Study of ion pairing in the solvolysis reactions of p-substituted t-cumyl chlorides using chlorine kinetic isotope effects

Thesis/Dissertation · Fri Jan 01 04:00:00 EST 1982

OSTI ID:5698369

Greer, E C

The solvolysis and reaction with azide of p-methyl, p-nitro, and unsubstituted t-cumyl chloride in aqueous acetone were investigated using kinetics, chlorine kinetic isotope effects (KIE), and product analysis by nmr. As determined by the observed kinetics, KIE, and increase in KIE on adding azide, p-methyl and p-hydrogen-t-cumyl chloride react via an ion pairing mechanism. The KIE in 90% aqueous acetone were: p-methyl (-5.0/sup 0/C) 1.0101 at f = 0.59 without and 1.0122 at f = 0.63 (0.0250 M with 0.0565 M azide); p-hydrogen (25.0/sup 0/C) 1.0101 at f = 0.57 and 1.0108 at f = 0.55 (0.0311 M with 0.0599 M azide). The increase in KIE with added azide is attributed to ion pair trapping by the azide. When temperature-corrected to 25/sup 0/C, the p-methyl results become 1.0091 and 1.0112, respectively. When compared with the unsubstituted compound, these values indicate the transition state of the p-methyl is more reactant-like, as predicted by the Hammond Postulate.

• Research Organization: Wisconsin Univ., Madison (USA)
• OSTI ID: 5698369
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
AROMATICS
AZIDO COMPOUNDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
EXPERIMENTAL DATA
INFORMATION
ION PAIRS
ISOTOPE EFFECTS
KINETICS
MAGNETIC RESONANCE
NITROGEN COMPOUNDS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
REACTION KINETICS
RESONANCE
SOLVOLYSIS