Environmental Science and Technology p. 528 - 536 (1995)
Update date:2022-08-11
Topics:
Atkinson
Aschmann
The products of the gas-phase reactions of the OH radical with 2,4- dimethyl-2-pentanol and 3,5-dimethyl-3-hexanol in the presence of NO(x) have been determined at atmospheric pressure of air and 296 ± 2 K to assess the occurrence and importance of alkoxy radical isomerization. The products identified and quantified and their formation yields were as follows: from 2,4-dimethyl-2-pentanol: acetone, 0.92 ± 0.15; 2-methylpropanal, 0.209 ± 0.022; 4-methyl-2-2-pentanone, 0.046 ± 0.008; and 4-hydroxy-4-methyl-2- pentanone, 0.116 ± 0.018; from 3,5-dimethyl-3-hexanol: acetone, 0.120 ± 0.029; 2-butanone, 0.275 ± 0.021; 2-methylpropanal, 0.169 ± 0.016; 4- methyl-2-pentanone, 0.161 ± 0.012; and 4-hydroxy-4-methyl-2-pentanone, 0.250 ± 0.023. The observed formation of 4-hydroxy-4-methyl-2-pentanone provides conclusive evidence for the occurrence of isomerization of the alkoxy radicals (CH3)2C(OH)CH2C(O)(CH3)2 and CH3CH2C(CH3)(OH)CH2C(O)(CH3)2 via 1,5-H shifts. The reaction mechanisms are discussed, and isomerization rate constants for 1,5-H-atom abstraction from the -CH3 and -CH2- groups in the RCH2C(CH3)(OH)- CH2C(O)(CH3)2 alkoxy radicals (R = H and CH3) are derived.
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