Regular Issue

Vol. 41, No. 4, 1995

20 data found. 1 - 20 listed
Communication | Regular issue | Vol 41, No. 4, 1995, pp. 641 - 646
Published online:
DOI: 10.3987/COM-94-6973
Exocyclization of Novel β,β-Difluoro-α-phenylvinyl Sulfide with Bidendate Heteroatom(N,O,S) Nucleophiles

Bum Tae Kim, Yong Ki Min, No Kyun Park, Kwang Yun Cho, and In Howa Jeong

*Korea Research Institute of Chemical Technology, Daejoen 305-606, Korea


The exocyclization of novel β,β-difluoro-α-phenylvinyl sulfide with bidentate heteroatom (N, O, S) nucleophiles afforded various types of heterocyclic ketene acetals (O,O-, O,S-, S,S- N,N- N,O- N,S-). The ease of exocyclization depended on the ring size of heterocyclic ketene acetals.

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Communication | Regular issue | Vol 41, No. 4, 1995, pp. 647 - 650
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DOI: 10.3987/COM-94-6996
A Convenient Synthesis of Benzofuran-3-acetic Acids

Yagamare Fall, Lourdes Santana, Marta Teijeira, and Eugenio Uriarte

*Departamento de Química Orgánica, Facultad de Farmacia, Universidad de Santiago de Compostela, E-15706 Santiago de Compostela, Spain


We described a two-step synthesis of benzofuran-3-acetic acids (1) from phenols (2) involving alkali-mediated rearrangement of 4-halomethylcoumarins (3) via α,β-unsaturated acids (4). Electron-donating substituents at the meta position of the phenol favour high yields of the coumarin, which in all cases rearranges to afford benzofuran-3-acetic acids in near quantitative yields.

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Communication | Regular issue | Vol 41, No. 4, 1995, pp. 651 - 653
Published online:
DOI: 10.3987/COM-94-7002
Synthesis of Cribrostatins 1 and 2

Shinsuke Nakahara, Ryuichi Numata, Yoshihiro Tanaka, and Akinori Kubo

*Meiji College of Pharmacy, 1-35-23 Nozawa, Setagaya-ku, Tokyo 154, Japan


Synthesis of the cytotoxic isoquinolinequinone cribrostatins 1 (1) and 2 (2), which were isolated from the blue marine sponge Cribrochalina sp., is described.

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Communication | Regular issue | Vol 41, No. 4, 1995, pp. 655 - 659
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DOI: 10.3987/COM-94-7004
Control of Highly Selective Ag+ Transport by Redox Reactions between Thiol and Disulfide Located inside a Cavity of Crown Ether

Tatsuya Nabeshima*, Hiroyuki Furusawa, Naoko Tsukada, Toshinobu Shinnai, Tsutomu Haruyama, and Yumihiko Yano

*Department of Chemistry, Faculty of Engineering, Gunma University, Kiryu, Gunma 376, Japan


A novel crown ether containing a thiol group inside the ring has been prepared in good yield and exhibits Ag+ selectivity on transport of metal ions through a liquid membrane. However, the corresponding disulfide loses the affinity significantly.

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Communication | Regular issue | Vol 41, No. 4, 1995, pp. 661 - 664
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DOI: 10.3987/COM-94-7015
INOC Reaction in Alkaloid Synthesis –- Preparation of Potential Intermediate for the Synthesis of (-)-Reserpine –-

Masahiro Toyota, Masaki Matsuura, and Keiichiro Fukumoto

*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-77, Japan


Intramolecular nitrile oxide cycloaddition (INOC) reaction of the nitro olefin (10) furnished the isoxazoline (11), potential synthon for the E ring segment of (-)-reserpine (1), in quantitative yield.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 665 - 673
Published online:
DOI: 10.3987/COM-93-6498
The Reaction of Quadricyclane with p-Anils

Fabrizio Fabris, Ottorino De Lucchi, Giovanni Valle, and Sergio Cossu

*Dipartimento di Chimica, Università di Venezia, Dorsoduro 2137, I-30123 Venezia, Italy


The reaction of quadricyclane (Q) with p-anils has been generalized in order to define its scope. Tetrafluoro-, tetrachloro-, and tetrabromo-p-benzoquinones in dichloromethane or chloroform, at or below room temperature give predominant or exclusive formation of the adduct to the C=O bond of the quinone as confirmed by the X-ray structure of the adduct to chloranil. In the case of DDQ (dicyanodichloro-p-benzoquinone), the major product is the standard [4+2]-cycloadduct, while the adduct to the C=O bond is formed as minor product and adds to a second molecule of quadricyclane to form bis-adduct (4). The structure of the latter has also been defined by X-ray analysis.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 675 - 688
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DOI: 10.3987/COM-94-6945
3,5-Dichloro-4-pyridinecarbonitrile as a Key Reagent in a Synthesis of Copper Containing Amine Oxidase Inhibitors

Vincenzo Bertini, Francesco Lucchesini, Marco Pocci, and Angela De Munno

*Instituto di Analisi e Tecnologie Farmaceutiche ed Alimentari, Università di Genova, Via Brigata Salerno, I-16147 Genova, Italy


Various synthetic approaches to 3,4,5-trifunctionalized pyridine derivatives useful as benzylamine oxidase inhibitors are extensively explored. Fully satisfactory preparations of the inhibitors 3,5-diethoxy-4-aminomethylpyridine (4), 3,5-bis(3-hydroxypropoxy)-4-aminomethylpyridine (11), 3,5-bis(4-hydroxybutoxy)-4-aminomethylpyridine (12) and 3-ethoxy-5-phenylmethoxy-4-aminomethylpyridine (16), all in the form of dihydrochloride salt, using 3,5-dichloro-4-pyridinecarbonitrile as key precursor, are reported.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 689 - 696
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DOI: 10.3987/COM-94-6955
An Efficient Synthesis of Pyrrolo[1',2':2,3]pyridazino[6,1-a]isoindoles from 1-Phthalimidopyrrole

Stephan Marchalin and Bernard Decroix

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


A synthesis of pyrrolo[1’,2’:2,3]pyridazino[6,1-a]isoindole was developed. Reduction of 1-phthalimidopyrrole, followed by Wittig reaction using ethoxycarbonylmethylidenetriphenylphosphorane gave the carboxylic acid intermediate (3) which cyclized in the presence of boron trifluoride etherate to furnish the tricyclic ketone (4). Mannich reaction, Schmidt rearrangement, and reduction of the above ketone were studied.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 697 - 707
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DOI: 10.3987/COM-94-6957
Synthesis and Characterization of 6-O-α- and 6-O-β-D-Glucopyranosylmorphine and 6-O-β-D-Glucopyranosylcodeine

Pavol Kovác and Kenner C. Rice

*Laboratory of Medicinal Chemistry, NIDDK, Bldg. 8, Rm. B1-23, National Institutes of Health, Bethesda, MD 20892-0815, U.S.A.


6-O-α- and β-D-glucopyranosylmorphine and 6-O-β-D-glucopyranosylcodeine have been prepared by condensations of 2,3,4,6-tetra-O-acyl-α-D-glucopyranosyl bromides with 3-O-acetylmorphine and codeine, respectively, followed by deprotection. Depending upon the method of condensation, variable amounts of orthoesters were found among the final products of condensation together with the desired glycosides. Highest yields of glycosides were obtained when 2,3,4,6-tetra-O-benzoyl-α-D-glucopyranosyl bromide was the glycosyl donor, and when the condensation was promoted with silver triflate in the presence of a less than stoichiometric amount of 2,4,6-trimethylpyridine as the acid scavenger.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 709 - 720
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DOI: 10.3987/COM-94-6974
Synthesis of Thieno-Diltiazem Analogues

Isolde Puschmann and Thomas Erker

*Institute for Pharmaceutical Chemistry, University of Vienna, A-1090 Vienna, Althanstr.14, Austria


The replacement of benzene by thiophene in a molecule might result in an altered metabolism of the modified drug, a different biochemical profile and/or an elimination of side effects to a certain extent. Replacement of the fused aromatic moiety in diltiazem with thiophene provides cis-4-[(2-dimethylamino)-ethyl]-4,5,6,7-tetrahydro-7-(4-methoxyphenyl)-5-oxo-thieno[2,3-b][1,4]thiaz-epin-6-yl acetate (20). The synthsis starts with the reaction of 3-nitro-2-thiophenethiol and racemic trans-(4-methoxyphenyl)glycidate. The resulting threo and erythro products are reduced, cyclized, alkylated and acetylated to give the desired compounds (20) and (21).

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 721 - 740
Published online:
DOI: 10.3987/COM-94-6976
Synthesis and Reactions of Dialkyl (1-R-5-Amino-3-methylsulfanyl-1H-pyrazol-4-yl)-phosphonates

Harald G. Krug, Richard Neidlein, Roland Boese, and Walter Kramer

*Pharmazeutisch-Chemisches Institut, Im Neuenheimer Feld 364, 69120 Heidelberg, Germany


Dialkyl (1-cyano-2,2-bismethylsulfanylvinyl)phosphonates (2) react with hydrazines (4) to yield pyrazoles (5). The composition of one reaction product is examined by X-ray crystal structure analysis. N-Unsubstituted pyrazoles (5a) treated with 1,3-diketones (6) give pyrazolo[1,5-a]pyrimidines (7).

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 741 - 752
Published online:
DOI: 10.3987/COM-94-6980
Additional Bioactive Triterpenoids from Melia volkensii (Meliaceae)

Lu Zeng, Zhe-ming Gu, Phillip E. Fanwick, Ching-jer Chang, David L. Smith, and Jerry L. McLaughlin

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


Meliavolen (1) and melianinone (2), new triterpenes with an apotirucallane skeleton, together with two known compounds, 3-episapelin A (5) and nimbolin B (6), have been isolated from the root bark of Melia volkensii (Meliaceae) by using brine shrimp lethality for bioactivity-directed fractionation. The structures have been elucidated by spectral data. The relative and absolute stereochemistries of 2 were determined by correlating 2 with melianin A (3). The stereochemistry of 3 was determined by X-ray crystallographic analysis and Mosher methodology. The stereochemistry of 5 was also determined by Mosher methodology. The four isolated compounds, meliavolen (1), melianinone (2), 3-episapelin (5), and nimbolin B (6), were all moderately active in the brine shrimp lethality test and were significantly cytotoxic among human solid tumor cell lines with noted selectivities toward the colon cell line (HT-29).

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 753 - 763
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DOI: 10.3987/COM-94-6982
Synthesis of Tetracyclic Arylpyridodiazepines as Potential Anti HIV-1 Agents

Giovanni Viti, Danilo Giannotti, Rossano Nannicini, Giuseppe Balacco, Vittorio Pestellini, Paola Paoli, and Paolo Dapporto

*Chemical Research Department , A. Menarini Industrie Farmaceutiche Riunite s.r.l., V. Sette Santi 3, Firenze, Italy


Some tetracyclic compounds containing the pyridodiazepine system condensed with the pyridofuro, pyridothieno, and indolo groups were synthesized. In the case of indole derivatives the outcome of the reaction is highly dependent by the nature of the substituents.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 765 - 772
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DOI: 10.3987/COM-94-6984
3-Methyl-1-phenacylbenzotriazolium Yilde : Cycloadditions with Acetylenic Esters and Aldehyde-mediated Dimerization

Alan R. Katritzky, Baozhen Yang, Jinlong Jiang, and Peter J. Steel

*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200, U.S.A.


Stable 3-methyl-1-phenacylbenzotriazolium ylide (2) adds acetylenecarboxylic esters to form tricycles (3). Araldehydes react with two moles of 2 give poly-substituted 4,5-dihydrofurans (5). The pyrazoloquinoxaline structure of 3 was confirmed by X-ray analysis.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 773 - 779
Published online:
DOI: 10.3987/COM-94-6991
Oxidation of 1,2,3,4-Tetrahydroisoquinolines to 3,4-Dihydroisoquinolines with Molecular Oxygen Catalyzed by Copper(Ö†) Chloride

Masao Shimizu, Hideo Orita, Takashi Hayakawa, Kunio Suzuki, and Katsuomi Takehira

*National Institute of Materials and Chemical Research, 1-1, Higashi, Tsukuba, Ibaraki 305, Japan


A catalytic oxidation system, a CuCl2-O2 system, was efficient for dehydrogenation of 1,2,3,4-tetrahydroisoquinolines to 3,4-dihydroisoquinolines. Oxidation of 1,2,3,4-tetrahydroquinoline was also carried out.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 781 - 788
Published online:
DOI: 10.3987/COM-94-6997
Pteridines, CIV. Regioselective Alkoxylation of Pteridines at the 6-Position by N-Bromo-succinimide and Alcohol

Takashi Sugimoto and Wolfgang Pfleiderer

*Department of Natural Science Informatics, School of Informatics and Sciences, Nagoya University, Chikusa-ku, Nagoya 464-01, Japan


Reaction of 1,3-dimethyllumazine with N-bromosuccinimide or bromine in an appropriate alcohol afforded 6-alkoxy-1,3-dimethyllumazine. N-Iodosuccinimide or iodine also brought about the same reaction. This procedure was applicable to other pteridine compounds, such as 2-dimethylamino-4(3H)-oxopteridine. The mechanism of this alkoxylation reaction is discussed.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 789 - 797
Published online:
DOI: 10.3987/COM-94-6998
6-Acyllumazines from the Marine Polychaete, Odontosyllis undecimdonta

Hisae Kakoi*, Hideo Tanino, Kunisuke Okada, and Shoji Inoue

*Faculty of Pharmacy, Meijo University, Tenpaku, Nagoya 468, Japan


Lumazine and its 3-methyl and 1,3-dimethyl derivatives having 6-acyl substituents such as acetyl, propionyl, β-methoxypropionyl, and β-hydroxypropionyl groups were isolated from the marine polychaete, Odontosyllis undecimdonta.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 799 - 805
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DOI: 10.3987/COM-94-7006
Leptocarpine, a New Protopine Alkaloid

Eva Táborská, Hana Bochoráková, Petr Sedmera, Ivo Válka, and Vilim Simánek

*Institute of Medical Chemistry, Palacky University, 775 15 Olomouc, Czech Republic


The structure of leptocarpine (1) a new protopine alkaloid isolated from the whole plant of Hypecoum leptocarpum was elucidated on the basis of spectral analysis, including 2D nmr spectroscopy and chemical transformation.

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 807 - 816
Published online:
DOI: 10.3987/COM-94-7010
Total Synthesis of Na,O-Di-Boc-5β-cyano-Z-geissoschizine and Na-Boc-21α-Cyanotetrahydroalstonine, the Latter a Synthetic Equivalent of Na-Boc-Cathenamine

Mauri Lounasmaa, Minna Halonen, and Reija Jokela

*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, FIN-02150 Espoo, Finland


Modified Polonovski reaction of the synthetically prepared Na,O-di-Boc-Z-geissoschizine cis-Nb-oxide (6), followed by cyano trapping of the formed iminium intermediates, led to four compounds (1), (5a), (7), and (8a) [and to two secondary products, (9) and (10)]. The most important of these compounds were Na,O-di-Boc-5β-cyano-Z-geissoschizine (5a) and Na-Boc-21α-cyanotetrahydroalstonine (8a) [synthetic equivalent of Na-Boc-cathenamine (8b)]. Change in the reaction temperature caused one (Δ4(21)) of the intermediate iminium ions to be strongly favoured, leading to the nearly exclusive formation of compound (8a) at the expense of compounds (5a), (7), (9), and (10).

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Paper | Regular issue | Vol 41, No. 4, 1995, pp. 817 - 825
Published online:
DOI: 10.3987/COM-94-7012
Carbon Functionalizations on Pyridine Ring via Trimethylstannyl Derivatives — An Example of Fusaric Acid Synthesis —

Yutaka Yamamoto, Takuo Tanaka, Hidekazu Ouchi, Masayo Miyakawa, and Yasuo Morita

*Tohoku College of Pharmacy, 4-1, Komatsushima 4 Chome, Aoba-ku, Sendai 981, Japan


Method for introduction of two types of carbon functional groups, acyl and tert-butoxycarbonyl groups, in pyridine ring via bis(trimethylstannyl)pyridine (1) is explored. Application of this method to the synthesis of fusaric acid (11) is also described.

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