The reactivity of the butoxy and 3-methylcyclohexyl radicals, as representatives of alkoxy radicals, was studied by MNDO-PM3 semiempirical MO method. In both cases it was found that the oxy radical underwent easily 1,5-H migration giving a δ-hydroxyalkyl radical. The hydrogen abstraction reaction goes through two transition states. The first transition state (TS) with short O-H distance has an energy very similar to, or lower than, the TS for 1,5-H migration. The second TS is of higher energy and is much product-like. The overall cyclisation reaction has a high activation energy (over 40 kcal mol-1), and is therefore unlikely to occur spontaneously. Most likely, the cyclisation step needs assistance of some other surrounding molecules to speed up the reaction.
Source:
Journal of the Chemical Society, Perkin Transactions 2, 1994, 4, 877-881
TY - JOUR
AU - Juranić, Ivan
AU - Mihailović, Mihailo Lj.
AU - Dabović, Milan
PY - 1994
UR - http://cer.ihtm.bg.ac.rs/handle/123456789/2710
AB - The reactivity of the butoxy and 3-methylcyclohexyl radicals, as representatives of alkoxy radicals, was studied by MNDO-PM3 semiempirical MO method. In both cases it was found that the oxy radical underwent easily 1,5-H migration giving a δ-hydroxyalkyl radical. The hydrogen abstraction reaction goes through two transition states. The first transition state (TS) with short O-H distance has an energy very similar to, or lower than, the TS for 1,5-H migration. The second TS is of higher energy and is much product-like. The overall cyclisation reaction has a high activation energy (over 40 kcal mol-1), and is therefore unlikely to occur spontaneously. Most likely, the cyclisation step needs assistance of some other surrounding molecules to speed up the reaction.
PB - Royal Society of Chemistry
T2 - Journal of the Chemical Society, Perkin Transactions 2
T1 - Cyclisation of alkoxy radicals. A semiempirical MNDO-PM3 study
IS - 4
SP - 877
EP - 881
ER -
@article{
author = "Juranić, Ivan and Mihailović, Mihailo Lj. and Dabović, Milan",
year = "1994",
url = "http://cer.ihtm.bg.ac.rs/handle/123456789/2710",
abstract = "The reactivity of the butoxy and 3-methylcyclohexyl radicals, as representatives of alkoxy radicals, was studied by MNDO-PM3 semiempirical MO method. In both cases it was found that the oxy radical underwent easily 1,5-H migration giving a δ-hydroxyalkyl radical. The hydrogen abstraction reaction goes through two transition states. The first transition state (TS) with short O-H distance has an energy very similar to, or lower than, the TS for 1,5-H migration. The second TS is of higher energy and is much product-like. The overall cyclisation reaction has a high activation energy (over 40 kcal mol-1), and is therefore unlikely to occur spontaneously. Most likely, the cyclisation step needs assistance of some other surrounding molecules to speed up the reaction.",
publisher = "Royal Society of Chemistry",
journal = "Journal of the Chemical Society, Perkin Transactions 2",
title = "Cyclisation of alkoxy radicals. A semiempirical MNDO-PM3 study",
number = "4",
pages = "877-881"
}
Juranić I, Mihailović ML, Dabović M. Cyclisation of alkoxy radicals. A semiempirical MNDO-PM3 study. Journal of the Chemical Society, Perkin Transactions 2. 1994;(4):877-881
Juranić, I., Mihailović, M. Lj.,& Dabović, M. (1994). Cyclisation of alkoxy radicals. A semiempirical MNDO-PM3 study.
Journal of the Chemical Society, Perkin Transactions 2Royal Society of Chemistry.(4), 877-881.
Juranić Ivan, Mihailović Mihailo Lj., Dabović Milan, "Cyclisation of alkoxy radicals. A semiempirical MNDO-PM3 study", no. 4 (1994):877-881
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