Showing papers on "Organomercury Compounds published in 1985"
TL;DR: In the last few years it has been increasingly achieved by radical addition to alkenes as discussed by the authors, which can be accomplished with organotin and organomercury hydrides, and has led to new synthetic methods.
Abstract: CC bond formation is one of the most important synthetic steps in the construction of organic molecules. In the last few years it has been increasingly achieved by radical addition to alkenes. In such reactions the adduct radicals have to be trapped by an donor subsequent to the CC bond formation in order to prevent polymerization. This task can be accomplished with organotin and organomercury hydrides, the use of which has led to new synthetic methods. The occurrence of radical chain reactions in which reactions take place between radicals and nonradicals is decisive for the success of the synthesis. In these cases small amounts of radical initiators suffice and numerous functional groups may be used in the CC bond-forming reactions. The yields and selectivities of these radical reactions are often very high.
228 citations
Book•
01 Jan 1985TL;DR: In this article, the authors present a method for the preparation of organomercury compounds, including organomethane and cyclopropane, in order to be used in the synthesis of Heteroatom-Containing Compounds.
Abstract: I. Introduction.- References.- II. Preparation of Organomercury Compounds.- A. Introduction.- B. Direct Mercuration of Organic Halides.- C. Organomagnesium and -Lithium Procedures.- D. Organoboranes.- E. Other Transmetallation Reactions.- F. Mercuration of Carbon Monoxide.- G. Mercury Substitution in Activated C-H Containing Compounds.- H. Mercuration of Cyclopropanes.- I. Mercuration of Alkenes.- J. Mercuration of Alkynes.- K. Mercuration of Aromatic Compounds.- L. Mercury Substitution in Aryldiazonium Salts, Hydrazines, Hydrazones, and Diazo Compounds.- M. Decarboxylation of Mercury Carboxylates.- N. Sulfinate and Sulfonate Elimination Reactions.- References.- III. Hydrogen and Halogen Substitution.- A. Hydrogen Substitution.- B. Halogen Substitution.- References.- IV. Synthesis of Heteroatom-Containing Compounds.- A. Introduction.- B. Oxygen Compounds.- C. Sulfur, Selenium, and Tellurium Compounds.- D. Nitrogen Compounds.- E. Phosphorus Compounds.- F. Silicon Compounds.- G. Conclusion.- References.- V. Dimerization.- References.- VI. Alkylation.- References.- VII. Alkene and Alkyne Addition and Substitution Reactions.- References.- VIII. Carbonylation.- References.- IX. Acylation.- References.- X. Divalent Carbon Transfer Reactions.- A. Introduction.- B. Preparation of the Reagents.- C. Synthesis of Cyclopropanes.- D. Organomercurial Reactivity.- E. Mechanism of Cyclopropane Formation.- F. Synthesis of Cyclopropenones.- G. Ring Expansion Reactions.- H. Reactions with Oxygen, Nitrogen and Sulfur Compounds.- J. Insertion Reactions in Metal-Carbon, Metal-Halide and Metal-Metal Bonds.- References.- Subject Inde.
80 citations
TL;DR: In this article, low-pressure and atmospheric-pressure microwave-induced helium plasma detectors were interfaced with a capillary column gas chromatograph for the separation of dialkyl mercury, diaryl mercury and monoalkyl mercury chlorides.
33 citations
TL;DR: The synthetic route to 6-chloromercuricholest-5-en-3β-ol has been studied and the yield improved from 2% to 20% as discussed by the authors.
Abstract: The synthetic route to 6-chloromercuricholest-5-en-3β-ol has been studied and the yield improved from 2% to 20%. The reaction of 6-chloromercuricholest-5-en-β-ol with fluorine, chlorine, bromine, a...
13 citations
TL;DR: Carbonylation par reaction dacylates daryl-, alkyl-, allyl-and vinyl-mercure avec CO dans l'eau ou dans des alcools en presence de complexes de Pd.
Abstract: Carbonylation par reaction d'acylates d'aryl-, alkyl-, allyl- et vinyl-mercure avec CO dans l'eau ou dans des alcools en presence de complexes de Pd
11 citations
TL;DR: In this article, the He(I) photoelectron spectra of 30 organomercury compounds of different structural types and of some model organic compounds were investigated, and the values of vertical ionization potentials (IP) of highest occupied molecular orbitals (HOMO) were determined.
7 citations
01 Jan 1985
4 citations
TL;DR: Decarboxylation of mercuric pyridine-2,3-dicarboxyate in hot dimethyl sulfoxide or hexamethylphosphoramide gives a mixture of 2-carboxylatopyridin-3-ylmercury(II) (major product) and 3- carboxyl atopyridisin-2-ylmerscury-II (minor product).
Abstract: Decarboxylation of mercuric pyridine-2,3-dicarboxylate in hot dimethyl sulfoxide or hexamethylphosphoramide gives a mixture of 2-carboxylatopyridin-3-ylmercury(II) (major product) and 3- carboxylatopyridin-2-ylmercury(II) (minor product). The mixture reacts ( i ) with acidified halide ions ( Cl - or I-) to yield a mixture of the corresponding carboxypyridinyl ( halogeno )mercury(II) derivatives, (ii) with tribromide ions to give the bromo ( carboxypyridinyl )mercury(ii) complexes, 3-bromopyridine-2-carboxylic acid, and 2-bromopyridine-3- carboxylic acid, and (iii) with iodide ions in hot aqueous acetic acid to yield bis (2-carboxypyridin-3-yl)mercury(II) hydrogen triiodomercurate (II). Solutions of the last compound in dimethyl sulfoxide deposit bis (2-carboxypyridin-3-yl)mercury(II). Reaction of pyridine-2,3-dicarboxylate ions with mercuric acetate in boiling aqueous acetic acid at pH 5.0-5.8 gives mercurated acetic acid as the sole organometallic product, and the reported1 decarboxylation yielding 3-carboxylatopyridin-2-ylmercury(II) is not observed.
3 citations
01 Jan 1985
TL;DR: The main focus of most of this work has been on studying the mechanism of electrophilic aliphatic substitution as discussed by the authors, and a number of reviews [1, 2] and one book [5] have appeared covering this topic.
Abstract: Hydrogen and halogen substitution in organomercury compounds have been extensively studied and a number of reviews [1–4] and one book [5] have appeared covering this topic. The primary emphasis of most of this work has been on studying the mechanism of electrophilic aliphatic substitution. Considerable kinetic and stereochemical information on these reactions is now available. The emphasis here, however, will be on possible synthetic applications of these reactions.
1 citations
TL;DR: In this article, a comparison of the polarographic behavior of a series of polybromine-substituted benzylmercuric bromides and the corresponding substituted benzyl bromide was made.
Abstract: On the basis of a comparison of the polarographic behavior of a series of polybromine-substituted benzylmercuric bromides and the corresponding substituted benzyl bromides it was shown in the case of benzyl bromides active in the preparative reaction with metallic mercury that the reduction takes place through the initial formation of organomercury compounds at the surface of the mercury electrode.
TL;DR: In the reactions of peralkyl organotin compounds containing a primary β-H atom with diary-lmethyl salts, β-elimination and substitution occur simultaneously as discussed by the authors.
Abstract: 1.
In the reactions of peralkyl organotin compounds containing a primary β-H atom with diarylmethyl salts, β-elimination and substitution occur simultaneously.
2.
The proportion of the β-elimination product in the reaction mixture increases as the stability of the diarylmethyl cation increases.
3.
The reactions of dipropylmercury with diarylmethyl salts, like those of peralkyl organotin compounds with triarylmethyl salts, result in exclusive β-elimination, irrespective of the stability of the corresponding cation.