Elucidation of the Nucleophilic Potential of Diazocyclopentadiene

Manfred Hartnagel; Armin R. Ofial; Herbert Mayr

doi:10.1055/s-0041-1737327

Synthesis, Table of Contents

Synthesis 2023; 55(02): 354-358
DOI: 10.1055/s-0041-1737327

paper

Special Issue dedicated to Prof. Alain Krief

Elucidation of the Nucleophilic Potential of Diazocyclopentadiene

Manfred Hartnagel

,

Armin R. Ofial

,

Herbert Mayr ∗

Abstract

All articles of this category

Dedicated to Professor Alain Krief on the occasion of his 80th birthday

Abstract

Diazocyclopentadiene reacts with benzhydrylium ions (Ar₂CH⁺) to give 2,5-dibenzhydryl-substituted diazocyclopentadienes. The kinetics have been determined photometrically in dichloromethane under pseudo-first-order conditions using diazocyclopentadiene in excess. Plots of the second-order rate constants (log k ₂) versus the electrophilicity parameters E of the benzhydrylium ions gave the nucleophilicity parameter N = 4.84 and susceptibility s _N = 1.06 for diazocyclopentadiene according to the correlation log k(20 °C) = s _N(E + N). Diazocyclopentadiene thus has a similar nucleophilic reactivity as pyrrole. Previously reported electrophilic substitutions of diazocyclopentadiene are rationalized by these parameters and new reaction possibilities are predicted.

Key words

diazo compounds - kinetics - linear free energy relationships - nucleophilicity - reactivity scales

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References

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