Aldehyde bisulfites

Figure 5. Infrared absorption spectra of the acidic furnish extract fraction fractionated further by sequential extraction into aldehydic (bisulfite), hydroxyl (bicarbonate), phenolic (hydroxide), and aliphatic (neutral residual) fractions...

Bisulfite addition products are readily formed at wine pHs (1, 23, 24). The bisulfite addition product is thought to be a more sensory-neutral compound and may be exploited by winemakers as a means of decreasing the aldehydic character of wines (1). Bisulfite addition has also been used to mask the stale flavor of beer which is thought to be largely due to the formation of trans-l-noneml (25). Kaneda et al. (25) used HPLC with fluorescent detection of an o-phthalaldehyde derivative to quantitate and identify individual aldehyde-bisulfite products, however, only acetaldehyde-bisulfite adducts were observed in commercial beers with this method. Hydrolysis of the adducts occurs at pHs greater than 8, therefore by adjusting the pH prior to analysis, total aldehydes (free plus bisulfite bound) can be estimated. At low pHs accurate estimation of free aldehydes is complicated however, by analysis conditions which alter the equilibrium between bound and free forms (temperature, dilution, solvent extraction, analysis time, etc.). 

The residual aldehyde-bisulfite solution is cooled to 40-50°, a suspension of 80 g. of sodiiun bicarbonate in 200 cc. of water is added carefully, and the free aldehyde is removed by steam distillation. The upper layer of the distillate is separated, washed with three 50-cc. portions of water (Note 4), dried with 20 g. of anhydrous sodium sulfate, and distilled through a 20-cm. column. The yield of -hexaldehyde, b.p. 126-129°, is 45 5o S- (45 5o per cent of the theoretical amount). 

Solid sodium metabisulfite (200 g.) is added to 81 g. of 37% aqueous formaldehyde solution with cooling to form an aqueous solution of the aldehyde bisulfite compound. After no more heat is evolved from... 

An elegant method for the gentle and selective oxidation of aldehydes to carboxylic acids is the oxidation of the aldehyde-bisulfite addition compound by dimethyl sulfoxide. Depending on the workup of the reaction mixture, the acid, its ester, or its amide can be prepared at room temperature (equation 353) [773]. 

Aldehyde bisulfite adducts are oxidized by dimethyl sulfoxide/acetic anhydride and converted to simple amides in good yield. ... 

Betterton, E. A., Y. Erel, and M. R. Hoffmann (1988), Aldehyde-Bisulfite Adducts Prediction of Some of Their Thermodynamic and Kinetic Properties, Environ. Technol. 22, 92-97. 

Finally, several equilibrium and kinetic properties of aldehyde-bisulfite adducts were found to be linearly related Taft s a parameter (Betterton et al.t 1988). These compounds, which include a-hydroxymethane sulfonate and other a-hydroxyalkyl sulfonates, may be important reservoirs of S(IV) species inj clouds, fog, and rain. Fairly good relationships were found between equilibrium properties (e.g. acidity constants) and Sir values, but rates constants for) nucleophilic addition of S03 to the aldehydes showed only a crude fit, Similarly, poor results were found in applying a to hydrolysis reactions of] volatile alkyl chlorides (T. Vogel, University of Michigan, personal communh cation, 1989), and this has been shown to be a general characteristic of reactioni of alkyl halides with nucleophiles (Okamoto et al., 1967). 

Nitriles from aldehyde-bisulfite compounds CH(OH)S03H —CH2CN Synthesis with addition of 1 C-atom... 

A large number of oc-amino sulfonic acids have been prepared from the hydrogen sulfite adducts ( -hydroxy sulfonic acids) and ammonia or amines at or slightly above room temperature. 976They are very important intermediates in the Knoevenagel-Bucherer form of the Strecker amino acid synthesis (cf. page 877). In this synthesis the aldehyde-bisulfite compounds are converted by ammonia or amines into a-amino sulfonic acids and thence by alkali cyanide or hydrogen cyanide into oc-amino nitriles, which are then hydrolysed ... 

However, reaction of aldehyde bisulfite compounds is more widely applicable for preparation of 1-amino-1-alkanesulfonic acids.76... 

In general the reaction of nitroalkanes with aldehydes can be carried out by one of three processes 125 (1) Just sufficient alkali may be added to provide a sufficiently rapid reaction without dehydration or polymerization the reaction is slow and with the more complex reactants yields are also much lowered. (2) An equimolar amount of 10N-sodium hydroxide solution may be added at not more than 10°, but this method gives good yields only with nitromethane and straight-chain aldehydes and it fails with secondary nitroalkanes. (3) A solution of the aldehyde bisulfite compound may be treated with a warm solution of the sodium salt of the nitroalkane, primary nitro compounds then giving 70-80% yields. 

Sulfomethylation. Sodium hydroxymethanesulfonates ( aldehyde bisulfites ) are used to sulfomethylate on reactive carbon atoms (e.g., in phenols or ketones) or oh nitrogen (i.e., amines, amides, or sulfoamides) by the following reactions ... 

Values for K in Tables II, III, and IV were derived by calculation of all uncombined sulfite as free sulfurous acid. This approach lacks validity to a certain extent since it assumes only HSOj", free sugar, and bisulfite addition compound in the equilibrium. Obviously, this is hardly possible in systems the pH values of which are so high or so low that little or no HSOa ion is present. In fact, the addition compounds obtained at the upper ranges might actually be some type of aldehyde-sulfite rather than aldehyde-bisulfite. There is an almost complete lack of quantitative application of the concept of variant HSOa ion content in sugar work however, Sundman did extend some of his data (Table II) by computing K on the basis of HSO rather than total sulfur dioxide calculated as bisulfite. The results are shown in Table V. 

Table XIII compares Sundman s values with Cantor and Pennis-ton s (1940) per cent open aldehyde forms (as determined polarigraphi-cally) and also with Delahay and Strassner s (1952) approximate rate constants and entropies of activation for the ring-to-aldehyde opening, also determined polarigraphically. In their study, Delahay and Strassner found marked temperature effects—an observation common to investigations of the aldehyde-bisulfite reaction.

Stewart, T. D., and Donnally, L. H. 1932a. The aldehyde bisulfite compounds. I. The rate of dissociation of benzaldehyde sodium bisulfite as measured by its first order reaction with iodine. J. Am. Chem. Soc. 64, 2333. 

The procedure of Jaulmes and Espezel (1935) is now widely used. It depends on fixing the aldehyde in a buffered sulfite solution, titrating the excess sulfite in acid solution, hydrolyzing the aldehyde-bisulfite complex under alkaline conditions, and then titrating the bisulfite released—which is equivalent to the aldehyde present. Joslyn and Comar (1938) studied this and other procedures. They noted that less than 100% of the aldehyde present is recovered. This procedure can be improved by controlling the pH when hydrolyzing the aldehyde-bisulfite complex, e.g., with a less alkaline solution such as bicarbonate. To improve the sensitivity of Jaulmes s procedure Roche (1948) recommended a more dilute iodine solution and a standard color to determine the end point. He proposed a dilute mixture of basic fuchsin and indigo carmine for this. 

In the first case, the typical problem of aldehyde oxidation and general instability has been ameliorated by the formation of the aldehyde bisulfite derivative (Chapter 9, IVb). Cleaner products result when the bisulfite derivative is formed first. 

OPA can be neutralized with sodium bisulfite as shown (Fig. 1). The neutralization is very fast and a colorless aldehyde-bisulfite adduct, 3, is formed. However, the product is toxic to fish even though sodium bisulfite itself is not. 

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. ... 

Wuts, P. G. M. Bergh, C. L. The Oxidation of Aldehyde Bisulfite Adducts to Carboxylic Acids and their Derivatives with Dimethyl... 

Sodium foi m..aldehyde bisulfite is soluble in water and methanol but only slightly soluble in ethanol . Potassium formaldehyde bisulfite, HOCH KSO3, may be obtained in a manner similar to that employed for the sodium derh ative. TCormal alkali sulfites react with formaldehyde to produce bisulfite compounds wfith liberation of alkali hydroxide ... 

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 ... 

---