Regular Issue

Vol. 20, No. 7, 1983

27 data found. 1 - 27 listed
Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1239 - 1242
Published online:
DOI: 10.3987/R-1983-07-1239
The Quaterization of cis and trans 1-Hydroxyquinolizidine

Luis Castedo and Ricardo Riguera

*Facultad de Química y Sección de Alcaloides, Deparamento de Química Orgánica, C. S. I. C., Santiago de Compostela, Spain


C-1-Hydroxyquinolizidine I gave with Mel a trans-fused quinolizidine methiodide II formerly believed to have a cis-fused structure. The t-1-hydroxyquinolizidine epimer III gave a mixture of two methiodides IV and V having trans and cis-fused quinolizidine structures respectively. Methiodide V exhibits temperature dependent nmr spectra (C-13 and 200 MHz 1H nmr) indicative of a conformational equilibrium.

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Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1243 - 1246
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DOI: 10.3987/R-1983-07-1243
The Reactions of 4-Pyrimidinone Derivatives with Sodium Amide and with Hydrazine: Synthesis of Triazole

Yoshiro Hirai, Hiroyuki Egawa, Shoko Yamada, and Takao Yamazaki

*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan


The 3,6-dialkyl-2-isopropyl-4-pyrimidinones (1)-(3) and 3,6-dimethyl-2-phenyl-4-pyrimidinone (6) were converted to the N-dealkylated 4-pyrimidinones (4), (5), and (7) by reaction with sodium amide in liq. ammonia. Also, these 4-pyrimidinones (1)-(3) and (6) were converted to the triazoles (10)-(12) by heating with hydrazine, respectively.

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Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1247 - 1254
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DOI: 10.3987/R-1983-07-1247
Solvent Effect on the Bischler-Napieralski Reaction. Synthesis of 3-Aryl-3,4-dihydroisoquinolines

Esther Domínguez and Esther Lete

*Departmento de Química, Facultad de Ciencias, Universidad del País Vasco, Apartado 450, 01080 Vitoria-Gasteiza, Spain


The classical Bischler-Napieralski cyclization of 1,2-diaryl-ethylamides always led to neutral compounds: the 3,4,3’,4’-tetramethoxystilbene (5) and/or the triaryl substituted tetralin (6). These characteristic by-products of the Bischler-Napieralski reaction arise as a consequence of competing equilibria involving nitrilium ions. The desired 3-aryl-3,4-dihydroisoquinolines were obtained in acceptable yields when the “appropiate” nitrile was used as solvent.

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Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1255 - 1258
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DOI: 10.3987/R-1983-07-1255
Indolines through Intramolecular Imine Cyclizations

Jan Dijkink, Johannes N. Zonjee, Bart S. de Jong, and W. Nico Speckamp

*Laboratory of Organic Chemistry, Institute of Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands


Indolines 3 are synthesized by intramolecular base-catalyzed cyclization of imines 2. Controlled basic hydrolysis of 3 affords indoline carboxylic acids 8 and 9. The compounds 3 are also useful for the synthesis of the mitomycin skeleton as exemplified by the preparation of 10.

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Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1259 - 1262
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DOI: 10.3987/R-1983-07-1259
Thallium (III) Nitrate (TTN) Oxidation of 2,8-Dioxo-1,7-cycloerythrinans: A New Skeletal Rearrangement

Yoshisuke Tsuda and Akira Nakai

*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan


Oxidation of 2,8-dioxo-1,7-cycloerythrinans (1a, b) with excess TTN in MeOH gave rearrangement products (2a, b), whose structures were elucidated mainly on the basis of spectral evidence. The intermediate to 2 from the ketone (1) was found to be the dimethylketal.

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Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1263 - 1266
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DOI: 10.3987/R-1983-07-1263
The Synthesis and Several Reactions of 2-Methylazuleno[2,1-d]thiazole

Kameji Yamane, Kunihide Fujimori, Shuji Ichikawa, Shiro Miyoshi, and Kenichi Hashizume

*Department of Chemistry, Faculty of Science, Shinshu University, Asahi, Matsumoto 390-8621, Japan


2-Methylazuleno[2,1-d]thiazole was synthesized from 2-amino, 2-formylamino, and 2-acetylamino derivatives of ethyl azulene-1-carboxylate in four steps. The 9-dimethylaminomethyl, 9-piperidinomethyl, and 9-morpholinomethyl derivatives were prepared by Mannich reaction of 2-methylazuleno[2,1-d]thiazole. The Vilsmeyer-Haack reaction of 2-methylazuleno[2,1-d]thiazole gave the 9-formyl derivative, and dehydration of its oxime afforded the 9-cyano derivative.

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Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1267 - 1269
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DOI: 10.3987/R-1983-07-1267
Structure of Murrayaquinone-B, a Novel Carbazole Alkaloid from Murraya euchrestifolia Hayata

Tian-Shung Wu, Tomoko Ohta, Hiroshi Furukawa, and Chang-Sheng Kuoh

*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan


The structure of murrayaquinone-B, a novel carbazole alkaloid isolated from the root bark of Murraya euchrestifolia Hayata was established as formula 1.

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Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1271 - 1274
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DOI: 10.3987/R-1983-07-1271
3-Hydroxypyrazolo[1,2-b]1,2,3-triazinium-1-olates: Novel Mesoionic 10π-Systems

Willy Friedrichsen, Andreas Böttcher, and Tony Debaerdemaeker

*Institut für Organische Chemie, Universität Kiel, Olshausenstrasse. 40, D-24098 Kiel, Germany


The syntheses and reactions of 3-hydroxypyrazolo[1,2-b] 1,2,3-triazinium-1-olates (7a,b) are reported. The structure of 7a has been confirmed by X-ray crystallography.

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Communication | Regular issue | Vol 20, No. 7, 1983, pp. 1275 - 1278
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DOI: 10.3987/R-1983-07-1275
Photochemical Reactions of 4-Methoxy-1-thiocoumarin and Synthesis of 1,2-Dihydrocyclobuta[c][1]benzothiopyran-3(3H)-ones

Chikara Kaneko, Toshihiko Naito, and Tetsuo Ohashi

*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan


4-Methoxy-1-thiocoumarin reacts photochemically with mono-substituted olefins to give the head-to-tail adducts: 1-substituted 8b-methoxy-1,2,2a,8b-tetrahydrocyclobuta[c] [1]benzothiopyran-3(3H)-ones, which eliminate methanol under appropriate conditions to give 1-substituted 1,2-dihydrocyclobuta[c][1]benzothiopyran-3(3H)-ones. Interesting photochemical ring-contraction reactions of 4-methoxy-1-thiocoumarin to benzo[b]thiophene derivatives are also reported.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1279 - 1284
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DOI: 10.3987/R-1983-07-1279
New Phthalazine- and Pyradazino[4,5-g]phthalazine Derivatives

Francesco De Sio, Stefano Chimichi, Rodolfo Nesi, and Lucia Cecchi

*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


Some new phthalazine- and pyridazino[4,5-g]phthalazine derivatives have been prepared through diethyl phthalazine-6,7-dicarboxylate (5), obtained by regioselective reduction of the tetraester (1) with sodium aluminium hydride at - 50 °C, and treatment of the intermediate diformyl derivative (2) with hydrazine. The tautomeric behaviour of both 1,4-dihydroxypyridazino[4,5-g]phthalazine (13) and the N-methyl derivative (14) were also investigated by comparison of their spectroscopic properties with those of the model compounds (15) and (16).

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1285 - 1290
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DOI: 10.3987/R-1983-07-1285
Reaction of 3,4-Dibenzoyl-1,2,5-thiadiazole with Ethylamine Derivatives. Formation of Shiff Bases and Their Base-catalyzed Ring Closure Reactions

Shuntaro Mataka, Kazufumi Takahashi, and Masashi Tashiro

*Research Institute of Industrial Science, Faculty of Engineering, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan


The reaction of 3,4-dibenzoyl-1,2,5-thiadiazole (1) with phenethylamine (2a) and β-aminopropionitrile (2b) gave the corresponding Schiff bases (4a and 4b), which, on treatment with DBU, cyclized into thiadiazolopyridines (5a and 5b). Compound 5a or 5b was directly obtained in the reaction of 1 and 2 in the presence of DBU. The reaction with α,β-diphenylethylamine (2c) gave the triphenylthiadiazolopyridine (5d) in poor yield. The Schiff base (4c) was obtained in the reaction with ethyl β-amino-β-phenylpropionate (2d) and treatment of 4c with a base afforded the pyrrolinyl-1,2,5-thiadiazole (7).

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1291 - 1294
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DOI: 10.3987/R-1983-07-1291
Synthesis and Elaboration of 3-Substituted 4-Nitroisoxazloles

John F. W. Keana and Garrick M. Little

*Department of Chemistry, University of Oregon, Eugene, OR 97403, U.S.A.


A regioselective Mukaiyama reaction involving nitroacetals 1 and 9, phenyl isocyanate and 1-morpholino-2-nitroethene 2 in benzene provided, respectively, the 4-nitroisoxazole acetals 3 and 10 in excellent yield. These acetals in turn served as convenient synthetic entries into the series of 3,4-difunctionalized isoxazoles of structures 4-8 and 11-13, respectively.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1295 - 1313
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DOI: 10.3987/R-1983-07-1295
Synthesis of 4-Substituted β-Carbolines

Günter Neef, Ulrich Eder, Andreas Huth, Dieter Rahtz, Ralph Schmischen, and Dieter Seidelmann

*Research Laboratories, Schering AG, Berlin / Bergkamen, D-1000 Berlin 65, Germany


Various 4-substituted β-carbolines are synthesized and further modified by electrophilic substitution reactions. The regioselectivity of electrophilic attack is demonstrated for a number of different reactions and strategies are outlined to achieve substitution at positions unaccessible by electrophilic attack.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1315 - 1320
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DOI: 10.3987/R-1983-07-1315
On the Reactivity of Some N-Amino Heterocycles towards Diazomethane

Fabio Ponticelli and Piero Tedeschi

*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


The occurrence of hydrogen bonding between the nitrogen atom of the NH2 group and a neighbouring enolic proton in tautomerizable N-amino heterocycles allows diazomethane methylation on the NH2 moiety.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1321 - 1324
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DOI: 10.3987/R-1983-07-1321
Photochemical Reactions of Condensed Azoles with Dimethyl Acetylenedicarboxylate IV

Tsuneo Itoh, Katsuko Matsuzaki, Shohei Suzuki, Kazuyuki Kishida, Haruo Ogura, Norio Kawahara, and Takako Nakajima

*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan


Adducts of azole derivatives and dimethyl acetylenedicarboxylate on irradiation are described.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1325 - 1329
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DOI: 10.3987/R-1983-07-1325
Saturated Heterocycles, 47. Synthesis of Some Tetrahydroisoquinoline Condensed 1,3-Heterocycles

Ferenc Fülöp, M. Sami El-Gharib, Attila Sohajda, Gábor Bernáth, Jenö Kóbor, and György Dombi

*Institute of Pharmaceutical Chemistry, University of Szeged, H-6720 Szeged, Eötvös u. 6, Hungary


Calycotomine (2) and homocalycotomine (3) reacted with isothiocyanates to give the corresponding thiocarbamides (4, 5). The latter were treated with methyl iodide, and subsequent elimination of methyl mercaptan on treatment with alkali afforded 1,3-oxazolo[4,3-a]isoquinolines (6) and 1,3-oxazino[4,3-a]isoquinolines (7). 1,3-Thiazolo[4,3-a]isoquinolines (8) and 1,3-thiazino[4,3-a]isoquinolines (9) were prepared from 4 and 5 with hydrogen chloride. Compound 7a was also synthesized by the reaction of 3 with phenyl isocyanate, followed by the elimination of water; 9a was obtainable from 7a by treatment with P4S10. The structures of compounds 6-9 were confirmed by 1H NMR.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1331 - 1334
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DOI: 10.3987/R-1983-07-1331
The Enantioselective Synthesis of (+)-Retronecine, (—)-Platynecine, and (+)-Croalbinecine and Its C-1 Epimer

Heinrich Rüeger and Michael Benn

*Department of Chemistry, The University of Alberta, Calgary, Alberta, T2N, 1N4, Canada


The Geissman-Waiss lactone, (+)-6-aza-2-oxabicyclo[3,3,0]octan-2-one, obtained from (2S,4R)-4-hydroxyproline was used as a synthon for the preparation of (+)-retronecine. (-)-platynecine, and (+)-croalbinecine (helifolinecine) and its C-1 epimer.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1335 - 1339
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DOI: 10.3987/R-1983-07-1335
Synthesis of Pyrazolo[4,3-d]oxazoles from 1-(2,4-Dinitrophenyl)-3-methyl-5-pyrazolon-4-oxime

Mohamed Salah Kamel Youssef

*Chemistry Department, Faculty of Science, Assiut University,Assiut 71516, Egypt


1-(2,4-Dinitrophenyl)-3-methyl-5-pyrazolon-4-oxime (I) reacts with benzylamine to give 1-(2,4-dinitrophenyl)-3-methyl-5-phenyl-1H-pyrazolo[4,3-d]oxazole (II). Its structure has been established by another route involving reaction of I with benzyl cyanide in the presence of sodium ethoxide. 1-(2,4-Dinitrophenyl)-3-methyl-1H-pyrazolo[4,3-d]oxazole (III) has been prepared by the interaction of I with methyl iodide in the presence of K2CO3. Its structure has been elucidated by an unambiguous synthesis involving reaction of diazomethane with I.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1341 - 1345
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DOI: 10.3987/R-1983-07-1341
The Synthesis of 2,2’:5’,3”-Terthiophene

Jacques Kagan, Sudershan K. Arora, Indra Prakash, and Ayse Üstünol

*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.


2,2’:5,3”-Terthiophene has been synthesized by two different routes. One utilized the Cadiot-Chodkiewicz coupling of 2-(bromoethynyl)thiophene with 3-ethynylthiophene, followed by sodium sulfide treatment of the resulting 1-(2-thienyl)-4-(3’-thienyl)-1,3-butadiyne. The other featured a Grignard reaction starting from 5-iodo-2,2’-bithiophene and 3-oxotetrahydrothiophene, followed by thermal aromatization with sulfur. The new terthiophene was an efficient singlet oxygen sensitizer.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1347 - 1354
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DOI: 10.3987/R-1983-07-1347
The Diterpenoid Alkaloids of Delphinium tatsienense Franch

S. William Pelletier, Jan A. Glinski, B. S. Joshi, 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.


From the roots of Delphinium tatsienense Franch (Ranunculaceae) two new and six known alkaloids have been isolated. The isolation and structure determination of deacetylambiguine (2) and a novel C19-diterpenoid alkaloid designated as tatsiensine (1) are described. The structure of tatsiensine was established on the basis of spectroscopic data and correlation with delpheline (12). Deacetylambiguine (2) has been isolated for the first time from a natural source. The known alkaloids that were isolated are the C19-diterpenoid alkaloids, browniine (3), delcosine (4), lycoctonine (8), and the C20-alkaloids ajaconine (6), hetisine (7) and hetisinone (5).

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1355 - 1362
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DOI: 10.3987/R-1983-07-1355
Lewis Acid Induced Electrophilic Substitution of Indoles: Part 6

Julie Banerji, Reba Mustafi, and James N. Shoolery

*Chemistry Department, University College of Science, 92 Acharya Prafulla Chandra Road, Calcutta-700009, India


The eleotrophilic substitution of 3-methylindole with mesityl oxide and acetone in the presence of BF3·Et2O has been discussed.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1363 - 1366
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DOI: 10.3987/R-1983-07-1363
An Alternative Chiral Route to Sulcatol

Seiichi Takano, Michiyasu Hirama, and Kunio Ogasawara

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


A key intermediate [(R)-(5)] for the enantioselective synthesis of both enantiomers of sulcatol (1), the aggregation pheromone of Gnathotrichus sulcatus, has been prepared from (S)-benzyl 2,3-epoxypropyl ether (8).

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1367 - 1371
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DOI: 10.3987/R-1983-07-1367
Mesoionic Six-membered Heterocycles, XVII. Cycloaddition of Benzyne to Mesoionic Pyrimidines

Thomas Kappe and Dietmar Pocivalnik

*Abteilung fur Angewandte, Organische Chimie, Institut fur Organische Chimie, Karl-Franzens Universitat, Heinrichstr. 28, A-8010 Graz, Austria


Benzyne (1) reacts with mesoionic pyrimidines (2a-e) yielding below 40 °C the primary cycloadducts 3a-e. At higher temperatures the isoquinolin-3-ones 4a-e are formed under the loss of phenyl isocyanate. Further addition of 1 to 4e yields the adduct 5, which is converted at 200 °C into the anthracene derivative 6.

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Report | Regular issue | Vol 20, No. 7, 1983, pp. 1373 - 1377
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DOI: 10.3987/R-1983-07-1373
Synthesis of Nitroethylindoles from Nitrovinylindoles by Alkoxyborohydride Reduction

Lawrence I. Kruse and Eileen L. Hilbert

*Chemical Reserch and Development, Smith Kline and French Laboratories, Philadelphia, PA 19101, U.S.A.


The reduction of substituted nitrovinylindoles to the corresponding nitroethylindoles proceeds in excellent yield, with the suppression of dimeric Michael byproducts, when an alkoxyborohydride is the reducing agent. A study of the reaction demonstrates the equivalence of preformed sodium trimethoxyborohydride and alkoxyborohydride generated in situ from excess sodium borohydride and methanol.

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Review | Regular issue | Vol 20, No. 7, 1983, pp. 1379 - 1406
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DOI: 10.3987/R-1983-07-1379
The Present Use and the Possibilities of Phase Transfer Catalysis in Drug Synthesis

Pierre Cocagne, José Elguero, and Roger Gallo

*Facluté des Sciences et Techniques de Saint Jérôme, Université d’Aix-Marseille III, Avenue Escardille Normandie Niemen (Case 552), 13397 Marseille Cedex 13, France


After a short introduction, the actual possibilities and the prospective use of phase transfer catalysis in drug preparation are reviewed (198 ref.)

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Review | Regular issue | Vol 20, No. 7, 1983, pp. 1407 - 1433
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DOI: 10.3987/R-1983-07-1407
Stereoselective Synthesis of the Geometric and Optical Isomers of Unsaturated 3-Mono- and 3,6-Disubstituted 2,5-Piperazinediones

Chung-gi Shin

*Departmnet of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan


Four kinds of naturally occurring 3,6-dibenzylidene (1)-, 3-(p)-anisilidene-6-benzylidene (2), -3-isobutylidene-6-benzylidene (3; antibiotic albonoursin)-, and 3-benzyl-6-benzylidene-2,5-piperazinediones (4), isolated from Streptomyces and Actinomyces strains, and their possible geometric and optical isomers were stereoselectively synthesized. Based on the spectral data and the independent preparation, the configuration and conformation of the natural products 1, 2, and 3 could be clearly determined to be (3Z, 6Z)-isomers and 4 to be (3R, 6Z)-isomer. Particularly, from the NMR and CD spectral data, the useful criterion for the configurational determination of the geometry of exocyclic C=C bond was obtained and the conformation of the half boat structure of 2,5-piperazinediones was unambiguously confirmed. Moreover, the methylation of 1, 2, and 3 was achieved to give mainly three kinds of derivatives, 1-, 4-mono-, and 1,4-dimethylated 1, 2, and 3 respectively.

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Review | Regular issue | Vol 20, No. 7, 1983, pp. 1435 - 1448
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DOI: 10.3987/R-1983-07-1435
Synthesis and Preparative Applications of Monosaccharide Thiocyanates

Zbigniew J. Witcazk

*Department of Organic Chemistry, Medical Academy, ul. Grodzka 9, 50-137 Wroclaw, Poland


This review describes the synthetic methods which have been developed for the preparation of monosaccharide thiocyanates as well as their transformation to derivatives such as deoxysugars thiosugars.

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27 data found. 1 - 27 listed