170963-72-1Relevant academic research and scientific papers
Synthesis of hetaryl-substituted 1,2,4-trithiolanes via a three-component reaction with dihetaryl thioketones, benzyl azide, and 2,2,4,4-tetramethyl-3-thioxocyclobutanone
Mlosto, Grzegorz,Celeda, Malgorzata,Linden, Anthony,Heimgartner, Heinz
, p. 14 - 22 (2016)
The three-component reactions with a hetaryl thioketone, 2,2,4,4-tetramethyl-3-thioxocyclobutanone, and excess benzyl azide performed at 60°C in the presence of LiClO4 lead to the formation of two types of 1,2,4-trithiolanes. As the major produ
111. Three-component reactions with sterically crowded 2,2,4,4-tetramethyl-3-thioxocyclobutanone, phenyl azide, and electron-deficient C,C-Dipolarophiles
Mlostoń, Grzegorz,Romański, Jaroslaw,Linden, Anthony,Heimgartner, Heinz
, p. 1305 - 1314 (2007/10/03)
In order to trap 'thiocarbonyl-aminides' A, formed as intermediates in the reaction of thiocarbonyl compounds with phenyl azide, a mixture of 2,2,4,4-tetramethyl-3-thioxocyclobutanone (1), phenyl azide, and fumarodinitrile (8) was heated to 80° until evolution of N2 ceased. Two interception products of the 'thiocarbonylaminide' A (Ar = Ph) were formed: the known 1,4,2-dithiazolidine 3 (cf. Scheme 1) and the new 1,2-thiazolidine 12 (Scheme 2). The structure of the latter was established by X-ray crystallography (Fig. 1). The analogous 'three-component reaction' with dimethyl fumarate (9) yielded, instead of 8, in addition to the known interception products 3 and 6 (Scheme 1), two unexpected products 15 and 16 (Scheme 3), of which the structures were elucidated by X-ray crystallography (Fig. 2). Their formation is rationalized by a primary [2 + 3] cycloaddition of diazo compound 18 with 1 to give 19, followed by a cascade of further reactions (Scheme 4).
Bildung von 1,2,4-Trithiolanen in Dreikomponenten-Gemischen aus Phenyl-azid, aromatischen Thioketonen und 2,2,4,4-Tetramethylcyclobutan-thionen: Eine Schwefel-Transfer-Reaktion unter Bildung von 'Thiocarbonyl-thiolaten' ((Alkylidensulfonio)thiolaten) als
Mloston, Grzegorz,Heimgartner, Heinz
, p. 1298 - 1310 (2007/10/02)
The reaction of PhN3 and aromatic thioketones 18 (two-component reaction) at 80 degree yields only the corresponding imines 22, S, and N2.Under similar conditions, in the presence of sterically crowded 2,2,4,4-tetramethyl-cyclobutanethiones 19 (three-comp
115. 1,3-Dipole mit Zentralem S-Atom aus der Umsetzung von Aziden mit Thiocarbonyl-Verbindungen: Eine unerwartete MeS-Wanderung im Abfangprodukt eines 'Thiocarbonyl-aminids' mit Dithiobenzoesaeure-methylester
Mloston, Grzegorz,Romanski, Jaroslaw,Linden, Anthony,Heimgartner, Heinz
, p. 1499 - 1510 (2007/10/02)
Reaction of PhN3 with O-methyl thiobenzoate (11a) and thioacetate (11c) as well as with the dithio esters 11b, d at 80 deg C 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 13 and 3a are trapping products of 1a and 'thiocarbonyl-aminide' 5a and 'thiocarbonyl-amidine' 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 (methyldithio)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.
