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Solvolysis of Substituted Benzoyl Chlorides in Nonionic and Mixed Micellar Solutions.

Campos-Rey, P; Cabaleiro-Lago, Celia LU and Hervés, P (2010) In The Journal of Physical Chemistry Part B 114(44). p.14004-14011
Abstract
The solvolysis of substituted benzoyl chlorides is sensitive both to substituent electronic effects and to medium effects. The solvolysis reactions of substituted benzoyl chlorides have been analyzed in the presence of nonionic micelles. The reaction is inhibited or catalyzed depending on the reaction mechanism, dissociative or associative, respectively. The micellar effects observed can be related to the low water content and low polarity of the interface as well as an increase of the nucleophilic character of the interfacial water. Moreover, the effect of the micellar surface charge on the solvolysis mechanism with high associative character was systematically studied. Mixed micelles of nonionic-ionic surfactants with a variable ionic... (More)
The solvolysis of substituted benzoyl chlorides is sensitive both to substituent electronic effects and to medium effects. The solvolysis reactions of substituted benzoyl chlorides have been analyzed in the presence of nonionic micelles. The reaction is inhibited or catalyzed depending on the reaction mechanism, dissociative or associative, respectively. The micellar effects observed can be related to the low water content and low polarity of the interface as well as an increase of the nucleophilic character of the interfacial water. Moreover, the effect of the micellar surface charge on the solvolysis mechanism with high associative character was systematically studied. Mixed micelles of nonionic-ionic surfactants with a variable ionic content were prepared and characterized regarding charge and polarity. A correlation between the net charge of the micelles and the rate constants at the micellar interface was observed. The results suggest that the transient state for this mechanism is highly stabilized in a positively charged environment while the negative surface given by anionic micelles strongly inhibit the solvolysis reaction. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
114
issue
44
pages
14004 - 14011
publisher
The American Chemical Society
external identifiers
  • wos:000283703400011
  • pmid:20954753
  • scopus:78149234768
ISSN
1520-5207
DOI
10.1021/jp107538v
language
English
LU publication?
yes
id
3e1f3aea-3d8e-4ed0-834e-9848ff9138c5 (old id 1711048)
date added to LUP
2010-11-05 11:13:10
date last changed
2018-05-29 11:12:27
@article{3e1f3aea-3d8e-4ed0-834e-9848ff9138c5,
  abstract     = {The solvolysis of substituted benzoyl chlorides is sensitive both to substituent electronic effects and to medium effects. The solvolysis reactions of substituted benzoyl chlorides have been analyzed in the presence of nonionic micelles. The reaction is inhibited or catalyzed depending on the reaction mechanism, dissociative or associative, respectively. The micellar effects observed can be related to the low water content and low polarity of the interface as well as an increase of the nucleophilic character of the interfacial water. Moreover, the effect of the micellar surface charge on the solvolysis mechanism with high associative character was systematically studied. Mixed micelles of nonionic-ionic surfactants with a variable ionic content were prepared and characterized regarding charge and polarity. A correlation between the net charge of the micelles and the rate constants at the micellar interface was observed. The results suggest that the transient state for this mechanism is highly stabilized in a positively charged environment while the negative surface given by anionic micelles strongly inhibit the solvolysis reaction.},
  author       = {Campos-Rey, P and Cabaleiro-Lago, Celia and Hervés, P},
  issn         = {1520-5207},
  language     = {eng},
  number       = {44},
  pages        = {14004--14011},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Solvolysis of Substituted Benzoyl Chlorides in Nonionic and Mixed Micellar Solutions.},
  url          = {http://dx.doi.org/10.1021/jp107538v},
  volume       = {114},
  year         = {2010},
}