Reinhold Tacke, B. Becker, H. Lange

• Die erstmalige Synthese der (Thioacetoxy-S-methyl)diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (9) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (10) und der (Mercaptomethyl) diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)SH (11) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SH (12) wird beschrieben. Während sich die Silane 9 und 10 leicht handhaben lassen, neigen die strukturanalogen (Hydroxymethyl)diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)OH (1) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OH (2) zu einer basenkatalysiertenDie erstmalige Synthese der (Thioacetoxy-S-methyl)diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (9) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (10) und der (Mercaptomethyl) diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)SH (11) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SH (12) wird beschrieben. Während sich die Silane 9 und 10 leicht handhaben lassen, neigen die strukturanalogen (Hydroxymethyl)diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)OH (1) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OH (2) zu einer basenkatalysierten Zersetzung (Bildung oligomerer (polymerer) Alkoxysilane und Wasserstoff). Im Gegensatz zu den thermisch labilen (Acetoxymethyl)diorganylsilanen (CH\(_3\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (3) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (4) (--+ Umlagerung zu den entsprechenden Acetoxy(methyl) diorganylsilanen (CH\(_3\)) \(_3\)SiOC(O)CH\(_3\) (5) und CH\(_3\)(C\(_6\)H\(_5\))\(_2\)SiOC(O)CH\(_3\) {6)) sind die Thio-Analoga 9 und 10 thermisch stabil (I-molare Lösungen in C\(_6\)D\(_6\), 30 h bei 180 o C).…
• The novel synthesis of the (thioacetoxy-S-methyl)diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (9) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (10) and the (mercaptomethyl) diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)SH (11) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SH (12) is described. The silanes 11 and 12 areeasy to handle, whereas the structurally analogous (hydroxymethyl)diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)OH (1) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OH (2) tend to undergo a base-catalyzed decompositionThe novel synthesis of the (thioacetoxy-S-methyl)diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (9) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (10) and the (mercaptomethyl) diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)SH (11) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SH (12) is described. The silanes 11 and 12 areeasy to handle, whereas the structurally analogous (hydroxymethyl)diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)OH (1) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OH (2) tend to undergo a base-catalyzed decomposition (formation of oligomeric (polymeric) alkoxysilanes and hydrogen). In cantrast to the thermally unstable (acetoxymethyl)diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (3) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (4) (--+ rearrangement to the corresponding acetoxy(methyl)diorganylsilanes (CH\(_3\)) \(_3\)SiOC(O)CH\(_3\) (5) and CH\(_3\)(C\(_6\)H\(_5\))\(_2\)SiOC(O)CH\(_3\) (6)), the thio-analogues 9 and 10 are thermally stable (1 molar solutions in C\(_6\)D\(_6\) , 30 h at 180°C).…