3299-93-2Relevant academic research and scientific papers
REACTION OF ORGANOMETALLIC COMPOUNDS CATALYZED BY TRANSITION METAL COMPLEXES. III. THE ACYLDEMETALLATION OF ORGANOTIN COMPOUNDS CATALYZED BY BIS(?-ALLYLPALLADIUM CHLORIDE)
Bumagin, N. A.,Bumagina, I. G.,Kashin, A. N.,Beletskaya, I. P.
, p. 977 - 981 (2007/10/02)
A study was carried out on the reaction of organotin compounds RSnMe3 with carboxylic acid chlorides R'COCl (R'=Me, PhCH2, PhCH=CH, Ph, o-FC6H4, p-ClCOC6H4, p-NO2C6H4) catalyzed by bis(?-allylpalladium chloride) in hexametapol and acetone.The reaction proceeds at room temperature and gives high yields of asymmetrical ketones RCOR'.The stoichiometry of the reaction of PhCOPdCl(PPh3)2 with PhSnMe3 was studied.A possible mechanism for the catalytic acyldemetallation reaction was discussed.
REACTIVITY OF ORGANOTIN COMPOUNDS. XX. ACYLDEMETALLATION OF RSnMe3 compounds
Kashin, A. N.,Bumagin, N. A.,Kalinovskii, I. O.,Beletskaya, I. P.,Reutov, O. A.
, p. 1329 - 1334 (2007/10/02)
The reactions of RSnMe3 with R=CH3 (I), C4H9 (II), C6H5 (III), 9-fluorenyl (IV), 9-methyl-9-fluorenyl (V), indenyl (VI), and C6H5CC (VII) with acetyl chloride (VIII), benzoyl chloride (IX), and trifluoroacetic anhydride (X) in methylene chloride at room temperature, leading to the formation of unsymmetrical ketones, were investigated.It was shown that the reactions of (I-III) with (VIII-X) and also of (VII) with (VIII) and (IX) only occur in the presence of aluminium chloride, whereas a catalyst is not required for the reactions of (VI) and (VII) with (X).Compounds(IV-VI) react with (VIII) and (IX) only in presence of Et4NCl or Bu4NBr, and this is explained by the participation of ion pairs R-+Sn(CH3)3, formed by coordination of the halide ion at the tin atom and possessing higher nucleophilicity than the covalent form RSn(CH3)3.The formation of 8-methyl-8-acetoxybenzofulvene in the reaction of (VI) with (VIII) shows that metallation of the strong CH acid 1-acetylindene by the action of compound (VI) occurs in the presence of a nucleophilic catalyst (Et4NCl).
