N-[(Methanesulfonyl)oxy]-N-methylmethanamine

synthetischePreparative Methods of N,N-Dimethyl-O-(methylsulfonyl)hydroxylamine: to a solution of 29.3 g (300 mmol) N,N-dimethylhydroxylamine hydrochloride and 35.6 g (300 mmol) Methanesulfonyl Chloride in 360 mL CH2Cl2 is added dropwise under stirring at - 20 °C a solution of 60.7 g (600 mmol) Triethylamine in 240 mL CH2Cl2. After stirring for 30 min at 0 °C the reaction mixture is poured into ice water, the organic phase is extracted another two times with ice water and then dried over MgSO4 at 0 °C. After removal of the solvent at 0 °C the noncrystalline residue is dissolved in 60 mL diethyl ether. On standing at -30 °C, N,N-dimethyl-O-(methylsulfonyl)hydroxylamine (1) crystallizes in colorless needles which are separated in a cooled frit. After one (or two) recrystallization(s) from diethyl ether between 21.9 and 26.4 g (53-63%) (1) are isolated. In a similar fashion the following compounds have been prepared and used in electrophilic amination reactions: N,N-dimethyl-O-(phenylsulfonyl)hydroxylamine, mp 18-19 °C; N,N-diethyl-O- (mesitylsulfonyl)hydroxylamine, mp 103-104 °C; N,N-diethyl-O-(phenylsulfonyl)hydroxylamine, mp 46-47 °C; N,N-diethyl-O-(mesitylsulfonyl)hydroxylamine, mp 68-69 °C; N-(O-phenylsulfonyl)hydroxypiperidine, mp 57-58 °C; N-(O-mesitylsulfonyl)hydroxypiperidine, mp 50- 51 °C; N-(O-mesitylsulfonyl)hydroxypyrrolidine, mp 23-24 °C.