UZH-Logo

Maintenance Infos

Desulfurization of 4-Nitro-N,2-diphenyl-3-(phenylamino)isothiazol-5(2H)-imine: Formation of a 3-Imino-2-nitroprop-2-enamidine


Moya Argilagos, Dally; Kunz, Roland W; Linden, Anthony; Heimgartner, Heinz (1998). Desulfurization of 4-Nitro-N,2-diphenyl-3-(phenylamino)isothiazol-5(2H)-imine: Formation of a 3-Imino-2-nitroprop-2-enamidine. Helvetica Chimica Acta, 81(12):2388-2406.

Abstract

The course of the desulfurization reaction of 4-nitro-N,2-diphenyl-3-(phenylamino)isothiazol-5(2H)-imine (3) is investigated and the formation of the unstable 3-imino-2-nitroprop-2-enamidine (A) as intermediate is discussed. Addition of amines and thiophenol to the reaction mixture yielded the amidine derivatives 5 and the thioimidate 6, respectively, via nucleophilic addition of the respective reagent to A (Scheme 2). Benzoic acid and thiobenzoic acid afforded the amide 7 and the thioamide 8, respectively, as secondary products of the expected adducts 7a and 8a (Schemes 3 and 4). The presence of (benzylidene)(methyl)amine in the reaction mixture of the desulfurization of 3 led to the 1,2,4-oxadiazole derivative 10, together with the quinoxaline N-oxide 4 as a minor product. Reaction mechanisms involving an intermediate ketene imine and participation of the NO2 group in the reaction leading to 1,2,4-oxadiazole 10 are proposed. Ab initio calculations of model structures for the nitroketene imine were performed and the results correlated with the experimental results. The structures of 8 and 10 were established by X-ray crystal-structure analysis.

The course of the desulfurization reaction of 4-nitro-N,2-diphenyl-3-(phenylamino)isothiazol-5(2H)-imine (3) is investigated and the formation of the unstable 3-imino-2-nitroprop-2-enamidine (A) as intermediate is discussed. Addition of amines and thiophenol to the reaction mixture yielded the amidine derivatives 5 and the thioimidate 6, respectively, via nucleophilic addition of the respective reagent to A (Scheme 2). Benzoic acid and thiobenzoic acid afforded the amide 7 and the thioamide 8, respectively, as secondary products of the expected adducts 7a and 8a (Schemes 3 and 4). The presence of (benzylidene)(methyl)amine in the reaction mixture of the desulfurization of 3 led to the 1,2,4-oxadiazole derivative 10, together with the quinoxaline N-oxide 4 as a minor product. Reaction mechanisms involving an intermediate ketene imine and participation of the NO2 group in the reaction leading to 1,2,4-oxadiazole 10 are proposed. Ab initio calculations of model structures for the nitroketene imine were performed and the results correlated with the experimental results. The structures of 8 and 10 were established by X-ray crystal-structure analysis.

Citations

Altmetrics

Downloads

1 download since deposited on 12 Nov 2013
0 downloads since 12 months
Detailed statistics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:1998
Deposited On:12 Nov 2013 13:55
Last Modified:05 Apr 2016 17:07
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Swiss National Science Foundation, F. Hoffmann-La Roche AG, Basel, Eidgenössische Stipendienkommission für ausländische Studierende
Publisher DOI:https://doi.org/10.1002/(SICI)1522-2675(19981216)81:12<2388::AID-HLCA2388>3.0.CO;2-H
Permanent URL: https://doi.org/10.5167/uzh-84637

Download

[img]
Content: Published Version
Filetype: PDF - Registered users only
Size: 257kB
View at publisher

TrendTerms

TrendTerms displays relevant terms of the abstract of this publication and related documents on a map. The terms and their relations were extracted from ZORA using word statistics. Their timelines are taken from ZORA as well. The bubble size of a term is proportional to the number of documents where the term occurs. Red, orange, yellow and green colors are used for terms that occur in the current document; red indicates high interlinkedness of a term with other terms, orange, yellow and green decreasing interlinkedness. Blue is used for terms that have a relation with the terms in this document, but occur in other documents.
You can navigate and zoom the map. Mouse-hovering a term displays its timeline, clicking it yields the associated documents.

Author Collaborations