Reactions of S-Trimethylstannyl and S-(3-Trimethylstannyl-propyl) Derivatives of 1,5-Pentanedithiol with N,4-Dichlorobenzenesulfonamide Sodium Salt

摘要

Difunctional derivatives of 1,5-pentanedithiol, 1,5-bis(trimethylstannylthio)pentane (CH_2)_5(SSnR_3)_2 and 1,5-bis(3-trimethylstannylpropylthio)pentane (CH_2)_5[S(CH_2)-3SnR_3]_2 (R = Me), differ by mutual arrangement of the tin and sulfur atoms and therefore react differently with N.4-dichlorobenzenesulfonamide sodium salt ArSO_2N(Na)Cl (Ar = 4-lC_6H-40. The first of these substrates possesses two direct Sn-S bonds which are cleaved by the action of 2 equiv of 4-ClC_6H_4SO_2N(Na)Cl (desulfurization). The resulting pentamethylenedithiobis-sulfonamide (CH_2)-5[SN(SnMe_3)SO_2Ar]_2 undergoes oxidative imination of both S(II) atoms with additional 2 equiv of 4-ClC_6H_4SO_2N(Na)Cl to afford sulfinimidamide derivative (CH_2)-5[S=NSO_2Ar)N(SnR_3)SO_2Ar]_2. By contrast, both pairs of the sulfur and tin atoms in the bissulfide (CH_2)_5[S(CH_2)_3SnR_3]_2 are separated by a trimethylene bridge, and this substrate reacts with 2 equiv of 4-ClC_6H_4SO_2N(Na)Cl to form tin-containing bis-sulfimide (CH_2)_5[S(=NSO_2Ar)(CH_2)_3SnR_3]_2. According to the ~1H and ~13C NMR data, interaction between two pairs of the tin and sulfur atoms at both ends of the bis-sulfimide molecule gives the to independent sterically favorable coordination rings.