Disulphones, hydrolysis

Use of a higher temperature (280 °C) at the final stage results in more extensive hydrolysis, with the amino group also being replaced by a hydroxy group, leading to the formation of naphthalene-1,8-diol-3,6-disulphonic acid (chromotropic acid). 

Candlin JP, Wilkins RG. Sulphur-nitrogen compounds. Part II. The hydrolysis of hydroxylamine trisulphamate and hydroxylamine-NO-disulphonate ions in perchloric acid. J Chem Soc 1961 3625-3633. 

Reaction of nitrosyl disulphonate, 0N(S03), with hydroxylamine-N-sulphonate is reported to be subject to catalysis by ferric salts at low concentrations, and to depend on the alkalinity through the hydrolysis of the catalyst . In mildly alkaline solution (pH 6-11), the rates of decomposition of this sul-phonate have been shown to be consistent with the existence of two reaction paths, one forming NO and the other sulphite radicals . The processes are assumed to represent bimolecular nucleophilic substitution by water. 

More recently, Sherk, Houpt and Brown decomposed phenyl azide in fuming sulphuric acid and isolated phenylhydroxylamine O,m-disulphonic acid (63) which, upon hydrolysis, rearranged to 4-aminophenol-2-sulphonic acid (64). The same product 64 (38%) was obtained in addition to -aminophenol (11%) on heating the azide in a 1 3 (v/v) mixture of sulphuric acid and water. 

The transmetallation reaction between AgBF4 and a tertiary bis(silyl)pyridylmethylh-thium compound afforded the dinuclear alkylsilver species (1), which is stable at room temperature for several days7. Despite the susceptibility of most organosilver compounds to hydrolysis, the argentate complex with a /S-disulphone carbanion (2) can be obtained by the reaction of 1,3-dithiane 1,1,3,3-tetraoxide with silver nitrate in alkaline aqueous solution8. 

Unlike the almost abandoned route for phenol from benzenesuiphonic acid by alkaline fusion, resorcinol is manufactured substantially by this methodology which was first described in 1878. The yield of resorcinol on benzene-1,3-disulphonic acid is 94% (ref.29) after recovery from the acidified alkaline solution and purification by distillation. For catechol, the hydrolysis of... 

Sodium salt of hydroxylamine disulphonic acid is produced. On warming the above solution with dilute sulphuric acid to 80°C, hydroxylammonium bisulphate is formed following hydrolysis. 

The combination of neutralisation/hydrolysis gives a product containing about 55-65% alkene sulphonates and 25-35% hydroxy alkane sulphonates and 5-15% disulphonates. The C(l,3) sultones and D(l,4) sultones have virtually disappeared in the plug flow reactor with a residence time of 30 minutes at HO C. The ratio between initial and final concentration of delta (1,4) sultones will be ... 

Preparations.—a-Mercapto-a-amino-acids R NHCR (SH)C02H are obtained from corresponding chloro-compounds or from 4-chloro-oxazol-5(4H)-ones. Conventional methods are also used for synthesis of thio-resorcinols (from benzene-1,3-disulphonic acids via sulphonyl chlorides, reduced with red P-Ir-AcOH, or from resorcinols via Newman-Kwart rearrangement of O-dimethylaminothiocarbonyl-resorcinols followed by alkaline hydrolysis ). Dithiols are unexpectedly obtained from ethyl a-acetonylacetate by treatment with H2S in acid solution at -40 "C. Mercapto-ethylation of aliphatic amines is best achieved by a modificaticm of the well-established method using episulphides, in aqueous solution in the presence of a silver salt. Methyl sulphides ArSMe may be demethylated by chlorination to ArSCCh followed by acid methanolysis, while aryl diphenylmethyl sulphides are susceptible to electrolytic reduction to the thiophenol. ... 

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