Kinetic Studies of the Reactions of Atomic Chlorine with N-Methylmethylenimine and 1,3,5-Trimethylhexahydro-1,3,5-triazine

Article abstract of DOI:10.1021/j100119a034

The reaction of Cl + CH3NH=CH2 -> HCl + CH2=NCH2* has been studied with the very low pressure (VLPR) technique in the temperature range 303-363 K.The rate constant for the forward reaction is given by the expression k₁ = (7.54 +/- 1.60) x 10^-11 exp(-826 +/- 240/RT) cm³ molecule^-1 s^-1 where R is expressed in cal mol^-1 K^-1.The rate constant for the reaction of atomic chlorine with 1,3,5-trimethylhexahydro-1,3,5-triazine was also measured in the temperature range 303-363 K and found to be k₄ = (5 +/- 2) x 10^-10 cm³ molecule^-1 s^-1 at all temperatures.The conventional transition state theory suggests that the TS for reaction 1 is bent with the Cl atom forming a Cl***H***C angle ca. 160 deg, and placed away from the nitrogen lone pair.The heat of formation of CH2=NCH2* radical is ca. 63 +/- 3 kcal/mol, and reaction 1 is exothermic by ca. 5 +/- 3 kcal/mol.