Linked Life Data

17894372

Source:http://linkedlifedata.com/resource/pubmed/id/17894372

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
5
pubmed:dateCreated
2008-3-4
pubmed:abstractText
The theoretical investigations were performed on the reaction mechanisms for the title reactions CH(3)C(O)CH(3) + Cl --> products (R1), CH(3)C(O)CH(2)Cl + Cl --> products (R2), CH(3)C(O)CHCl(2) + Cl --> products (R3), and CH(3)C(O)CCl(3) + Cl --> products (R4) by ab initio direct dynamics approach. Two different reaction channels have been found: abstract of the H atom from methyl (--CH(3)) group or chloromethyl (--CH(3-n)Cl(n)) group of chloroacetone and addition of a Cl atom to the carbon atom of the carbonyl group of chloroacetone followed by methyl or chloromethyl eliminations. Because of the higher potential energy barrier, the contribution of addition-elimination reaction pathway to the total rate constants is very small and thus this pathway is insignificant in atmospheric conditions. The rate constants for the H-abstraction reaction channels are evaluated by using canonical variational transition state theory incorporating with the small-curvature tunneling correction. Theoretical overall rate constants are in good agreement with the available experimental values and decrease in the order of k(1) > k(2) > k(3) > k(4). The results indicate that for halogenated acetones the substitution of halogen atom (F or Cl) leads to the decrease in the C--H bond reactivity and more decrease of reactivity is caused by F-substitution.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Apr
pubmed:issn
1096-987X
pubmed:author
pubmed:copyrightInfo
(c) 2007 Wiley Periodicals, Inc.
pubmed:issnType
Electronic
pubmed:day
15
pubmed:volume
29
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
809-19
pubmed:meshHeading
pubmed:year
2008
pubmed:articleTitle
Theoretical dynamic studies on the reactions of CH3C(O)CH3-nCl(n) (n = 0-3) with the chlorine atom.
pubmed:affiliation
Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun, Jilin, 130023, People's Republic of China.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't