Regular Issue

Vol. 41, No. 2, 1995

23 data found. 1 - 23 listed
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 209 - 214
Published online:
DOI: 10.3987/COM-94-6923
Cycloaddition Reactions of 7-Substituted Acenaphtho[1,2-d]pyrazolo[1,2-a]benzotriazoles with Dimethyl Acetylenedicarboxylate

Otohiko Tsuge*, Taizo Hatta, Masafumi Sugaya, Eiji Yunoki, Hidenori Gau, and Akikazu Kakehi

*Department of Industrial Chemistry, Kumamoto Institute of Technology, 4-22-1, Ikeda, Kumamoto 860, Japan


The reactions of the title 7-phenyl- and 7-methylacenaphthopyrazolobenzotriazoles (triazapentalenes) with dimethyl acetylenedicarboxylate gave a mixture of the corresponding initial azomethine imidic cycloadduct and its isomeric pyrazinopyrimidine, whose yields greatly depended on the reaction conditions. Structures of both the initial and isomeric products were determined by X-ray crystallographic analyses. The initial cycloadduct readily isomerized to the pyrazinopyrimidine. It has been found that the methyl-substituted pyrazinopyrimidine underwent the Michael-type addition reaction.

PDF (163KB)
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 215 - 218
Published online:
DOI: 10.3987/COM-94-6926
Regiospecific Synthesis of N-Alkyl-4- and 5-Substituted Imidazoles

Gideon Shapiro* and Berta Gomez-Lor

*Preclinical Research, Sandoz Pharma Ltd., CH-4002 Basel, Switzerland


A facile regiospecific synthesis of 4- and 5-substituted N-alkyl imidazoles has been developed from N-trimethylsilyloxyethylimidazole(s). The method combines directed metallation with alkyl triflate mediated imidazole quaternization and SEM group cleavage.

PDF (145KB)
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 219 - 223
Published online:
DOI: 10.3987/COM-94-6937
Unexpected Iodine Catalyzed Cyclization for Synthesis of 2,2-Dialkyl-2,3-dihydrobenzofurans

Kyoung Mahn Kim and Eung K. Ryu*

*Korea Research Institute of Chemical Technology, P. O. Box 107, Yusong, Taejon 305-606, Korea


2-(β-Methylallyl)phenol and 2-isobutenylphenol derivatives were easily cyclized to 2,2-dimethyl-2,3-dihydrobenzofurans in the presence of a catalytic amount of iodine without any formation of iodinated products.

PDF (131KB)
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 225 - 228
Published online:
DOI: 10.3987/COM-94-6939
Diene-transmissive Diels-Alder Reaction of 2-Vinyl-1-oxabutadiene System

Otohiko Tsuge*, Taizo Hatta, Hideki Yoshitomi, Katsumi Kurosaka, Toshitsugu Fujiwara, Hironori Maeda, and Akikazu Kakehi

*Department of Industrial Chemistry, Kumamoto Institute of Technology, 4-22-1, Ikeda, Kumamoto 860, Japan


The first example for the diene-transmissive Diels-Alder reaction of 2-vinyl-1-oxabutadiene system is presented by the reactions of 1,5-diphenyl- and 1,5-di(2-thienyl)-1,4-pentadien-3-ones with electron-rich enamines as the first dienophiles and then with electron-deficient dienophiles as the second.

PDF (126KB)
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 229 - 236
Published online:
DOI: 10.3987/COM-94-6943
Isolation and Structural Elucidation of Bioactive C-12,15-cis Non-adjacent Bis-THF Annonaceous Acetogenins

Zhe-Ming Gu, Lu Zeng, and Jerry L. McLaughlin*

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


In further investigation on the EtOH extract of the bark of Annona bullata, two novel Annonaceous acetogenins, C-12,15-cis-bullatanocin (1) and C-12,15-cis-bullatalicin (2), were successfully separated by hplc from fractions in which they were mixed with bullatanocin (7) and bullatalicin (8), their respective C-12/15-trans diastereomers. Their relative stereochemistries between the two THF rings were determined through preparations of their respective 16,19-formaldehyde acetal derivatives (1a and 2a). The absolute configurations of 1 and 2 were resolved by analyses of the 1H nmr data of the (S)- and (R)-Mosher ester derivatives (1b,1c and 2b,2c) of 1a and 2a. Compounds (1) and (2) are the first examples of C-12/15-cis non-adjacent bis-THF Annonaceous acetogenins and showed potent bioactivities, comparable to those of 7 and 8, with notable cytotoxic selectivities among six human solid tumor cell lines.

PDF (231KB)
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 237 - 244
Published online:
DOI: 10.3987/COM-94-6952
Synthesis of New Armed Cyclopolyamines and Their Selective Extraction Properties for Metal Ions

Kiyoshi Matsumoto*, Keisuke Fukuyama, Hirokazu Iida, Mitsuo Toda, and J. William Lown

*Graduate School of Human and Environmental Studies, Kyoto University, Kyoto, 606-01, Japan


A variety of new armed cyclopolyamines were prepared by high pressure SNAr reactions (0.8 GPa, 100°C) of cyclopolyamines with heteroaromatic halides. Certain of these agents show selective extraction properties for Hg2+ and Ag+ ions.

PDF (203KB)
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 245 - 248
Published online:
DOI: 10.3987/COM-94-6965
A Synthesis of Optically Active Platyphyllide. Determination of Its Absolute Configuration

Shigeru Nagashima, Hitomi Ontsuka, Motoo Shiro, and Ken Kanematsu*

*Institute of Synthetic Organic Chemistry, Faculty of Pharmaceutical Sciences, Kyushu University 62, Higashi-ku, Fukuoka 812, Japan


The first enantioselective total synthesis of platyphyllide (1), based on the allenyl ether intramolecular cycloaddition strategy, is described, revealing the absolute configuration of this compound.

PDF (89KB)
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 249 - 253
Published online:
DOI: 10.3987/COM-94-6969
Synthesis and 1H Nmr Complexation Study of a Novel Macrocyclic Polyether Containing 1,1'-Biazulene Unit

Der-Seang Lee, Paw-Wang Yang, Tadayoshi Morita*, and Tetsuo Nozoe

*Department of Chemistry, Tohoku University, Aoba-ku, Sendai 980-77, Japan


A new class of chiral macrocyclic polyethers containing 1,1’-biazulene unit was prepared from the reaction of 2,2’-dihydroxy-3,3’-bis(methoxycarbonyl)-1,1’-biazulene with tetra- or pentaethyleneglycol ditosylate by a high dilution technique. Complexation study with alkali metals by 1H nmr indicated ion selectivity for these macrocycles. The crystal structure was studied by X-ray diffraction.

PDF (166KB)
Communication | Regular issue | Vol 41, No. 2, 1995, pp. 255 - 258
Published online:
DOI: 10.3987/COM-94-6978
A Synthesis of 6-Methylindole Derivatives by Methylthiomethylation at 6-Position in Indole Nucleus

Satoshi Hirano, Ritsuko Akai, Yoshihiko Shinoda, and Shin-ichi Nakatsuka*

*Faculty of Agriculture, Gifu University, Yanagido, Gifu 501-11, Japan


6-Methylindole derivatives were synthesized by introduction of methylthiomethyl group onto the 6-position of indole nucleus and subsequent desulfurization.

PDF (119KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 259 - 265
Published online:
DOI: 10.3987/COM-94-6831
Synthesis of 6-Fluoroquinolones Substituted at C-7 by 1'-Demethyllincomycin and by Dihydroconessimine

Sandrine Deloisy, Alain Olesker*, and Gabor Lukacs

*Institut de Chimie des Substances Naturelles, C.N.R.S., 91198 Gif sur Yvette, France


The boron-chelated carboxylic acid of 6,7-difluoroquinolone (8) was substituted at C-7 by the 2,3,4,7-tetra-O-acetate of 1’-demethyllincomycin (4) and by dihydroconessimine (14). The resulting dechelated products did not reveal any antibacterial activity. A new efficient procedure for the preparation of the 2,3,4,7-tetra-O-acetate of 1’-demethyllincomycin (4) is proposed.

PDF (232KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 267 - 276
Published online:
DOI: 10.3987/COM-94-6862
Hypotensive Constituents from the Bark of Holarrhena pubescens (Holarrhena antidysenterica)

Bina Shaheen Siddiqui*, Shahid Bader Usmani, Sabira Begum, Salimuzzaman Siddiqui, Khalid Aftab, and Anwar-ul-Hassan Gilani

*H. E. J. Research Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan


Two new alkaloids of conanine series, holamide (N-(N’-methylacetamido)-3-oxo-1,4-conadiene) (1), pubescinine (11α-acetoxy-N-demethyl-3-oxo-1,4,17(20)-conatriene) (2) and a known alkaloid norconessine (3-N-methylamino-5-conanene) (3), have been isolated from the bark of Holarrhena pubescens Buch. Ham (Holarrhena antidysenterica Linn.) (Apocynacea). Their structures have been established through spectroscopic studies. Both 1 and 2 showed hypotensive activity in rats at a does of 3 mg/kg.

PDF (235KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 277 - 287
Published online:
DOI: 10.3987/COM-94-6904
A Synthesis of the Polyhydroxylated Pyrrolidines : Synthesis of 1,4-Dideoxy-1,4-imino-D-lyxitol and N-Benzyl-4-epi-(-)-Anisomycin

Shi Zhi-cai, Zeng Chun-min, and Lin Guo-qiang*

*Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China


A synthesis of 1,4-dideoxy-1,4-imino-D-lyxitol and N-benzyl-4-epi-(-)-anisomycin was described.

PDF (374KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 289 - 292
Published online:
DOI: 10.3987/COM-94-6912
Reaction of Pentachloropyridine with α-Lithiated Arylacetonitriles and Methyllithium in Ether

Edward R. Biehl*, Hala Mohammed Refat, and Amamed A. Fadda

*Department of Chemistry, Southern Methodist University, Dallas, TX 75275, U.S.A.


Ether slurries of α-lithioarylacetonitriles (3) when added to ether solutions of 2,3,5,6-tetrachloro-4-pyridyllithium (2) at -70°C give clear, red solutions upon warming to -20°C. Further warming to room temperature, produces bright scarlet precipitates which upon proton quench provide α-aryl-2,3,5,6-tetrachloro-4-pyridylacetonitriles (4) in excellent yields (98-80%). A mechanism is proposed in which the key step involves a lithium-chlorine exchange between 2 and α-lithio-α-chloroarylacetonitriles (7). Experimental evidence for the intermediacy of 7 in these reactions is presented.

PDF (98KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 293 - 301
Published online:
DOI: 10.3987/COM-94-6921
Synthesis and Structure Assignment of 1-[(2-Hydroxyethoxy)methyl]- and 1-[(1,3-Dihydroxy-2-propoxy)methyl]-6-azaisocytosine

Long-Chih Hwang, Chyi-Jia Wang, Gene-Hsiang Lee, Yu Wang, and Cherng-Chyi Tzeng*

*School of Chemistry, Kaohsiung Medical College, Kaohsiung City 807, Taiwan, R.O.C.


1-[(2-Acetoxyethoxy)methyl]-6-azaisocytosine and 1-[(1,3-dibenzyloxy-2-propoxy)methyl]-6-azaisocytosine have been prepared, and their unambiguous assignment of 1H and 13C peaks through the 1H-13C heteronuclear correlation (HETCOR) nmr experiments is described. The X-ray crystallographic analysis reveals unambiguously the site of glycosylation at N1. Deprotection of both acyclonucleosides provided 1-[(2-hydroxyethoxy)methyl]-6-azaisocytosine and 1-[(1,3-dihydroxy-2-propoxy)methyl]-6-azaisocytosine, respectively.

PDF (217KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 303 - 308
Published online:
DOI: 10.3987/COM-94-6929
Synthesis of Triazolidine-1,3,5,7-tetraone and Pyrimidin[1,5]diazepine Derivatives by Carbon Suboxide

Leonardo Bonsignore* , Filippo Cottiglia, Giuseppe Loy, and Daniela Secci

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


A one step synthesis of 6H-pyrazolidin[1,2-a][1,2,4]triazolidine-1,3,5,7-tetraones and pyrimidino[1,5]diaza- and thiazepines by carbon suboxide is here described.

PDF (122KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 309 - 314
Published online:
DOI: 10.3987/COM-94-6936
Regiocontrolled Syntheses of Benzo[b]quinolizinium and Heteroisoquinolinium Cations

William G. Earley*, John A. Dority Jr., Virendra Kumar, and John P. Mallamo

*Sterling Winthrop Pharmaceuticals Research Division, Department of Medicinal Chemistry, 1250 S. Collegeville Rd., Collegeville, PA 19426-0900, U.S.A.


A regiocontrolled synthesis of 10-alkoxy and alkyl substituted benzo[b]quinolizinium salts is described. Synthesis of a novel 9-alkoxythiazolo[3,2-b]isoquinolinium cation is reported. In addition the synthesis of several new N-alkylimidazo[1,2-b]isoquinolin-4-ium cations is described. Condensation of dianions (1) with heteroaromatic aldehydes and ketones provides diols in 35-85% yield. Cyclization of diols (2) with POCl3 gives previously unreported 10-substituted benzo[b]quinolizinium cations and heteroisoquinolinium cations (3) in 35-90% yield.

PDF (159KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 315 - 322
Published online:
DOI: 10.3987/COM-94-6940
Effect of Fluorine-Substitution on Basicity of Benzo[h]quinoline, Benzo[f]quinoline and Quinoline

Wei Wu, Ken-ichi Saeki, and Yutaka Kawazoe*

*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabedori, Mizuho-ku, Nagoya 467, Japan


The effect of fluorine-substitution on the acid-dissociation constant was examined using 19 types of mono- and difluorinated derivatives of benzo[h]quinoline, benzo[f]quinoline and quinoline. Decrease in pKa were induced by fluorine substitution and were dependent on the number of bonds between the substituent F atom and the basic N atom, whereas pKa-increases were induced by a substituent F atom spatially interacting with the basic N atom. The spatial interaction between F and N was analyzed by means of a semiempirical molecular orbital method MOPAC PM3.

PDF (227KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 323 - 328
Published online:
DOI: 10.3987/COM-94-6948
An Improved Procedure for the Preparation of Aromatic Heterocyclic N-Oxides

Soo Young Rhie and Eung K. Ryu*

*Korea Research Institute of Chemical Technology, P. O. Box 107, Yusong, Taejon 305-606, Korea


An improved procedure for the preparation of aromatic heterocyclic N-oxides is described. Nitrogen containing heterocyclic compounds gave their N-oxides in excellent yields by the reaction of m-CPBA in DMF/MeOH in the presence of HF in a short time under mild reaction conditions. The presence of HF and MeOH is crucial for the reaction.

PDF (153KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 329 - 336
Published online:
DOI: 10.3987/COM-94-6950
Thermal Reaction of 1,2,4-Triazolium N-Allylides: Formation of Mesomeric Betaines, 1,2,4-Triazolo[4,3-a]pyridiniumides, via Back-donated 1,6-Cyclization

Yoshiro Matsuda*, Yasushige Chiyomaru, Chieko Motokawa, and Takanobu Nishiyori

*School of Pharmaceutical Sciences, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852, Japan


The reaction of 1,2,4-triazolium salt (7) with polarized olefins (2, 3a,b) in the presence of K2CO3 in CHCl3-EtOH gave the corresponding triazolium N-allylides (8a-c). Thermolyses of the N-allylides (8a,c) afforded the mesomeric betaine (9a) and the 8-amino-1,4-triazolo[4,3-a]pyridine derivative (10). Similar treatment of the salt (7) with polarized olefins (3c,d, 4a) directly yielded mesomeric betaines (9c-e), while the reaction of the salt (7) with polarized olefin (4b) gave the pyrrolo[1,2-d]-1,2,4-triazine derivative (11). The formation of mesomeric betaines is suggested to proceed via back-donated 1,6-cyclization.

PDF (225KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 337 - 344
Published online:
DOI: 10.3987/COM-94-6958
Synthesis of a Novel N-Methoxymethylpyrrole-containing DNA Minor Groove Binding Oligopeptide Related to Distamycin

Rulin Zhao and J. William Lown*

*Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2


A novel N-methoxymethylpyrrole-containing DNA minor groove binding oligo-peptide designed for increased solubility and enhanced cellular uptake and related to distamycin has been synthesized.

PDF (227KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 345 - 352
Published online:
DOI: 10.3987/COM-94-6959
Synthesis of 4-Hydroxy-1-methylbenzimidazole and 7-Hydroxy-1-methylbenzimidazole

Alan R. Katritzky*, Richard P. Musgrave, Bogumila Rachwal, and Chris Zaklika

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


4-Hydroxy-1-methylbenzimidazole (1) was synthesised via condensation of 2-amino-3-nitrophenol (3) with trimethyl orthoformate, reduction of the resulting 4-nitrobenzoxazole (4) to amine (5), reaction with hydroxymethylbenzotriazole to form benzotriazolyl adduct (6), reduction to give 4-methylaminobenzoxazole (7), and finally base catalyzed rearrangement. The synthesis of 7-hydroxy-1-methylbenzimidazole (2) was accomplished by reduction of 4 with sodium borohydride to form 3-nitro-2-methylaminophenol (8), followed by hydrogenation to give amino derivative (9) and condensation with trimethyl orthoformate.

PDF (192KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 353 - 362
Published online:
DOI: 10.3987/COM-94-6960
Transformation of Na-Boc-tetrahydroalstonine to Na-Boc-5β-cyanotetrahydroalstonine, Na-Boc-21α-cyanotetrahydroalstonine, and Na-Boc-3,14-didehydrotetrahydroalstonine

Minna Halonen, Reija Jokela, and Mauri Lounasmaa*

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


Tetrahydroalstonine (1) was transformed to its Na-Boc-derivative (4), which was then oxidized to the corresponding cis-Nb-oxide (5a). The modified Polonovski reaction of the cis-Nb-oxide (5a), followed by KCN treatment, led to Na-Boc-5β-cyanotetrahydroalstonine (7), Na-Boc-21α-cyanotetrahydroalstonine (8a), and Na-Boc-3,14-didehydrotetrahydroalstonine (9), of which the first (7) is a good model for the naturally occurring 5β-carboxytetrahydroalstonine (2b) and the second (8a) the chemical equivalent of Na-Boc-20,21-didehydro-tetrahydroalstonine (Na-Boc-cathenamine) (8b).

PDF (252KB)
Paper | Regular issue | Vol 41, No. 2, 1995, pp. 363 - 371
Published online:
DOI: 10.3987/COM-94-6961
A Facile Synthesis of 6-Amino-1-benzyl-4-methyl- and 6-Amino-1,4-dimethylhexahydro-1H-1,4-diazepines, the Amine Part of Substituted Benzamides with a Potent Serotonin 3 Receptor Antagonistic Activity

Hiroshi Harada, Yoshimi Hirokawa, Toshiya Morie, and Shiro Kato*

*Exploratory Research Laboratories, Dainippon Pharmaceutical Co., Ltd., Enoki 33-94, Suita, Osaka 564, Japan


A facile synthesis of 6-amino-1-benzyl-4-methyl- and 6-amino-1,4-dimethylhexahydro-1H-1,4-diazepines (16a and 16b) which have been served as the amine part of the new and novel benzamides (3 and 4) with a potent serotonin 3 receptor antagonistic activity is reported. The formation of 1,4-diazepine ring system was achieved by the reaction of tris(hydroxymethyl)nitromethane (11) with N,N’-disubstituted ethylenediamines (12a and 12b). The dehydroxymethylation of the resultant 6-hydroxymethyl-6-nitro-1,4-diazepines (13a and 13b) and successive reduction gave the target compounds (16a and 16b), in approximately 15-30% overall yield.

PDF (224KB)
23 data found. 1 - 23 listed