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Author(s):   Herize, A.; Dominguez, R.M.; Rotinov, A.; Nunez, O.; Chuchani, G.
Title:   Gas-phase elimination kinetics of ethyl, isopropyl and tert-butyl N,N-diethylcarbamates. Application of Taft-Topsom correlation for substituents other than carbon at the acid side of organic ethyl esters
Journal:   J. Phys. Org. Chem.
Volume:   12
Page(s):   201 - 206
Year:   1999
Reference type:   Journal article
Squib:   1999HER/DOM201-206

Reaction:   (CH3CH2)2NCO(O)C(CH3)3 → (C2H5)2NH + iso-C4H8 + CO2
Reaction order:   1
Temperature:   493 - 553 K
Pressure:  2.27E-2 - 0.21 bar
Rate expression:   7.41x1012 [±6.6x1012 s-1] e-158600 [±6200 J/mole]/RT
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   None reported
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Thermal
Time resolution:   In real time
Analytical technique:   Pressure measurement
Overall kinetics were determined by following pressure vs. time, although the stoichiometry of the reaction was also confirmed by quantitative GLC analysis of the starting substrate and identification of the isobutene reaction product.

The authors suggest the reaction is a two-step process, first involving a molecular elimination to give the alkene + (C2H5)2NCO2H , followed by the rapid decomposition of the latter species to (C2H5)2NH and CO2. Uncertainties are precision only and are at the 90% confidence level.

View full bibliographic record.

Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [s-1]
493 1.19E-4
500 2.00E-4
525 1.23E-3
550 6.42E-3
553 7.58E-3