Sodium bisulphite, addition product

The adrenochrome-sodium bisulphite addition product [28, 29] has been isolated in the solid state as a pale yellow crystalline solid [194, 195]. This substance reacts with substituted hydrazine-type ketone reagents (such as semicarbazide) to give mono-condensation products, which can be easily converted to the corresponding adrenochrome monohydrazone derivative by the action of either heat or alkali [194]. This, together with other evidence [28, 29], suggested that the bisulphite residue was not attached to the C-5-carbonyl group directly [194]. 

Recent studies on the n.m.r. spectra of this compound in solution in D2O and dimethyl sulphoxide-Dg have confirmed that (KM) is the structure of the adrenochrome-sodium bisulphite addition product [196]. There was no... 

Addition products, structurally similar to the aminochrome-sodium bisulphite addition products, are also formed reversibly during the interactions of some aminochromes with some thiols (see p. 310). 

A sensitive spectrophotometric method for the determination of urinary noradrenaline, adrenaline, normetanephrine, metanephrine and dopamine involving the formation of aminochrome-sodium bisulphite addition products has been described [197] and is based on an earlier method for noradrenaline and adrenaline [198]. 

Cool the beaker in a bath of cold water and add 150 ml of cold water. Filter off the crude phenanthraquinone with suction and wash it with water until free from chromium salts. Suspend the solid in 20 ml of rectified spirit and add, with stirring, 20 ml of saturated sodium metabisulphite solution. Break up the lumps of the addition product with a glass rod and allow to stand, with frequent stirring, for 10 minutes. Add 150 ml of water to dissolve the addition product and filter with suction. Reject the precipitate which consists of the impurities present in the phenanthrene. Add saturated sodium carbonate solution to the filtrate until the bisulphite addition product is completely decomposed allow the precipitate to settle for 1 minute, then add a few drops of sodium carbonate solution and note whether any further precipitation occurs. Stir the precipitate for 2-3 minutes, filter with suction, wash with three 20 ml portions of water and drain well. Dry the product between filter papers and then in a desiccator over calcium chloride. The yield of phenanthraquinone, m.p. 206 °C, is 1.4 g (60%). The product may be recrystallised from glacial acetic acid (about 20 ml), but the m.p. is unaffected. 

The bisulphite addition products deserve mention, for the free hydroxy-sulphonic acids from pyridine-2- and -4-aldehydes are exceptionally stable, possibly because their structures are zwitterionici 3(l). The derivative of pyridine-3-aldehyde is known only as its sodium salt. ... 

Removal of a carbonyl confound. A compound containing a carbonyl group may be removed from a mixture by treatment of the latter (or an ethereal solution of it) with saturated sodium bisulphite solution. After vigorous shaking, the bisulphite addition product of the carbonyl compoimd, if predpitated, is removed by filtration and decomposed by distilling with an excess of sodium carbonate solution, when the carbonyl compound is recovered from the distillate, or if it is non-volatile, by ether extraction of the residue in the distilling flask. In the event of the bisulphite compound being water-soluble, the aqueous solution is treated with sodium carbonate solution and the carbonyl compound recovered as already described. 

The experimental procedure to be followed depends upon the products of hydrolysis. If the alcohol and aldehyde are both soluble in water, the reaction product is divided into two parts. One portion is used for the characterisation of the aldehyde by the preparation of a suitable derivative e.g., the 2 4-dinitrophenylhydrazone, semicarbazone or di-medone compound—see Sections 111,70 and 111,74). The other portion is employed for the preparation of a 3 5-dinitrobenzoate, etc. (see Section 111,27) it is advisable first to concentrate the alcohol by dis tillation or to attempt to salt out the alcohol by the addition of solid potassium carbonate. If one of the hydrolysis products is insoluble in the reaction mixture, it is separated and characterised. If both the aldehyde and the alcohol are insoluble, they are removed from the aqueous layer separation is generally most simply effected with sodium bisulphite solution (compare Section Ill,74),but fractional distillation may sometimes be employed. 

Fission of ethers with hydriodic acid. Reflux 1 ml. of the compound with 5 ml. of freshly distilled constant b.p. hydriodic acid (b.p. 126-128°) for 2-3 hours in a small flask fitted with a double surface condenser. Add 10 ml. of water, distil and collect about 7 ml. of liquid. Decolourise the distillate by the addition of a little sodium bisulphite and separate the two layers by means of a dropper pipette. If the original compound is suspected to be an aliphatic ether, determine the b.p. of the iodide by the Siwoloboff method (Section 11,12) if the amount of product is insufficient, repeat the original experiment. 

This is generally done during an experimental work up where the products of the reaction are dissolved in a water immiscible organic solvent. Aqueous sodium bisulphite is then added and the mixture is shaken thoroughly in a separating funnel. Once the layers have separated, any aldehydes and methyl ketones will have undergone nucleophilic addition with the bisulphite solution and will be dissolved in the aqueous layer as the water soluble salt. The layers can then be separated. If the aldehydes or methyl... 

A typical case is the structural assignment of the product obtained by addition of sodium bisulphite to anthocyanins.90... 

Because of the presence of the carbonyl group in the molecule, they react with sodium bisulphite to form well-crystallised additive products. This behaviour is employed in practice to separate the halogenated ketones from the secondary products of the reaction. 

Reactions.—The general properties and reactions of the aromatic aldehydes and ketones are like those of their aliphatic relatives. The aldehydes are easily oxidized to acids and reduce ammoniacal silver nitrate solution. Both aldehydes and ketones are easily reduced to alcohols. The aldehydes form addition products with sodium bisulphite and with hydrogen cyanide. With ammonia, however, they do not form addition products but react with the elimination of wafer and the formation of a condensation product which is a derivative of two molecules of ammonia. 

A mixture of 200 kilos of water, 230 kilos of crude aubepine, and a solution of 120 kilos of solid sodium bisulphite in 185 kilos of water is heated in an enameled vessel (the oxidation vessel maybe used) to 50° for six hours. The stirred and steam are then stopped and the product is allowed to settle overnight. The aqueous liquor is separated from a certain amount of undissolved oil (Oil R) and stirred in another vessel (fitted with reflux condenser) 50 kilos of benzene for 3-4 hours without heating. The aqueous layer, freed in this way from nonaldehyde constituents, contains the bisulphite compound of anisaldehyde, and is transferred to the fresh vessel again, where it is decomposed by the addition of 60 kilos of soda ash and distilled in steam. 

The method suggested by Caro 2 for the purification of aurin tricarboxylic acid seems to be unnec sary when the dye is to be used as a test for aluminium. In this /nethod the crude product is dissolved in sodium hydroxide, sodium bisulphite is added until the solution is decolorized, and the addition compound of the free acid is precipitated by adding hydrochloric acid. 

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