Regular Issue

Vol. 27, No. 5, 1988

27 data found. 1 - 27 listed
Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1105 - 1107
Published online:
DOI: 10.3987/COM-87-4427
Electron Transfer Photochemistry of 1,8-Naphthalimide and Phenylcyclopropane

Paul H. Mazzocchi* and Kazuaki Oda

*Department of Chemistry, University of Maryland, College Park, Marykland 20742, U.S.A.


Photolysis of N-methyl-1,8-naphthalimide (NMN) with phenylcyclopropane in methanol gave the novel photoproduct 11. Photoproduct 11 presents strong evidence for the formation of the ntermediate 6 proposed in the photochemistry of the NMN/2-phenylpropene system.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1109 - 1113
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DOI: 10.3987/COM-87-4445
The Diterpenoid Alkaloids from Aconitum napellus

Gabriel de la Fuente,* Matías Reina, Emir Valencia, and Antonio Rodríguez-Ojeda

*Instituto de QUímica Orgánica, Instituto de Productos Naturales Orgánicos, C. S. I. C./ Unversidad de La Laguna, La Laguna, Tenerife, Canary Islands, Spain


From Aconitum napellus L. subsp. castellanum J. Molero et C. Blanché, were isolated three new diterpenoid alkaloids, 12-epidehydronapelline (1), 12-epi-acetyldehydronapelline (2), and 1,14-diacetylneoline (6), together with neoline (7), aconitine, and songoramine (5). The structures of the new bases were determined by spectroscopic data and chemical correlation.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1115 - 1117
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DOI: 10.3987/COM-87-4459
One pot Synthesis of 3,4-Bis(methoxycarbonyl)-2-trimethylsilylfurans by Diels-Alder Reaction

Akira Tanaka,* Yoshiharu Harigaya, Noriyuki Nishino, and Kouji Nakayama

*Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan


2-Trimethylsilylfurans (1a-c) were heated with dimethyl acetylenedicarboxylate to give 3,4-bis(methoxycarbanyl)-2-trimethylsilylfurans (2a-c). In organic solvents, 1a-c reacted with dimethyl acetylenedicarboxylate to give the corresponding oxabicyclo adducts.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1119 - 1122
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DOI: 10.3987/COM-87-4463
Novel Synthesis of Quinolone-3-sulfonic Acid Derivatives

Choung Un Kim* and Bing-Yu Luh

*Pharmaceutical Reearch and Development, Bristol-Myers Company, P. O. Box 5100, Wallingford, CT 06492-5100, U.S.A.


The synthesis of 1-ethyl-6-fluoro-7-(1-piperazinyl)-1,4-dihydro-4-oxoquinoline-3-sulfonic acid is described. The use of a 2-bromophenyl sulfonate as a protected sulfonic acid is readily hydrolyzed under basic conditions is described.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1123 - 1126
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DOI: 10.3987/COM-87-4464
Titanium (III) Mediated Synthesis of Dicarboxypyrazines

Charles K. Sercher and Marvin J. Miller*

*Department of Chemistry, University of Notre Dame, Notre Dame, IN 46556, U.S.A.


Titanium (III) induced reductions of α-hydroxyimino-β-ketoesters lead to the formation of tetrasubstituted pyrazines.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1127 - 1130
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DOI: 10.3987/COM-87-4467
A Novel Synthesis of Benzopyranyl Isoxazolines: Cycloaddition Reaction of Chromone Nitrile Oxide

Arpan K. Baruah, Dipan Prajapati, and Jagir S. Sandhu*

*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India


A new nitrile oxide successfully prepared from 3-formylchromone is illustrated by reacting it with a variety of alkenes to afford novel benzopyranyl isoxazolines.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1131 - 1134
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DOI: 10.3987/COM-87-4473
A Simple Preparation of (R)-(+)-β-(3,4,5-Trimethoxybenzyl)-butanolide, and Its Use in tne Total Syntheses of Naturally Occurring Dibenzylbutanolide Lignans

Khalid Lalami, Robert Dhal, and Eric Brown

*Laboratorie de Synthèse, Faculté des Sciences, Route de Laval, BP 535, 72017 Le Mans Cedex, France


Resolution of methyl α-(3,4,5-trimethoxybeneyl)hemisuccinate by means of (-)-ephedrine, followed by calcium borohydride reduction, afforded (R)-(+)-β-(3,4,5-triméthoxybenzyl)butanolide. This lactone was used as s starting material for the optically active syntheses of 8 recently discovered lignans belonging to, or deriving from the α,β-dibenzylbutanolide series, such as isoyatein, cubebinone and dihydroclusin.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1135 - 1139
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DOI: 10.3987/COM-87-4477
A New Synthesis of (—)-Isopretronecanol and (—)-Trachelanthamidine through Orthoester Claisen Rearrangement for Allylic Alcohol Functionality Tagged at C(2) of Pyrrolidine as a Key Step

Toshio Moriwake,* Shin-ichi Hamano, and Seiki Saito*

*Department of Applied Chemistry, Faculty of Engineering, Okayama Universityg, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan


Orthoester Claisen rearrangement of (2S)-2-[1’(E)-3’-hydroxypropenyl]-Pyrrolidine derived from (S)-proline gave (2S)-2-[1’-(ethoxycarbonylmethyl)-2’- propenyl]-N-(t-butoxycabonyl)-pyrrolidin which is ready for further elaboration directed to necine base skeleton. Title compounds have been synthesized using this key intermediate.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1141 - 1144
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DOI: 10.3987/COM-88-4489
Reactions of 2- and 3-Thiophenecarbaldehyde Tosylhydrazone Sodium Salt with Acrylonitrile: Concentration Dependencen of Reaction Species Generated from 2- and 3-thiophenecarbaldehyde Tosylhydrazone Sodium Salt

Katsuhiro Saito,* Hiraku Ishihara, and Kensuke Takahashi

*Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan


The reactions of 2- and 3-thiophenecarbaldehyde tosylhydrazone sodium salt with an equimolar amount of acrylonitrile afforded the corresponding cyclopropane derivatives via 1,2-additions of 2- or 3-thienylmethylene to acrylonitrile. On the other hand, when the sodium salts were reacted with ten-molar requivalents of acrylonitrile, pyrazoline derivatives were formed via 1,3-dipolar additions of 2- or 3-thienyldiazomethane.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1145 - 1148
Published online:
DOI: 10.3987/COM-88-4497
Synthesis of 6-Inimo-1,9-dimethyl-8-oxopurine, a Constituent of the Marine Sponge Hymeniacidon sanguinea Grant

Tozo Fujii,* Tohru Saito, and Shigeji Mori

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


The marine 8-oxopurine I was synthesized from 8-bromo-9-methyladenine (VI) through the intermediates VII.HI and VII or, more effectively, through 6-amino-9-methyl-8-oxopurine (VIII). The N6-acetyl derivative II and the rearranged isomer X were also prepared.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1149 - 1154
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DOI: 10.3987/COM-88-4498
Four New Bisbenzylisoquinoline Alkaloids from the Root of Stephania Tetrandra (Fen-Fang Ji)

Tatsunori Ogino,* Toshitsugu Sato, Hiroshi Sasaki, Masao Chin (Chen Zhengxiong), and Hiroshi Mitsuhashi

*Kampo & Pharmacognosy Laboratory, Central Research Laboratory, Tsumura & Co., 3586 Yoshiwara, Ami-machi, Inashiki-gun, Ibaraki 300-1192, Japan


Four new bisbenzylisoquinoline (BBI) alkaloids named fenfangjines A, B, C and D were isolated from the root of Stephania tetrandra S. Moore, the Chinese traditional medicine “Fen-Fang-Ji”, along with thirteen known alkaloids (1-13). The chemical structures of fenfangjines A, B, C and D were respectively determined to be (14),(15), (16) and (17) by spectral analyses and chemical methods.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1155 - 1158
Published online:
DOI: 10.3987/COM-88-4508
Selective Synthesis of 1-Alkoxycarbonyloxymethyl-5-fluorouracils via 1,3-Bis(hydroxymethyl)-5-fluorouracil

Toshio Nagase,* Katsuto Shiraishi, Yutaka Yamada, and Shoichiro Ozaki*

*Faculty of Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, 790-8577 Ehime, Japan


Esterification of 1,3-bis(hydroxymethyl)-5-fluorouracil with various alkyl chloroformates in the presence of tert- or hindered secalkylamine selectively gave potentially antitumor active 1-alkoxycarbonyloxymethyl-5-fluorouracils in moderate to good yields.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1159 - 1162
Published online:
DOI: 10.3987/COM-88-4510
t-Butyl Lithioacetate on ortho-Hydroxyphenones Providing 2-Methylchromones, an Easy Access to Khellin

Kazuo Nagasawa,* Hajime Kanbara, Kazuya Matsushita, and Keiichi Ito

*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan


Reaction of t-butyl lithioacetate with several kinds of poly-substituted ortho-hydroxyphenones including khellinone and subsequent acid-hydrolysis of the resulting hemiacetals provide the corresponding 2-methylchromone derivatives in excellent overall yields.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1163 - 1166
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DOI: 10.3987/COM-88-4519
Alternative Syntheses of Azepinomycin

Tozo Fujii,* Tohru Saito, and Tetsunori Fujisawa

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


Three alternative syntheses of the antibiotic azepinomycin (XI) have now become feasible through a route starting from the monocycles Va-c and proceeding through the intermediates VIa-c, VIIa-c, VIIIa-c, IXa-c, and XIIa,b and 3-β-D-ribofuranosylazepinomycin (XIIc). The permutation IXa→ Xa→XI was also found to be feasible. The starting materials Va-c were readily prepared from IIa-c through IIIa-c and IVa-c.

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Communication | Regular issue | Vol 27, No. 5, 1988, pp. 1167 - 1168
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DOI: 10.3987/COM-88-4525
A General Procedure for the Catalytic Hydrogenolysis of N-Benzylamines under Extremely Mild Conditions

Kiyoshi Yoshida,* Shigekazu Nakajima, Takeshi Wakamatsu, Yoshio Ban, and Masakatsu Shibasaki*

*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan


A general procedure for debenzylation of N-benzylamines, which contain acid sensitive functional groups, by the catalytic hydrogenolysis using 20% Pd(OH)2-C is reported.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1169 - 1177
Published online:
DOI: 10.3987/COM-87-4262
The Mass Spectrometric Behaviour of Isomeric 1,3-Benzoxathiole and 1,4-Benzoxathiane Derivatives

Maria Teresa Cocco, Antonio Maccioni, and Gianni Podda*

*Istituto di Chimica Farmaceutica, Tossicologica ed Applicate, University of Cagliari, Via Ospedale 72, 09100 Cagliari, Italy


The mass spectrometric behaviour of isomeric 1,3-benzoxathiole and 1,4-benzoxathiane derivatives has been studied in detail with the aid of accurate mass measurements, B/E and B2/ E linked scans and Mass Analyzed Ion Kinetic Energy Spectra. While the molecular ions maintain the original structures, some fragment ions ieomerize to a common structure(s). The related electron impact induced decomposition mechanics are discussed in detail.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1179 - 1190
Published online:
DOI: 10.3987/COM-87-4412
Synthesis of Vinca Alkaloids and Related Compounds XXXV1. Preparation of 1-Ethyl-1-hydroxyethyl-octahydroindolo[2,3-a]quinolizine Derivatives and Reactions of Their Mesylates with Cyanide Ion

György Kalaus, Numan Malkieh, Mária Kajtár-Peredy, János Brlik, Lajos Szabó, and Csaba Szántay*

*Institute of Organic Chemistry, Technical University, 1521 Budapest, Hungary


Starting from (±)-eburnamonine (1a) and (±)-3-epieburnamonine (1b), compounds 5 and 11 were prepared. The reaction of the mesylate of 5 or 11 with NaCN in DMF led to a mixture of 16 and 17. The structures of the new compounds were elucidated.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1191 - 1196
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DOI: 10.3987/COM-87-4439
A New, Efficient Synthesis of 5-Undecyl-6-hydroxy-4,7-dioxobenzothiazole (UHDBT), a Potent Electron Transport Inhibitor

David S. Selwood* and Karamjit S. Jandu

*Department of Medical Chemistry, The Wellcome Research Laboratories, Langley Court, Beckenham, Kent BR3 3BS, U.K.


An efficient preparation of 5-undecyl-6- hydroxy-4,7-dioxobenzothiazole (UHDBT) is described. The synthesis in 5 stages and 38% overall yield utilises thermal rearrangement of a 4-hydroxy-4-(5-thiazolyl)cyclobuten-3-one as its key step.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1197 - 1205
Published online:
DOI: 10.3987/COM-87-4456
1,4-Additions of Amines to 5-Methoxyfuran-1(5H)-one; an Efficient Synthesis of Amino Diols

Ben L. Feringa* and B. de Lange

*Department of Organic Chemistry, University of Groningen, Nijenborgh 16, 9747 AG Groningen, The Netherlands


The 1,4-addition of various primary and secondary amines to 5-methoxyfuran-2(5H)-one in N,N-dimethylformamide or methylene chloride at room temperature affords quantitatively β-amino lactones 1a-g. The latter compounds are conveniently reduced to amino diols in high yields. Under similar conditions 1-(α)-methylbenzylamine gave optically active amino diols.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1207 - 1216
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DOI: 10.3987/COM-87-4461
Pyrazolo[1,2-a]indazole and its Reaction with Dimethyl Acetylenedicarboxylate

Angelo Albini, Gianfranco Bettinetti,* and Giovanna Minoli

*Dipartamento di Chimica Organica, Università di Pavia, V. le Taramelli 10, 27100 Pavia, Italy


Pyrazolo[1,2-a]indazole (2) is prepared by dehydrohalogenation of 2-bromo-2,3-dihydro-1H-pyrazolo[1,2-a]indazolium bromide (7). This diazapentalene 2 reacts with dimethyl acetylenedicarboxylate (DMAD) at room temperature. The main products in aprotic solvents are 10cH-1,2-dimethoxycarbonyl-10c-(1’,2’-dimethoxycarbonylethenyl)-1,2-diazocino[1,2,3-ab]indazole (15) and 11H-2,3-dimethoxycarbonyl-11-(1’,2’-dimethoxycarbonylethenyl) pyrazolo[1,2,3-ab]1,2-benzodiazocine (16) arising from a stepwise process involving addition of two molecules of DMAD and rearrangement. A minor product is 1,2-dimethoxycarbonyl-5,9c-diazapentaleno[1,7,6-ab]indazole (9). In methanol 1 to 2 addition and proton shift leads to 2,3-dihydro-1,2,3,4-tetramethoxycarbonyl-7,11c-diazaaruleno[1,9,8-ab]indazole (19) as the main reactions product. These processes are discussed in the frame of the general mechanism for heteropentalene addition reactions.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1217 - 1226
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DOI: 10.3987/COM-87-4469
Syntheses in the Isocamphane Series. XXXI1. 7-Oxacamphenilone, 7-Oxacamphene and 7-Oxacampheneilanic Acid

Gerhard Buchbauer* and Herbart Holbik

*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 10, A-1090 Vienna, Austria


The syntheses of the title compounds and their organoleptic properties are described. 7-Oxacamphenilone (2) has been obtained by twofold methylation of 7-oxanorbornan-2-one (1). The synthesis of 7-oxacamphene (5) has been accomplished by dehydration of 7-oxamethylcamphenilol (4). 7-Oxacamphenilanic acid (8) and some derivatives have been prepared starting with 5 by means of a hydroboration step and subsequent oxidation.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1227 - 1231
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DOI: 10.3987/COM-88-4487
The Reactivity of 2-Fromylthiophene, 1-Methyl-2-formylpyrrole, Benzaldehyde and 2-Formylfurane N,N-Dimethylhydrazones with Dimethyl Acetylenedicarboxylate

M. Eugenia Gonzalez, Pedro Sancho, Concepción Soriano, Rafael Ballesteros, Belén Abarca, and José Sepúlveda

*Departamento de Química Orgánica, Facultad de Farmacia, Universidad de Valencia, Calle Dr. Moliner, 50, E-46100 Burjassot (Valencia), Spain


N,N-Dimethylhydrazones derived from 2-formylthiophene, benzaldehyde, and 1-methyl-2-formylpyrrole react with dimethyl acetylenedicarboxilate (DMAD),giving the corresponding nitrlies. The reaction with furfural N,N-dimethylhydrazone takes place the intermediacy of a Diels-Alder adduct with the furan ring.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1233 - 1240
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DOI: 10.3987/COM-88-4493
Synthetic Uses of 1-[(Methythio)thiocarbonylmethyl]pyridinium Iodide. Synthesis of New Benzimidazole Derivatives

Ana M. Cuadro, Julio Alvarez-Builla,* and Juan J. Vaquero

*Departamento de Química Orgánica, Universidad de Alcalá de Henares, 28871 Alcalá de Henares (Madrid), Spain


Reaction of 1-[(methylthlo)thiocarbonylmethyl]pyridinium iodide with substituted o-phenylenediamines gave 1-[(2’-benzimidazolyl)methyl]pyridinium salts which were acylated and mono- and dialkylated by standard procedures. In addition. 2-(1’-piperidinylmethyl)benzimidazole derivatives were prepared by reduction of pyridinium moiety with sodium dithionite.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1241 - 1248
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DOI: 10.3987/COM-88-4501
Diastereoconversion of Threo 2-Amino Alcohols to Erythro Isomers Through a New Cyclocarbamation

Shinzo Kano,* Yoko Yuasa, Tsutomu Yokomatsu, and Shiroshi Shibuya

*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan


A diastereoconversion of threo 2-amino alcohols to erythro isomers was achieved by treatment of N-Boc derivatives with thionyl chloride or with methanesulfonyl chloride in the presence of triethylamine, hereby cis-4,5-disubstituted oxazolidin-2-ones being produced.

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Paper | Regular issue | Vol 27, No. 5, 1988, pp. 1249 - 1252
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DOI: 10.3987/COM-88-4502
Studies on Aconitum Species VI1. Yesoline, a new C20-Diterpenoid Alkaloid from Aconitum Yesoense Var. Macroyesoense (Nakai) Tamura

Koji Wada, Hideo Bando, and Takashi Amiya*

*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan


A new C20-diterpenoid alkaloid, yesoline, and a known alkaloid, 14-dehydrodelcosine were isolated from Aconitum yesoense var. macroyesoense (Nakai) Tamura. Structure of the new alkaloid was determined by means of spectral and chemical methods.

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Review | Regular issue | Vol 27, No. 5, 1988, pp. 1253 - 1268
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DOI: 10.3987/REV-87-379
New Diels-Alder Reactions with Vinylindoles: A Regio- and Stereocontrolled Access to Annellated Indoles and Derivatives

Ulf Pindur*

*Department of Chemistry and Pharmacy, Institute of Pharmacy, University of Mainz, Saarstrasse 21, D-55122 Mainz, Germany


New structural aspects of vinylindoles for predicting the outcome of Diels-Alder reactions are presented for the first time. Novel, mostly regio- and stereoselective cycloaddition reactions with 3- and 2-vinylindoles are described briefly and, in some cases, new applications for the syntheses of alkaloids are discussed.

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Review | Regular issue | Vol 27, No. 5, 1988, pp. 1269 - 1300
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DOI: 10.3987/REV-87-380
Morphinandienone Alkaloids

Gábor Blasko and Geoffrey A. Cordell*

*Program for Collaborative Research in the Pharmaceutical Sciences, College of Pharmacy, University of Illinois at Chicago, 833 South Wood St., Chicago, IL 60612-7231, U.S.A.


Morphinandienone, homomorphinandienone and related alkaloids are reviewed with respect to their isolation, structure elucidation, spectroscopy and synthesis.

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27 data found. 1 - 27 listed