Sciences et Techniques, Université du Havre, 30, rue Gabriel Péri, 76600 Le Havre,France


A simple and efficient synthesis of thieno[2,3(3,2)-b]indolizidin-9-ones is described starting from 2(3)-halogenomethylthiophene. The reactivity (Beckmann and Schmidt rearrangements) of these ketones is studied and compared with the reactivity of thienoquinolizidinones and thienoindolizidinediones

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2315 - 2325
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DOI: 10.3987/COM-93-6449
Synthesis of 2,5,8(1H)-Quinolinetrione Derivatives through Vilsmeier-Haack Formylatioin of 2,5-Dimethoxyanilides

Miguel Angel Alonso, Ma del Mar Blanco, Carmen Avendaño,* and J. Carlos Menéndez

*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain


The preparation of 2,5,8(1H)-quinolinetrione derivatives bearing both electron-withdrawing and electron-releasing groups at C3 is described. The reaction sequence employed involves Vilsmeier-Haack cyclization of 2,5-dimethoxyanilides into 3-substituted 5,8-dimethoxy-2-chloroquinolines, followed by hydrolysis to the corresponding 2(1H)-quinolinones and oxidative demethylation with cerium ammonium nitrate.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2327 - 2333
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DOI: 10.3987/COM-93-6450
Synthesis and Serotonergic Activity of 8-[4-(2,3-Dihydro-1,4-dioxino[2,3-b]pyridin-2-yl-methylamino)butyl]-8-azaspiro[4,5]decane-7,9-dione

Abdelhakim Benarab and Gerald Guillaumet*

*Laboratoire de Chimie Bioorganique et Analytique, URA-CNRS N° 499, Université d’Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France


The synthesis of compound (9), a nitrogen-containing bioisostere of the 1,4-benzodioxane moiety of the MDL 72832, is detailed. This compound showed a moderate affinity for the 5-HT1A receptors.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2335 - 2344
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DOI: 10.3987/COM-93-6463
Application of the Photo-Fries Rearrangement of Aryl N-Chloroacetylanthranylates as Key Step in the Synthesis of 5-(2-Hydroxyphenyl)-1,3-dihydro-2H-1,4-benzodiazepin-2-ones

Felipe Algarra and Miguel A. Miranda*

*Departamento de Química/Instituto de Tecnología Química, UPV-CSIC, Universidad Politécnica de Valencia, Apartado 22012, E-46071 Valencia, Spain


Condensation of isatoic anhydride with phenols, followed by treatment of the resulting aryl anthranylates (4) with chloroacetyl chloride gives aryl N-chloroacetylanthranylates (5). Their uv-irradiation results in photo-Fries rearrangement, to afford benzophenones (6). Direct treatment of the latter with ammonia gives rise to 1,3-quinazolines (7); by contrast, treatment of 6 with potassium iodide and subsequently with ammonia leads to 1,3-dihydro-2H-1,4-benzodiazepin-2-ones (1).

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2345 - 2366
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DOI: 10.3987/COM-93-6465
Photocyclization of Enamides. 38. Reductive Photocyclization of α-(Methylthio)- and α-(Arylthio)enamides

Takeaki Naito,* Hiromi Tanada, Yumiko Suzuki, Haruko Saito, Toshiko Kiguchi, and Ichiya Ninomiya

*Kobe Women's College of Pharmacy, Motoyamakita, Higashinada, Kobe 658-8558, Japan


Reductive photocyclization of α-(methylthio)enamide (2) gave exclusively six-membered lactams (3) and (4) while the same reaction of α-(arylthio)enamides (6) and (12) was found to afford five-membered lactams (7) and (13) as major proucts. A novel total synthesis of (±)-polyzonimine (18b) was accomplished by applying the newly found reductive photocyclization of α-(naphthylthio)enemide leading to the formation of five-membered lactams.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2367 - 2371
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DOI: 10.3987/COM-93-6472
A New Alkaloid, 2-Hydroxy-7-methyl-9H-carbazole from Cimicifuga simplex

Genjiro Kusano,* Makio Shibano, Mayumi Idoji, and Katsuhiko Minoura

*Osaka University of Pharmaceutical Sciences, 2-10-65 Kawai, Matsubara, Osaka 580, Japan


A new alkaloid was isolated from the aerial parts of Cimicifuga simplex and was formulated as 2-hydroxy-7-methyl-9H-carbazole on the basis of the spectroscopic evidence.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2373 - 2382
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DOI: 10.3987/COM-93-6473
Complete 1H-Nmr Spectral Assignments of Six 3-Etyl Indolo[2,3-a]quinolizidine N-Oxides. NOE Difference Spectroscopy Applied to Conformational Analysis

Reija Jokela and Mauri Lounasmaa*

*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, P.O. Box 6100, FIN-02150 HUT Espoo, Finland


Complete 1H-nmr spectral assignments of six 3-ethylindole[2,3-a]quinolizidine N-oxides are reported. The predominant conformaions of the compounds were determined by NOE difference spectroscopy.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2383 - 2396
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DOI: 10.3987/COM-93-6476
The Novel Reduction of Pyridine Derivatives with Samarium Diiodide

Yasuko Kamochi* and Tadahiro Kudo

*Daiichi College of Pharmaceutical Sciences, 22-1 Tamagawa-cho, Minami-ku, Fukuoka 815-0037, Japan


Pyridine was rapidly reduced into piperidine with samarium diiodide in the presence of water at toom temperature in excellent yield. On the similar reactions of pyridine derivatives bearing chloro, amino and cyano functionalities with samarium diiodide-H2O-THF system, these functionalities were partly eliminated with this system to afford pyridine or piperidine. Furthermore, pyridinecarboxamides were reduced with this system to give the corresponding methylpyridines and 2-pyridinecarboxylic acid was reduced to give 2-methylpyridine as the major products.

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Paper | Regular issue | Vol 36, No. 10, 1993, pp. 2397 - 2405
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DOI: 10.3987/COM-93-6482
Synthesis of a Key Intermediate for D-Biotin via 1,3-Cycloaddition of a Thiocarbonyl Ylide and Sila-Pummerer Rearrangement

Toru Yamano, Mitsutaka Tanaka, and Kunio Takanohashi*

*Technology Development Laboratories, Takeda Chemical Industries, Ltd., Juso-honmachi, Yodogawa-ku, Osaka 532, Japan


An efficient preparation of a d-biotin intermediate, (±)-(3aα,4α,6aα)-1,3-dibenzyl-3a,4,6,6a-tetrahydro-4-hydroxy-1H-thieno[3,4-d]imidazol-2(3H)-one was accomplished by use of 1,3-cycloaddition of a thiocarbonyl ylide, Curtius rearrangement and sila-Pummerer rearrangement. Addition of p-toluenesulfonic acid was found to be effective to promote sila-Pummerer rearrangement of sterically unfavorable anti-2-trimethylsilyl sufoxide.

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27 data found. 1 - 27 listed