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Spontaneous Formation of Thiuram Disulfides in Solutions of Iron(III) Dithiocarbamates.

Bergendorff, Ola LU and Hansson, Christer LU (2002) In Journal of Agricultural and Food Chemistry 50(5). p.1092-1096
Abstract
Dithiocarbamates are used as pesticides and rubber additives. Dithiocarbamates are the reduced forms of thiuram disulfides and both of these groups of substances induce allergic contact dermatitis. The allergic cross-reactivity pattern between dithiocarbamates and thiurams is unclear. The aim of this study was to investigate why these cross-reactions occur sometimes but not always. HPLC-analysis of buffer solutions of iron(III) dithiocarbamates demonstrated that thiuram disulfides were formed spontaneously and rapidly in high yield. No such oxidation was observed in solutions of copper(II), zinc(II), or sodium dithiocarbamates. However, sodium diethyldithiocarbamate and zinc diethyldithiocarbamate were oxidized in buffer solution when... (More)
Dithiocarbamates are used as pesticides and rubber additives. Dithiocarbamates are the reduced forms of thiuram disulfides and both of these groups of substances induce allergic contact dermatitis. The allergic cross-reactivity pattern between dithiocarbamates and thiurams is unclear. The aim of this study was to investigate why these cross-reactions occur sometimes but not always. HPLC-analysis of buffer solutions of iron(III) dithiocarbamates demonstrated that thiuram disulfides were formed spontaneously and rapidly in high yield. No such oxidation was observed in solutions of copper(II), zinc(II), or sodium dithiocarbamates. However, sodium diethyldithiocarbamate and zinc diethyldithiocarbamate were oxidized in buffer solution when ferric salt was added. The influence of different metal ions on the oxidation reaction is probably an explanation for the cross-reactivity patterns seen between dithiocarbamates and thiurams. These findings also show that careful handling is necessary in analytical and biological studies with solutions of iron(III) dithiocarbamates. Oxidation of dithiocarbamates in aqueous buffer at physiological pH has not been shown before. (Less)
Please use this url to cite or link to this publication:
author
organization
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type
Contribution to journal
publication status
published
subject
keywords
Kinetics, Hydrogen-Ion Concentration, Industrial/*chemistry, Chromatography, High Pressure LiquidFungicides, Oxidation-Reduction
in
Journal of Agricultural and Food Chemistry
volume
50
issue
5
pages
1092 - 1096
publisher
The American Chemical Society
external identifiers
  • wos:000173995400025
  • pmid:11853487
  • scopus:0037180972
ISSN
0021-8561
DOI
10.1021/jf011143n
language
English
LU publication?
yes
id
82ea46fa-2887-418a-a820-7e374bb02f72 (old id 105894)
alternative location
http://www.ncbi.nlm.nih.gov:80/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=11853487&dopt=Abstract
date added to LUP
2007-07-02 16:54:42
date last changed
2017-01-01 04:24:37
@article{82ea46fa-2887-418a-a820-7e374bb02f72,
  abstract     = {Dithiocarbamates are used as pesticides and rubber additives. Dithiocarbamates are the reduced forms of thiuram disulfides and both of these groups of substances induce allergic contact dermatitis. The allergic cross-reactivity pattern between dithiocarbamates and thiurams is unclear. The aim of this study was to investigate why these cross-reactions occur sometimes but not always. HPLC-analysis of buffer solutions of iron(III) dithiocarbamates demonstrated that thiuram disulfides were formed spontaneously and rapidly in high yield. No such oxidation was observed in solutions of copper(II), zinc(II), or sodium dithiocarbamates. However, sodium diethyldithiocarbamate and zinc diethyldithiocarbamate were oxidized in buffer solution when ferric salt was added. The influence of different metal ions on the oxidation reaction is probably an explanation for the cross-reactivity patterns seen between dithiocarbamates and thiurams. These findings also show that careful handling is necessary in analytical and biological studies with solutions of iron(III) dithiocarbamates. Oxidation of dithiocarbamates in aqueous buffer at physiological pH has not been shown before.},
  author       = {Bergendorff, Ola and Hansson, Christer},
  issn         = {0021-8561},
  keyword      = {Kinetics,Hydrogen-Ion Concentration,Industrial/*chemistry,Chromatography,High Pressure LiquidFungicides,Oxidation-Reduction},
  language     = {eng},
  number       = {5},
  pages        = {1092--1096},
  publisher    = {The American Chemical Society},
  series       = {Journal of Agricultural and Food Chemistry},
  title        = {Spontaneous Formation of Thiuram Disulfides in Solutions of Iron(III) Dithiocarbamates.},
  url          = {http://dx.doi.org/10.1021/jf011143n},
  volume       = {50},
  year         = {2002},
}