Header

UZH-Logo

Maintenance Infos

Umsetzungen von 1,3-Thiazol-5(4H)-thionen mit Grignard- und Organolithium-Verbindungen: Carbophile und Thiophile Additionen


Jenny, Christjohannes; Heimgartner, Heinz (1986). Umsetzungen von 1,3-Thiazol-5(4H)-thionen mit Grignard- und Organolithium-Verbindungen: Carbophile und Thiophile Additionen. Helvetica Chimica Acta, 69(4):773-785.

Abstract

Organolithium compounds and 1,3-thiazole-5(4H)-thiones 9 reacted via thiophilic addition on the exocyclic S-atom. The intermediate anion E has been trapped by protonation to give 12 and by alkylation to yield 16, respectively (Schemes 5 and 6). In competition with protonation of E, a fragmentation to benzonitrile and a dithioester 14 was observed (Scheme 5). In some cases, the alkylation of E led to the formation of dithioacetals 17 instead of 16 (Scheme 6). Methyl, ethyl, and isopropyl Grignard reagents and 9 in THF underwent again a thiophilic addition yielding 4,5-dihydro-1,3-thiazoles of type I2 (Scheme 3). In contrast to this result, MeMgI reacted with 9a in Et2O via carbophilic addition to 11. Again a carbophilic attack at C(5) of 9 was observed with allylmagnesium and 2-propynylmagnesium bromide, respectively,in Et2O.

Abstract

Organolithium compounds and 1,3-thiazole-5(4H)-thiones 9 reacted via thiophilic addition on the exocyclic S-atom. The intermediate anion E has been trapped by protonation to give 12 and by alkylation to yield 16, respectively (Schemes 5 and 6). In competition with protonation of E, a fragmentation to benzonitrile and a dithioester 14 was observed (Scheme 5). In some cases, the alkylation of E led to the formation of dithioacetals 17 instead of 16 (Scheme 6). Methyl, ethyl, and isopropyl Grignard reagents and 9 in THF underwent again a thiophilic addition yielding 4,5-dihydro-1,3-thiazoles of type I2 (Scheme 3). In contrast to this result, MeMgI reacted with 9a in Et2O via carbophilic addition to 11. Again a carbophilic attack at C(5) of 9 was observed with allylmagnesium and 2-propynylmagnesium bromide, respectively,in Et2O.

Statistics

Citations

17 citations in Web of Science®
4 citations in Scopus®
Google Scholar™

Altmetrics

Downloads

1 download since deposited on 04 Jun 2014
0 downloads since 12 months
Detailed statistics

Additional indexing

Other titles:Reactions of 1,3-ThiazoIe-5(4H)-thiones with Grignard- and Organolithium Compounds: Carbophilic and Thiophilic Additions
Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:German
Date:1986
Deposited On:04 Jun 2014 08:06
Last Modified:05 Apr 2016 17:54
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung, F. Hoffmann-La Roche & Co. AG, Basel
Publisher DOI:https://doi.org/10.1002/hlca.19860690404

Download

Preview Icon on Download
Content: Published Version
Filetype: PDF - Registered users only
Size: 897kB
View at publisher