Eight defined primary and secondary alkylhydroperoxides were decomposed in n-alkanes as the solvent, mostly in the presence of manganese stearate. In all cases the corresponding alcohols and carbonyl compounds were formed as the main products with yields of 60-90 %. Besides, difunctional products were formed by an intramolecular H-transfer in the alkoxy radicals corresponding to the starting hydroperoxides. Products possibly formed by an intramolecular H-transfer in the corresponding alkylperoxy radical could be found only in the case of 4-methyl-2-hydroperoxy pentane. The amount of products formed by intramolecular H-transfer depended on the nature of the C-H bond in &position to the original hydroperoxy group and lay between 4 % (primary C-H in the case of 4-hydroperoxy heptane) and 13 % (tertiary C-H in the case of 2hydroperoxy-5-methyl hexane) with respect to the starting hydroperoxide.The amount of products formed by oxidative attack of the alkoxy and alkylperoxy radicals at the normal paraffins used as the solvents was unexpectedly low (always less than 10 % with respect to the starting hydroperoxide).An increment system is proposed for the calculation of I3C-nmr shifts in alkyl hydroperoxides. 'I) 3 m column with 10 % Triton X-I00 on Chromatone HMDS; 130 "C; 2.4 Ih-' H,: katharometer "proportion of heptane-1,4-diol to the sum of the nonanols
A facile and efficient synthesis of novel seven-membered heterocyclic derivatives containing 3-aminoazepan-2-one backbone is described using 1,4-protected piperazine-2,5-diones and alkynes as starting materials. The reaction may undergo Michael addition, unusual nucleophilic attack to an amide group, and keto-enol tautomerization. The reaction showed different reactivity when using substrates with different protecting groups: it had higher efficiency when using either alkanoyl-protecting group with cesium carbonate as the base, or benzoyl-protecting group with triethylamine as the base, but no reaction when using benzyl or allyl protecting groups with a variety of bases (Et
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