Organomercurials in organic synthesis

Thiocyanatomercuration des acetyleniques. Synthese de derives β-(iso)thiocyanatoalcenyl mercuriques, d'α-halo β-thiocyanato alcenes et de thiocyanato-1 alcynes-1

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.

Hydrogen and Halogen Substitution

1.

The kinetics of the reaction of trans-β-chlorovinylmercury chloride with iodine was studied in nonpolar solvents-carbon tetrachlorine and benzene.




2.

In nonpolar solvents the reaction proceeds without conservation of the geometrical configuration. Each of the isomers ofβ-chlorovinylmercury chloride gives the same equimolar mixture of trans- and cis-1,2-chloroiodoethylenes.

Study of electrophilic substitution reactions at the olefinic carbon atom Communication 4. Kinetics and stereochemistry of the reaction of cis-and trans-β-chlorovinyl-mercury chlorides with iodine in carbon tetrachloride and benzene

1.

The stereochemistry of the reaction of the isomeric ω-styrylmercury bromides with bromine in various solvents was studied.




2.

In dimethyl sulfoxide (SEl mechanism) the reaction goes with a retention of the geometric configuration, while in C6H6 and CCl4 (sR mechanism) the configuration is not retained.

Stereochemistry of the reaction of the cis-trans isomers of styrylmercury bromide with bromine

1.

A study has been made of the reaction of trans-β-chlorvinylmercury chloride with iodine in excess cadmium iodide in 85% dioxane.




2.

The over-all order of the reaction is equal to two. It is first-order for each of the components. The rate constants of the second-order reaction have been determined at various temperatures.




3.

The following parameters have been found for the Arrhenius equation: E=13.6 kcal/mole, log10A=10.0, and activation entropy ΔS=−12.8 entropy units at 25°.




4.

A study has been made of the stereochemistry of the reaction. Under the conditions used, the reaction proceeds with strict conservation of configuration.

Study of the electrophilic substitution reaction at an olefine carbon atom

1.

The kinetics of the reaction of trans-,β-chlorovinyl mercury chloride with iodine in dimethyl sulfoxide was studied.




2.

The reaction, with a summary of first order, is first order with respect to the organomercury and zero order with respect to iodine.




3.

The parameters of the Arrhenius equation were determined and the entropy of activation was calculated.




4.

The stereochemistry of the process was studied for both isomers. Under the conditions used, the reaction proceeds with a strict conservation of geometrical configuration.

Study of the reactions of electrophilic substitution at the olefinic carbon atom Communication 5. Kinetics and stereochemistry of the reaction of trans-β-chlorovinylmercury chloride with iodine in dimethyl sulfoxide

V. I. Karpov

Papers

Study of electrophilic substitution reactions at the olefinic carbon atom Communication 4. Kinetics and stereochemistry of the reaction of cis-and trans-β-chlorovinyl-mercury chlorides with iodine in carbon tetrachloride and benzene

Stereochemistry of the reaction of the cis-trans isomers of styrylmercury bromide with bromine

Study of the electrophilic substitution reaction at an olefine carbon atom

Study of the reactions of electrophilic substitution at the olefinic carbon atom Communication 5. Kinetics and stereochemistry of the reaction of trans-β-chlorovinylmercury chloride with iodine in dimethyl sulfoxide