NDLI: The versatile electrophilic reactivity of 4,6-dinitrobenzo[d]isoxazole-3-carbonitrile

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Organic & Biomolecular Chemistry Vol - 7 Issue - 5

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Organic & Biomolecular Chemistry Vol - 7 Issue - 3

Organic & Biomolecular Chemistry Vol -6

Organic & Biomolecular Chemistry Vol -5

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Organic & Biomolecular Chemistry Vol -2

The versatile electrophilic reactivity of 4,6-dinitrobenzo[d]isoxazole-3-carbonitrile

Content Provider	Royal Society of Chemistry (RSC)
Author	Shevelev, Svyatoslav Vichard, Dominique Cottyn, Betty Goumont, Régis Terrier, François Starosotnikov, Alexei
Copyright Year	2009
Abstract	The interaction of 4,6-dinitrobenzo[d]isoxazole-3-carbonitrile (5a) with methoxide ion has been kinetically investigated in methanol and a 20:80 (v/v) MeOH-Me2SO mixture. In methanol, stopped-flow experiments have revealed that a monomethoxyl σ-adduct (5a-Me) is first formed, resulting from a fast MeO− addition at the unsubstituted 7-carbon. Rate and equilibrium constants for this σ-complexation process could be determined, allowing a ranking of 5a within the pKa scale established for Meisenheimer electrophiles in methanol. With a pKa value of 13.50, the electrophilicity of 5a falls in the range of 1,3,6,8-tetranitronaphthalene, 2,4-dinitrothiophene or 4-nitrobenzofuroxan. This corresponds to a two-pKa units increase in electrophilicity from that of TNB, the common reference in σ-complex chemistry but it is notably below that of so-called superelectrophilic molecules like 4,6-dinitrobenzofuroxan. In addition to its ease of σ-complexation, 5a is found to undergo a slow but thermodynamically favourable addition of MeO− to the cyano group bonded to the isoxazole ring, leading to a complete conversion of the adduct 5a-Me into a dinitroimidate 6. The reactivity of 6 could be kinetically assessed. Going to 80% Me2SO still afforded initially the adduct 5a-Me but this anionic species undergoes addition of a second molecule of MeO− to the CN group, giving a dianion whose structure is unprecedented in the literature. Combining the above results with synthetic observations showing that 5a can readily contribute to SNAr reactions under appropriate experimental conditions emphasizes the multifaceted electrophilic reactivity of this electron-deficient heterocycle.
Starting Page	1137
Ending Page	1146
Page Count	10
File Format	HTM / HTML PDF
ISSN	14770520
Volume Number	7
Issue Number	6
Journal	Organic & Biomolecular Chemistry
DOI	10.1039/b820256g
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Organic chemistry Nucleophilic aromatic substitution Acid dissociation constant Isoxazole TNB Ion Meisenheimer Carbon Adduct Heterocyclic compound Methanol Electrophile
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Physical and Theoretical Chemistry

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