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NOT FOR PUBLICATION JUL 17 2012

MOLLY C. DWYER, CLERK
UNITED STATES COURT OF APPEALS U.S. C O U R T OF APPE ALS

FOR THE NINTH CIRCUIT

CELESTE GONZALES GOMEZ, No. 08-74682

Watch Movies Online Shortbus Dublado.Determination of the first-order rate constant for the photo-induced irreversible oxidation of dopamine quinone by singlet oxygen: evidence for the absence of radical intermediates in the process.
The main reaction involved in the photo-induced oxidation of dopamine-o-quinone is supposed to be the oxidation of the exocyclic amino group of the quinone followed by hydrolysis of the N-O bond. In the present paper, we evaluate the validity of this hypothesis by measuring the first-order rate constant for the photo-induced oxidation of dopamine-o-quinone by singlet oxygen, k, by the use of stopped-flow spectrophotometry and computer kinetic analysis. The results obtained by the two methods were indistinguishable and yielded values for k of 0.019 M(-1) s(-1) at 293 K and of 0.0086 M(-1) s(-1) at 293 K for pH 9.0. A comparison with the corresponding values obtained in the presence of radical traps such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and 4,4,5,5-tetramethyl-1-pyrrolidine-N-oxyl (TPROXYL) suggests that the dopamine-o-quinone oxidation is not a radical chain reaction but that it proceeds via a less reactive intermediate. We also present evidence for the absence of radical intermediates in the oxidation process.The halogenated phenolic products of crotonaldehyde are important intermediates in the manufacture of insecticides, herbicides, and plant growth regulators, as discussed in U.S. Pat. No. 4,209,532 and U.S. Pat. No. 4,686,262.
One of the problems associated with the manufacture of halogenated phenolic compounds is the formation of by-products which are themselves undesirable. In the case of the phenoxy and phenyl acetonitrile compounds, a by-product is the 3-methyl-3-phenyl butanenitrile. In the case of the phenyl cyclohexanone compounds, a by-product is 3-methyl-3-phenyl hexanenitrile.
In the case of a mixed phenoxy-acetonitrile compound, such as 3-chlorophenoxy-3-methyl acetonitrile, a by
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