Showing papers on "Organomercury Compounds published in 1966"

Organomercury compounds. Part I. Mercury pentafluorobenzoates and their decarboxylation to pentafluorophenylmercury compounds

Abstract: The preparations of some mercury derivatives of pentafluorobenzoic acid and their decarboxylation to give pentafluorophenylmercury compounds are described. Mercuric pentafluorobenzoate and C6F5CO2HgR (R = Ph, p-MeC6H4, or p-MeOC6H4) have been prepared by reaction of pentafluorobenzoic acid with mercuric acetate and RHgOAc, respectively, and methylmercuric pentafluorobenzoate has been made from methylmercuric iodide and silver pentafluorobenzoate. The complexes (C6F5CO2)2HgL (L = 2,2′-bipyridyl, 1,10-phenanthroline, or 1,2-bisdiphenylphosphinoethane) were obtained from reactions of these ligands with mercuric pentafluorobenzoate. The pentafluorobenzoates are monomeric and have low conductances in acetone. Conductances of representative compounds in methanol and pyridine have also been measured. Infrared data suggest that the compounds may contain unidentate pentafluorobenzoate groups.Mercuric pentafluorobenzoate and 2,2′-bipyridylmercuric pentafluorobenzoate decarboxylate at their melting points and the other pentafluorobenzoates decarboxylate on heating in dry pyridine to give the corresponding pentafluorophenylmercury compounds. In acetone and benzene, the complexes (C6F5)2HgL dissociate into L and and bispentafluorophenylmercury.

Organomercury compounds. Part II. Preparations of complexes of bisperfluoroalkylmercurials by decarboxylation reactions

Abstract: The preparations of 1,10-phenanthroline (phen) and 2,2′-bipyridyl (bipy) complexes of bistrifluoromethylmercury, bispentafluoroethylmercury, and bisheptafluoropropylmercury by thermal decarboxylation of the corresponding complexes of mercuric trifluoroacetate, mercuric pentafluoropropionate, and mercuric heptafluorobutyrate, respectively, are described. The phenanthroline complexes of the mercurials are monomeric in benzene, but the bipyridyl complexes undergo dissociation into bipyridyl and the corresponding mercurial. The relative stabilities of the bipyridyl complexes are (C2F5)2Hg bipy (C3F7)2Hg bipy > (CF3)2Hg bipy.

Decarboxylation of mercury salts of organic acids under the action of peroxides and ultraviolet radiation

Abstract: 1. Under the action of peroxides or UV radiation mercuric alkanoates undergo initiated free-radical decarboxylation with formation of alkylmercury compounds. 2. For the lower alkanoates — mercuric acetate and propionate — the decarboxylation reaction has a chain character and provides a convenient method for the synthesis of organomercury compounds, particularly (alkanoyloxy) methylmercurys. 3. In the aromatic series the decarboxylation of mercuric salts goes much less readily. The introduction of a substituent into the aromatic nucleus hinders the decarboxylation of mercuric arenecarboxylates. 4. Mercurous carboxylates react with peroxy compounds with formation of organomercury compounds. The reaction is of preparative interest and can be applied for the fixation of free radicals in the liquid phase.

Interaction of hydrazones and azines with metal salts Communication 7. Comparative investigation of the diazoaliphatic and hydrazone methods for the synthesis of organomercury compounds

Abstract: 1. A comparative investigation was made of two methods for the synthesis of organomercury compounds — the diazoaliphatic method and the oxidation of hydrazone complexes of mercuric halides with mercuric oxide — for the case of 2,3-bornanedione and benzil derivatives. 2. In the case of 2,3-bornanedione both methods lead to the formation of the same types of organomercury compound in approximately the same yields. 3. In the case of benzil the method of synthesizing organomercury compounds by the oxidation of complexes formed by the monohydrazone with mercuric halides is inapplicable.

Reactions of hydrazones and azines with metal salts Communication 6. Synthesis of organomercury compounds from mercuric halide complexes of hydrazones

Abstract: 1. The oxidation of mercuric halide complexes of alicyclic and aliphatic hydrazones with yellow mercuric oxide leads to the formation of organomercury compounds whose structures depend on the oxidation medium. 2. A new method was developed for the synthesis of organomercury compounds from complexes of acetaldehyde, acetone, cyclopentanone, cyclohexanone, and camphor hydrazones.

Study of the mechanism of the alkylation reaction of organomercury compounds by triarylmethane derivatives

Abstract: 1. The reaction of ethyl esters ofα-bromomercuryarylacetic acids proceeds at the carbon atom in dichloroethane and at the oxygen atom in nitromethane. 2. The reaction of mercurated esters with Ar3CBr is accomplished through the preliminary formation of a complex between the reagents and is first order with respect to the complex. The reaction of mercurated esters with Ar3CBr · HgBr2 proceeds according to a bimolecular mechanism. 3. The reactions of arylmercury bromides with tetraphenylbromomethane and its complex with mercuric bromide proceed according to a single mechanism. The reaction with trityl bromide is accelerated by additions of iodide ions.

News in reactions of electrophilic substitution of organomercury compounds nucleophilic promotion and nucleophilic catalysis

Abstract: The influence of nucleophilic catalysis and nucleophilic promotion in various reactions of electrophilic substitution of organomercury compounds was considered.