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Solvent effects on the ionic decomposition of t-butylperoxyformate : and empirical correlation of rate with solvent properties

University of British Columbia

Rate constants for the pyridine catalyzed ionic decomposition of t-butylperoxyformate (TBF) are measured in 15 non-hydroxylic solvents. The second order rate constants varied by a factor of 40 from the "slowest" solvent, tetra-chloroethylene, to the "fastest", 1,2-dichloroethahe. Ten different empirical equations are found and their ability to correlate the rate constants with bulk solvent properties is compared. The best of the ten equations involves the polarizability and dipole moment of the solvent as follows. log krel = 1.207 (no²-1/no²+2) + 3.99 μ + 0.003 -3 The rate constants for TBF decomposition in other non-hydroxylic solvents are calculated by the empirical equations and are compared with values previously reported. The average deviation of the log k is 0.22. The rate constants for the reaction of methyl iodide with triethylamine are calculated from solvent properties and the values compared to literature values. In this case the average deviation of the log k is 0.31.

Text

2011-11-02

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http://hdl.handle.net/2429/38659

Chemistry

University of British Columbia

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