Regular Issue

Vol. 45, No. 11, 1997

23 data found. 1 - 23 listed
Communication | Regular issue | Vol 45, No. 11, 1997, pp. 2089 - 2092
Published online:
DOI: 10.3987/COM-97-7932
A Novel Synthesis of 4-Perfluoroalkylquinolines and Related Substituted Quinolines

Agnieszka Czarny, Hyeran Lee, Martial Say, and Lucjan Strekowski*

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


In spite of inefficient hydrolysis of 1-(2-aminophenyl)-2,2,3,3,4,4,4-heptafluorobutan-1-one diethyl acetal (2), this compound undergoes readily the acid-catalyzed Friedländer reaction with enolizable ketones to give the corresponding quinolines (4-6). The reaction of 2 with pentanal yields quinoline (12) as the major product.

PDF (110KB)
Communication | Regular issue | Vol 45, No. 11, 1997, pp. 2093 - 2095
Published online:
DOI: 10.3987/COM-97-7933
Formation and Trapping of 1,2-Dimethyleneazulene

Kunihide Fujimori,* Kameji Yamane, Masafumi Yasunami, and Kahei Takase

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


1,2-Dimethyleneazulenes, an o-xylylene type reactive intermediate, have been generated by the heating of 1,3-dihydroazuleno[1,2-c]thiophene dioxides. The reactive intermediates were efficiently trapped by dienophiles, such as N-phenylmaleimide and diethyl azodicarboxylate, to form [4+2] cycloaddition products in high yields.

PDF (75KB)
Communication | Regular issue | Vol 45, No. 11, 1997, pp. 2097 - 2100
Published online:
DOI: 10.3987/COM-97-7941
Asymmetric Induction in Intramolecular [5+2] Cycloaddition of 2-(4-Alkenyl)-5-benzoyloxy(or 5-Silyloxy)-4-pyrones Involving Migration of the Pyrone O-5 Group to O-4

Naoki Ohmori, Miki Yoshimura, and Katsuo Ohkata*

*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-hiroshima, Hiroshima 739-8526, Japan


Heating of the title compounds (1a,b) at 130 °C in o-dichlorobenzene afforded [5+2] annulation products (2a,b) in 70% yield; 27-33% d.e. via 3-oxidopyrylium ylide. Reaction of the title compounds (1a,c) in the presence of ZnCl2 at 40 °C furnished [5+2] annulation products (2b,c) in 23-64% yield and 53-59% d.e. In the event, treatment of the 5-silyloxy derivatives (1d,e) with TBSOTf in the presence of 2,6-lutidine at even 20 °C for 16 h gave [5+2] annulation products (2d,e) with 75% d.e. and 78% d.e. in high yields, respectively

PDF (151KB)
Communication | Regular issue | Vol 45, No. 11, 1997, pp. 2101 - 2104
Published online:
DOI: 10.3987/COM-97-7945
Synthesis and Characterization of Fused Mesoionic 1,3,4-Oxadiazolium-2-thiolates from N-Amino-N,N’-dihydrodiazinediones

Dong Ju Jeon, Sung Chul Shin, and Youn Young Lee*

*Department of Chemistry, Seoul National University, San 56-1, Shillim-Dong, Kwanak-Gu, Seoul 151-742, Korea


The novel fused mesoionic 1,3,4-oxodiazolium-2-thiolates were synthesized from N-amino-N,N’-dihydrodiazinediones by treatment with carbon disulfide in the presence of 1,3-dicyclohexylcarbodiimide.

PDF (95KB)
Communication | Regular issue | Vol 45, No. 11, 1997, pp. 2105 - 2108
Published online:
DOI: 10.3987/COM-97-7954
Stereoselectivity in Addition of Phenylselenyl Chloride to Bicyclo[2.2.1]hept-2-ene Derivatives and Synthesis of 3'-Chloro Substituted Carbovir

Akemi Toyota,* Akiko Nishimura, and Chikara Kaneko

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


Addition of phenylselenyl chloride to bicyclo[2.2.1]hept-2-enes was examined and the stereoselectivities have been clarified. The adducts derived from 2-azabicyclo[2.2.1]hept-5-en-3-ones having an electron-withdrawing group at 2-position were converted to 3’-chloro substituted carbovir.

PDF (111KB)
Communication | Regular issue | Vol 45, No. 11, 1997, pp. 2109 - 2112
Published online:
DOI: 10.3987/COM-97-7964
A Novel Abnormal Rearrangement in the Fischer Indole Synthesis

Hideaki Fujii, Akira Mizusuna, Ryuji Tanimura, and Hiroshi Nagase*

*Basic Research Laboratories, Toray Industries, Inc., 111, Tebiro, Kamakura, Kanagawa, 248, Japan


In the Fischer indole synthesis of naltrexone N-methyl-N-(5,6,7,8-tetrahydro-1-naphthyl)hydrazone, an abnormal rearrangement of the fused 6-membered ring was observed. This abnormal rearrangement was not observed without the N-alkyl group of the hydrazone. The mechanism for the unexpected products was assumed to involve the [3,3] sigmatropic rearrangement at the substituted and more hindered ortho position and the subsequent rearrangement of the fused 6-membered ring via a spiro intermediate.

PDF (115KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2113 - 2129
Published online:
DOI: 10.3987/COM-97-7873
Complex Base-induced Generation of 3,4-Didehydropyridine Derivatives : New Access to Aminopyridines or Pyridones

Karine Vinter-Pasquier, Brigitte Jamart-Grégoire, and Paul Caubère*

*INCMFU CNRS 0008, Faculte des Sciences-Campus Victor Grignard, Université Henri-Poincare, Bat. 2e cycle, Bld des Aiguillettes, BP 239 - 54506 Vandeceuvre Les Nancy Cedex, France


The complex base, NaNH2-tert-BuONa, in THF easily transforms 3-bromopyridine and 2-pyridone derivatives into the corresponding hetarynes. The reaction of representative amines (dialkylamines, morpholine, piperidine) with these reactive intermediates leads to the preparation of aminopyridines in good yields and illustrates the synthetic usefulness of such reactions.

PDF (541KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2131 - 2136
Published online:
DOI: 10.3987/COM-97-7885
Synthesis of 2H-1-Benzopyran-2,4(3H)-dione-3-carboxamide and 2H,3H-[1]Benzopyrano[4,3-b]pyrano-2-hydroxy-3-carboxamide-4,5-dione Derivatives via Carbon Suboxide

Leonardo Bonsignore* and Giuseppe Loy

*Dipartimento Farmaco Chimico Tecnologico, Universita di Cagliari, Via Ospedale 72, I-09124 Cagliari, Italy


The reaction of substituted 2-hydroxybenzmides with carbon suboxide is described. By varying the weight ratio of the reagent, this reaction leads to the coumarin and/or pyranocoumarin derivatives in one step and with satisfactory yields.

PDF (149KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2137 - 2157
Published online:
DOI: 10.3987/COM-97-7909
Synthesis and Conformational Analysis of Hexahydroisoquino[3,2-b][3]benzazepines (iso-B-Homoberbines)

Darius Paul Zlotos and Werner Meise*

*Pharmaceutical Institute Poppelsdorf, University of Bonn, Kreuzbergweg 26, D-53115 Bonn, Germany


A new simple synthetic approach to the hexahydroisoquino[3,2-b][3]benzazepines has been developed. 3-Benzyl-2-tetralones (3a-c) were prepared in two different ways from 2-tetralone and 6-methoxy-2-tetralone. Regioselective methoxycarbonylation with dimethyl carbonate or with magnesium methyl carbonate gave the known β-keto esteres (1) or (1’), respectively, which could be alkylated to benzyl derivatives (2) and (2’), respectively. Demethoxycarbonylation using lithium iodide afforded the desired 3-benzyl-2-tetralones (3a-c), which furnished the lactams (4a-c) by submitting to the Schmidt reaction. Reduction usign borane and a final Pictet-Spengler cyclization gave the title compounds (6a-c). NMR measurements indicated that iso-B-homoberbines exist as equilibrium mixture of the cis and trans conformers in CDCl3 solution at room temperature, whereas the hydrochloride salt of 6b adopts a cis B-fused conformation.

PDF (540KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2159 - 2173
Published online:
DOI: 10.3987/COM-97-7914
Aroylation of Fused Pyrimidines; Synthesis of 4-Aroylfuro[2,3-d]-, 4-Aroylthieno[2,3-d]-, and 4-Aroylisoxazolo[5,4-d]pyrimidines

Akira Miyashita,* Kazuhiro Obae, Yumiko Suzuki, Etsuo Oishi, Ken-ichi Iwamoto, and Takeo Higashino

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


4-Aroylfuro[2,3-d]- (4), 4-aroylthieno[2,3-d]- (7 and 8), and 4-aroylisoxazolo[5,4-d]pyrimidines (13) were synthesized by aroylation of the fused chloro- (3a and 12) or bromopyrimidines (3b, 5, and 6) with arenecarbaldehydes (2) catalyzed by an imidazolium salt (1a). The fused aroylpyrimidines (4 and 7) were also synthesized by oxidative decyanation of α-phenylheteroareneacetonitriles (10 and 11).

PDF (427KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2175 - 2184
Published online:
DOI: 10.3987/COM-97-7919
Crystal and Molecular Structure of a Rimazolium®Decomposition Product.Calculation of Pyramidality of Analogous Cyclic Amides

Kálmán Simon,* Levente Pusztay, Miklós Hanusz, Zsolt Böcskei, Benjamin Podányi, Miklós Fehér, and István Hermecz

*CHINOIN Pharmaceutical and Chemical Works Ltd., P. O. Box 110, H-1325 Budapest, Hungary


The solid state structure of 10 was determined by X-Ray investigations, and stereostructure of 1,6,7,8,9,9a-hexahydro-4H-pyrido[1,2-a]pyrimidin-4-ones were studied by semiempirical quantum chemical calculations at the AM1 level. While 9a-unsubstituted 1-methyl-1,6,7,8,9,9a-hexahydro-4H-pyrido[1,2-a]pyrimidin-4-ones adopt a cis-fused conformation, 9a-ethoxy-1-methyl derivative has a trans-fused conformation to avoid a serious non-bonding interaction between 9a-ethoxy and 1-methyl groups in cis-fused one.

PDF (255KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2185 - 2195
Published online:
DOI: 10.3987/COM-97-7936
Novel Formation and Crystal Structure of 2-(2,2,2-Trifluoroethylidene)-6-trifluoro-methyl-2,3-dihydro-4H-1,4-oxazin-3-ones from N-Acetyl-N-alkyl-α-amino Acids

Masami Kawase,* Setsuo Saito, Hiroyuki Kikuchi, and Hiroshi Miyamae

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


The title compounds (2a-g) were formed from N-acetyl-N-alkyl-α-amino acids (1a-g) on treatment with trifluoroacetic anhydride in the presence of pyridine. The structure of the product (2a) was determined by single crystal X-Ray analysis.

PDF (291KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2197 - 2208
Published online:
DOI: 10.3987/COM-97-7948
Synthesis of Mesomeric Betaines, Quinoliziniumides, via Back-donated 1,6-Cyclization

Yoshiro Matsuda,* Keisuke Katou, Takanobu Nishiyori, Takashi Uemura, and Maki Urakami

*Faculty of Environmental Studies, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan


The reaction of 3-aminopyridinium salts (4) with polarized olefins (2a, b, 3) in the presence of triethylamine yielded the corresponding 3-aminopyridinium N-allylides (5a). Thermolysis of 3-aminopyridinium N-allylides (5a-c, h-j, l-n) in refluxing xylene afforded the 1,5-dipolar cyclization products, 8-aminoindolizines (6) togeher with the back-donated 1,6-cyclization products quinoliziniumides (7). In addition, thermolysis of N-allylides (5a-c, h-j, l-n) in refluxing AcOH gave quinoliziniumides (7).

PDF (392KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2209 - 2216
Published online:
DOI: 10.3987/COM-97-7955
Synthesis of 6-, 7-, 8-, or 9-Substituted 1H-Pyrano[4,3-b]quinoline Derivatives by the Cyclization of 3-Acetyl-4-arylamino-2H-pyran-2-one Derivatives

Atsuko Sato, Mieko Morone, and Yutaka Azuma*

*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan


Heating of 3-acetyl-4-arylamino-6-methyl-2H-pyran-2-one derivatives in concd H2SO4 gave 6-, 7-, 8- or 9-substituted 6,10-dimethyl-1H-pyrano[4,3-b]quinoline derivatives.

PDF (172KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2217 - 2221
Published online:
DOI: 10.3987/COM-97-7956
Suzuki Couplings with Phthalimidines - An Efficient Route to Staurosporinone Analogs

Kenneth C. Rupert, John H. Dodd, and James R. Henry*

*The R. W. Johnson Pharmaceutical Research Institute, Route 202, P.O. Box 300, Raritan, NJ 08869-0602, U.S.A


Staurosporinone analogs have been prepared by an efficient process. The key step is a palladium mediated Suzuki coupling between a bromophthalimidine and an aromatic boronic acid.

PDF (85KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2223 - 2228
Published online:
DOI: 10.3987/COM-97-7960
Synthesis of a New Annulenoannulene, Cycl[3.2.2]azino[1,2-a]cycl[3.2.2]azine

Yoshiro Matsuda,* Shinya Kohra, Keisuke Katou, Takahiro Itou, and Takashi Uemura

*Faculty of Environmental Studies, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan


A new nitrogen-bridged annulenoannulene, cycl[3.2.2]azino[1,2-a]cycl[3.2.2]azine (8) was synthesized from the starting bispyridylmethane (1) via cycloaddition reaction of the indolizinocyclazine derivative (5) with diemthyl acetylenedicarboxylate (DMAD) as the key step.

PDF (160KB)
Paper | Regular issue | Vol 45, No. 11, 1997, pp. 2229 - 2237
Published online:
DOI: 10.3987/COM-97-7963
Synthesis of a Pyrido[2,3-d]pyrimidine Analogue of the Multitargeted Antifolate LY231514

Edward C. Taylor* and Koo Lee

*Department of Chemistry, Princeton University, Princeton, New Jersey 08544, U.S.A.


Synthesis of pyrido[2,3-d]pyrimidines (9) and (21), ring-expanded analogues of the antitumor agent LY231514 (7), and its 4-amino analog, respectively, are described. Preliminary in vitro cell culture evaluation has shown that expansion of the pyrrole ring of the latter two pyrrolo[2,3-d]pyrimidines through introduction of a carbonyl group between positions 6 and 7 results in complete loss of cell growth inhibitory activity.

PDF (255KB)
Note | Regular issue | Vol 45, No. 11, 1997, pp. 2239 - 2246
Published online:
DOI: 10.3987/COM-97-7861
Condensation of 2-Amino-5-chlorobenzoxazole with α-Bromoketones: A Mechanistic Study

Patrick J. Roy,* Kerri Landry, Yves Leblanc, Chun Li, and Nancy Tsou

*Department of Medicinal Chemistry, Merck Frosst Centre for Therapeutic Research, P.O. Box 1005, Pointe-Claire-Dorval, Quebec, H9R 4P8, Canada


The condensation of 2-aminobenzothiazoles with α-bromo ketones products the fused imidazothiazole (2) whereas the analogous reaction with 2-aminobenzoxazoles gives the unexpected carbamate (10) or the fused imidazooxazole (13), depending on the nature of the starting materials. Isotope labelling studies as well as a proposed mechanism will be discussed.

PDF (218KB)
Note | Regular issue | Vol 45, No. 11, 1997, pp. 2247 - 2252
Published online:
DOI: 10.3987/COM-97-7923
A Neoclerodane Diterpenoid from Scutellaria guatemalensis (Labiatae)

Baldomero Esquivel,* Rosa María Domínguez, Miguel Angel Martínez, and Georgina Espinosa-Pérez

*Instituto de Química, Universidad Nacional Autónama de México, Circuito Exterior, Ciudad Universitaria, Coyoacán 04510 Mexico, D.F., Mexico


A new neoclerodane diterpenoid, (13R)-6α,11β-diacetoxy-1β,12α-diisobutyryloxy-4α,18;18β,13-diepoxy-neo-clerodan-15,16-olide (Scuteguatemalin) has been isolated from the aerial parts of Scutellaria guatemalensis besides the known skullcapflavone II. The structure of the new diterpenoid was established by spectroscopic methods and confirmed by X-Ray analysis.

PDF (180KB)
Note | Regular issue | Vol 45, No. 11, 1997, pp. 2253 - 2260
Published online:
DOI: 10.3987/COM-97-7935
Studies on Inhibitory Activity against Acetylcholinesterase of New Bisbenzylisoquinoline Alkaloid and Its Related Compounds

Tatsunori Ogino,* Takuji Yamaguchi, Toshitsugu Sato, Hiroshi Sasaki, Ko Sugama, Minoru Okada, and Masao Maruno

*Central Research Laboratory, Tsumura & Co., 3586 Yoshiwara, Ami-machi, Inashiki-gun, Ibaraki, 300-11, Japan


A new phenolic bisbenzylisoquinoline (BBI) alkaloids named 2’-N-norfangchinoline was isolated from the root of Stephania tetrandra S. MOORE along withfangchinoline (2) and atherospermoline (3). The chemical structure of 2’-N-norfangchinoline was proved to be 4 by spectral analyses and chemical methods. Moreover three phenolic BBI alkaloidal compounds, 2,2’-N,N-dinorfangchinoline (8), 2’-N-noratherospermoline (9), 2-N-norfangchinoline (10) were derived from tetradrine (1). And 12-O-acetyl antherospermoline (11) was obtained by partial acetylation of atherospermoline (3). Seven phenolic BBI compounds (2, 3, 4, 8, 9, 10, and 11) also have the inhibitory effect on acetylcholinesterase.

PDF (264KB)
Note | Regular issue | Vol 45, No. 11, 1997, pp. 2261 - 2272
Published online:
DOI: 10.3987/COM-97-7946
Cesium Fluoride-mediated Claisen Rearrangements of Phenyl Propargyl Ethers: Substituent Effects of an ortho-Alkoxy Group on the Benzene Ring or Modified Propargyl Residues

Tsutomu Ishikawa,* Akiko Mizutani, Chizue Miwa, Yumie Oku, Naoko Komano (nee Ohkubo), Atsuya Takami, and Toshiko Watanabe

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


The expected 7-alkoxy-2-emthylbenzo[b]furans were effectively given in the CsF-mediated Claisen rearrangement of phenyl propargyl ethers with an o-alkoxy substituent on the benzene ring. On the other hand CsF did not affect the production of the corresponding benzo[b]furans when ethers, carrying a propargyl residue modified by either 1,1-dimethyl or 3-ethoxycarbonyl functions, were used as substrates in the rearrangement.

PDF (367KB)
Note | Regular issue | Vol 45, No. 11, 1997, pp. 2273 - 2276
Published online:
DOI: 10.3987/COM-97-7947
Ring-Expansion of 2-Methylbenzo[b]furan to 3-Hydroxychromen-4-one: A Potential Approach to a Flavonol Skeleton

Tsutomu Ishikawa* and Chizue Miwa

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


A 2-methylbenzo[b]furan, prepared by the CsF-mediated Claisen rearrangement of a propargyl ether, could be smoothly transformed into a 3-hydroxychromen-4-one, a potential flavonol skeleton, by three successive treatment with NBS, OsO4, and Na2SO3.

PDF (110KB)
Note | Regular issue | Vol 45, No. 11, 1997, pp. 2277 - 2282
Published online:
DOI: 10.3987/COM-97-7952
Design and Synthesis of Photoactivatable Coumarin-containing HIV-1 Integrase Inhibitors

He Zhao, Nouri Neamati, Yves Pommier, and Terrence R. Burke, Jr.*

*Laboratories of Medicinal Chemistry, Division of Basic Sciences, National Cancer Institute, Building 37, Room 5C06, National Institute of Health, Bethesda, MD 20892, U.S.A.


Three dimeric coumarin analogues (1 - 3) were prepared, each containing the photoactivatable benzophenone moiety. These compounds exhibited low micromolar IC50 values against HIV-1 integrase mediated 3’-processing and strand transfer, and may represent useful probes for elucidating enzyme-inhibitor interactions.

PDF (144KB)
23 data found. 1 - 23 listed