Sulfonic acids from sulfites

Sodium hydrogen sulfite Sulfonic acids from alcohols s. 17,661... 

For many years phenol was made on a large industrial scale from the substitution reaction of benzene sulfonic acid with sodium hydroxide. This produced sodium sulfite as a by-product. Production and disposal of this material, contaminated with aromatic compounds, on a large scale contributed to the poor economics of the process, which has now been replaced by the much more atom economic cumene route (see Chapter 2, Schemes 2.2 and 2.3). 

A class of enzymes capable of removing sulfur from alkane sulfonates exists, which may have relevance in microbial desulfurization of alkyl sulfides. A gene cluster ssuEADCB was identified in E. coli. The enzyme SsuD was capable of conversion of pentane sulfonic acid to pentaldehyde and sulfite. It was reported to be capable of conversion of alkyl sulfonates from C2 to CIO, as well as substituted ethanesulfonates and sulfonated buffers. The SsuE was a flavin-reducing enzyme that provided FMNH2 to the SsuD. 

Figure 4.8. The sulfur cycle where S° is elemental sulfur, H2S is hydrogen sulfide, S2032" is thiosulfate, SO32" is sulfite, SO/- is sulfate, R-OSO3H represents a sulfate ester, R-SO3H a sulfonic acid, R-S-R a thioether, and R-SH a thiol. (Adapted from Coyne MS. Soil Microbiology An Experimental Approach. Boston Delmar Publishers 1999.)...

Furthermore, the cleavage of organic sulfites and sulfates by hydrogen fluoride gives the corresponding alkyl or acyl fluorides in fair to good yield,287 e.g. formation of acetyl fluoride from the mixed anhydride287 or sulfonyl fluorides from sulfonic acid anhydrides.287... 

Taurine is generally prepared from ox bile1 or the large muscle of the abalone.2 It has been synthesized from isethionic acid through chloroethanesulfonic acid followed by the action of aqueous ammonia 3 from ethyleneimine and sulfur dioxide 4 from 2-mercaptothiazoline by oxidation with bromine water 5 from bromoethylamine and ammonium sulfite 6 and from acetaldehyde by a complex set of reactions involving sulfonation, formation of the aldehyde ammonia and the imido sulfonic acid and finally reduction.7 The method given in the procedure has recently appeared in the literature.8... 

Crude TNT contains isomers and nitrated phenolic compounds resulting from side reactions. The usual method of purification is to treat crude TNT with 4% sodium sulfite solution at pH 8-9, which converts the unsymmetrical trinitro compounds to sulfonic acid derivatives. These by-products are then removed by washing with an alkaline solution. Pure TNT is then washed with hot water, flaked and packed. It is important to remove the waste acid and unsymmetrical trinitrotoluenes together with any by-products of nitration as they will degrade the TNT, reduce its shelf life, increase its sensitivity and reduce its compatibility with metals and other materials. Trace amounts of unsymmetrical trinitrotoluenes and by-products will also lower the melting point of TNT. TNT can be further recrystallized from organic solvents or 62% nitric acid. 

MARATHON-HOWARD PROCESS. A treatment of waste sulfite liquor from sulfite pulp manufacture In recover chemicals and reduce steam pollution. The waste sulfite is treated with line and precipitates. (I) calcium sulfite for use in preparing fresh cooking acid for the sulfite pulp process, and 121 a basic calcium salt tif ligmn sulfonic acid (lignin sullYmalesi that can be pressed and used as a fuel of used as raw- material for vanillin, lignin plasties, and other chemicals. The remaining liquor with its BOD reduced X() ( is the effluent. 

It is not possible to dissolve the asphaltenes in water by treatment of the halo derivatives with aqueous sodium hydroxide or with aqueous sodium sulfite (II). The hydrolyzed products remained insoluble even in a strongly alkaline solution. The decreased (H + Cl)/C ratios and the increased O/C ratios of the products relative to those of the parent halo-asphaltenes indicate that partial reaction occurs. The infrared spectra of the products showed a broad band centered at 3450 cm 1, a region assigned to the presence of hydroxyl groups in the products, but it was not possible to establish conclusively the presence of sulfonic acid group(s) in the product from the sodium sulfite reaction by assignment of infrared absorption bands to this particular group. 

Fig. 7-12. Reactions of phenolic /8-aryl ether and a-ether structures (1) during neutral sulfite pulping (Gierer, 1970). R = H, alkyl, or aryl group. The quinone methide intermediate (2) is sulfonated to structure (3). The negative charge of the a-sulfonic acid group facilitates the nucleophilic attack of the sulfite ion, resulting in /8-aryl ether bond cleavage and sulfonation. Structure (4) reacts further with elimination of the sulfonic acid group from a-position to form intermediate (5) which finally after abstraction of proton from /8-position is stabilized to a styrene-/8-sulfonic acid structure (6). Note that only the free phenolic structures are cleaved, whereas the nonphenolic units remain essentially unaffected.

As an example of a-fi carbon bond cleavage may be cited the fragmentation arising from the alkaline hydrolysis of guaiacylglycerol-a-guaiacoxy-a-sulfonic acid-type compounds (reaction O, Fig. 1.5) (Kratzl et al. 1974). This reaction is the basis for the commercial manufacture of vanillin from spent sulfite liquor. 

Can be prepd by diazotization of 6-nitro-4-aminotoluene-3-sulfonic acid with K nitrite and dil sulfuric acid. It has also been isolated by Batik (Ref 2) from the wash w in the sulfite purification of TNT. It was assumed that the following reaction takes place ... 

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