Regular Issue

Vol. 55, No. 11, 2001

16 data found. 1 - 16 listed
Communication | Regular issue | Vol 55, No. 11, 2001, pp. 2043 - 2050
Published online:
DOI: 10.3987/COM-01-9318
Javaberine A, New TNF-α and Nitric Oxide Production Inhibitor, from the Roots of Talinum paniculatum

Hiroshi Shimoda, Norihisa Nishida, Kiyofumi Ninomiya, Hisashi Matsuda, and Masayuki Yoshikawa*

*Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8412, Japan


The methanolic (MeOH) extract from the roots of Talinum paniculatum was found to exhibit inhibitory activities on the lipopolysaccharide (LPS)-induced tumor necrosis factor (TNF)-α and nitric oxide (NO) production from mouse peritoneal macrophages, and on the TNF-α production from rat epididymal adipose tissue. From the MeOH extract, two new 8-benzyltetrahydro-protoberberine–type alkaloids, named javaberines A and B, were isolated and their structures were elucidated on the basis of chemical and physicochemical evidence. The principal alkaloid, javaberine A, inhibited LPS-induced TNF-α and NO production from mouse peritoneal macrophages and TNF-α production from rat epididymal adipose tissue.

PDF (472KB)
Communication | Regular issue | Vol 55, No. 11, 2001, pp. 2051 - 2054
Published online:
DOI: 10.3987/COM-01-9333
Synthesis of 3,4-Dihydro-2H-benzopyrans from Phenols and α,β-Unsaturated Carbonyl Compounds

Hiroyuki Saimoto, Yoshie Ogo, Mie Komoto, Minoru Morimoto, and Yoshihiro Shigemasa*

*Tottori University, Faculty of Engineering, Department of Materials Science, 4-101 Koyama-minami, Tottori 680-8552, Japan


The reaction between 2’,4’-dihydroxyacetophenone and methyl vinyl ketone catalyzed by CaCl2/KOH in aqueous methanol yielded a 1,4-adduct, which was cyclized to 3,4-dihydro-2H-benzopyran (4) by acidic treatment. Analogous reaction using α,β-unsaturated aldehydes afforded benzopyrans (4) or (5) in a one-pot reaction. This method was successfully applied to the synthesis of β-tubaic acid (6), an antimicrobial 2H-1-benzopyran-6-carboxylic acid.

PDF (63KB)
Communication | Regular issue | Vol 55, No. 11, 2001, pp. 2055 - 2057
Published online:
DOI: 10.3987/COM-01-9334
Simple Synthesis of 1,3,4,5a,6,10b,11,11a-Octahydro-2H-pyrazino[1’,2’:1,5]pyrrolo[2,3-b]indole Derivatives Based on 1-Hydroxyindole Chemistry

Yoshikazu Fukui and Masanori Somei*

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


3-Substituted (3S,6S)-6-(1-hydroxyindol-3-ylmethyl)-2,5-piperazine- diones are prepared for the first time. They are shown to be suitable intermediates for the synthesis of 3,10b-disubstituted (3S,5aR,10bS,11aS)-1,3,4,5a,6,10b,11, 11a-octahydro-2H-pyrazino[1’,2’:1,5]pyrrolo[2,3-b]indole-1,4-dione derivatives.

PDF (71KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2059 - 2074
Published online:
DOI: 10.3987/COM-01-9301
Stereoselective Syntheses of (E)- and (Z)-2,3-Dihydro-3-(1,2,4-triazolyl)-4H-1-benzopyran-4-one Oxime Ethers

Saeed Emami and Abbas Shafiee*

*Department of Chemistry, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran


A synthesis of (E)- and (Z)-2,3-dihydro-3-(1H-1,2,4-triazol-1-yl)-4H-1-benzopyran-4-one oxime ethers [(E)- and (Z)-13] and (Z)-2,3-dihydro-3-(4H-1,2,4-triazol-4-yl)-4H-1-benzopyran-4-one oxime ethers [(Z)-17] are described. Ring closure of 2-(1,2,4-triazolyl)-2¢-hydroxyacetophenones (5 or 6) followed by reaction with HONH2.HCl gave the corresponding (Z)-oximes [(Z)-11 or (Z)-16]. O-Alkylation of (Z)-oximes afforded (Z)-oxime ethers [(Z)-13 or (Z)-17]. Reaction of (Z)-3-bromo-2,3-dihydro-4H-1-benzopyran-4-one oxime (18) with 1,2,4-triazole afforded (E)-oxime [(E)-11]. O-Alkylation of (E)-oxime gave the desired (E)-oxime ethers [(E)-13]. In addition, (Z)-oxime ethers [(Z)-13 or (Z)-17)] could also be obtained from the reaction of 2,3-dihydro-3-(1,2,4-triazolyl)-4H-1-benzopyran-4-ones (2 or 14) with O-(arylmethyl)hydroxylamine hydrochloride (19).

PDF (93KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2075 - 2084
Published online:
DOI: 10.3987/COM-01-9303
3,5-Dichloro-4-pyridinecarbonitrile: A Multisite Substrate for Carbon Nucleophiles

Nevio Picci, Marco Pocci,* Annarosa Gugliuzza, Francesco Puoci, Angela De Munno, Francesca Iemma, and Vincenzo Bertini

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


The reactivity of 3,5-dichloro-4-pyridinecarbonitrile (1) towards lithium or magnesium organo-metallic reagent is described. Conditions for substitution of cyano with alkyl or phenyl group, alkylation at the position 2 with removal of the 5-positioned chlorine, and formation of methyl or phenyl dichloro-pyridyl imines are reported. The obtained 4-alkyl-3,5-dichloropyridines can undergo a further alkylation at the position 2. The 3,5-dichloro-4-pyridyl residue is shown to be a good leaving group in form of anion yielding 3,5-dichloropyridine either from 1 or 3,5-dichloro-4-pyridinecarboxaldehyde.

PDF (60KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2085 - 2098
Published online:
DOI: 10.3987/COM-01-9305
Synthesis of Bis-substituted Amidinobenzothiazoles as Potential Anti-HIV Agents

Livio Racane, Vesna Tralic-Kulenovic, Lelja Fiser-Jakic, David W. Boykin, and Grace Karminski-Zamola*

*Department of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, Marulicev trg 20, P.O Box 177, HR-10000 Zagreb. Croatia


In the multistep syntheses of the title compounds we obtained some new cyano-substituted heterocycles (1a, 1b, 2a, and 2b) as intermediates. Starting from dinitriles (2a and 2b) as well as from two formerly prepared dinitriles, substituted bisamidines (3a, 3b, 5a, 5b, 7a, and 7b) and amidino dihydrochlorides (4a, 4b, 6a, 6b, 8a, 8b, 9a, and 9b) have been synthesized.

PDF (171KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2099 - 2108
Published online:
DOI: 10.3987/COM-01-9308
A Facile Entry to Bicyclic Systems from L-Glutamic Acid

Bryan A. Frieman, Charles W. Bock, and Krishna L. Bhat*

*Department of Chemistry, School of Science and Health, Philadelphia University, School House Lane & Henry Avenue,Philadelphia, PA 19144-5497, U.S.A.


An efficient synthesis of bicyclic heterocycles has been realized from L-glutamic acid. The key step is the construction of the pyrrole ring in a single step, using tosylmethyl isocyanide (TosMIC) methodology. Structures of reaction intermediates and final products were investigated using density functional theory calculations.

PDF (394KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2109 - 2121
Published online:
DOI: 10.3987/COM-01-9313
A Multinuclear NMR Spectral Study of Parent Azoles and Benzazoles: Experimental Results and GIAO Ab initio Calculations

Rosa M. Claramunt,* Concepción López, Dionisia Sanz, Ibon Alkorta, and José Elguero

*Departamento de Química Orgánica y Biologiá, Faclutade de Ciencias, UNED, Senda del Rey 9, E-28040 Madrid, Spain


The 13C and 15N chemical shifts of twelve azoles and benzazoles have been determined in the solid state at room temperature and in methanol solution at 178 K. The experimental values were compared with the absolute shieldings calculated at the GIAO/B3LYP/6-31G* level. These comparisons show that some signals, 13C NMR but especially 15N NMR, have to be corrected for hydrogen bonds present in certain solvents and in the solid state. The linear regressions are good enough to be used to predict some missing values.

PDF (104KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2123 - 2130
Published online:
DOI: 10.3987/COM-01-9317
Four New Glucosides of Stilbene Oligomers from the Stem of Gnetum gnemonoides

Ibrahim Iliya, Toshiyuki Tanaka,* Miyuki Furasawa, Zulfiqar Ali, Ken-ichi Nakaya, Munekazu Iinuma, Yoshiaki Shirataki, Jin Murata, and Dedy Darnaedi

*Gifu Prefectrual Institute of Health and Environmental Sciences, 1-1 Nakafudogaoka, Kakamigahara, Gifu 504-0838, Japan


Four new stilbene oligomeric glucosides, gnemonoside A, B, C and D, were isolated from the stem of Gnetum gnemonoides (BRONGN) along with four known stilbenoides, trans-resveratrol, gnetins C, D and E. The structures were elucidated on the basis of spectral evidence.

PDF (107KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2131 - 2137
Published online:
DOI: 10.3987/COM-01-9322
Convenient Preparation of Heteroazulenes by the Reaction of 2-Aminotropone with Heterocumulenes in the Presence of a Base

Yuhki Mitsumoto and Makoto Nitta*

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


Reactions of 2-aminotropone with heterocumulenes, N,N’-diphenylcarbodiimide, phenyl isothiocyanate, phenyl isocyanate, and carbon disulfide, in the presence of t-BuOK afforded 1-phenylcycloheptaimidazole-2(1H)-phenylimine, 1-phenylcyclohepataimidazole-2(1H)-thione, 1-phenylcycloheptaimidazol-2(1H)-one along with 2H-cycloheptaoxazol-2-one, and 2H-cycloheptathiazol-2-one along with 2H-cycloheptaoxazole-2-thione in good to moderate yields, respectively.

PDF (49KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2139 - 2145
Published online:
DOI: 10.3987/COM-01-9328
Synthesis of a Thiino[2,3,4-d,e]phthalazine

Abdel Karim Karim, Montserrat Armengol, and John A. Joule*

*Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.


The reaction of 5-(1,2-dibromo-2-phenylethenyl)phthalazine (16) with Na2CS3 gives 5-phenylthiino[2,3,4-d,e]phthalazine (17).

PDF (93KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2147 - 2155
Published online:
DOI: 10.3987/COM-01-9329
Synthesis of Vinca Alkaloids and Related Compounds. Part 97. Epimerization with the Aid of Iodine

István Moldvai, Csaba Szántay Jr., and Csaba Szántay*

*Chemical Research Center, Institute of Chemistry, Hungarian Academy of Sciences, H-1525 Budapest, P.O.Box 17, Hungary


(-)-15b-Hydroxy-14,15-dihydroeburnamenine (6) has been epimerized at the C(3) position with the aid of iodine. Octahydroindoloquinolizine derivatives containing hydroxyl group (11, 14, 17) gave the appropriate epimeric alcohols (13,16, 19) via pentacyclic intermediates (12, 15, 18).

PDF (59KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2157 - 2170
Published online:
DOI: 10.3987/COM-01-9330
Copper(I) Iodide-promoted Hydroxylation onto the Lithium or Potassium Enolate of Lactones and Lactams

Norio Nakazawa, Keiko Tagami, Hitoshi Iimori, Shigeki Sano, Tsutomu Ishikawa, and Yoshimitsu Nagao*

*Sho-machi, Tokushima 770-8505, Japan


After enolization of lactones (1a,b) and lactams (2a,b) with lithium or potassium hexamethyldisilazide in THF, each resultant enolate was treated with a solution prepared by mixing copper(I) iodide, pyridine, and tert-butyl hydroperoxide or N-methylmorpholine N-oxide in THF to give α-hydroxy lactones (3a,b) and α-hydroxy lactams (4a,b) in satisfied yields. This hydroxylation method was successfully applied to conversion of dl-desoxycamptothecin (dl-7) to dl-camptothecin (dl-5).

PDF (88KB)
Paper | Regular issue | Vol 55, No. 11, 2001, pp. 2171 - 2187
Published online:
DOI: 10.3987/COM-01-9338
3-Hydroxy-4(1H)-pyridinone-containing Linear and Cyclic Hexapeptides and Their Iron(III) Complexes —Synthesis, Property, and the Growth-Promotion Activity

Akira Katoh,* Yasushi Hikita, Manabu Harata, Junko Ohkanda, Taro Tsubomura, Akon Higuchi, Ryota Saito, and Kazuo Harada

*Faculty of Engineering, Seikei University, Musashino, Tokyo 180-8633, Japan


Linear and cyclic hexapeptides composed of ε-(3-hydroxy-1,4-dihydro-2-methyl-4-oxo-1-pyridyl)-L-norleucine and glycine or β-alanine residue have been successfully synthesized. These hexapeptides formed 1:1 iron(III) complexes at neutral pH region. Glycine linear (8a)- and β-alanine cyclic hexa-peptide (10)-iron(III) complexes predominantly existed in Δ-configuration, while β-alanine linear hexapeptide (8b)-iron(III) complex existed in Λ-one. The relative stability constants of 8a, 8b, and 10-iron(III) complexes were estimated to be 31.6, 33.4, and 31.7, respectively. From iron(III) removal from human transferrin, linear hexapeptides (8a,b) were found to efficiently remove iron(III) compared with desferrioxamine B. The growth-promotion activity was also discussed.

PDF (490KB)
Note | Regular issue | Vol 55, No. 11, 2001, pp. 2189 - 2198
Published online:
DOI: 10.3987/COM-01-9285
Reaction of N-Substituted 3,4-Dichloromaleimides with α-Mercaptoazaheterocycles

Galina G. Dubinina, Yulian M. Volovenko, Svetlana V. Shishkina, Oleg V. Shishkin, and Sergiy M. Yarmoluk*

*Institute of Molecular Biology and Genetics, National Academy of Sciences of Ukraine, 150 Zabolotnogo St., 03143 Kyiv, Ukraine


Reaction of N-substituted 3,4-dichloromaleimides (1) with α-mer-captoazaheterocycles, 2-mercapto-1H-benzo[d]imidazole (2) and 3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-5-ones (4) in the presence of triethylamine, led to the formation of condensed thiazole ring resulting in 2,3-dihydro-1H-benzo[4,5]imidazo[2,1-b]pyrrolo[3,4-d][1,3]thiazole-1,3-diones (5) and 7,8-dihy-dro-2H,6H-pyrrolo[3’,4’:4,5][1,3]thiazolo[3,2-b][1,2,4]triazine-2,6,-8-triones (8), respectively. Refluxing of 8 in aqueous dioxane-triethylamine produced derivatives of 7-oxo-7H-[1,3]thiazolo[3,2-b][1,2,4]triazine-2-carboxamides (9) by destruction of maleimide ring with decarboxylation. The structure of 9i was confirmed by X-Ray analysis. 1 reacted with 2-thioxo-1,2,3,4-tetrahydro-4-quinazolinone (3) with cyclization at N-1 and N-3 positions.

PDF (250KB)
Note | Regular issue | Vol 55, No. 11, 2001, pp. 2199 - 2206
Published online:
DOI: 10.3987/COM-01-9319
Synthesis of 3-Azabicyclo[3.3.1]nonane-6,9-diones

Brian D. Williams,* Birute Williams, Francis Bernardoni, Robert C. Finn, and Jon Zubieta

*Department of Chemistry, King's College, Wilkes-Barre, Pennsylvania 18711, U.S.A.


A one pot synthesis of 3-azabicyclo[3.3.1]nonane-6,9-diones is described via the addition of acryloyl chloride to enamines of N-carboxy-4-piperidones. Yields of bicycle were highest when additions were made to vigorously boiling solutions of morpholine enamines. X-Ray analysis of an azabicyclic system revealed a chair-chair structure to be the preferred conformation. Hydrolysis of 3-azabicyclo[3.3.1]nonane-6,9-diones (IIa) and (IIb) yielded the monocyclic carboxylic acids (IIIa) and (IIIb).

PDF (47KB)
16 data found. 1 - 16 listed