Über Substitutionsreaktionen an 1,3‐Dithietan‐1,1,3,3‐tetraoxid (Disulfen)

Substitution Reactions of 1,3‐Dithietane 1,1,3,3‐Tetraoxide (Disulfene) Alkylation of 1,3‐dithietane 1,1,3,3‐tetraoxide (disulfene, 5 ) with alkyl iodides in the presence of NaH provides a mixture of cis / trans 1‐isomers 4a‐c (Me, Et, i Pr), which are further alkylated to 7a, b or brominated to 1a, b . Only by using the respective nonafluorobutanesulfonic acid esters (nonaflates, C 4 F 9 SO 2 OR) silylations, germylation, or stannylation of 5 is achieved with formation of the 2,4‐disilyl ( 6a, b, d, e ), ‐digermyl ( 3f ), and ‐distannyl ( 3g ) compounds as well as the mixed alkyl/silyl species 2a, b . Attempts to synthesize compounds with a 2,4‐bridged structure by treatment of 5 with I–(CH 2 ) 3 –I/NaH were unsuccessful, but yielded the unusual dispiro disulfene 8 , whereas the dicyclic 2,4‐bridged compound 9 has been obtained from 5 and the respective 1,2‐disilyl ester of ethane. The first example of a 1λ 6 ,3λ 6 ‐1,3‐dithiete 10 is obtained by tetrasilylation of 5 accompanied by a rearrangement of two of the bulky Et 3 Si groups to the sulfone groups.