Notiz über die Darstellung von O.N‐Dialkyl‐hydroxylaminen

Abstract

Die Darstellung von 0.N-Dialkyl-hydroxylaminen (4) erfolgte bisher durch Alkylierung von N-Hydroxy-urethanen und anschlieBende Hydrolyse der Reaktionsprodukte durch z. TI. langes Erhitzen mit Saure oder Lauge, meist im Autoklavenl-4). Einfacher und schneller gelangt man zu 4, wenn man von N-Hydroxy-N'-phenyl-harnstoff (1) oder von N-Hydroxyharnstoff (2) ausgeht. Diese Verbindungen sind aus Hydroxylamin durch Umsetzung mit Phenylisocyanats) oder Urethanens) leicht zuganglich.

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

“…N-nitroso-0,N-diethylhydroxylamine is known (9) to cause cancer in rats, so it, and its homologues, should be handled with great care.) 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).…”

Product Class 5: Hydroxylamines

“…Alkylation of N-hydroxyor N-alkoxyureas smoothly gives 1-alkoxy-1-alkylureas 454, [614,[640][641][642][643][644][645][646] which are cleaved by alkaline hydrolysis to provide O,N-dialkylhydroxylamines 455 in moderate to good yields (Scheme 183). [647] Alternatively, the O,N-dialkylhydroxylamines 455 are also accessible from 1-alkoxy-1-alkyl-3-arylureas 454 (R 1 = aryl) by reaction with an arylamine, the yields being somewhat higher in this case. [647,648] Scheme 183 Synthesis of O,N-Dialkylhydroxylamines from 1-Alkoxy-1-alkylureas [647,648] [614,649] iPr 71 [649] Bu 73 [649] iBu 61 [649] CH 2 CH=CH 2 75 [649] (CH 2 ) 2 Br 92 [649] (CH 2 ) 4 Br 74 [649] Bn 66 [556,649] Analogously, diethyl {3-[(benzyloxy)amino]propyl}phosphonate, a core precursor of fosmidomycin, [51,650,651] which is an effective antimalarial [652] and antibacterial [653] agent, is obtained in 66% yield from alkylation of O-benzyl-N-(diethoxyphosphoryl)hydroxylamine.…”

“…[647] Alternatively, the O,N-dialkylhydroxylamines 455 are also accessible from 1-alkoxy-1-alkyl-3-arylureas 454 (R 1 = aryl) by reaction with an arylamine, the yields being somewhat higher in this case. [647,648] Scheme 183 Synthesis of O,N-Dialkylhydroxylamines from 1-Alkoxy-1-alkylureas [647,648] [614,649] iPr 71 [649] Bu 73 [649] iBu 61 [649] CH 2 CH=CH 2 75 [649] (CH 2 ) 2 Br 92 [649] (CH 2 ) 4 Br 74 [649] Bn 66 [556,649] Analogously, diethyl {3-[(benzyloxy)amino]propyl}phosphonate, a core precursor of fosmidomycin, [51,650,651] which is an effective antimalarial [652] and antibacterial [653] agent, is obtained in 66% yield from alkylation of O-benzyl-N-(diethoxyphosphoryl)hydroxylamine. [649] O-Benzyl-N-methylhydroxylamine Hydrochloride (458, R 1 = Me); Typical Procedure: [649] CAUTION: Inhalation, ingestion, or skin absorption of iodomethane can be fatal.…”