Sulfamic sulfonation with

Chlorobenzene reacts with an equimolar amount of chlorosulfonic acid to give mainly the p-sulfonic acid together with a little of the sulfonyl chloride and the sulfone. With an excess of the reagent good yields of p-chlorobenzenesulfonyl chloride are obtained. The kinetics of the sulfonation of chlorobenzene with chlorosulfonic acid have been studied, and the reaction has been reported in several patents. These involved various modifications such as the use of excess reagent in hydrocarbon solvents containing alkali metal or ammonium salts, or a mixture of the reagent with thionyl chloride in the presence of sulfamic acid, sodium sulfate or dimethylformamide. In the reaction, the yield of 4,4 -dichlorodiphenyl sulfone can be increased under a variety of conditions the... 

Sulfation by sulfamic acid has been used ia the preparation of detergents from dodecyl, oleyl, and other higher alcohols. It is also used ia sulfating phenols and phenol—ethylene oxide condensation products. Secondary alcohols react ia the presence of an amide catalyst, eg, acetamide or urea (24). Pyridine has also been used. Tertiary alcohols do not react. Reactions with phenols yield phenyl ammonium sulfates. These reactions iaclude those of naphthols, cresol, anisole, anethole, pyrocatechol, and hydroquinone. Ammonium aryl sulfates are formed as iatermediates and sulfonates are formed by subsequent rearrangement (25,26). 

Amides react ia certain cases to form ammonium salts of sulfonated amides (22). For example, treatment with ben2amide yields ammonium A/-ben2oylsulfamate [83930-12-5] C H CONHSO NH, and treatment with ammonium sulfamate yields dianmioiiiumimidodisulfonate [13597-84-17, HN(S020NH 2 Ammonium sulfamate or sulfamic acid and ammonium carbonate dehydrate Hquid or soHd amides to nitriles (27). 

Sulfation andSulfamation. Sulfamic acid can be regarded as an ammonia—SO. complex and has been used thus commercially, always in anhydrous systems. Sulfation of mono-, ie, primary and secondary, alcohols polyhydric alcohols unsaturated alcohols phenols and phenolethylene oxide condensation products has been performed with sulfamic acid (see Sulfonation and sulfation). The best-known appHcation of sulfamic acid for sulfamation is the preparation of sodium cyclohexylsulfamate [139-05-9] which is a synthetic sweetener (see Sweeteners). 

Before coupling, excess nitrous acid must be destroyed. Nitrite can react with coupling components to form nitroso compounds causiag deHterious effects on the final dyestuff. The presence of nitrite can be detected by 4,4 -diamiQO-diphenyHnethane-2,2 -sulfone [10215-25-5] (Green reagent) or starch—iodide. Removal of nitrite is achieved by addition of sulfamic acid or urea [57-13-6], however, sulfamic acid [5329-14-6] has been more effective ia kinetic studies of nine nitrous acid scavangers (18). 

Zinc chloride is a Lewis acid catalyst that promotes cellulose esterification. However, because of the large quantities required, this type of catalyst would be uneconomical for commercial use. Other compounds such as titanium alkoxides, eg, tetrabutoxytitanium (80), sulfate salts containing cadmium, aluminum, and ammonium ions (81), sulfamic acid, and ammonium sulfate (82) have been reported as catalysts for cellulose acetate production. In general, they require reaction temperatures above 50°C for complete esterification. Relatively small amounts (<0.5%) of sulfuric acid combined with phosphoric acid (83), sulfonic acids, eg, methanesulfonic, or alkyl phosphites (84) have been reported as good acetylation catalysts, especially at reaction temperatures above 90°C. 

Sulfonates react with a variety of nucleophiles. Synthesis of M A -bis(trifluoro-methyl)aminotnfluoromethanesulfonate and its reactions with nucleophiles were investigated [33] (equation 31) (Table 13). Nucleophilic attack occurs at either nitrogen or sulfur amines give complex mixtures [33]. Polyfluoroalkyl fluorosul-fates react with amines, alcohols, or alkoxides to yield polyfluoroalkyl sulfamates and dialkyl sulfates, respectively [34] (equation 32) (Table 13). In these reactions. 

Salts of /3-styrenesulfonic acid have been prepared by the sulfonation of styrene with dioxane sulfotrioxide,2 by heating styrene with ammonium sulfamate,3 or by the reaction of styrene with sodium bisulfite in the presence of oxygen.4... 

Polystyrene-bound aliphatic sulfonic esters and O-aryl sulfamates can be cleaved by treatment with potassium carbonate or other nucleophiles, whereby the corresponding alcohols are released into solution (Entries 11 and 12, Table 3.34). O-Alkyl sulfamates, on the other hand, do not react with nucleophiles and cannot be used as linkers for alcohols [245],... 

PIRIA REACTION. Formation of arylsulfamic acids or sulfonation pioducts oi both by refluxing aromatic nitro compounds with a metal sulfite and boiling the mixture with dilute add to yield the amines and sulfamic acids. 

Thiazolyl sulfamic acids, rearrangement of sulfonic acid, 70 rearrangement to sulfonic acid, 75 by sulfonation, 75 2-Thiazolyl sulfenyl chloride, transformation to, thiazolyl disulfides. 412 2-Thiazolyl sulfide, in hydrocarbon synthesis, 406 oxidation of, with m-chloroperbenzoic acid, 415 with CrOj, 415 with Hj02,405,415 with KMn04,415 physical properties, infrared, 405 NMR, 404 pKa, 404 ultraviolet, 404 preparation of, from 2-halothiazoles and 5-Thiazolyl sulfides, bis-5-thiazolyl sulfide, oxidation of, 415 general, 418 5-(2-hydroxythiazolyl)phenyl sulfide case, 418 physical properties, 418 preparation of, 417-418 table of compounds, 493-496 uses of. 442 2-Thiazolyl sulfinic acid, decomposition of, 413 preparation of, from 2-acetamidothiazole sulfonyl chloride, 413 from A-4-thiazoline-2-thione and H, 0, 393,413 table of compounds, 472-473 5-Thiazolyl sulfinic add, preparation of,... 

The use of tertiary amines, amides, ethers, and thioethers also gives this kind of adduct. Because the stability of the complex varies directly with the basic strength of the ligand, it is found that the reactivity (which is determined by the ease with which sulfur trioxide is released from the complex) is inversely related to the stability of the complex and hence the basic strength of the ligand. It is found that the typical reactions of sulfur trioxide (e.g., sulfonation, sulfation, and sulfamation) are also reactions of the sulfur trioxide adducts, but coordination moderates the reactivity of the sulfur trioxide and usually makes it easier to control the reaction. 

The antibacterial activity of monobactams has provided a great stimulus for synthetic work, and a large number of different compounds have been prepared.7 Sulfamic acid (86) can be used for sulfamation of fatty acid monoglycerides and other compounds. Reaction of aniline with hot sulfamic acid (170°C) afforded a mixture of sulfonic acids, namely orthanilic acid (99), sulfanilic acid (100) and the 2,4-disulfonic acid (101) (Scheme 43). 

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