Regular Issue

Vol. 51, No. 5, 1999

25 data found. 1 - 25 listed
Communication | Regular issue | Vol 51, No. 5, 1999, pp. 961 - 964
Published online:
DOI: 10.3987/COM-98-8470
Synthesis of 2,5-Heptano-1,2-dihydropyridine Derivatives

Volker Kirsche, Werner Tochtermann,* Eva-Maria Peters, Karl Peters, and Hans George von Schnering

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


The title compounds have been synthesized by reaction of the dihydromethoxyoxepine (1) with hydrochiorides of amino esters (2a-2c) or of hydrazides (2d-2e) in the presence of sulfuric acid.

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Communication | Regular issue | Vol 51, No. 5, 1999, pp. 965 - 968
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DOI: 10.3987/COM-99-8478
Synthesis and Emission Behavior of Double-armed Tetrathiacrown Carrying Two Naphthalenes

Kanji Kubo,* Yoshihiro Miyazaki, Katsuhito Akutsu, and Tadamitsu Sakurai

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


Double-armed tetrathiacrown having two naphthalenes shows specific photophysical properties for Pd2+ and Au3+ ions selectively, based on cooperative actions of parent thiacrown and fluorometric side arms.

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Communication | Regular issue | Vol 51, No. 5, 1999, pp. 969 - 973
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DOI: 10.3987/COM-99-8485
Oxidation Activity of Long Conjugative and Metal-coordinative Flavin Model: Bent-Benzodipteridine

Hideki Ohshiro, Hirobumi Takahashi, Shin-ichi Kondo, Yumihiko Yano,* Masakazu Koga,* and Fumio Yoneda

*Faculty of Engineering, Gunma University, 1-5-1 Tenjin-cho, Kiryu 376-8515, Japan


Redox behavior of 11,14-diethyl-3,8-dimethyl-1,3,5,6,8,10,11,14-octaazapentaphene-2,4,7,9 (14H,3H,8H,11H)-tetrone (bent-BDP) was studied in aqueous solution, and a metal ion effect was also examined for the oxidation of an NADH model in acetonitrile.

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Communication | Regular issue | Vol 51, No. 5, 1999, pp. 975 - 978
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DOI: 10.3987/COM-99-8499
A Shortcut and Stereoselective Synthesis of 1-β-Alkyl-2-deoxy-D-ribose Derivatives via Wittig-Horner-Emmons Reaction

Naoko Matsuura, Yoshitaka Yashiki, Shouji Nakashima, Minoru Maeda, and Shigeki Sasaki*

*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan


A shortcut and stereoselective synthesis of 1-β-alkyl-2-deoxy-D-ribose derivatives has been achieved via Wittig-Horner-Emmons reaction followed by intramolecular 1,4-addition. After the systematic investigation of the effects of the base and the solvent, the best β-selectivity, as much as 12:1, was obtained with potassium tert-butoxide in THF.

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Communication | Regular issue | Vol 51, No. 5, 1999, pp. 979 - 982
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DOI: 10.3987/COM-99-8509
The Conversion of Mixed N,O-Diacylated 2-Aminophenols to 2-Substituted Benzoxazoles

Mark R. DeLuca, Irach B. Taraporewala, and Sean M. Kerwin*

*Division of Medicinal Chemistry, College of Pharmacy, The University of Texas at Austin, Austin, Texas 78712-1074, U.S.A.


When N,O-diacylated 2-aminophenols that have different acyl substituents on nitrogen and oxygen are treated with p-toluenesulfonic acid in refluxing xylenes, mixtures of benzoxazoles are produced. The major product is the benzoxazole in which the substituent at the 2-position is derived from the acyl group on nitrogen. This product may arise from an unusual case of acid-mediated neighboring amido-group assisted hydrolysis.

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Communication | Regular issue | Vol 51, No. 5, 1999, pp. 983 - 987
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DOI: 10.3987/COM-99-8513
Novel Synthesis and Properties of [n](2,4)Pyridinophanes and [n](2,4)Quinolinophanes

Hideo Miyabara, Tohru Takayasu, and Makoto Nitta*

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


A new short synthesis of cyclohexenone-annulated [n](2,4)pyridinophanes (n=9-7), which were easily converted to [n](2,4)quinolinophanes (n=9-7), respectively, was accomplished by the reaction of 3-amino-2-cyclohexenone with 2-cycloalkenones

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Communication | Regular issue | Vol 51, No. 5, 1999, pp. 989 - 1002
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DOI: 10.3987/COM-98-8447
Preliminary Study of the Total Synthesis of Bao Gong Teng A Analogs Using 8-Benzyl-2-oxo-8-azabicyclo[3.2.1]oct-3-ene-6-endo/exo- and 7-endo/exo-carbonitrile

Stéphane Rézel, François Estour, Damien Canitrot, Elena V. Bejan Voinea, Jean-M. Chezal, Claire Lartigue, Yves Blache, Alain Gueiffier, Gérard Dauphin, Jean C. Teulade, and Olivier Chavignon*

*Département d'Analyse Structurale et de Pharmacologie, Laboratoire de Chimie Organique, Faculté de Pharmacie, Université d'Auvergne, 28, Place Henri Dunant, B.P. 38, 63001 Clermont-Ferrand Cedex, France


The use of four cycloadducts from the Katritzky reaction for subsequent preparation of Bao Gong Teng A analogs was studied. We show that the reduction of 2-oxo-8-azabicyclo[3.2.1]octanes (1-4) to alcohols allows the 2-exo/endo isomerism to be exploited. The 7-endo compound (4) also yielded azatricyclo[5.2.l.04,8]decanone (12) from alcohol (11). When the nitrile was converted into an acetyl group, 6-endo products (13) and (14) were isornerized to 6-exo. Trimethylsilyloxy derivatives (13-18) ultimately yielded 2-hydroxy-azabicyclooctethanone (22-24). These results afford an approach to the synthesis of the 6-exo 2-endo, 7-exo 2-exo and 7-exo 2-endo isomers of Bao Gong Teng A.

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Paper | Regular issue | Vol 51, No. 5, 1999, pp. 1003 - 1014
Published online:
DOI: 10.3987/COM-98-8466
Reactivity of Heterocyclic Enaminones: Regioselective Synthesis of Some Pyridobenzodiazepines and Imidazopyridines

Yves Blache,* Mohammed Hichour, Genoveffa Di Blasi, Jean-Michel Chezal, Henri Viols, Olivier Chavignon, Jean-Claude Teulade, and Jean-Pierre Chapat

*E. A. 2414 Pharmacochimie et Biomolécules, Laboratoire de Chimie Organique Pharmaceutique, Université Montpellier I, 15 Avenue Charles Flahault, 34060 Montpellier, France


Reactivity of enaminones derived from various diaminopyridines toward electrophilic carbons (imines, carbodiimides, isocyanates) is reported. The reactions leading to diazepinic or imidazolic ring systems are shown to be dependent of the electrophilic species as well as of the position of the nitrogen atom in the heterocyclic ring.

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Paper | Regular issue | Vol 51, No. 5, 1999, pp. 1015 - 1024
Published online:
DOI: 10.3987/COM-98-8469
Synthesis of Alkylthio- and Arylthioheteroarenes by Regioselective Grignard Reaction of Thiocyanatoheteroarenes

Izuru Nagasaki, Miyuki Matsumoto, Masanori Yamashita, and Akira Miyashita*

*Schol of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan


Treatment of thiocyanatoheteroarenes (1) with Grignard reagents (2) afforded alkylthio- or arylthioheteroarenes (3-6) in good yields. Grignard reagents regioselectively attacked the sulfur atom of the thiocyanato group owing to the metal-chelating effect of this group in combination with the hetero ring-nitrogen. 2-Thiocyanatopyridine (1a), 2-thiocyanatopyrimidine (1b), 2-thiocyanatobenzothiazole (1c), and 4-thiocyanatoquinazoline (1d) were converted into a variety of sulfides. Sulfides consisting of two heteroarenes linked by a sulfur atom were readily obtained by this method.

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Paper | Regular issue | Vol 51, No. 5, 1999, pp. 1025 - 1034
Published online:
DOI: 10.3987/COM-99-8473
Stereochemistry of Fluoride-promoted Protio-Desilylation of α-Thiasilanes

Vanda Cerè,* Francesca Peri, and Salvatore Pollicino

*Dipartimento di Chimica Organica "A Mangini", Universita degli Studi di Bologna, Viale Risorgimento, 4, I-40136 Bologna, Italy


We have investigated the stereochemistry of fluoride-promoted protiodesilylation of α-thiasilanes on a rigid structure like the thiahydrindane, compound in which the stabilization of a negative charge on the carbon a to sulfur can be gradually increased from sulfide to sulfoxide and at last to sulfone. For the desilylation of sulfoxides and sulfones relatively free carbanions can be hypothesized, for sulfides the intermediate can probably be captured, to some extent stereospecifically, by an electrophile.

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Paper | Regular issue | Vol 51, No. 5, 1999, pp. 1035 - 1050
Published online:
DOI: 10.3987/COM-99-8477
Pyridazines, 89. On the Synthesis of Novel 1,2-Diazine Containing Tricyclic Systems: Preparation of Dipyridazinodiazepinones

Gottfried Heinisch, Elisabeth Huber, Barbara Matuszczak,* and Kurt Mereiter

*Institute of Pharmaceutical Chemistry, University of Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria


A synthetic method for the so far unknown dipyridazino[4,3-b:3’,4’-e][1,4]diazepinone system (7a) was elaborated. Cyclisation of 6-chloro-N-(3,6-dichloropyridazin-4-yl)-3-(4-methoxybenzylamino)-N-propylpyridazine-4-carbox-amide (5) under basic conditions was found to yield in addition to the expected compound (7a) an isomeric dipyridazino[3,4-b:3’,4’-e][1,4]diazepinone (7b) resulting from Smiles rearrangement. The 7a/7b ratio was found to be influenced by the nature of the base and the solvent.

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Paper | Regular issue | Vol 51, No. 5, 1999, pp. 1051 - 1058
Published online:
DOI: 10.3987/COM-99-8482
A One-Step Transformation of (S)-1-Benzoyl-3[(E)-dimethylaminomethylidene]-5-methoxycarbonylpyrrolidin-2-one into Quinolizinyl- and 2H-2-Pyranonyl-substituted Alanine Derivatives

Marko Skof, Jurij Svete,* and Branko Stanovnik*

*Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, P.O. Box 537, SLO-1000 Ljubljana, Slovenia


(S)-1-Benzoyl-3-[(E)-dimethylaminomethylidene]-5-methoxycarbonylpyrrolidin-2-one (1) was transformed in one step with various 1,3-dinucleophiles (2-14) into the corresponding N-benzoyl-3-quinolizinyl-(15-18) and N-benzoyl-3-(2H-2-pyranonyl)alanine methyl esters (19-27).

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Paper | Regular issue | Vol 51, No. 5, 1999, pp. 1059 - 1065
Published online:
DOI: 10.3987/COM-99-8483
Synthesis of [2.n]Thiophenophanes by Intramolecular [2+2] Photocycloaddition

Yosuke Nakamura, Masayoshi Kaneko, Teruo Shinmyozu, and Jun Nishimura*

*Department of Chemistry, Faculty of Engineering, Gunma University, 1-5-1 Tenjin-cho, Kiryu 376-8515, Japan


[2.n](2,5)Thiophenophanes (n = 3–5) having a cyclobutane ring were successfully synthesized by the intramolecular [2 + 2] photocycloaddition of α,ω-bis(5-vinyl-2-thienyl)alkanes. The yields, conformation, and dynamic behavior of the thiophenophanes were significantly dependent on the oligomethylene chain length, n.

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Paper | Regular issue | Vol 51, No. 5, 1999, pp. 1067 - 1071
Published online:
DOI: 10.3987/COM-99-8489
Highly Enantioselective Synthesis of 3-Hydroxy-2-phenylpiperidine via the Sharpless AD-Reaction

Heinz Stadler* and Michael Bös

*Pharma Division, Pharma Preclinical Research & Development, F.Hoffmann-La Roche Ltd., Grenzacherstrasse 124, CH-4070 Basel, Switzerland


Asymmetric dihydroxylation (AD) of the silyl enol ether (3) provided after hydrolysis the hydroxy ketone (4). Subsequent hydrogenation yielded the title compound (1) as a diastereomeric mixture. The cis-isomer is an important building block for the synthesis of potent NK1 receptor antagonists.

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1073 - 1078
Published online:
DOI: 10.3987/COM-98-8317
Preparation of 1,4-Dioxenes from α-Diazo-β-ketoesters

Ramona Hilgenkamp, John B. Brogan, and Charles K. Zercher*

*Department of Chemistry, College of Engineering and Physical Sciences, Parsons Hall, University of New Hampshire, Durham, NH 03824, U.S.A.


A novel preparation of 1,4-dioxenes is reported in which a rhodium carbenoid generated from an α-diazo-β-ketoester reacts with a 1,2-diol. Insertion of the carbenoid into the O-H bond followed by hemiacetal formation and acid-catalyzed dehydration generates the targeted 1,4-dioxene.

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1079 - 1086
Published online:
DOI: 10.3987/COM-98-8450
Alternative Synthesis of Tryptophan Pseudodipeptides

Valérie Marcq, Catherine Mirand,* Hervé Emonard, and William Hornebeck

*Facluté de Pharmacie, UPRES-A/CNRS 6013, Insitut des Biomoleculés, 51, rue Cognacq-Jay, F-51096 Reims Cedex, France


The tryptophan pseudodipeptides (8) and (13) were synthesized via generation of the tryptophan backbone through the reaction of a succinylaminomalonate with a quaternarized gramine.

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1087 - 1092
Published online:
DOI: 10.3987/COM-98-8464
A New Approach to 5H-Pyrrolo[3,2-d]pyrimidines (9-Deazapurines) from 3-Aminopyrrole-2-carboxylates

Lovro Selic and Branko Stanovnik*

*Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, P.O. Box 537, SLO-1000 Ljubljana, Slovenia


3-Arnino-4-ethoxycarbonyl-1-methyl-1H-pyrrole-2-carboxylate (2) was used to prepare 9-deazapurines in a single step reaction.

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1093 - 1099
Published online:
DOI: 10.3987/COM-98-8467
Synthesis and Spectroscopic Properties of 9-Substituted Benz[g]indoles

Yoshinobu Nagawa,* Koichi Honda, and Hiroshi Nakanishi

*National Institute of Bioscience and Human-Technology, 1-1, Higashi, Tsukuba, Ibaraki, 305-8566, Japan


Photolysis of 1,1’-(1,8-naphthylene)di-1H-1,2,3-triazoles in methanol has given new benz[g]indoles with a triazole ring at 9-position. Similar photoreaction of 1-(8-dimethylamino-1-naphthyl)-1H-1,2,3-triazoles also gives new benz[g]indoles with a dimethylamino group at 9-position. The spectral properties of these compounds were studied in comparison with those of corresponding benz[g]indoles obtained from the similar photolysis of 1-(1-naphthyl)-1H-1,2,3-triazoles. Since the substituent at 9-position and the pyrrole moiety exist in close proximity, unique properties such as the strong intramolecular hydrogen bonding and the restricted rotation of C(sp2)-N(sp3) bond are observed in the 9-substituted benz[g]indoles.

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1101 - 1107
Published online:
DOI: 10.3987/COM-99-8472
Synthesis of 2-Amino-4-aryl-3-cyano-6-methyl-5-ethoxycarbonyl-4H-pyrans

Anatoliy M. Shestopalov,* Zukhra I. Niazimbetova, Dennis H. Evans,* and Murat E. Niyazymbetov

*Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, U. S. A.


A one-step electrochemical synthesis of the title compounds has been devised. The starting materials are aromatic and heteroaromatic aldehydes, malononitrile and ethyl acetoacetate. The overall reaction is catalyzed by electrogenerated base (EGB) formed at a platinum cathode in acetonitrile.

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1109 - 1118
Published online:
DOI: 10.3987/COM-99-8474
3',4-Dialkylthio-3,4'-diquinolinyl Sulfides with Nonidentical Alkyl Groups

Malgorzata Nowak, Krystian Pluta,* Malgorzata Szmielew, Maria J. Maslankiewicz, and Andrzej Maslankiewicz

*Department of Organic Chemistry, The Medical University of Silesia, Jagiellonska Str. 4, 41-200 Sosnowiec, Poland


3’,4-Dialkylthio-3,4’-diquinolinyl sulfides (6) were obtained by three methods in the reaction of thioquinanthrene (1) with sodium hydrosulfide followed by sequential S-alkylation of the 3- and 4-thiolate functions. Competitive S-alkylation of 3- and 4-qui-nolinethiolates (4) and (10) in DMSO showed three times greater susceptibility of the 3-thiolate function to the alkylating agent than the 4-thiolate function. 4-Quinolinethio-lates (3) were converted into 4(1H)-quinolinethiones (8).

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1119 - 1124
Published online:
DOI: 10.3987/COM-99-8480
Synthetic Studies on Trifluoroacetylindoles

Hitoshi Takami, Hirokazu Koshimura, and Toshiaki Kumazawa*

*Pharmaceutical Research Institute, Kyowa Hakko Kogyo Co., Ltd., Nagaizumi, Shizuoka, 411-8731, Japan


Trifluoroacetylindoles were obtained regioselectivcly through the reaction of indolylorganometallic species, prepared by halogen-metal exchange or direct metalation of N-substituted or -nonsubstituted indoles, with TFAA in good yield

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1125 - 1130
Published online:
DOI: 10.3987/COM-99-8486
Total Synthesis of (±)-Deethyleburnamonine and Vindeburnol (RU 24722) with the Corresponding Nitriles as Starting Material

Mauri Lounasmaa,* David Din Belle, and Arto Tolvanen

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


Cyclisation occurred during base treatment of cis-nitrile (5). The resulting new imine (6) was converted into the therapeutically important deethyleburnamonine (4). Total synthesis of vindeburnol (RU 24722) (3), another important drug, was achieved in one step starting from the trans-nitrile (9).

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1131 - 1135
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DOI: 10.3987/COM-99-8492
A New Synthesis of Psilocin

Hideki Sakagami and Kunio Ogasawara*

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


A new route to the hallucinogenic alkaloid psilocin, isolated from the mushroom species Psilocybe mexicana, has been established.

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Note | Regular issue | Vol 51, No. 5, 1999, pp. 1137 - 1140
Published online:
DOI: 10.3987/COM-99-8530
Michael Reactions of β-Keto Phosphonates with Arylmethylene-malononitriles: The First Synthesis of Densely Functionalized 5-Diethylphosphinyl-2-amino-4H-pyrans

José L. Marco* and Pilar M. Chinchón

*Laboratorio de Radicales Libres, Instituto de Química OrgÁnica General , C. S. I. C., Calle Juan de la Cierva 3, E-28006 Madrid, Spain


A convenient synthesis of densely functionalized derivatives of 5-diethylphosphinyl-2-amino-4H-pyrans (1a-d) is described for the first time.

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Review | Regular issue | Vol 51, No. 5, 1999, pp. 1141 - 1170
Published online:
DOI: 10.3987/REV-98-517
The Chemistry of Nx,Ny,Nz-Trimethyladenines and More Highly N-Methylated Adenines

Tozo Fujii* and Taisuke Itaya

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


Various tri- and poly-N-substituted adenines are represented by the corresponding positional isomers of Nx, Ny, Nz-trimethyladenine and of more highly N-methylated adenines. The chemistry of known isomers of these tri- and poly-N-methylated adenines is reviewed with 120 reference citations.

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25 data found. 1 - 25 listed