Aldehydes bisulfite adducts

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). 

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. 

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

The Strecker reaction has been performed on the aldehyde 182 prepared from L-cysteine [86] (Scheme 28). The imine was formed in situ by treatment with benzylamine, then TMS cyanide was added to afford prevalently in almost quantitative yield the syn-diamine 183, which is the precursor of (-l-)-biotin 184. The syn selectivity was largely affected by the solvent, toluene being the solvent of choice. Since the aldehyde 182 is chemically and configurationally unstable, a preferred protocol for the synthesis of 183 involved the prehminary formation of the water-soluble bisulfite adduct 185 and the subsequent treatment with sodium cyanide. Although in this case the syn selectivity was lower, both diastereomers could be transformed to (-l-)-biotin. 

Bisulfite Adduct. A bisulfite addition complex of an aldehyde or dialdehyde has been proposed for use as an antimicrobial agent [1858,1859]. The complex is less toxic than free glutaraldehyde. In oil wells, its digestion by the sulfate-reducing bacteria releases the free dialdehyde that controls the bacteria. In these ways, a more economic and environmentally safer use of antimicrobial additives is likely. 

RCOOH - RCHO (12,485). This borane (2 equiv.) reduces acids at room temperature to thexylboronic acid and aldehydes, which are best isolated as the sodium bisulfite adduct. Yields of aliphatic aldehydes are in the range 80-95%. Reduction of aromatic acids is slow, and yields are significantly lower. 

RCH(NH2)COOH - RCHO. Tryptophane is oxidized to indole-3-acetalde-hyde by Chlorox in C6H6 at 50-55°. The crude aldehyde thus obtained (33-60% yield) is purified via a bisulfite adduct. The overall yield of pure product is 60%. Careful control of the pH to > 7.7 is essential since the substrate is unstable to base. 

The second reason that bisulfite compounds are useful is that they are soluble in water. Some small (that is, low molecular weight) aldehydes and ketones are water-soluble—acetone is an example. But most larger (more than four or so carbon atoms) aldehydes and ketones are not. This does not usually matter to most chemists as we often want to carry out reactions in organic solvents rather than water. But it can matter to medicinal chemists, who make compounds that need to be compatible with biological systems. And in one case, the solubility of bisulfite adduct in water is literally vital. 

The 2-methyl-3-phenylpropanal is 90% pure by GLC. The product mixture contains 6% of another isomer, 2-methyl-2-phenylpropanal, and a small amount of 2-phenyl-2-propen-l-ol. A completely pure sample of the aldehyde is readily obtained by stirring the crude aldehyde with excess saturated aqueous sodium bisulfite solution for several hours, filtering the solid bisulfite adduct, washing with ether, and liberating the aldehyde with excess aqueous sodium bicarbonate. Redistillation gives the completely pure aldehyde in about 60% yield. 

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 addition of sulfur nucleophiles to aldehydes and ketones may be exemplified by the formation of hydrogensulfite (bisulfite) adducts (3.12). These are sulfonates that are water soluble. However, their stcric bulk means that whereas they are formed from aldehydes and methyl ketones, more highly substituted ketones are reluctant to form these derivatives. 

Reduction of saturated carboxylic acids with the borane derivative, thexylchloro-borane, provides a direct route to aldehydes without their prior conversion to carboxylic acid derivatives. The aldehydes initially formed were isolated either as their bisulfite adducts or as their hydrazones, from which the aldehydes were regenerated. 

Sodium bisulfite adducts are readily formed from aldehydes by reaction with NaHSOs. These derivatives are often crystalline and thus serve as a convenient method for purification of aldehydes. Reversion to the aldehyde usually is accomplished by treatment with aqueous acid or base. TMSCl can be used to regenerate the aldehyde under nonaqueous conditions. ... 

Acetyl-2(6)-methoxyhenzaldehyde/537-99-7/M 166.2, m 144. Extract a solution of the aldehyde in C6H6 with 20% aqueous sodium bisulfite, and the bisulfite adduct in the aqueous solution is decomposed by acidifying and heating whereby the aldehyde separates. It is collected, washed with H2O, dried in a vacuum. It is recrystallised from EtOH (m 140-141 ) and then from Et20 (m 143-144 ). [Gray Bonner J Am Chem Soc 70 1249 1948, Angyal et al. J Chem Soc 2142 1950, Beilstein 8 IV 1984.]... 

The 2-cyclohexylacetaldehyde is too air sensitive and needs to be protected to be further handled and stored. The aldehyde was protected either as a dimethylacetal or as a sodium bisulfite adduct. However, we discovered that the dimethylacetal derivative was unreactive in the reaction conditions (acidic) in the Pictet-Spengler reaction generating the tetrahydro-p-carboline derivative. In addition, the dimethylacetal derivative is an oil, making its isolation difficult on the plant scale. Therefore, we choose to isolate the 2-cyclohexylacetaldehyde as a bisulfite adduct, yielding a white crystalline solid. 

The acid-catalyzed Pictet-Spengler reaction between tryptamine derivatives and aldehydes is a well-established method for preparing tetrahydro-p-carboline (THpC) derivatives." Our first trials were aimed at using the bisnlfite adduct as the carbonyl sonrce in order to minimize the number of process steps. The reaction was performed by reacting the 5-methyltryptamine hydrochloride with an excess (1.3 eqniv) of the sodium bisulfite adduct in EtOH at reflnx, in the presence of one extra eqnivalent of HCl. The rac-THpC was simply isolated as a hydrochloride salt by filtration of the reaction mixture (Scheme 6.8). 

Pictet-Spengler Reaction Using Sodium Bisulfite Adduct or Free Aldehyde... 

The a-amino nitrile 139, a key intermediate in the synthesis of (+)-biotin, is prepared through a highly diastereoselective Strecker reaction of the bisulfite adduct 138 <04TL6579>. This bisulfite is derived from the a-amino aldehyde 137 upon treatment with sodium bisulfite. 

M. Igawa, Y. Fukushi and T. Hayashita, Selective transport of aldehydes across an anion exchange membrane via the formation of bisulfite adducts, Ind. Eng. Chem. Res., 1990, 29, 857-861. 

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 ... 

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