A process for the preparation of a compound of the sterically hindered alkoxyamine class is described, the process comprises the step of alkylating a sterically hindered
hydroxylamine compound to a corresponding sterically hindered alkoxyamine by reacting said sterically hindered
nitroxyl compound with a compound capable of producing a carbon-central
alkyl radical, typically a territorial or secondary
alkyl radical, the compounds capable of generating carbon-center
alkyl radicals are selected from thermal radical initiators that form radical species in the temperature range of 40 DEG C to 200 DEG C, and from photoinitiators that undergo
light excitation when irradiated with UV light or visible light in the range of 180 to 700 nm, in particular UV light in the range of 180 to 380 nm, the compounds capable of generating carbon center
alkyl radicals are typically selected from the class of organic peroxides, azo compounds, benzoyl derivatives,
benzophenone derivatives,
thioxanthone derivatives,
benzoin derivatives, benzoyl
phosphine oxide derivatives, and the like. The invention relates to a
peroxide, for example, selected from the group consisting of diacyl peroxides of formula (A), peracid esters of this formula (A), and
oxalic acid peracid esters of formula (D) R-CO-O-O-Z-R (A), r-Z ''-X-CO-CO-O-O-Z''-R (D) wherein each R independently represents a primary or secondary alkyl or cycloalkyl group, preferably comprising from 1 to 15 carbon atoms, and X is
oxygen-O-or peroxy-O-O-, Z represents CO or an alkylene group bonded to a
quaternary carbon atom, the
quaternary carbon atom being an alkylene group of formula (C) R '-C-R' (C), wherein each R'is selected from alkyl groups having 1 to 15 carbon atoms, and Z "represents the alkylene group bonded to a
quaternary carbon atom having the formula (C). The described process produces the corresponding O-alkylated derivatives of the sterically hindered hydroxylamines, typically compounds of the class referred to as N-O-alkyl HALS, with very
high selectivity and conversion and without the need for the use of catalysts, in particular
metal catalysts.