Kinetic parameters of the cyclization and decyclization reactions of nitrogen- and oxygen-containing radicals
Tóm tắt
The intersecting parabolas model is used to analyze experimental data for the following radical cyclization and decyclization reactions: RCH=CH(CH2)
n
N·R1 → cyclo-[NR1CH(CH2)
n
]C·HR, R(CH2)2OOCH2C·HR → cyclo-[RCHOCH2] + RCH2CH2O·, cyclo-[(CH2)
n
OOCHC· HR] → cyclo-[RCHOCH](CH2)
n
O·, cyclo-[(CH2)
n
OC·RO] → RC(O)O(CH2)
n − 1C·H2, and cyclo-[(CH2)
n
CHO·] → CH(O)(CH2)
n − 1C·H2. The activation energy of the thermally neutral reaction (E
e,0) is calculated for each class of reactions. E
e,0 depends on the electronegativity of the heteroatom Y of the reaction center C
$$\underline \cdots$$
C...Y, the force constants of the reacting bonds, and the strain energy of the ring formed. For the cyclization and decyclization of six-membered rings, the empirical relationship between the elongation of the reacting bonds in the transition state (r
e) and the difference in electronegativity (ΔEA) between the C and Y atoms (Y = C, N, O) has the form r
e × 1011, m = 3.83 − 0.0198(ΔEA, kJ/mol).
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