Regular Issue

Vol. 31, No. 9, 1990

28 data found. 1 - 28 listed
Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1565 - 1569
Published online:
DOI: 10.3987/COM-90-5462
A Novel Route to 7-(Substituted Amino)-5,6-dihydrobenz[c]acridines

Lucjan Strekowski,* Roman L. Wydra, Donald B. Harden, and Vidya A. Honkan

*Department of Chemistry, Georgia State University, University Plaza, Atlanta, GA 30303, U.S.A.


The title compounds (3) are produced in a novel, lithium alkylamide- and dialylamide-mediated cyclization of N-(1,2,3,4-tetrahydro-1-naphthylidene)-2-trifluoromethylaniline (2). The mechanism of this unusual transformation that involves the trifluoromethyl group is discussed.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1571 - 1574
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DOI: 10.3987/COM-90-5463
Synthesis of a Phosphonate Isostere of Acycylovir Monophosphate: A Herpesvirus Active Phosphonate Nucleotide Analogue

Choung Un Kim,* Peter F. Misco, Bing Y. Luh, and John C. Martin

*Bristol-Myers Squibb Company, Pharmaceutical Research and Development, 5 Research Parkway, Wallingford, CT 06492-5100, U.S.A.


A novel synthetic methodology for the acyclic acetal functionality was developed. The rationally designed phosphonate analogue (3) of acyclovir monophosphate was active against herpesviruses.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1575 - 1576
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DOI: 10.3987/COM-90-5474
Preparation of Benzopolythia Compounds as Two-dimensionally Expanded Polythia Systems and the ESR Spectra of the Related Compounds

Tatusya Nabeshima, Naomichi Furukawa,* Tohru Ishizawa, Kenji Morihashi, and Osamu Kikuchi

*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan


Benzopolythia compounds, dibenzo-1,4,5,8-tetrathiaphenanthrene and tribenzo-1,4,5,8,9,12-hexathiatriphenylene, have been prepared. The esr spectra of cation radicals of several polythia compounds reveal delocalization of spin density at the sulfur atoms by the aromatic or olefinic moietyies.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1577 - 1580
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DOI: 10.3987/COM-90-5483
Synthetic Stuides on Nine-membered Ring Diterpenoids: Stereoselective Construction of Optically Active 1-Oxaspiro[2.8]undecenone Derivatives

Tetsuo Furuno, Hiroshi Hirota,* Masaki Takai, Hiroko Inagaki, and Takeyoshi Takahashi

*Department of Chemistry, School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan


Enantiomeric isomers of 1-oxaspiro[2.8]undecenone derivative (10), which are key compounds to synthesis nine-membered ring diterpenoids, were synthesized stereoselectively from optically active monoterpene, limonene, via anionic oxy-Cope rearrangement reaction.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1581 - 1584
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DOI: 10.3987/COM-90-5485
Epoxidation of 5-Alkylidene and 5-Benzylidene Substituted 1,3-Dioxane-4,6-dione Derivatives by Hydrogen Peroxide without Catalyst

Takashi Tsuno and Kunio Sugiyama*

*Department of Industrial Chemistry, College of Industrial Technology, Nihon University, Narashino-shi, Chiba 275, Japan


5-Alkylidene and 5-benzylidene substituted 1,3-dioxane-4,6-dione derivatives readily reacted with hydrogen peroxide at room temperature without any catalyst to give the corresponding spiro- and polyspirocyclic compounds containing oxirane ring in good yields.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1585 - 1588
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DOI: 10.3987/COM-90-5486
Synthesis of (+)-trans-Whisky Lactone, (+)-trans-Cognac Lactone and (+)-Eldanolide

Takashi Ebata,* Katsuya Matsumoto, Hajime Yoshikoshi, Koshi Koseki, Hiroshi Kawakami, and Hajime Matsushita

*Life Science Research Laboratory, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan


A new and usefur synthesis of (+)-trans-whisky lactone (3), (+)-trans-cognac lactone (4) and (+)-eldanolide (5) starting from levoglucosenone (1) is described.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1589 - 1592
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DOI: 10.3987/COM-90-5502
Accentuation of the Di-π-Methane Reactivity by Central Carbon Substitution in the 4-(Phenylmethyl)-2(5H)-furanone System

Osamu Muraoka,* Genzoh Tanabe, and Takefumi Momose*

*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama 930-01, Japan


The effect of ’central methane’ substitution on the di-π-methane rearrangement in 4-(phenylmethyl)-2(5H)-furanones (1b-d) was investigated. Significant enhancement of efficiency in the reaction leading in high combined yields to two isomeric products (endo-2 and exo-2) was descussed in terms of both the substituent effects at the allyic methane carbon and the restrained feature of the ring-enrolled π-system.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1593 - 1596
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DOI: 10.3987/COM-90-5505
Synthesis of the 1-N-Oxides and 1-Methoxy and N6-Methoxy Derivatives of 2-Deuterioadenines Substituted or Unsubstituted at the 9-Position

Tohru Saito, Hiromi Hayashibara, Yukinari Kumazawa, Tetsunori Fujisawa, and Tozo Fujii*

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


Peracid oxidations of adenine-2-d (1a) and its 9-substituted derivatives (1b-e) produced the corresponding 1-N-oxides (3a-e) in fair yields. Methylations of 9-methyl- (3b) and 9-benzyladenine-2-d 1-oxide (3d) and adenosine-2-d 1-oxide (3e) with MeI in AcNMe2 afforded the corresponding 1-methoxy derivatives 5b,d and 11e in good yields. Dimroth rearrangement of 5b, 5d, and 11e gave the N6-isomers 9b, 9d, and 9e, but their isotopic purities were unsatisfactory. Unambiguous assignments of the purine-ring proton signals in the nmr spectra of the unlabeled adenines (4a-e, 6b,d, and 12e) have been made by comparison with those of the labeled species (3a-e, 5b,d, and 11e).

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1597 - 1600
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DOI: 10.3987/COM-90-5514
Highly Diastereoselective Synthesis of N-Boc Dolaisoleuine, Unusual Amino Acid in Dolastatin 10

Shinzo Kano, Yoko Yuasa, and Shiroshi Shibuya*

*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-03, Japan


Photolysis of 5-phenylthiooxazolidin-2-one (4) in the presence of (n-Bu3Sn)2 and n-Bu3SnCH2CH=CH2 afforded 5-allyl derivative (5) which was led to N-Boc dolaisoleune (11), one component of dolastatine 10 (2), via 6-10.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1601 - 1604
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DOI: 10.3987/COM-90-5524
The Reaction of 3-Substituted 2-(N-Cyanoimino)thiazolidine Derivatives with Hydrazine: Novel Synthesis of Triazoles

Chuzo Iwata,* Michitaro Fujimoto, Shigeha Okamoto, Chihiro Nishihara, Masatoshi Sakae, Masanori Katsurada, Mayumi Watanabe, Tetsuya Kawakami, Tetsuaki Tanaka, and Takeshi Imanishi

*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565, Japan


The reaction of 3-subsituted 2-(N-cyanoimino)thiazolidine (NCT) derivatives with hydrazine hydrate afforded two types of 1,2,4-triazoles via a selective C2-S or C2-N3 bond fission, in which the selectivity was controlled by the N3-substituent.

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Communication | Regular issue | Vol 31, No. 9, 1990, pp. 1605 - 1608
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DOI: 10.3987/COM-90-5532
The First Total Syntheses of 9-Methoxycarbazole-3-carboxaldehyde and Methoxybrassinin (The Chemistry of 1-Methoxyindole)

Toshiya Kawasaki and Masanori Somei*

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


The first total syntheses of an alkaloid 9-methoxycarbazole-3-carboxaldehyde and a phytoalexin methoxybrassinin are reported.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1609 - 1615
Published online:
DOI: 10.3987/COM-89-4975
Spectroscopic Analysis of Iodinated Molecular Complexs of Thiazole and Thiazoline Derivatives

Jean-françois Lagorce, Jacques Buxeraud,* Anne-Catherine Jambut-Absil, and Claude Raby

*Laboratoire de Chimie Organique et de Chimie Thérapeutique, Faculté de Pharmacie, 2, rue du Docteur Marcland, 87025 Limoges Cedex, France


Molecular interactions between iodine and the heterocyclic compounds, thiaole, 4-methylthiazole, clomethiazole, cloprothiazole, 2-methyl-2-thiazoline and 2-thiazoline-2-thiol were studied by uv/vis spectroscopy. These molecules were found to form charge tranfer complexes with iodine of the n-σ type in a 1:1 stoichiometry. Formation constants of the iodinated complexes of thiazole, 4-methylthiazole, clothiazole and cloprothiazole ranged from 10 M-1 to 30 M-1. The much higher values found for 2-methyl-2-thiazoline and 2-thiazoline-2-thiol indicated a strong donor-acceptor interaction. Only the latter two derivatives have an action on the thyroid gland, and might, therefore, be suitable starting compounds for the synthesis of new antithyroid agents.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1617 - 1628
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DOI: 10.3987/COM-89-5297
The Chemistry of the 6β-Thioamidopenam 1β-Sulfoxides. The 1,2,4-Dithiazineacetidinones and Thiazolineazetidinones

Ronald G. Micetich,* Rajeshwar Singh, Daniel M. Tetteh, and Robert B. Morin

*Faculty of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada


6β-Thioamidopenam 1β-sulfoxides on thermolysis gave methyl 2-(3-substituted 4,5-dithia-2,7-diazabicyclo[4.2.0]oct-2-en-8-one-7-yl)-3-methyl-but-3-enate (1,2,4-dithiazineazetidinones). The reaction of these compounds with halogenating agents is discussed.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1629 - 1633
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DOI: 10.3987/COM-90-5450
Synthesis of Novel 1,2,4-Triazole-containing Oligopeptides

Toyomi Matsumoto, Kouhei Toyooka, Eiji Nishiwaki, and Masayuki Shibuya*

*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi 1, Tokushima 770-8505, Japan


Novel 1,2,4-triazole-containing oligopeptides (12 - 17) were synthesized from 1-methyl-3-nitro-1,2,4-triazole-5-carboxylic acid (10).

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1635 - 1640
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DOI: 10.3987/COM-90-5471
Pyrazolo[1,5-a]pyrido[3,4-e]pyrimidine: A New Heterocyclic Ring System

Fabrizio Bruni,* Stefano Chimichi,* Barbara Cosimelli, Annarella Costanzo, Gabriella Guerrini, and Silvia Selleri

*Dipartimento di Scienze Farmaceutiche, Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy


Treatment of 6-acetyl-7-(2-dimethylaminovinyl)pyrazolo[1,5-a]pyrimidine (1) with hydroxylamine afforded in high yields the pyridine N-oxide (2), a key intermediate in the preparation of new functionalized pyrazolo[1,5-a]pyrido[3,4-e]pyrimidines as well as in the synthesis of the parent ring system (8).

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1641 - 1646
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DOI: 10.3987/COM-90-5472
Synthesis and X-Ray Analysis of 1-Benzyl-6-chlorouracil

Ichiro Ishikawa, Tsuneo Itoh, Raphael G. Melik-Ohanjanian, Hiroaki Takayanagi, Yoshihisa Nizuno, Haruo Ogura*, and Norio Kawahara

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


1-Benzyl-6-chlorouracil (3) was prepared by benzylation of 6-chlorouracil (2) which was obtained by alkaline hydrolysis of 2,4,6-trichloropyrimidine (1).

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1647 - 1653
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DOI: 10.3987/COM-90-5473
An Efficient Synthesis of 3-Alkyl-5-aryl-2(1H)-pyrazinones

Robert H. Bradbury,* David Griffiths, and Janet E. Rivett

*Department of Chemistry, ICI Pharmaceuticals, Mereside, Alderley Park, Macclesfield, Cheshire, SK10 4TG, U.K.


The preparation of several 3-alkyl-5-aryl-2(1H)-pyrazinones is described. The regiochemical outcome of the condensation reaction between aminoacid amides and phenylglyoxal is discussed and an alternative, more efficient route is reported, involving ring-closure of α-oxo-N-(2-oxoethyl)carboxamides.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1655 - 1662
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DOI: 10.3987/COM-90-5479
Emeheterone: Synthesis and Structural Revision

Akihiro Ohta,* Akihiko Kojima, and Yutaka Aoyagi

*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan


Emeheterone, a fungal metabolite, was synthesized from DL-phenylalanine. Based on the results of this synthesis, the structure of emeheterone was redetermined as 3,6-dibenzyl-2-hydroxy-5-methoxypyrazine 4-oxide.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1663 - 1667
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DOI: 10.3987/COM-90-5480
Indole Alkaloids from Vinca sardoa, a New Species of Vinca

Sergio Crippa, Bruno Danieli, Giordano Lesma,* Giovanni Palmisano,* Daniele Passarella, and Vittorio Vecchietti

*Dipartimento di Chimica Organica e Industriale, Università degli Studi di Milano, Via Venzian 21, 20133 Milano, Italy


Four natural N-methylindolines have been isolated from the roots of Vinca sardoa (Stearn) Pignatti. They are ent-N(1)-methyl-14,15-didehydroaspidospermidine (7), N(1)-methyl-14,15-didehydroaspidofractinine (10), N(1)-methylaspidofractinine (11) and N(1)-methyl-14,15-didehydrotuboxenine (13).

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1669 - 1685
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DOI: 10.3987/COM-90-5488
Synthesis and Antiviral Activity of 1,2,3-Triazole and 8-Azapurine Derivatives Bearing Acyclic Sugars

Masataka Yokoyama,* Eiko Nakao, Keiko Sujino, Satoshi Watanabe, and Hideo Togo

*Department of Chemistry, Faculty of Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan


A variety of 1,2,3-triazole and 8-azapurine derivatives bearing acyclic sugar moieties were synthesized by the reaction of acyclic sugar azides with α-cyanoacetamide, norbornadiene, and acetylene derivatives, respectively. Antiviral tests of these compounds are also described.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1687 - 1691
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DOI: 10.3987/COM-90-5492
Synthesis of β-Lactam Derivatives of 1,5-Benzoxazepines and 1,5-Benzothiazepines

Ines Torrini, Giampiero Pagani Zecchini, Mario Paglialunga Paradisi,* and Francesca Scazzocchio

*Dipartimento di Studi Farmaceutici, Facolta di Farmacia, Università degli Studi di Roma "La Sapienza", P.O.Box 36, P. le Aldo Moro 5, 00185 Roma, Italy


Condensed β-lactam derivatives fo 1,5-benzoazepines (2a-i) and of 1,5-benzothiazepines (2j-r) have been synthesized by the reaction of quino[2,3-b][1,5]benzoxazepines (1a-c) or the corresponding benzothiazepines (1d-f) with some acyl chlorides in the presence of triethylamine. The formyl chloroacetamido derivatives (4a,b) were instead obtained by treating 1a,d with chloroacetyl chloride in the absence of the base. The mechanism of the reactions is discussed. No antibacterial activity was shown by the title compounds (2a-r) in the test experimental conditions.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1693 - 1697
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DOI: 10.3987/COM-90-5494
1,3-Dipolar Cycloaddition: Molecular Sieves Assisted Generation of Nitrile Oxides from Hydroximoyl Chlorides

Jae Nyoung Kim and Eung K. Ryu*

*Division of Organic Chemistry, Korea Research Institute of Chemical Technology, P.O.Box 9, Daedeog Danji, Daejoen 305-606, Korea


Molecular sieves irrespective of their pore size convert hydroximoyl chlorides into the corresponding nitrile oxides very slowly and cleanly in the presence of dipolarophiles to give isoxazolines in good to excellent yields.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1699 - 1704
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DOI: 10.3987/COM-90-5496
Reaction of 2-Methylene-1,3-dicarbonyl Compounds with Furan

Masashige Yamauchi,* Miwa Shirota, and Toshio Watanabe

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


The mono- and/or di-substituted furans (2 and 3) were synthesized by the reaction of 2-methylene-1,3-dicarbonyl compounds (1) with furan under moderate selectivity

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1705 - 1709
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DOI: 10.3987/COM-90-5497
15-Hydroxypinusolidic Acid, a New Diterpene from the Pericarp of Platycladus orientalis Franco

Yueh-Hsiung Kuo* and Wen-Ching Chen

*Department of Chemistry, National Taiwan University, Roosevelt Road Section 4, Taipei 106, Taiwan, R.O.C.


A new labdane-type diterpene, 15-hydroxypinusolidic acid, together with α-cedrol, β-sitosterol, and 5-hydroxy-7,4’-dimethoxyflavone was isolated from the pericarp of Platycladus orientalis. The structure of new diterpene has been elucidated by spectroscopic and chemical methods.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1711 - 1714
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DOI: 10.3987/COM-90-5498
The Kinetic Study on the Desulfurization of 4,5-trans- and 4,5-cis-5-Phenylthiooxazolidin-2-ones via Cyclic Carbamoloxyradical Species

Shinzo Kano, Tsutomu Yokomatsu, and Shiroshi Shibuya*

*Tokyo College of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan


The relative rate for generation of cyclic carbamoyloxy radicals from 4,5-trans-5-phenylthiooxazolidin-2-ones (6a-c) and cis-isomers (7a-c) was determined and trans-isomers were found to be about six times as reactive as cis-isomers by comparison with their half life.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1715 - 1719
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DOI: 10.3987/COM-90-5522
Practical Preparation of Optically Active O-Benzylglycidol from Optically Active Epichlorohydrin

Seiichi Takano,* Yoshinori Sekiguchi, Masaki Setoh, Takehiko Yoshimitus, Kohie Inomata, Michiyasu Takahashi, and Kunio Ogasawara

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


Practical preparation of optically active O-benzylglycidol has been developed starting from optically active epichlorohydrin by employing either basic or acidic conditions in the key stage.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1721 - 1725
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DOI: 10.3987/COM-90-5523
Practical Synthesis of (S)-1-Octyn-3-ol: A Key Intermediate for the Prostaglandin Synthesis

Seiichi Takano,* Takumichi Sugihara, and Kunio Ogasawara

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


Practical synthesis of (S)-octyn-3-ol is devised starting from (2S,3S)-2,3-O-isopropylidenedioxyoctanol readily accessible from diethyl (L)-tartrate.

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Paper | Regular issue | Vol 31, No. 9, 1990, pp. 1727 - 1731
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DOI: 10.3987/COM-90-5526
Biomimetic Synthesis of (-)-Deoxyrhexifoline, (-)-Tecostidine, and (-)-Actinidine

Yvonne Ranarivelo, Françoise Hotellier, Alexios-Léandros Skaltsounis, and François Tillequin*

*Département de Pharmacognosie de l’Université René Descartes, U.R.A. au C.N.R.S. n°1310, Faculté des Sciences Pharmaceutiques et Biologiques, 4, Avenue de l’Observatoire, F-75006 Paris, France


The title monoterpene pyridine alkaloids were synthesized by transformations of the iridoid glycoside loganin.

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28 data found. 1 - 28 listed