Sodium Sulphite ketones with

C HgNjOjS. Colourless needles, with iH20. Prepared by reducing diazotized sulphanilic acid with an excess of sodium sulphite. It is a typical hydrazine in its reactions with ketones, and with acetoacetic ester. The latter reaction gives rise to the tartrazine dyestuffs, and is much used commercially. 

The aldehyde and ketone compounds formed with the sodium sulphite are readily soluble in water, and H. E. Burgess makes use of this fact... 

Obtemperanskaya and Kareva25 determined a, /J-unsaturated ketones and sulphones by adding sodium sulphite to the sample in p-dioxan. After 5-10 min they titrated with standard sulphuric acid potentiometrically or to thymolphthalein ... 

Nonen-2-one. J. Gen. Chem. (USSR), Vol. 33, p. 134 of the English translation. Oxidation of the ketone is accomplished in this manner 0.5 mole of n-hexylideneacetone (this should be freshly distilled at 93-95° with 16 mm of vacuo) is shaken in an oxygen atmosphere at 30° for 8 hours. Decompose the hydroperoxides with a little sodium sulphite. Fractionally distill in three steps about 40° at 16 mm vacuo, 93-95° at 16 mm vacuo, and the product is obtained by reducing the vacuum to 1 mm and raising the temp to 107-108°. Yield of pale, yellow, viscous liquid, 6 g. The unreacted starting material (93-95° 16 mm) is used over and over until reacted. 

Tlie reduction of vinyl azides with sodium sulphite followed by hydrolysis can lead to ketones [71). 

Asymmetric dihydroxylation of the side-chain of Z-1-(4-meth-oxyphenyl)-1-(tert-butyldimethylsiloxy)-1-propene to give (R)-l-hydroxyethyl 4-methoxyphenyl ketone in 94% yield (99% e.e.) was effected by addition of the alkene to a stirred mixture of osmium tetroxide, potassium ferricyanide, potassium carbonate, a 9-0-(9 -phenanthryl)ether(PHN) of dihydroquinidine and 1 mole of methanesulphonamide in aqueous tert-butanol (1 1), with reaction during 16 hours at ambient temperature. Then treatment with sodium sulphite prior to work-up to gave the product (ref. 130). Other best ligands were the 9-0-(4 -methyl-2 -quinolyl) ethers (MEQ) of dihydroquinine. 

The oil was shaken, first with dilute sodium carbonate, next with sodium hydrogen sulphite solution, then with dilute sodium hydroxide, and finally with 50 per cent, resorcinol solution to absorb cineol. From the results of this treatment and the subsequent examination of the various products, the composition of the oil was found to be approximately as follows Cineol, 69 per cent., characterised by the crystalline additive product with iodol aldehydes and ketones, 27 5 per cent., consisting mainly of citral, which was characterised by means of the semi-carbazone and the j3-naphtbacinchoninic acid phenols, 1 5 per cent. acids, 1 per cent. A small quantity of crystalline acid, melting-point, 46 to 48 was isolated, but not in sufficient quantity for identification. The residue, amounting to about 1 per cent., seemed, from its odour, to consist chiefly of terpenes. 

ALDEHYDES AND KETONES. Formerly aldehydes and ketones were usually determined by absorption with neutral sodium sulphite or sodium... 

Spearmint Oil. Use 1 5 g for the determination of ketones. The N.F. requires the oil to contain not less than 55 per cent by volume of carvone when determined by the neutral sulphite method, using saturated sodium sulphite solution and keeping neutrality to phenolphthalein with 30 per cent sodium bisulphite solution. 

The acid sulphites possess the property of forming crystalline additive compounds with aldehydes and ketones. Sodium hydrogen sulphite is therefore largely used for the purification of compounds of these classes the sulphite adds on at the carbonyl group, >C O, forming the group-OH... 

A Favorskii-like intermediate (655), and the rearranged product (657), arise in a novel way from fragmentation of the a-ketol enol-sulphite (654). Loss of sulphur dioxide is thought to afford the zwitterion (655), which gives the methoxy-ketone (656) in methanol, but the A-nor carboxylic ester (657) with sodium methoxide in ether. ... 

The reactions of the ketones are similar to those of acetone. Most ketones, however, which do not contain the group CH3CO do not unite with sodium hydrogen sulphite. 

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