Sodium bisulfite, addition compounds

The sodium bisulfite addition compounds must have a free (or potentially free) ketone-type carbonyl group, since they readily form derivatives with typical ketone reagents such as semicarbazide and 2,4-dinitrophenylhydrazine.174 Decomposition of these derivatives with alkali gives the corresponding adrenochrome derivatives e.g., adrenochrome monosemicarbazone would be obtained from the semicarbazone of the adrenochrome-sodium bisulfite complex.174 If one accepts Tse and Oesterling s formulation of the adrenochrome-sodium bisulfite complex, the semicarbazone would probably have a basically similar structure (i.e. 82). This type of structure is more... 

The yields of nitro alcohols from simple nitroparaffins and aliphatic aldehydes or benzaldehyde are usually above 60%. The condensations are generally carried out with aqueous ethanolic sodium hydroxide, although weaker bases are sometimes desirable to prevent polymerization of the aldehyde. Sodium bisulfite addition compounds of the aldehydes are sometimes used. Better results are obtained with sodium methoxide than with alkali hydroxides in the condensation of nitroethane with formaldehyde. Sodium alkoxides are also used to effect the condensation of nitroethane with acetone and cyclohexanone. Condensation proceeds to the nitroalkanediol stage in certain cases with both nitromethane and with formaldehyde. ... 

Bearrangemente might alao be expected but ee n to have Uw, BeMom obeerved The isolation of the sodium bisulfite addition compound of piopkmaldehyde firom the reaction of trimethylene oxich-with eodium bisulfite, however, provides an example. It is intereaUn CH.-CH ... 

Preparation, (a) By addition of 40% sulfuric acid to an aqueous solution of acetone and sodium cyanide at 10-20°. (b) Reaction of potassium cyanide with the sodium bisulfite addition compound of acetone gives material which is less pure but satisfactory for immediate use. ... 

Hinsberg oxindolc synthesis. Formation of oxindoles from secondary aryl amines and sodium bisulfite addition compound of glyoxal primary aryl amines give glycine or glycinamide derivatives. 

The reaction of 6-hydrazinopyrimidin-4-ol with glyoxal (sodium bisulfite addition compound) followed by treating the intermediate with trifluoroacetic acid gives pyrimido[4,5-c]-pyridazin-5-ol in 16% yield.40... 

For coagulant activity the isoprenoid side chains are not mandatory. Thus menadione, which is a naphthaquinone carrying only a methyl group at the 3-position, is considered a synthetic K vitamin (K3). It has the same actions as the natural products. It, and two derivatives—the water-soluble sodium bisulfite addition compound and the disodium salt of the phosphate ester of reduced menadione—are all used clinically as hemostatics, and to antidote overdoses of anticoagulants. 

Acraldehyde - sodium bisulfite addition compound tetrahydrate... 

C3H1 i,Na20i 1S2, Acraldehyde - sodium bisulfite addition compound tet-rahydrate, 20, 521... 

This reaction can be used for the detection of aldehydes in the presence of ketones and for the differentiation of aliphatic aldehydes from aromatic ones. In a neutral medium aldehydes produce a black color or a precipitate other transient colors are sometimes formed which, in the case of aromatic aldehydes, last a bit longer. In an acid medium aliphatic aldehydes behave similarly as in a neutral medium, while in the presence of aromatic aldehydes a yellow color is produced first sometimes a precipitate is formed which persists for a certain time. Some other derivatives also react similarly to aide-hydes, such as, for example, cyanohydrins, aldehyde-ammonia adducts, sodium bisulfite addition compounds of aldehydes, and oximes. For modification with detection tubes containing the reagent see (62). 

The soiution is aliowed to cool and the crystals of the P2P-bisulfite addition compound are then separated by vacuum filtration, washed with a little clean dH20 then washed with a couple hundred mLs of ether, DCM or benzene. The filter cake of MD-P2P-bisulfate is processed by scraping the crystals into a flask and then 300mL of either 20% sodium carbonate solution or 10% HCi soiution are added (HCI works best). The soiution is stirred for another 30 minutes during which time the MD-P2P-bisulfite complex will be busted up and the P2P will return to its happy oil form. The P2P is then taken up with ether, dried and removed of the solvent to give pure MD-P2P. Whaddya think of that ... 

Miscellaneous Reactions. Sodium bisulfite adds to acetaldehyde to form a white crystalline addition compound, insoluble in ethyl alcohol and ether. This bisulfite addition compound is frequendy used to isolate and purify acetaldehyde, which may be regenerated with dilute acid. Hydrocyanic acid adds to acetaldehyde in the presence of an alkaU catalyst to form cyanohydrin the cyanohydrin may also be prepared from sodium cyanide and the bisulfite addition compound. Acrylonittile [107-13-1] (qv) can be made from acetaldehyde and hydrocyanic acid by heating the cyanohydrin that is formed to 600—700°C (77). Alanine [302-72-7] can be prepared by the reaction of an ammonium salt and an alkaU metal cyanide with acetaldehyde this is a general method for the preparation of a-amino acids called the Strecker amino acids synthesis. Grignard reagents add readily to acetaldehyde, the final product being a secondary alcohol. Thioacetaldehyde [2765-04-0] is formed by reaction of acetaldehyde with hydrogen sulfide thioacetaldehyde polymerizes readily to the trimer. 

Sodium bisulfite adds to the carbonyl double bond to give a hydroxysulfonate (bisulfite addition compound). 

Ketones are more stable to oxidation than aldehydes and can be purified from oxidisable impurities by refluxing with potassium permanganate until the colour persists, followed by shaking with sodium carbonate (to remove acidic impurities) and distilling. Traces of water can be removed with type 4A Linde molecular sieves. Ketones which are solids can be purified by crystallisation from alcohol, toluene, or petroleum ether, and are usually sufficiently volatile for sublimation in vacuum. Ketones can be further purified via their bisulfite, semicarbazone or oxime derivatives (vide supra). The bisulfite addition compounds are formed only by aldehydes and methyl ketones but they are readily hydrolysed in dilute acid or alkali. 

Both 1- and 2-naphthylhydrazine have been shown to react in good yield with 2-hydroxy-3-naphthoic acid in the presence of sodium bisulfite to give, after acidic workup, dibenzocarbazole 30 and 31, respectively7 When either 1- or 2-naphthylhydrazine is heated with sodium bisulfite, dibenzocarbazoles 32 and 31, respectively, are isolated after acidic work-up7 It is suggested that loss of the hydrazine residue to form a bisulfite addition compound of the parent naphthol occurs initially further reaction of this adduct with naphthylhydrazine then affords, after work-up, the products. 

The sodium bisulfite purification step may be omitted, and the alkylidene ester purified directly by distillation. Care must be taken to separate the product from ethyl cyanoacetate by fractionation through a moderately efficient column. Purification through the bisulfite addition compound is recommended for alkylidene cyanoacetic esters derived from ketones containing four and five carbon atoms, but not for the higher homologs. 

Seventeen grams of acetaldehyde are dissolved in 20ml of water and added dropwise to a suspension of 40g of sodium bisulfite in 30ml of water. The reaction mixture is kept cold in an ice bath to prevent loss of the aldehyde by volatilization much heat Is liberated by the formation of the bisulfite addition compound. The temperature of the solution is adjusted to 50°C and 17ml of 20% aqueous ammonia are added. The latter is prepared from 13ml of the... 

Possible toxic reactions of sulfur dioxide are also indicated in Table I. The reaction of bisulfite with aldehydes has a classic position in biochemistry since Neuberg demonstrated in 1918 that the products of fermentation by yeast were altered by the addition of sodium sulfite, which caused the production of equal amounts of the bisulfite addition compound of acetaldehyde and of glycerol. This was concomitant with the blockage of conversion of acetaldehyde to ethanol. Addition compounds can also be formed with quinones and with ,/ -unsaturated compounds. None of these reactions has been adequately assessed as a possible contributor to toxicity. 

The last nucleophile of this chapter, sodium bisulfite, NaHSC, adds to aldehydes and some ketones to give what is usually known as a bisulfite addition compound. The reaction occurs by nucleophilic attack of a lone pair on the carbonyl group, just like the attack of cyanide. This leaves a positively charged sulfur atom but a simple proton transfer leads to the product. 

The products are useful for two reasons. They are usually crystalline and so can be used to purify liquid aldehydes by recrystallization. This is of value only because this reaction, like several you have met in this chapter, is reversible. The bisulfite compounds are made by mixing the aldehyde or ketone with saturated aqueous sodium bisulfite in an ice bath, shaking, and crystallizing. After purification the bisulfite addition compound can be hydrolysed back to the aldehyde in dilute aqueous acid or base. 

The procedure employed for tetrahydroxyquinone is based on an observation by Homolka. Tetrahydroxyquinone may also be prepared by treatment of the glyoxal-bisulfite addition compound with sodium carbonate or magnesium hydroxide and potassium cyanide or by treatment of 50% glyoxal with sodium hydro-sulfite. ... 

Aminoimidazo[l,2-a]pyrazine (456) has been prepared by the reaction of 2-aminopyrazine (455) with sodium cyanide and the bisulfite addition compound from formaldehyde (68TL3873). Another 3-aminoimidazo[l,2-a]pyrazine (458) was made by the reaction of the tetrahydropyrazine (457) with a-amino-a-cyanoacetamide (67MI41000, 67MIP41000). 

Since these bisulfite addition compounds are ionic water-soluble compounds and can be formed in up to 90% yield, they serve as a useful means of separating aldehydes and methyl ketones from mixtures of organic compounds. At high sodium bisulfite concentrations these adducts crystallize and can be isolated by filtration. The aldehyde or ketone can be regenerated by adding either a strong acid or base ... 

If either of these ketones is required in very pure form, it may be purified by the bisulfite addition compound or, more conveniently, with the sodium iodide addition compound. A solution of 100 g of sodium iodide in 440 ml of acetone is prepared by heating under reflux, and the solution is cooled in an ice-salt mixture (—8°). The crystals (NaT3C,H,iO) are filtered off and quickly transferred to a dry distilling flask. On gentle warming, the addition compound loses acetone, which distills over. 

The best derivative from which an aldehyde can be recovered readily is its bisulfite addition compound, the main disadvantage being the lack of a sharp melting point. The aldehyde (sometimes in ethanol) is shaken with a cold saturated solution of sodium bisulfite until no more solid adduct separates. The adduct is filtered off, washed with a little water, followed by alcohol. A better reagent to use is a freshly prepared saturated aqueous sodium bisulfite solution to which 75% ethanol is added to near-saturation. (Water may have to be added dropwise to render this solution clear.) With this reagent the aldehyde need not be dissolved separately in alcohol and the adduct is finally washed with alcohol. The aldehyde is recovered by dissolving the adduct in the least volume of water and adding an equivalent quantity of sodium carbonate (not sodium hydroxide) or concentrated hydrochloric acid to react with the bisulfite, followed by steam distillation or solvent 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. ... 

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