Cyanide ions reactions

Contents Introduction and Principles. - The Reaction of Dichlorocarbene With Olefins. - Reactions of Dichlorocarbene With Non-Olefinic Substrates. -Dibromocarbene and Other Carbenes. - Synthesis of Ethers. - Synthesis of Esters. - Reactions of Cyanide Ion. - Reactions of Superoxide Ions. - Reactions of Other Nucleophiles. - Alkylation Reactions. - Oxidation Reactions. - Reduction Techniques. - Preparation and Reactions of Sulfur Containing Substrates. -Ylids. - Altered Reactivity. - Addendum Recent Developments in Phase Transfer Catalysis. 

The same phenomenon, i.e. that the secondary a-deuterium KIE is determined by the changes in only the shorter reacting bond in the SN2 transition state rather than by the nucleophile-leaving group distance, has been found in a completely different reaction system. Matsson, Westaway and co-workers (Matsson et al., 1996) used ku/k14 carbon incoming nucleophile, chlorine leaving group (Hill and Fry, 1962), and ku/ku a-carbon (Fry, 1970) KIEs to model the transition states for a series of SN2 reactions between p-substituted benzyl chlorides and labelled cyanide ion (reaction (17)). 

The most important point about the alkyl halide reactivities in triphase catalysis is that the reactions which have the highest intrinsic rates are the most likely to be limited by intraparticle diffusion. The cyanide ion reactions which showed the greatest particle size and cross-linking dependence with 1-bromooctane had half-lives of 0.5 to 2 h and with benzyl bromide had half-lives of 0.13 to 0.75 h. The reactions of 1-bromooctane and of benzyl chloride which were insensitive to particle size and cross-linking had half-lives of 14 h and 3 h respectively. Practical triphase liquid/ liquid/solid catalysis with polystyrene-bound onium ions has intraparticle diffusional limitations. 

Carbon monoxide Ketone synthesis using cyanide ion Reactions with a-halo-carbonyl compounds Polyene Cyclisations Looking Forwards... 

While these results do not identify the reason the two methods of determining transition state structure predict very different transition states for the ethyl chloride-cyanide ion reaction, they do suggest that theory gives the more accurate transition state structure for the reaction. The following arguments support this view. 

Although the recently observed discrepancy between the transition state structure predicted by theory and by interpreting the experimental KIEs using the traditional methods appears to favor the transition state structure predicted by theory, it is worth noting that none of the 39 theoretical methods calculated all six KIEs that were measured for the ethyl chloride-cyanide ion reaction within the experimental error. Obviously there is a need for further investigations of the relationship between observed KIEs and transition state structure. 

Reaction with Cyanide Ion Reaction with Ilalide Ions Reaction with Amines Acetoxylation Reaction with Aromatics Reaction with Olefins Reaction with Ketones... 

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