Formaldehyde, bisulfite addition product

This method is based on the quantitative liberation of sodium hydroxide when formaldehyde reacts with sodium sulfite to form the formaldehyde-bisulfite addition product. The volume of sample may be varied depending on the formaldehyde content but the solution to be titrated must contain excess sodium sulfite. Formaldehyde solutions containing substantial amounts of acid or base must be neutralized before analysis. 

The sodium bisulfite addition products of aldehydes have been converted by the action of potassium cyanide and an amine to a-alkylamino cyanides. The procedure is best suited for obtaining amino nitriles derived from formaldehyde and simple amines and is illustrated in the preparation of diethylaminoacetonitrile (90%). ... 

There can be no doubt that there is a carbon-sulfur bond in the bisulfite addition product. Fusion of iodomethane sulfonic acid (which itself can be converted into methane sulfonic acid) with potassium acetate leads to the same acetoxymcthane sulfonic acid that can be obtained from the acetylation of the bisulfite addition product of formaldehyde 11... 

From a theoretical point of view this is an extremely interesting reaction. The displacement of a hydroxyl group from a saturated carbon atom appears to be unknown in basic solution. The fact that amino-methane sulfonic acid can be isolated from the bisulfite addition product of formaldehyde on treatment with ammonia does not prove, of course, that a direct displacement, such as is indicated in XVI to XVII, actually occurred. Furthermore, it is quite clear that preliminary formation of an imine (XVIII) is not necessary for the reaction of aromatic amines with sodium bisulfite (steps XIX to XVIII to XVII, etc.). 1-Dimethyl-aminonaphthalene-4-sulfonic acid (XX) and l-aminonaphthalene-4-sulfonic acid (XIX) show similar reaction kinetics 16a when treated with sodium bisulfite, yet with the tertiary amine (XX) it is not possible to write an imino structure corresponding to XVIII. 

This difference in kinetics was exploited to develop a procedure to determine free and reversibly bound sulfite in food. The mobile phase consisted of an aqueous solution of 0.05 M tetra-butylammonium hydroxide adjusted to the desired pH by the addition of glacial acetic acid (34). Fluorimetric detection is also possible, because a reaction of the formaldehyde-bisulfite complex with 5-aminofluorescein gives a nonfluorescent product. The sulfite is measured indirectly by its suppresion of the fluorescence of the reagent (31). This method is applicable to the determination of S02 at > 10 ppm and is not applicable to dark-colored foods or ingredients where SO, is strongly bound, e.g., caramel color. This method does not detect naturally occurring sulfite. Sulfur dioxide is released by direct alkali extraction. 

Ingles heated a solution of n-glucose, sodium sulfite, and bisulfite, removed the cations, and steam-distilled the residue. The product, free of carbonyl-bisulfite addition compounds, was chromatographed on an ion-exchange resin, giving a sulfonic acid. This acid yields a crystalline brucine salt and phenyl- and (2,4-dinitrophenyl)-osazones. The osazones consume 1 mole of periodate per mole, liberating 1 mole of formaldehyde but no formic acid. The (2,4-dinitrophenyl)osazone also forms a diacetate. The acid is oxidized by sodium hypoiodite, taking up 1 mole of oxidant per mole. From these reactions and the possible reaction mechanisms for its formation, structure (41), a 3,4-dideoxy-4-sulfo-n-hexosulose, was proposed for the sulfonic acid. ... 

In some reactions, thiosulfates and notably selenosulfates behave as though they are loose addition products of sulfite ion and sulfur or selenium. In contrast to thiosulfate, which remains totally unaltered, selenosulfate reacts with formaldehyde as though it consists of a mixture of selenium and sulfite, i.e., aldehyde-bisulfite is formed and free selenium is precipitated. ... 

Sulfoalkylated naphthol compounds are effective as dispersants in aqueous cement slurries. The compounds can also be applied in an admixture with water-soluble inorganic compounds of chromium to provide additives of increased overall effectiveness. Particularly suitable are sodium chromate or ammonium dichromate. a-Naphthol is reacted in an alkaline aqueous medium with formaldehyde to create condensation products. The aldehyde can be reacted with bisulfite to produce sulfoalkylated products [1404,1410]. 

The method of Fan and Dasgupta (1994) relics on tlie reaction of formaldehyde with 1,3-cyclohexane-dione in acidified ammonium acetate to form the fluorescent dihydropyridine derivative in a flow injection analysis system. Formaldehyde trapped in water can be reacted with pararosaniline and sodium sulfite under mild conditions (neutral pH, room temperature equilibration) to produce a colored product that is measured at 570 nm (Petreas et al. 1986). The presence of bisulfite is an interference in this reaction so the method cannot be used to sample atmospheres that contain sulfur dioxide. In addition, the method is reported to suffer from interferences resulting from the presence of other aldehydes and phenol (Hoogenboom et al. 1987). The indirect method of Hoogenboom et al. (1987) relies on the reaction of excess bisulfite in an aqueous solution of formaldehyde with 5,5 -dithiobis(2-nitrobenzoic acid) to form a colored product, the absorbance of which is measured at 412 nm. The method reported by Naruse et al. (1995) relies on the formation of a colored product obtained by reacting the aqueous formaldehyde with acetylacetone and ammonium acetate in acetic acid. Absorbance is measured at 414 nm. 

On reaction of formaldehyde solution, sodium bisulfite, and ammonia at 1Q-7TYC an arnino derivative of the aldehyde bisulfite compound is produced. On cooling and acidifying, the parent acid crystallizes from the reaction mixture b Backer and Mulder haA e showm that this product is aminomethanesulfonic acid (NHaCHjSOgH) and not a sulfurous ester, as was fiii st supposed. This evidence ser es as an additional check on the bisulfite compound structure. The formation of sodium aminomethane sulfonate is indicated in the following equation ... 

---