A-Disulfones

Sulfonates with ether linkages include ring-sulfonated alkylphenol ethoxylates and a disulfonated alkyldiphenyl oxide, Dowfax 2A1, and 3B2 (Dow Chemical Company). This surfactant is characterized by high solubiUty in salt solutions, strong acids, or bases. It is used in industrial and institutional cleaners. 

Anthraquinone-a,a -disulfonic acids and Related Compounds. Anthraquinone-a,a -disulfonic acids and their derivatives are important intermediates for manufacturing disperse blue dyes (via 1,5-, or 1,8-dihydroxyanthraquinone, or 1,5-dichloroanthraquinone) and vat dyes (via... 

Phenyl-l,2-benzisoxazole has been reported to give a disulfonic acid of unknown structure on treatment with 40% oleum (67AHC(8)277). The chlorosulfonation of 1,2-benzisoxazole-3-acetic acid has been reported to give a mixture of the two products shown in Scheme 26. 

The first of these can be made by careful hydrolysis of the A, A -disulfonate which is itself made by the reaction of SO2 and a nitrite in cold alkaline solution ... 

Oxidation of hydroxylamine A, A -disulfonate with permanganate or Pb02 yields the intriguing... 

Hydroxylamine trisulfonates, e.g. (K03S)0N-(S03K)2 are made by the reaction of K2SO3 with potassium nitrosodisulfonate (Fremy s salt). Acidification of the product results in rapid hydrolysis to the 0,A-disulfonate which can be isolated as the exclusive product ... 

Sulfonation with sulfur trioxide, pyridine sulfur trioxide, pyridine bis-sulfur trioxide, and dioxane sulfur trioxide, which are useful sul-fonating agents for acidophobic substances, have been applied to the thiophene seriesd At room temperature the 2-monosulfonic acid (isolated as the barium salt) is obtained in 86% yield. Higher temperatures lead to a disulfonic acid. However, sulfonation with chloro-sulfonic acid appears to be more convenient,as the sulfonyl chloride obtained can be used directly for the preparation of derivatives. 

Flooding. The nucleophilic reaction of phenyl a-disulfone with hydrazine25 occurs according to the equation... 

Dimethyl a-disulfone forms the fragments shown in equation (35) under electron impact at 70 eV. The fragmentation processes are closely related to the thermal484 and photochemical48 results reported for diaryl a-disulfones. In contrast to MeS02SMe, MeS02S02Me shows no indication of the formation of MeS(OH)2 + 48b. 

FIG. 25 Interfacial tension isotherms for homologous n-alkanesulfonates and a disulfonate mixture in the heptane/water system (1-9 RS03Na, R = C9H20 to C17H36 10 disulfonate mixture). 

The hydrophobicity index is also suitable for correlating the cM values of various substituted sodium alkane 1-sulfonates [68]. The perfluoroalkyl substituent, e.g., 8 17 has a pronounced hydrophobic effect (/ = 1.66 at 75°C, sodium salt), whereas the hydrophilic disulfonates have values distinctly below 1 (for a-disulfonates, / = 0.75 was derived [70]). Further, it was somewhat surprisingly shown that substituents like 1-hydroxymethyl, 3-hydroxyethoxy, or even the hydroxyethoxyethoxy groups have hydrophobic effects. 

A study over a broader range of disulfonate monosulfonate ratios was then conducted with a series of AOS 2024 surfactants. Results are shown in Fig. 5. The carbon number and hydrophobe branching were held constant. The AS HAS ratio was 75 25. At a disulfonate monosulfonate ratio (D M) of 7 93, addition of less than 200 ppm calcium ion decreased solution transmittance to less than 10% of its initial value. When the disulfonate content of AOS 2024 was increased to 38 wt % (di monosulfonate ratio of 38 62), slightly more than 1000 ppm calcium ion was required to reduce solution transmittance to less than 10% of its initial value. When the surfactant consisted predominantly of disulfonate (di monosulfonate ratio of 84 16), the addition of more than 41,000 ppm calcium ion reduced the transmittance by less than 5% from its initial value. 

In spite of the good calcium and magnesium tolerance of AOS systems, situations can arise whereby too many exchangeable hardness ions present themselves to the surfactant formulation. One way to overcome this is by blending AOS with a divalent cation-tolerant surfactant. A product which has been field-tested [87] is a blend of AOS and a disulfonated alkyldiphenyloxide (DPOS). Calcium and magnesium salts of DPOS are water-soluble and remain soluble even in solutions which are very concentrated in calcium and magnesium salts. 

In view of the immense commercial importance of phthalocyanines as pigments, it is perhaps surprising that only a few are of importance as textile dyes. This is primarily due to the size of the molecules they are too large to allow penetration into many fibres, especially the synthetic fibres polyester and polyacrylonitrile. An example of a phthalocyanine dye which may be used to dye cellulosic substrates such as cotton and paper is C. I. Direct Blue 86 (96), a disulfonated copper phthalocyanine. In addition, a few blue reactive dyes for cotton incorporate the copper phthalocyanine system as the chromophoric unit (Chapter 8). 

Anthraquinone-1-sulfonic acid, 9 313-314 Anthraquinone-a,a -disulfonic acids, 9 314-315... 

Reactivity toward nucleophiles and comparison with other electrophilic centers 152 Paths for nucleophilic substitution of sulfonyl derivatives 156 Direct substitution at sulfonyl sulfur stereochemistry 157 Direct substitution at sulfonyl sulfur stepwise or concerted 158 The elimination-addition path for substitution of alkanesulfonyl derivatives 166 Homolytic decomposition of a-disulfones 172 10 Concluding remarks 173 Acknowledgement 174 References 174... 

Although most oxidations of sulfinic acids lead to sulfonic acids, some do not. Oxidation with Co(III) gives the corresponding a-disulfones in reasonably good yield (104) (Denzer et al., 1966). The mechanism of this synthetically useful reaction is not known. Two possibilities have been suggested (Denzer et... 

From Table 6 one sees that hypochlorite ion is one of the most reactive nucleophiles toward a sulfinyl sulfone. Examination of its reaction with phenyl benzenesulfinyl sulfone, PhS(0)S02Ph, reveals that, while the majority of the products are ones resulting from a cleavage of the S—S bond, about 10% of the original sulfinyl sulfone is converted to phenyl a-disulfone (Kice and Puls, 1977). The most straightforward mechanistic explanation for this result is to assume that attack of OC1 on the sulfinyl sulfone leads initially to intermediate [51]. This can then break up either by cleavage of the S—S bond (path a) or by expulsion of a chloride ion (path b), this latter path yielding the a-disulfone. Other explanations for the formation of the small amount of a-disulfone seem either much less likely, or very contrived (Kice and Puls, 1977). The reaction of... 

That an a-disulfone may properly be considered to be a mixed anhydride of a sulfinic and a sulfonic acid is shown by the fact that a-disulfones undergo relatively easy spontaneous hydrolysis (188) to give one molecule each of a sulfinic and a sulfonic acid (Kice and Kasperek, 1969). 

Aryl a-disulfones do undergo thermal decomposition by a homolytic mechanism but about 101 times slower than the corresponding aryl sulfinyl sulfones (Kice and Favstritsky, 1970). The reason is that AHX for homolytic dissociation of the S—S bond in the tr-disulfone (210) is about 13 kcal mol-1... 

M acid ORG chem NH2CioH5(OH)S03H A sulfonic acid formed by alkaline fusion of a disulfonic acid of a-naphthylamine used as a dye intermediate. em, as-3d Macquer s salt See potassium arsenate. mo kerz, s6lt ... 

Can be prepd by fusing benzene-met a-disulfonic acid with NaOH, and dissolving the melt in water. After acidifying the soln with HC1, the resorcinol is extracted with a volatile solvent and the solvent evaporated, purification can be achieved by distillation... 

The rates of spontaneous hydrolysis of aryl a-disulfones and aryl sulfinyl sulfones in dioxan-water are similar in their response to reaction variables solvent composition, electronic effects (p = +3.5), activation parameters and solvent deuterium isotope effects AfeoMuio = 2.3,BS. The difference in rate (the aryl a-disulfone hydrolyzing some 10,000 times more slowly) is principally the result of a more unfavorable energy of activation and not a change in... 

There is surprisingly little reliable information on the sulfonation of benzo[6]thiophene or its derivatives. Benzo[6]thiophene is more readily sulfonated than naphthalene.699 Reaction with concentrated sulfuric acid at 80° gives a mixture of mono-, di-, and trisulfonic acids, reaction with 70% sulfuric acid at 80° gives a monosulfonic acid,699 and reaction with 18% oleum gives a disulfonic acid 86 in each case the orientation of the products is unknown. Treatment of benzo[6]thiophene with concentrated sulfuric acid in acetic anhydride at 20° gives 3-acetylbenzo[6]thiophene (ca. 10%) and a sulfonation product (isolated as the potassium salt), which was believed to be the 3-sulfonic acid.660 Recently, the sulfonation product has been shown to contain the 2- (8%) and 3-isomer (92%), by conversion into the sulfonyl chlorides and reduction to a separable mixture of 2- and 3-mercaptobenzo[6]thiophene.84... 

Potassium benzo[6]thiophene-4-sulfonate may be prepared by treating 4-mercaptobenzo[6]thiophene in dimethylformamide with oxygen in the presence of potassium hydroxide. It gives a disulfonic acid of undetermined structure on further sulfonation.86... 

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