Sulfites, organic

Sulfites, organic s. Sulfurous acid esters Sulfocarboxyiic acid anhydrides... 

Rhenium oxides have been studied as catalyst materials in oxidation reactions of sulfur dioxide to sulfur trioxide, sulfite to sulfate, and nitrite to nitrate. There has been no commercial development in this area. These compounds have also been used as catalysts for reductions, but appear not to have exceptional properties. Rhenium sulfide catalysts have been used for hydrogenations of organic compounds, including benzene and styrene, and for dehydrogenation of alcohols to give aldehydes (qv) and ketones (qv). The significant property of these catalyst systems is that they are not poisoned by sulfur compounds. 

Sulfitation and Bisulfitation of Unsaturated Hydrocarbons. Sulfites and bisulfites react with compounds such as olefins, epoxides, aldehydes, ketones, alkynes, a2iridines, and episulftdes to give aHphatic sulfonates or hydroxysulfonates. These compounds can be used as intermediates in the synthesis of a variety of organic compounds. 

The reactions of thionyl chloride with organic compounds having hydroxyl groups are important. Alkyl chlorides, alkyl sulfites, or alkyl chlorosulfites form from its reaction with aUphatic alcohols, depending on reaction conditions, stoichiometry, and the alcohol stmcture ... 

Physical Properties. Anhydrous sodium sulfite [7757-83-7] Na2S02, is an odorless, crystalline soHd and most commercial grades other than by-product materials are colorless or off-white (331—334). It melts only with decomposition. The specific gravity of the pure soHd is 2.633 (15.4°C). Sodium sulfite is quite soluble in water. It has a maximum solubiHty of 28 g/100 g sol at 33.4°C at higher and lower temperatures, it is less soluble in water. Below this temperature, the heptahydrate crystallizes above this temperature, the anhydrous salt crystallizes. Sodium sulfite is soluble in glycerol but insoluble in alcohol, acetone, and most other organic solvents. 

Miscellaneous. In ore flotation, sodium sulfite functions as a selective depressant. In textile processing, sodium sulfite is used as a bleach for wood (qv) and polyamide fibers and as an antichlor after the use of chlorine bleach. Synthetic appHcations of sodium sulfite include production of sodium thiosulfite by addition of sulfur and the introduction of sulfonate groups into dyestuffs and other organic products. Sodium sulfite is useful as a scavenger for formaldehyde in aminoplast—wood compositions, and as a buffer in chrome tanning of leather. 

Addition of sodium dithionite to formaldehyde yields the sodium salt of hydroxymethanesulfinic acid [79-25-4] H0CH2S02Na, which retains the useful reducing character of the sodium dithionite although somewhat attenuated in reactivity. The most important organic chemistry of sodium dithionite involves its use in reducing dyes, eg, anthraquinone vat dyes, sulfur dyes, and indigo, to their soluble leuco forms (see Dyes, anthraquinone). Dithionite can reduce various chromophores that are not reduced by sulfite. Dithionite can be used for the reduction of aldehydes and ketones to alcohols (348). Quantitative studies have been made of the reduction potential of dithionite as a function of pH and the concentration of other salts (349,350). 

Candida utilis is grown on sulfite waste Hquor in Western Europe and North America, on sugar cane molasses in Cuba and Taiwan and on ceUulose acid hydrolysates in Eastern Europe and the former Soviet Union. C. ///i/if utilizes hexoses, pentoses, and many organic acids. Sulfite Hquor from hardwoods contains 2—3% fermentable sugars of which 20% are hexoses and 80% pentoses in softwood Hquors the proportions are reversed. The SO2 must be stripped out to allow yeast growth, which is carried out in large, highly-aerated fermentors. Eor continuous fermentations, carried out at pH 4 and 30°C, the dilution rate is 0.27—0.30 (34). 

Tetrachloroethane [79-34-5] acetylene tetrachloride, CHCI2CHCI2, is a heavy, nonflammable Hquid with a sweetish odor. It is miscible with the chlorinated solvents and shows high solvency for a number of natural organic materials. It is also a solvent for sulfur and a number of inorganic compounds, eg, sodium sulfite. 

A detailed procedure for the use of MCPBA recently appeared in Reagents for Organic Synthesis by Fieser and Fieser. The commercially available MCPBA (Aldrich) is 85% pure the contaminant, m-chlorobenzoic acid, can be removed by washing with a phosphate buffer of pH 7.5. The epoxidation is usually performed as follows a solution of 3 -acetoxy-5a-androst-16-ene (2.06 g, 6.53 mmoles) in 25 ml of chloroform (or methylene dichloride) is chilled to 0° in a flask fitted with a condenser and drierite tube and treated with a solution of commercial MCPBA (1.74 g, 20% excess) in 25 ml chloroform precooled to the same temperature. The mixture is stirred and allowed to warm to room temperature. After 23 hr (or until TLC shows reaction is complete) the solution is diluted with 100 ml chloroform and washed in sequence with 100 ml of 10% sodium sulfite or sodium iodide followed by sodium thiosulfate, 200 ml of 1 M sodium bicarbonate and 200 ml water. The chloroform extract is dried (MgS04) and evaporated in vacuo to a volume of ca. 10 ml. Addition of methanol (10 ml) followed by cooling of the mixture to —10° yields 0.8 gof 16a,17a-epoxide mp 109.5-110°. Additional product can be obtained by concentration of the mother liquor (total yield 80-90%). 

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