HETEROCYCLES

■ Contents

■ Inclusion Complexes Containing Quaternary Azaaromatic Moieties

Wanda Sliwa* and Jerzy Peszke

*Institute of Chemistry and Environmental Protection, Jan Dlugosz University of Czestochowa, al. Armii Krajowej 13/15, 42-201 Czestochowa, Poland

Abstract

In the paper inclusion complexes of cyclodextrins, cucurbiturils and calixarenes containing quaternary azaaromatic moieties are described, followed by complexes of crown ethers, tweezers and clips.

■ Design and Synthesis of Novel Ring-Expanded Arbekacin Analogues

Nobuto Minowa,* Yukiko Hiraiwa, Yoshihisa Akiyama, Kazunori Maebashi, Takayuki Usui, and Daishiro Ikeda

*Pharmaceutical Research Center, Meiji Seika Kaisha Ltd., 760 Morooka-cho, Kohoku-ku, Yokohama 222-8567, Japan

Abstract

Novel homologated aminoglycosides having a seven-membered ring were designed and synthesized by treatment of 5-keto arbekacin with diazomethane in CH₂Cl₂-Et₂O. The ring-expanded arbekacin analogue showed good antibacterial activity against Staphylococcus aureus and Escherichia coli including aminoglycoside-resistant bacterial strain.

■ Molecular Design and Synthesis of 4,8-Di(hetero)arylquinazolines with Potential Applications in Quadratic Nonlinear Optics. Diazines Part 48

Alexandrine Busch, Alain Turck, Kamila Nowicka, Alberto Barsella, Chantal Andraud, and Nelly Plé*

*Department of Heterocyclic Chemistry (LCOFH), UMR 6014 CNRS, IRCOF-INSA, 8 rue Tenière, 76131 Mont-Saint-Aignan Cedex, France

Abstract

In the aim to define a structure NLO properties relationship, theoretical calculations have been used to investigate the role of different parts (substituents and π-system) of disubstituted conjugated systems based on naphthalene, cinnoline and quinazoline moieties. Using metallation and cross-coupling reactions we report here the synthesis of new 4,8-di(hetero)arylquinazolines and their quadratic NLO properties.

■ The Thorpe-Ingold Effect in Cyclic Imides. Part III

Michal Pawlowski, Krystyna Wojtasiewicz, Jan K. Maurin, Andrzej Leniewski, Dariusz Blachut, and Zbigniew Czarnocki*

*Faculty of Chemistry, Warsaw University, Pasteura St.1, 02-093 Warsaw, Poland

Abstract

Reactivity of phenyllithium with a number of succinimide derivatives were studied. We have shown that the Thorpe-Ingold effect affected both the reaction products distribution and their structures. Regioselectivity of these reactions were rationalized. Structures were confirmed with NMR and crystallographic methods.

■ Synthesis of 2-Aryl-2H-indazoles via Copper(I)-Catalyzed Intramolecular Amination Reaction

Rui Liu, Yong-ming Zhu,* Lie-na Qin, Shun-jun Ji, and Hajime Katayama

*College of Pharmacy, Soochow University, Suzhou 215123, China

Abstract

A versatile method for the preparation of 2-aryl-2H-indazoles was developed by copper(I)-catalyzed intramolecular amination reaction under the conditions of [CuI/Cs₂CO₃(250mol%)/1,4-dioxane/105 °C] starting from N’-aryl -N’-(o-bromobenzyl)acetylhydrazines. The method was applied to a wide scope of substrates and afforded indazole products in high yields.

■ Synthesis and Antimicrobial Evaluation of Novel Pyrazolo[1,5-a]pyrimidine, Triazolo[1,5-a]pyrimidine and Pyrimido[1,2-a]benzimidazole Derivatives

Mohamed R. Shaaban, Tamer S. Saleh, and Ahmad M. Farag*

*Department of Chemistry, Faculty of Science, University of Cairo, Giza 12613, Egypt

Abstract

The applicability and synthetic potency of E-1-(1-methylbenzimidazol- 2-yl)-3-N,N-dimethylaminoprop-2-enone towards some nitrogen nucleophiles was investigated as a convenient route for the synthesis of some novel aminopyrimidine, pyrazolo[1,5-a]pyrimidine, triazolo[1,5-a]pyrimidine, pyrimido[1,2-a]benzimidazole, and pyrido[2,3-d]pyrimidine derivatives. Some of the newly synthesized compounds were tested in vitro for their antibacterial and antifungal activities, and showed promising results.

■ New Constituents from the Roots of Erythrina x bidwillii

Hitoshi Tanaka,* Hisanori Hattori, Masaru Sato, Ryozo Yamaguchi, Toshio Fukai, Toshihiro Tanaka, and Eiji Sakai

*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tempaku-ku, Nagoya 468-8503, Japan

Abstract

Three new compounds, erythbidins C-E (1-3), together with five known compounds 4-8 were isolated from the roots of Erythrina x bidwillii. Their structures were established on the basis of spectroscopic evidence. Among the isolated compounds, erythbidin E (3) showed a potent antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA).

■ Stereoselective Synthesis of D-1-Deoxynojirimycin and Its Stereoisomers

In Su Kim, Ho Young Lee, and Young Hoon Jung*

*College of Pharmacy, Sung Kyun Kwan University, 300 Jangangu, Chonchondong, Suwon 440-746, Korea

Abstract

A stereoselective synthesis of D-1-deoxynojirimycin (1), D-1-deoxymannojirimycin (2), and D-1-deoxyallonojirimycin (3) was achieved via the regioselective and diastereoselective amination of anti-1,2-dibenzyl ether using chlorosulfonyl isocyanate (CSI), ring-closing metathesis, diastereoselective dihydroxylation, and the regioselective stereochemical inversion of the resulting diol.

■ Synthesis of Arnoamine B and Related Compounds

Shinsuke Nakahara,* Akinori Kubo, Yuzuru Mikami,* and Hiroki Mitani

*Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan

Abstract

The synthesis of arnoamine B (4), which inhibits the catalytic activity of topoisomerase II and exhibits selective cytotoxicity against human tumor cell lines, was achieved in four steps from 4-bromo-8-methoxy-6-methyl-5-nitroquinoline (6). The related compounds 11~14 were also synthesized, and the antimicrobial activities of 4 and its seven related compounds 6, 8, 9, and 11~14 were investigated.

■ New Kehokorins and Trichiols from the Myxomycete Trichia favoginea

Kousuke Watanabe, Takashi Ohtsuki, Yukinori Yamamoto, and Masami Ishibashi*

*Graduate School of Pharmaceutical Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan

Abstract

Two new dibenzofurans, kehokorins D (1) and E (2), and two new sterols with a 2,6-dioxabicyclo[2.2.2]octan-3-one ring, trichiols C (3) and D (4), have been isolated from field-collected fruiting bodies of the myxomycete, Trichia favoginea, and their structures were elucidated by spectral analysis. Kehokorins D (1) and E (2) showed cell growth inhibition activity against HeLa cells with IC₅₀ values of 6.1 and 4.5 μg/mL, respectively.

■ One-Pot Conversion of N-Arylglycines to Sydnones Efficiently Promoted by Bis-chlorine-1,4-diazabicyclo[2.2.2]octane Complex (Cl₂-DABCO) in the Presence of NaNO₂/Ac₂O under Neutral Conditions

Davood Azarifar,* Hassan Ghasemnejad-Bosra, Mahmood Tajbaksh, and Setareh Habibzadeh

*Department of Chemistry, School of Science, Bu-Ali Sina University, Mehdieh St., Hamadan 65174, Iran

Abstract

Bis-chlorine-1,4-diazabicyclo[2.2.2]octane complex, (Cl₂-DABCO), has been found as an active chlorine complex for effective one-pot conversion of various N-arylglycines to sydnones in high yields (85-95%) under mild and neutral condition.

■ A Simple and Efficient Method for Synthesis of Benzimidazoles Using FeBr₃ or Fe(NO₃)₃·9H₂O as Catalyst

Huiqiang Ma, Xiangming Han, Yulu Wang,* and Jinye Wang*

*College of Chemistry and Environmental Science, Henan Normal University, Xinxiang, 453007, Henan, China

Abstract

2-Substituted benzimidazoles have been synthesized in good yields in a single pot from o-phenylenediamine and aldehydes using FeBr₃ or Fe(NO₃)₃·9H₂O as catalyst. The salient features of this method include a simple procedure, mild conditions, shorter reaction time, less toxic catalyst and easy purification.

■ A Facile Synthesis of 1,1-Disubstituted Isoindoline Derivatives by Intramolecular Iodoamination of 2-Vinylbenzylamine Derivatives

Kazuhiro Kobayashi,* Shizuka Kondo, Kenichi Hashimoto, Shuhei Fukamachi, Osamu Morikawa, and Hisatoshi Konishi

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

Abstract

The intramolecular iodoamination of N-(2-vinylbenzyl)acetamide derivatives, derived from α-substituted 2-vinylbenzonitriles in two steps, afforded the corresponding 2-acetyl-1-iodomethylisoindoline derivatives, which were transformed into the1-methyl or 1-sulfenylmethyl derivatives by tributyltin hydride reduction or substitution by sodium thiolates, respectively, in reasonable yields.

■ A Green Method for the Synthesis of 2-Arylbenzothiazoles

Chhanda Mukhopadhyay* and Arup Datta

*Department of Chemistry, University of Calcutta, 92, APC Road, Kolkata-700009, India

Abstract

Aromatic aldehydes with both electron withdrawing and electron donating substituents were smoothly converted to the corresponding 2-arylbenzothiazoles by direct condensation of aromatic aldehydes with 2-aminothiophenol in one pot in a microoven under solvent-free conditions without any catalyst. The study revealed that the synthesis proceeded in three stages; first the formation of the aryl imine followed by its cyclisation to the benzothiazoline which in turn underwent oxidation and dehydration to the final product benzothiazole. Isolation of intermediates in all the stages confirmed the mechanism. This is therefore the first report of a “green” synthesis of the 2-arylbenzothiazoles under solvent-free conditions in the absence of any catalyst.

■ Synthesis of Enantiomerically Pure (+)- and (-)-3-Methyl-3-(2-naphthyl)-2H-
benzo[e][1,2]thiazine 1,1,4-Triones

Zhao-Peng Liu*

*Department of Organic Chemistry, School of Pharmaceutical Sciences, Shandong University, No. 44, WenHua XiLu, Jinan 250012, China

Abstract

Treatment of N-t-butylbenzenesulfonamide with an excess of BuLi, followed by the reaction with methyl 2-naphthylpropanoate, gave the corresponding 2-carboxybenzenesulfonamide, which underwent cyclization under TMSCl-NaI-MeCN reflux conditions to afford the N-sulfonylimine. Bromination of the N-sulfonylimine and ring expansion mediated by 20% KOH (aq.), formed the 3-methyl-3-(2-naphthyl)benzo[e][1,2]thiazine 1,1,4-trione. Optical resolution of the racemic benzosultam using (-)-menthoxyacetyl chloride, furnished the (+)- and (-)- 3-methyl-3-(2-naphthyl)benzo[e][1,2]thiazine 1,1,4-triones.