The yeast Rhodotorula mucilaginosa was able to grow in media containing triethanolamine or diethanolamine as the sole nitrogen source. During growth in the presence of triethanolamine, extracts of yeast cells contained increased levels of cytochrome P-450 dependent monooxygenase which catalyzed the oxidative N-dealkylation of aminoalcohols. Formation of diethanolamine, ethanolamine and glyoxylate from triethanolamine was demonstrated, and the identity of the products was verified by thin layer chromatography. These observations suggested the following scheme of triethanolamine catabolism: triethanolamine----diethanolamine + glycolaldehyde, diethanolamine----ethanolamine + glycolaldehyde, ethanolamine----NH3 + glycolaldehyde----glycolate----glyoxylate----glycerate pathway.

The primary oxidation stages of 3O2 model acyclic and cyclic alkanes and their subsequent triplet and singlet elementary events were studied for the first time by the DFT method with the density functional B3LYP and basis set 6-311++g(df,p). According to quantum chemical DFT calculations the C–H radical cleavage of the bonds of acyclic and cyclic alkanes upon interaction with 3O2 is almost completely thermodynamically shifted toward the initial state of the reaction system. This energy of primary oxidizing events explains the extremely low reactivity of saturated alkanes in comparison with asphaltene structural fragments under the conditions of SCF technology for the extraction of heavy oils and asphaltenes by a propane-butane mixture. It has been demonstrated that for all elementary acts of primary alkane oxidation the product of the direct reaction direction is not a free pair of radicals but a triplet hydrogen complex with a pronounced hydrogen bond between the hydroperoxyl radical and the radical form of the corresponding hydrocarbon. A new, previously not taken into account very exothermic (H = -29.25 – -30.77 kcal/mol) reaction direction is described which corresponds to triplet recombination of alkyl radicals and a hydroperoxyl radical in its oxygen-concentrated part. The products of this recombination are triplet forms of alkane hydroperoxides in which there is a fairly loosened triplet O---O bond with a length of 2.20-2.23 Å, which is ~0.72-0.77 Å more than bond length in the singlet state.

No abstract

ContentsI. Introduction 935 II. The influence of fluorine-containing substituents on the properties of the P(III) atom. Photoelectron 935 spectroscopic and electrochemical data III. Synthesis of fluoroalkoxy-derivatives of P(III) 938 IV. Reactions of fluoroalkyl phosphites 948 V. Conclusion 966 Abstract. The review surveys and gives a systematic account of the electronic structures, syntheses, and chemical properties of fluoroalkyl derivatives of trivalent phosphorus (phosphites, thiophosphites, and amidophophites). The methods of preparation and reactivities of fluoroalkyl phosphites are compared with those of unsubstituted phosphites. The bibliography includes 420 references.

No abstract