ChemInform Abstract: DIE HYDROSILYLIERUNG VON AETHINYL‐ALPHA‐GLYKOLEN IN GEGENWART DES SPEIER‐KATALYSATORS

Abstract

Die Addition von Triäthylsilan (II) an 3,4‐Dimethyl‐pentin‐(l)‐ bzw. 3,4‐Dimethylhexin‐(1)‐diol‐(3,4), 3‐(1‐Hydroxycyclohexyl)‐ bzw. 3‐(1‐Hydroxycyclopentyl)‐butin‐(1)‐ol‐(3)(I) in Gegenwart von Hexachlorplatinsäure (0,1 m) in Isopropanol (Speier‐Katalysator) bei 90°C liefert die Verbindungen (III) in 20‐36%iger, die Verbindungen (IV) in 6 ‐ 9%iger Ausbeute, d.h. die Addition von (II) an (I) erfolgt überwiegend nach der Farmerschen Regel.

Addition of Nitrile Oxides to Silyl- And Germyl-Disubstituted Ethylenes

“…According to literature data, the hydrosilylation of mono-substituted acetylenes with trialkyl-and triarylsilanes in the presence of H 2 PtCI 5 leads, in most cases, to a mixture of £-(ß-isomer) and geminal (α-isomer) products [15][16][17][18][19][20][21][22][23][24][25], The Ε-Configuration of the ß-isomer is the result of a c/s-addition to the triple C^C bond of acetylenes [26][27][28], The ratio of the a-and ß-fEj-isomers formed in the reaction 656 Brought to you by | Purdue University Libraries Authenticated Download Date | 6/13/15 9:59 PM strongly depends upon the electron acceptor properties of the substituent R in the acetylene derivatives ROCH. According to literature data, the hydrosilylation of mono-substituted acetylenes with trialkyl-and triarylsilanes in the presence of H 2 PtCI 5 leads, in most cases, to a mixture of £-(ß-isomer) and geminal (α-isomer) products [15][16][17][18][19][20][21][22][23][24][25], The Ε-Configuration of the ß-isomer is the result of a c/s-addition to the triple C^C bond of acetylenes [26][27][28], The ratio of the a-and ß-fEj-isomers formed in the reaction 656 Brought to you by | Purdue University Libraries Authenticated Download Date | 6/13/15 9:59 PM strongly depends upon the electron acceptor properties of the substituent R in the acetylene derivatives ROCH.…”