The Direct Synthesis ofN-t-Alkyl-O-t-butylhydroxylamines fromt-Butyl Peroxybenzoate and the Lithium Salts of Primaryt-Alkylamines

The formation of azoxyalkanes in reactions of some organometallic reagents with N-nitroso-O,N-dialkylhydroxylamines: the nonphotochemical synthesis of an acyclic (E)-azoxyalkane

“…Of the hydroxylamines, 0,N-dimethylhydroxylamine hydrochloride was obtained as a commercial product (Aldrich Chemical Co.), the others were synthesized by a standard procedure (10) or the sodium cyanoborohydride reduction (11) of the 0-alkyl oximes (themselves obtained by condensing the appropriate 0-alkylhydroxylamines and aldehydes). Exceptional was 0,N-di-tert-butylhydroxylamine, for which we had to devise a special synthesis (12).…”

O2‐Mediated Oxidation of Aminoboranes through 1,2‐N Migration

“…[22] Furthermore,i nb oth control experiments with organic peroxides (Scheme 2e/f, O-tert-butyl) and in all other reactions throughout the study (O-ethyl), no O-alkylated hydroxylamines were obtained, thus making ar adical mechanism very unlikely.T he product of the oxidation with lithium tertbutyl hydroperoxide (Scheme 2e)i sc onsistent with an oxidation mechanism involving an ionic addition/1,2-migration sequence. This also allowed am ore in-depth analysis of the nature of the oxidizing agent.…”

Product Class 5: Hydroxylamines

“…Scheme 203 Synthesis of N-{[(1S,2S)-2-(Dimethylamino)-1-phenylpropyl]oxy}oct-3-yn-2amine[699] BF 3 •OEt 2 , toluene Bu Oxime ethers 495 derived from glyoxylate and pyruvate are efficiently converted by reaction with organolithium reagents into the corresponding a-alkoxyamino carboxylic acids 496,[700] which are of interest because of manifold biological activities (Scheme 204) [701][702][703][704]. Scheme 204 Synthesis of a-Alkoxyamino Carboxylic Acids[700] R 1 = H, Me; R 2 = Bn, CHMePh, THP; R 3 = Me, Bu, s-Bu, t-Bu, Ph Oxidation of Tertiary Alkyl Lithium Amides with tert-Butyl Peroxybenzoate Oxidation of tertiary alkyl lithium amides 497 by tert-butyl peroxybenzoate provides access to sterically crowded O,N-disubstituted hydroxylamines 498 (Scheme 205) [705]. Thus, treatment of freshly prepared lithium tert-butylamide with tert-butyl peroxybenzoate in diethyl ether at 20 8C for 2 hours and subsequent reaction with hydrochloric acid affords O,N-di-tert-butylhydroxylamine hydrochloride (498, R 1 = t-Bu) in 20% yield [705,706].…”

“…Scheme 204 Synthesis of a-Alkoxyamino Carboxylic Acids[700] R 1 = H, Me; R 2 = Bn, CHMePh, THP; R 3 = Me, Bu, s-Bu, t-Bu, Ph Oxidation of Tertiary Alkyl Lithium Amides with tert-Butyl Peroxybenzoate Oxidation of tertiary alkyl lithium amides 497 by tert-butyl peroxybenzoate provides access to sterically crowded O,N-disubstituted hydroxylamines 498 (Scheme 205) [705]. Thus, treatment of freshly prepared lithium tert-butylamide with tert-butyl peroxybenzoate in diethyl ether at 20 8C for 2 hours and subsequent reaction with hydrochloric acid affords O,N-di-tert-butylhydroxylamine hydrochloride (498, R 1 = t-Bu) in 20% yield [705,706]. Scheme 205 Synthesis of Sterically Crowded O,N-Disubstituted Hydroxylamines[705] Electroreduction of O-alkyl ketoximes with ketones affords polyfunctional O,N-disubstituted hydroxylamines 499, which offer access to 2-amino alcohols 500 by reduction (Scheme 206) [707].…”

“…Thus, treatment of freshly prepared lithium tert-butylamide with tert-butyl peroxybenzoate in diethyl ether at 20 8C for 2 hours and subsequent reaction with hydrochloric acid affords O,N-di-tert-butylhydroxylamine hydrochloride (498, R 1 = t-Bu) in 20% yield [705,706]. Scheme 205 Synthesis of Sterically Crowded O,N-Disubstituted Hydroxylamines[705] Electroreduction of O-alkyl ketoximes with ketones affords polyfunctional O,N-disubstituted hydroxylamines 499, which offer access to 2-amino alcohols 500 by reduction (Scheme 206) [707]. The electroreduction of a mixture of ketone and O-alkyl oxime proceeds smoothly with a tin cathode and a carbon anode in propan-2-ol containing tetraethylammonium 4-toluenesulfonate.…”