Sulfonate behavior

The difference in sulfonation behavior between a-olefins (AO) and internal olefins (IO) has been a longstanding problem [14] and the literature is replete with earlier explanations [14,15] and practical solutions [16-20] to the problem of IO sulfonation. In their studies of IO sulfonation chemistry, Stapersma and colleagues [4], Radici et al. [21], Yoshimura et al. [22,23], and Roberts and Jackson [24] identified the origins of the poor sulfonatability of IO, and the process modifications required to produce good-quality IO sulfonate. 

The fragmentation of dibenzothiophene sulfoxide resembles that of dibenzothiophene rather than that of the sulfone. This is due to primary loss of 0 to give the dibenzothiophene ion, which is the strongest feature of the spectrum. Much of the breakdown which follows is due to that of the dibenzothiophene ion. There are, however, some aspects of sulfone behavior, notably the formation of the dibenzofuran ion (14) by the loss of sulfur from the rearranged molecular ion (13). ... 

Figure 10. Logarithm of self-diffusion coefficient vs. polymer-fraction function for 1200-EW perfluorosulfonate polymer, at 25°C. Na and Cs" lines without data points polystyrene sulfonate behavior. (Refs. 163 and 207 reprinted by permission of the publisher. The Electrochemical Society, Inc.)...

Alonso, I., Alcami, M., Mauledn, P. and Carretero, J.C. (2006) Understanding sulfone behavior in palladium-catalyzed domino reactions with aryl iodides. Chem. Eur. J., 12, 4576-83. 

Thus, in its sulfonation behavior quinoline resembles naphthalene with respect to the kinetic and thermodynamic product control. 

Fig. XI-13. Adsorption isotherms for SNBS (sodium p-3-nonylbenzene sulfonate) (pH 4.1) and DPC (dodecyl pyridinium chloride) (pH 8.0) on mtile at approximately the same surface potential and NaCl concentration of O.OlAf showing the four regimes of surfactant adsorption behavior, from Ref. 175. [Reprinted with permission from Luuk K. Koopal, Ellen M. Lee, and Marcel R. Bohmer, J. Colloid Interface Science, 170, 85-97 (1995). Copyright Academic Press.]...

Amphoteric Detergents. These surfactants, also known as ampholytics, have both cationic and anionic charged groups ki thek composition. The cationic groups are usually amino or quaternary forms while the anionic sites consist of carboxylates, sulfates, or sulfonates. Amphoterics have compatibihty with anionics, nonionics, and cationics. The pH of the surfactant solution determines the charge exhibited by the amphoteric under alkaline conditions it behaves anionically while ki an acidic condition it has a cationic behavior. Most amphoterics are derivatives of imidazoline or betaine. Sodium lauroamphoacetate [68647-44-9] has been recommended for use ki non-eye stinging shampoos (12). Combkiations of amphoterics with cationics have provided the basis for conditioning shampoos (13). 

EPDM-Derived Ionomers. Another type of ionomer containing sulfonate, as opposed to carboxyl anions, has been obtained by sulfonating ethylene—propjlene—diene (EPDM) mbbers (59,60). Due to the strength of the cross-link, these polymers are not inherently melt-processible, but the addition of other metal salts such as zinc stearate introduces thermoplastic behavior (61,62). These interesting polymers are classified as thermoplastic elastomers (see ELASTOLffiRS,SYNTHETIC-THERMOPLASTICELASTOLffiRS). 

Linear alkylbenzenesulfonic acid is the largest intermediate used for surfactant production in the world. In the United States it has been determined that 2.6 g/d of material is used per inhabitant (46). Owing to the large volumes of production and consumption of linear alkylbenzenesulfonate, much attention has been paid to its biodegradation and a series of evaluations have been performed to thoroughly study its behavior in the environment (47—56). Much less attention has been paid to the environmental impact of other sulfonic acid-based materials. 

Because a neutral molecule is eliminate4 rather than an anion, there is no electrostatic attraction (ion pairing) between the products of the dissociation step. As a result, the carbocations generated by diazonium-ion decomposition frequently exhibit somewhat different behavior from those generated from halides or sulfonates under solvolytic conditions. ... 

The relative stability of the intermediates determines the position of substitution under kinetically controlled conditions. For naphthalene, the preferred site for electrophilic attack is the 1-position. Two factors can result in substitution at the 2-position. If the electrophile is very bulky, the hydrogen on the adjacent ring may cause a steric preference for attack at C-2. Under conditions of reversible substitution, where relative thermodynamic stability is the controlling factor, 2-substitution is frequently preferred. An example of this behavior is in sulfonation, where low-temperature reaction gives the 1-isomer but at elevated temperatures the 2-isomer is formed. ... 

In conclusion, all results obtained thus far on this reaetion show that it is espeeially the 4-position in the 3-nitro-l,8-naphthyridines whieh is strongly favored toward the attaek of the earbanion of ehloromethyl phenyl sulfone. When position 4 is oeeupied by a substituent no reaetion oeeurs. Tliis behavior is in aeeordanee with the behavior observed in reaetions with liquid ammonia and liquid methylamine. 

Allyl sulfonates (35, 36) show analogous behavior. Transfer constants are reported in Tabic 6.8. Other compounds with weak A-R bonds cf. 11) that have the capacity to act as transfer agents are listed in fable 6,9. Allyl bromides 43a, 44, and 45a give predominantly chain transfer whereas, the chlorides (e.g. 45b)... 

Normally, reactive derivatives of sulfonic acids serve to transfer electrophilic sulfonyl groups259. The most frequently applied compounds of this type are sulfonyl halides, though they show an ambiguous reaction behavior (cf. Section III.B). This ambiguity is additionally enhanced by the structure of sulfonyl halides and by the reaction conditions in the course of electrophilic sulfonyl transfers. On the one hand, sulfonyl halides can displace halides by an addition-elimination mechanism on the other hand, as a consequence of the possibility of the formation of a carbanion a to the sulfonyl halide function, sulfenes can arise after halide elimination and show electrophilic as well as dipolarophilic properties. 

Several theoretical and experimental characteristics of the sulfone and sulfoxide groups are substantially modified when these are incorporated within a cyclic array. As a rule, the smaller the ring size the larger the deviation from the normal expected properties and behavior of the sulfone and sulfoxide groups. 

Similarly, only selected cyclic systems containing more than one sulfoxide or sulfone groups have been included and discussed here, primarily in the thietane (i.e. 1,2- and 1,3-dithietanes) and thiane (i.e. 1,2-, 1,3- and 1,4-dithianes) series. The criterion for the inclusion of these multifunctional heterocycles was their contribution to the understanding of the physical properties and chemical reactivity of cyclic sulfones and sulfoxides, and the effects of these groups on either their immediate vicinity or on the behavior of the whole molecule. 

Stereochemical constraints in cyclic sulfones and sulfoxides impart increased weight to strain and conformational factors in the generation of carbanions and their stability, causing distinct differences between the behavior of cyclic and open-chain systems233, due primarily to the prevention of extensive rotation about the C —S bond, which is the major way that achiral carbanions racemize. Study of the a-H/D exchange rate fce and the racemization rate ka may provide information concerning the acidity-stereochemical relationships in optically active cyclic sulfone and sulfoxide systems. 

The distorted sp3 angles at both carbon and sulfur atoms in small ring sulfoxides and sulfones approach their normal size beginning with the thianes. Consequently, the characteristics and chemical behavior of six- and higher-membered sulfoxides and sulfones are expected to be similar to those of the acyclic counterparts. However, in view of the constraints imposed by the cyclic array, three issues deserve study ... 

In principle, the properties and chemical behavior of cyclic sulfoxides and sulfones having a ring size of seven and up are expected to be quite similar to those of the analogous acyclic systems. 

Meyers212 collected together several examples of the anomalous behavior of sulfones in which the group was close to the reaction center and interpreted these in terms of the negative direct field effect of the S02 oxygen atoms (cf. Meyers and colleagues141). 

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