Diisopropyl ketone oxygen

First the interaction of selected tetramethylpiperidine (TMP) derivatives with radicals arising from Norrish-type I cleavage of diisopropyl ketone under oxygen was studied. These species are most probably the isopropyl peroxy and isobutyryl peroxy radicals immediately formed after a-splitting of diisopropyl ketone and subsequent addition of O2 to the initially generated radicals. Product analysis and kinetic studies showed that the investigated TMP derivatives exercise a marked controlling influence over the nature of the products formed in the photooxidative process. The results obtained point to an interaction between TMP derivatives and especially the isobutyryl peroxy radical. 

Diisopropyl ketone photolysis under exclusion of oxygen... 

Diisopropyl ketone photolysis in the presence of oxygen and IZNO as additive... 

Irradiation of diisopropyl ketone under oxygen in the presence of the hindered piperidine II likewise results in formation of isobutyric acid, acetone and small amounts of isopropanol. At the same time the amine is quantitatively oxidized to the corresponding nitroxide I (Fig. 7, reaction (17)) ... 

The effect of substituting oxygen-18 for oxygen-16 in the infra-red spectra of a molecule should be detectable, and has been calculated by Halmann and Pinchas (1958a) to be of the order of 40 cm. in carbonyl compounds. Shifts of this order have been found in 0 -labeled benzo-phenone (Halmann and Pinchas, 1958a), triphenylphosphine oxide (Halmann and Pinchas, 1958b), and also in nitromethane (Halmann and Pinchas, 1960), benzamide, Af-methyl and Af,Af -dimethyl benzamide, benzoic acid, benzoyl chloride and methyl benzoate, diphenylsulfoxide and sulfone (Pinchas, Samuel and Weiss-Broday, 1961, and previous papers), diisopropyl ketone (Karabatsos, 1960). 

As an alternative to the manner in which the stability of the intermediate species 277 is raised by increasing electron input to phosphorus, a reduction in nucleophilic character of the original carbonyl oxygen might be contemplated. In this respect, it may be noted that a reaction between the lithium salt of diisopropyl (fluoromethyl)phosphonate and the ketones R R CO affords both the alkene (s) predicted from the Wittig mechanism, but also the alcohols (Pr 0)2p(0)CHFC(0H)R R as mixtures of diastereoisomers, distinguishable spectroscopically but not separable ... 

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