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Determination of the isomerization rate constant HOCH2CH2CH2CH(OO·)CH3 →HOC·HCH2CH2CH(OOH)CH3. Importance of intramolecular hydroperoxy isomerization in tropospheric chemistry

✍ Scribed by Olivier Perrin; Adolphe Heiss; Krikor Sahetchian; Lucien Kerhoas; Jacques Einhorn

Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
234 KB
Volume
30
Category
Article
ISSN
0538-8066

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✦ Synopsis

The rate constant of the title reaction is determined during thermal decomposition of di-n-pentyl peroxide in oxygen over the temperature range The C H O9OC H 463-523 K. 5 11 5 11 pyrolysis of di-n-pentyl peroxide in O 2 /N 2 mixtures is studied at atmospheric pressure in passivated quartz vessels. The reaction products are sampled through a micro-probe, collected on a liquid-nitrogen trap and solubilized in liquid acetonitrile. Analysis of the main compound, peroxide was carried out by GC/MS, GC/MS/MS [electron impact EI and NH 3 chemical C H O , 5 10 3

ionization CI conditions]. After micro-preparative GC separation of this peroxide, the structure of two cyclic isomers (3S*,6S*)3␣-hydroxy-6-methyl-1,2-dioxane and (3R*,6S*)3␣-hydroxy-6methyl-1,2-dioxane was determined from 1 H NMR spectra. The hydroperoxy-pentanal OHC 9(CH 2 ) 2 9 CH(OOH)9 CH 3 is formed in the gas phase and is in equilibrium with these two cyclic epimers, which are predominant in the liquid phase at room temperature. This peroxide is produced by successive reactions of the n-pentoxy radical: a first one generates the CH 3 CиH(CH 2 ) 3 OH radical which reacts with O 2 to form CH 3 CH(OOи)(CH 2 ) 3 OH; this hydroxyperoxy radical isomerizes and forms the hydroperoxy HOCиH(CH 2 ) 2 CH(OOH)CH 3 radical.

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