Thallium-mercury bonds reactions with

Sulfonation. Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of S03 or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Thphenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thallium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Iron.—Mercury(ii) and thallium(iii) perchlorates react with pyridino-methyldicarbonyl-TT-cyclopentadienyliron ions (6) to cleave the iron-carbon bond, producing [Fe(CO)2(A -C5H5)(OH2)]+ and pyridiniomethyl-mercury(n) or -thallium(m). As for similar reactions of pyridiniomethyl-chromium and -manganese compounds described in earlier paragraphs, the mechanism is 5 E2(open). The pyridiniomethylthallium(ni) produced is itself unstable. ... 

The reactions of acetylenes with thallium(III) salts are of considerable interest in that the results can be used in a qualitative comparison of reactivity between thallium(III) and mercury(II). Mercury(II) salt-catalyzed hydration of the C=C bond is a much studied and synthetically very useful process, although the detailed mechanism of the reaction is not known. The only published data available on the reactions of acetylenes with thallium-(III) salts are due to Uemura et al. 161), who employed thallium(III)... 

Cyclopropane bonds are susceptible to oxidative cleavage (see Section 2.1.1.2.). Most of the oxidation reactions of activated cyclopropanes involve phenyl-substituted derivatives. When phenylcyclopropane was treated with lead(IV) acetate, 1,3-diacetoxy-l-phenylpropane (63%) and the elimination product cinnamyl acetate (32%) were obtained. The occurrence of traces of l,3-diacetoxy-2-phenylpropane could not be confirmed in later studies. The kinetics of the oxidation of various arylcyclopropanes with lead(IV) acetate, thallium(III) acetate and mercury(II) acetate have been studied. 4-Methoxyphenyl, 4-tolyl, and 4-chlorophenyl derivatives and their meta analogs were treated with these reagents and the rates of reaction and product distributions analyzed. Using lead(IV) acetate, diacetates 1 and cinnamyl acetates 2 were obtained in ratios of about 4 1, whereas thalhum(III) acetate gave the diacetates almost exclusively (see following table). ... 

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