ChemInform Abstract: EINFLUSS VON METALLHALOGENIDEN AUF DIE REAKTIVITAET VON ORGANOCADMIUMVERBINDUNGEN GEGENUEBER CARBONYLVERBINDUNGEN

Abstract

Die Reaktion von Diäthyl‐Cd (II) mit Benzaldehyd (I) zu den Alkoholen (IV) und (V) sowie zu den Carbonylverbindungen (VI)‐(VIII) bzw. von Dibutyl‐Cd (IX) mit Diacetyl (X) zum Hydroxyketon (XI) wird durch die Metallhalogenide (III) beeinflußt. Die Ausbeute des Alkohols (IV) fällt, die des Alkohols (V) und des Ketons (VI) steigen in der Reihe der angegebenen Metallhalogenide.

The less familiar reactions of organocadmium reagents

“…Infrared evidence has been presented for structures of type 1, where the metal halide is magnesium bromide.58 Magnesium halides promote addition reactions far more effectively than do zinc, cadmium, lithium85 or aluminum salts. 82 The nature of the halide plays a noticeable but less pronounced role. Among magnesium salts, iodides are most effective100,101 and chlorides least effective (fluorides have not been investigated).…”

“…), and benzalpropiophenone and ethylidenepropiophenone (aldol condensation) were detected in minimal amounts. 82 The side reactions (in particular the M-P-V reduction, Oppenauer oxidation) are enhanced as the amount of added metal halide is decreased; that is, the side reactions predominate as the reagent approaches the "purified" state, when simple addition is very slow. The addition of CdBr2 was reported to have no effect, but in this case the solvent was DMF.…”

“…[(C2H5)3Ge]2Cd + (CeHs^CCI ~* (C2Hs)3GeC(CeH5)3 (82) [(C2H5)3Ge]2Cd + CH2=CHCH2Br -»(C2H5)3GeCH2CH=CH2 (83) [(C2H5)3Ge] 2Cd + C2H5Br -(C2H5)4Ge (84) [(C2H5)3Ge]2Cd + C6H5CH2Br -(C2H5).3GeGe(C2H5) 3 + C6H5CH2CH2C6H5 (85)…”