Sulfonation effect

Chemical shifts and coupling constants have been used for structural, conformational and stereochemical assignments and preferences and for the establishment of the four-membered ring sulfone effect . ... 

Block, E., Bazzi, A.A., Lambert, J.B., Wharry, S.M., Andersen, K.K., Dittmer, D.C., Patwardhan, B.H., and Smith, J.H., Carbon-13 and oxygen-17 nuclear magnetic resonance studies of organosulfur compounds the four-membered-ring-sulfone effect, J. Org. Chem., 45, 4807, 1980. 

Emulsion, oil-soluble sulfonate. Effective wetting, surface tension reducer and defocuner over a wide pH range. 

An example of the time effects in irreversible adsorption of a surfactant system is shown in Fig. XI-8 for barium dinonylnapthalene sulfonate (an oil additive) adsorbing on Ti02 (anatase). Adsorption was ineversible for aged systems, but much less so for those equilibrating for a short time. The adsorption of aqueous methylene blue (note Section XI-4) on TiOi (anatase) was also irreversible [128]. In these situations it seems necessary to postulate at least a two-stage sequence, such as... 

Carbamates such as Aldicarb undergo degradation under both aerobic and anaerobic conditions. Indeed the oxidation of the sulfur moiety to the sulfoxide and sulfone is part of the activation of the compound to its most potent form. Subsequent aerobic metaboHsm can completely mineralize the compound, although this process is usually relatively slow so that it is an effective iasecticide, acaricide and nematocide. Anaerobically these compounds are hydrolyzed, and then mineralized by methanogens (61). 

Nitrations can be performed in homogeneous media, using tetramethylene sulfone or nitromethane (nitroethane) as solvent. A large variety of aromatic compounds have been nitrated with nitronium salts in excellent yields in nonaqueous media. Sensitive compounds, otherwise easily hydroly2ed or oxidized by nitric acid, can be nitrated without secondary effects. Nitration of aromatic compounds is considered an irreversible reaction. However, the reversibihty of the reaction has been demonstrated in some cases, eg, 9-nitroanthracene, as well as pentamethylnitrobenzene transnitrate benzene, toluene, and mesitylene in the presence of superacids (158) (see Nitration). 

Sulfonated styrene—divinylbensene cross-linked polymers have been appHed in many of the previously mentioned reactions and also in the acylation of thiophene with acetic anhydride and acetyl chloride (209). Resins of this type (Dowex 50, Amherljte IR-112, and Permutit Q) are particularly effective catalysts in the alkylation of phenols with olefins (such as propylene, isobutylene, diisobutylene), alkyl haUdes, and alcohols (210) (see Ion exchange). Superacids. 

Solid Superacids. Most large-scale petrochemical and chemical industrial processes ate preferably done, whenever possible, over soHd catalysts. SoHd acid systems have been developed with considerably higher acidity than those of acidic oxides. Graphite-intercalated AlCl is an effective sohd Friedel-Crafts catalyst but loses catalytic activity because of partial hydrolysis and leaching of the Lewis acid halide from the graphite. Aluminum chloride can also be complexed to sulfonate polystyrene resins but again the stabiUty of the catalyst is limited. 

A.lkyl Sulfosuccinate Half Asters. These detergents are prepared by reaction of maleic anhydride and a primary fatty alcohol, followed by sulfonation with sodium bisulfite. A typical member of this group is disodium lauryl sulfosucciaate [26838-05-1]. Although not known as effective foamers, these surfactants can boost foams and act as stabilizers when used ia combination with other anionic surfactants. In combination with alkyl sulfates, they are said to reduce the irritation effects of the latter (6). 

A.lpha-Olefm Sulfonates. Sulfonation of alpha-olefins yields a mixture of alkene sulfonates, hydroxyalkane sulfonates, and some amount of various disulfonates. These detergents are excellent foamers with good detergency properties. They are unaffected ia hard water and thek effects are considered superior to the alkyl ether sulfates (9). 

Sulphenone /5 (9-J(9-, /)-chlorophenyl phenyl sulfone (142), is a white soHd (mp 98°C). The technical material consists of ca 80% of this compound, with small amounts of 0- and y -isomers, bis(/)-chlorophenyl) sulfone, and diphenyl sulfone. Sulphenone is effective against all stages of mites. Its oral LD q to the rat is >2000 mg. 

Although most greases offer some inherent protection against msting, additives, eg, amine salts, sodium sulfonate, cycloparaffin (naphthenate) salts, esters, and nonionic surfactants (qv), are often used to provide added protection against water and salt-spray corrosion. A dispersion of sodium nitrite has been particularly effective in some multipurpose greases. 

Sulfonation increases the water solubiUty of dyes. A sulfonic group is electron withdrawing but has a weakening effect on the fluorescence only if it is ortho to the donor group. For example, in Brilliant Sulfoflavine FF [2391-30-2] (17), where R = p-tolyl, —it has a weakening effect, although the cleanness of the fluorescent color is somewhat improved compared to that of the unsulfonated compound. 

Acid mixtures containing nitric acid and a strong acid, eg, sulfuric acid, perchloric acid, selenic acid, hydrofluoric acid, boron trifluoride, or an ion-exchange resin containing sulfonic acid groups, can be used as the nitrating feedstock for ionic nitrations. These strong acids are catalysts that result in the formation of nitronium ions, NO" 2- Sulfuric acid is almost always used industrially since it is both effective and relatively inexpensive. 

A further measure of improvement has resulted ia a cycHc process for the electrochemical syathesis of NH (196). The catalyst is /n j -W(N2)2(dppe)2 or less effectively its Mo analogue. The choice of acid is important so as to provide a ligand duriag part of the cycle, yet also an effective leaving group when the catalyst is reformed. A sulfonic acid is used. 

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