1736-10-3Relevant academic research and scientific papers
Selectivity of the Aromatic Plumbylation Reaction
Stock, Leon M.,Wright, Terry L.
, p. 4645 - 4648 (1980)
The plumbylation of toluene in dichloroacetic acid yields initially 5.4percent 2-, 1.8percent 3-, and 92.7percent 4-methylphenyllead(IV) dichloroacetates.The toluene to benzene rate ratio under these conditions is 59.9.The partial rate factors are oMef = 9.64, mMef = 3.21, pMef = 331.The plumbylation of toluene in trifluoroacetic acid yields aryl trifluoroacetates and biaryls.Analysis of these products suggest that the plumbylation reaction yields 17.9percent 2-, 3.2percent 3-, and 78.9percent 4-methylphenyllead (IV) trifluoroacetates in the initial step of the reaction.The toluene to benzene rate ratio is 114 under these conditions.The partial rate factors are oMef = 61.2, mMef = 10.8, and pMef = 540.These observations suggest that the plumbylation reaction is a typical electrophilic substitution and that the reaction is significantly more selective than thallation or mercuration.
OXIDATION BY THE SALTS OF METALS. VII. PLUMBATION AND OXIDATIVE SUBSTITUTION OF AROMATIC COMPOUNDS IN THE LEAD TETRAACETATE-LITHIUM CHLORIDE SYSTEM IN THE PRESENCE OF PERFLUORINATED CARBOXYLIC ACIDS
Serguchev, Yu. A.,Davydova, V. G.,Makhon'kov, D. I.,Beletskaya, I. P.
, p. 1006 - 1011 (2007/10/02)
The oxidation of benzene and substituted benzenes PhX with electron-donating (X = CH3, OCH3) and electron-withdrawing (X = Hlg, CF3, NO2) substituents in the Pb(OAc)4-LiCl system was investigated in the presence of perfluorinated carboxylic acids RfCOOH (Rf = CF3, C6F13).The reaction leads to the plumbation, chlorination, and acyloxylation products.It was shown that the reactions take place through the formation of aryl derivatives of lead(IV) with the participation of mixed-ligand complexes of lead.The products from the plumbation of toluene (in C6F13COOH in the absence of lithium chloride) and benzotrifluoro were isolated.In trifluoroacetic acid these intermediates undergo intramolecular redox decomposition with ligand transfer.The halogenobenzenes and benzotrifluoride are oxidized selectively in the CF3COOH-Pb(IV)-LiCl system, giving the corresponding aryl chlorides with yields close to quantitative (80-90percent).
