Electrophilic aromatic substitution

Nasielski, Jacques; Buchman, Ouri; Grosjean, Mireille; Jauquet, M.

doi:10.1016/s0022-328x(00)85306-1

Cited by 11 publications

(2 citation statements)

References 17 publications

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“…Several reports describe the reactions of substituted phenyltrimethyltin compounds in anhydrous methanol with the electrophiles acetic acid, hydrochloric acid, iodine and bromine. Previously we reported that SO 2 fits into the electrophile activity series for this reaction system:

C {boldH}_{bold3} COOH < S {boldO}_{bold2} < HCl < < {boldI}_{bold2} < < B {boldr}_{bold2}

…”

Section: The Nature Of the Transition State In Sulphur Dioxide Insertmentioning

confidence: 99%

“…By using data characterising the {SO 2 ―benzene} solvent system, the present study reexamines the kinetics in benzene, and from the derived solvent effects on the rate of insertion, provides a clearer description of the transition states (TS) in the polar methanol and nonpolar benzene solvents. Previously published data of the electrophilic cleavage of the carbon―tin bond in a range of substituted phenyltin compounds in methanol and aqueous solutions have been examined to shed light on the effect of solvent polarity on the insertion transition state. We have used molecular orbital (MO) computations to identify details of TS that are otherwise not available.…”

Section: Introductionmentioning

confidence: 99%

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Sulphur dioxide insertion into tin―carbon bonds: solvent effects and the nature of the transition state

Fong¹,

Kitching

2013

J of Physical Organic Chem

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Data describing the insertion of sulphur dioxide into the carbon―tin bond of a range of substituted phenyltrimethyltin compounds in methanol and benzene solvents have been reconsidered. The reaction in methanol is cleanly second order, but the reaction in benzene has both a second‐order and third‐order component, the latter ascribable to an initial equilibrium formation of a SO2 complex with the phenyl ring followed by the insertion of a second SO2 molecule into the carbon–tin bond. Molecular orbital calculations have identified the transition states (TS) and the favoured reaction pathways for the second‐order and third‐order reaction pathways in benzene. The effects of solvents on TS and enthalpies of reaction have also been examined. New insights into the types of TS involved in electrophilic substitution reactions are revealed. Copyright © 2013 John Wiley & Sons, Ltd.

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