Preparation of Substituted Methyl o-Nitrophenyl Sulfides 英文参考文献.docVIP

Molecules 2002, 7, 7-17 molecules ISSN 1420-3049 Preparation of Substituted Methyl o-Nitrophenyl Sulfides Katerina Dudova?, Frantisek Castek, Vladimir Machacek* and Petr Simunek Department of Organic Chemistry, University of Pardubice, ?s. legií 565, 532 10 Pardubice, Czech. ? Republic, Tel. +420 40 603 7015, Fax +420 40 603 7068, e-mail: katerina.dudova@seznam.cz * Author to whom correspondence should be addressed; e-mail: vladimir.machacek@upce.cz Received: 27 September 2001; in revised form 9 November 2001 / Accepted: 13 November 2001 / Published: 31 January 2002 Abstract: The nucleophilic substitution of substituted o-nitrochlorobenzenes with substituted methanethiolates, catalysed with triethylamine or pyridine, has been used to prepare a series of appropriately substituted methyl-o-nitrophenylsulfides. The prepared compounds were identified by their 1H- and 13C-NMR spectra. The base catalysed ring closure of methyl 2-(methoxycarbonylmethylsulfanyl)-3,5-dinitrobenzenecarboxylate only results in an attack of carbanion on the ester group, not on a nitro group as with the other compounds prepared. The cyclisation product is methyl 3-hydroxy-5,7-dinitro- benzo[b]thiophene-2-carboxylate (11). Keywords: Nucleophilic aromatic substitution, sulfur nucleophiles, ring closure. Introduction Wagner et al. [1] have described the base-catalysed reaction of substituted 2-nitrochlorobenzenes with esters of sulfanylethanoic acid giving the correspondingly substituted 2-alkoxycarbonyl- benzo[d]thiazol-3-oxides. The expected intermediate of this reaction, i.e. a substituted alkyl (2- nitrophenylsulfanyl)ethanoate, was isolated and identified in a single case – the case of ethyl (4-cyano- 2,6-dinitrophenylsulfanyl)ethanoate [1]. It is interesting that 2,6-dinitrochlorobenzene reacts with methyl sulfanylethanoate in methanol (with triethylamine catalysis) to give 2-meth