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1,3-Dipole rnit zentralem S-Atom aus der Umsetzung von Aziden mit Thio- carbonyi-Verbindungen: Eine unerwartete MeS-Wanderung im Abfangprodukt eines ‘Thiocarbonyl-aminids’ mit Dithiobenzoesäure-methylester


Mloston, Grzegorz; Romanski, Jaroslaw; Linden, Anthony; Heimgartner, Heinz (1995). 1,3-Dipole rnit zentralem S-Atom aus der Umsetzung von Aziden mit Thio- carbonyi-Verbindungen: Eine unerwartete MeS-Wanderung im Abfangprodukt eines ‘Thiocarbonyl-aminids’ mit Dithiobenzoesäure-methylester. Helvetica Chimica Acta, 78:1499-1510.

Abstract

1,3-Dipoles with a Central S-Atom from the Reaction of Azides and Thiocarbonyl Compounds: An Unexpected MeS Migration in the Trapping Product of a ‘Thiocarbonyl-aminide’ with Methyl Dithiobenzoate Reaction of PhN3 with O-methyl thiobenzoate (11a) and thioacetate (11c) as well as with the dithio esters 11b,d at 80° yields the corresponding imidates and thioimidates 12 (Scheme 3). The formation of 12 is rationalized by a 1,3-dipolar cycloaddition of the azide and the C=S group followed by successive elimination of N2 and S. In the three-component reaction of 11b, PhN3, and the sterically crowded thioketone 1a , 1,2,4-trithiolane 13a and 1,4,2-dithiazolidine 3a are formed in addition to 12b (Scheme 4). The heterocycles 13a and 3a are trapping products of 1a and ‘thiocarbonyl-thiolate’ 5a and ‘thiocarbonyl-aminide’ 2a (Ar=Ph), respectively (Scheme 6). These 1,3-dipoles are formed as reactive intermediates. Surprisingly, in the presence of catalytic amounts of acids, the major product is the (methy1dithio)cyclobutyl thioimidate of type 14 (Scheme 5), formed by an acid-catalyzed MeS migration in dithiazolidine 17. A reaction mechanism is proposed in Scheme 7.

Abstract

1,3-Dipoles with a Central S-Atom from the Reaction of Azides and Thiocarbonyl Compounds: An Unexpected MeS Migration in the Trapping Product of a ‘Thiocarbonyl-aminide’ with Methyl Dithiobenzoate Reaction of PhN3 with O-methyl thiobenzoate (11a) and thioacetate (11c) as well as with the dithio esters 11b,d at 80° yields the corresponding imidates and thioimidates 12 (Scheme 3). The formation of 12 is rationalized by a 1,3-dipolar cycloaddition of the azide and the C=S group followed by successive elimination of N2 and S. In the three-component reaction of 11b, PhN3, and the sterically crowded thioketone 1a , 1,2,4-trithiolane 13a and 1,4,2-dithiazolidine 3a are formed in addition to 12b (Scheme 4). The heterocycles 13a and 3a are trapping products of 1a and ‘thiocarbonyl-thiolate’ 5a and ‘thiocarbonyl-aminide’ 2a (Ar=Ph), respectively (Scheme 6). These 1,3-dipoles are formed as reactive intermediates. Surprisingly, in the presence of catalytic amounts of acids, the major product is the (methy1dithio)cyclobutyl thioimidate of type 14 (Scheme 5), formed by an acid-catalyzed MeS migration in dithiazolidine 17. A reaction mechanism is proposed in Scheme 7.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:German
Date:1995
Deposited On:04 Dec 2013 14:04
Last Modified:05 Apr 2016 17:12
Publisher:Wiley-Blackwell
ISSN:0018-019X
Funders:Polnisches Nationalkomitee zur Förderung der wissenschaftlichen Forschung, Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung, F. Hoffmann-La Roche AG, Basel

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