The Reaction of Hydroxylamine-O-sulfonic Acid with Ketones¹

Abstract

2-( p-Chlorophenyl)-2-mesitylvinyl Alcohol.-The decomposition of this peroxide, carried out in the usual way, yielded only a very small amount of the vinyl alcohol.It crystallized from its solution in low-boiling petroleum ether only after standing for several weeks. It was recrystallized from low-boiling petroleum ether. It formed colorless prisms melting at 92-93°. The analytical sample decomposed after standing five months.

Amination of Tyrosine in Liver Cytosol Protein of Male F344 Rats Treated with 2-Nitropropane, 2-Nitrobutane, 3-Nitropentane, or Acetoxime

“…The yields are low, possibly because the hydrolysis of oxime-O-sulfonates to hydroxylamine-O-sulfonic acid is slow and hydrolysis to oximes and ketones, which are not aminating agents, is probably a competing reaction. Oximes were isolated in quantitative yields by others during reactions of ketones with hydroxylamine-O-sulfonic acid when water was used to isolate the products (24).…”

Action of nitrogen trichloride on certain proteins II. Synthesis of methionine sulphoximine and other sulphoximines

“…(VI) (VII) § It has more recently been shown, however, by many groups of workers, that the Lination of a carbonyl group by means of hydrazoic acid in the presence of a irong mineral acid proceeds instead by the electrophilic attack of a carbonium in, [P2COH]+, [i?CO]+ or [EC(OH)2]+, on the nitrogen atom carrying a hydrogen iom in the intact molecule of hydrazoic acid; this gives an intermediate of the jjrpe (VII), which subsequently loses nitrogen and then undergoes a Beckmann |rpe rearrangement (Hurd 1938;Briggs & Lyttleton 1943> Sanford, Blair, Arroya Sherk 1945Wolff 1946;Newman & Gildenhorn 1948;Smith 1948;Schuerch & S 'untress 1949)-A similar mechanism has been shown to operate in the reaction etween hydrazoic acid and diarylethylenes (McEwen, Gilliland & Sparr 1950). in the other hand, it appears to be established that the direct amination of romatic compounds by hydrazoic acid involves the free radical NH in ultraiolet light or -NH2 in strong mineral acids (Keller & Smith 1944), so that there re grounds for presuming that this mechanism can operate in systems where no insaturated group with carbonyl type reactivity is available.…”