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Title: Neighbouring group participation in the gas-phase pyrolysis kinetics of 4-(N-methyl-N-phenylamino)-1-butyl acetate and 4-(N-phenylamino)-1-butyl acetate
Journal: J. Phys. Org. Chem.
Volume: 13
Page(s): 266 - 271
Year: 2000
Reference type: Journal article
Squib: 2000CHU/ALA266-271
Reaction:
C6H5NHCH2CH2CH2CH2OC(O)CH3 → aniline + CH3C(O)OH + 1,3-Butadiene
Reaction order:
1
Temperature:
633 - 673
K
Pressure: 3.17E-2 - 0.13 bar
Rate expression:
1.12x1011 [±9.26x1011 s-1] e-187500 [±6300 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:
By end product analysis
Analytical technique:
Pressure measurement
Comments:
Overall kinetics were determined by following pressure vs. time with the individual channels determined by GC product analysis. A free radical inhibitor (toluene) was added in varying amounts. No induction period was observed and varying the surface/volume ratio had no effect on the kinetics in seasoned reactors.
Uncertainties are precision only and are at the 90% confidence level.
The authors suggest that aniline is formed in the secondary decomposition of the initial product in the reaction C6H5NHCH2CH=CHCH3 -> PhNH2 + 1,3-butadiene. However the rate constants appear to be derived on the assumption that aniline is an initial product (they do not clearly indicate the procedure, but the sum of the rate constants for the 3 channels equals k(total) exactly, which is not the case if secondary kinetics are used for one channel). It is thus unclear if their mechanism or rate constants are wrong. Note that the aniline could be formed directly in the reaction:
4-(N-phenylamino)-1-butyl acetate -> aniline + H2C=CHCH2CH2OC(O)CH3.
The authors make no mention of 3-butene acetate as a product however, nor do they indicate if butadiene was found as a product or merely assumed.
View full bibliographic record.
Rate constant values calculated from the Arrhenius expression:
| T (K) | k(T) [s-1] |
|---|---|
| 633 | 3.79E-5 |
| 650 | 9.59E-5 |
| 673 | 3.10E-4 |