Halogenation, using chlorosulfonic acid

Both types of wax are readily oxidized (24) and halogenated (116). The latter is an important commercial outlet, the products of which are used as extreme pressure additives for oil (112,113) and as intermediates in Friedel-Crafts condensations (119). Air oxidation leads to carboxylic acids, for which considerable use has been found both here and abroad. Sulfonates can be made by reaction of waxes with chlorosulfonic acid (37,104) or with sulfur dioxide and chlorine (46,99). 

When polystyrene is sulfonated in chlorinated hydrocarbons with a complex of dioxane-SOs, the polymer precipitates from solution at low concentrations. Complexes of ketones with SO3 can also be used to sulfonate polystyrene in halogenated solvents. The ratio of sulfonation is more favorable for poly(vinyl toluene) than it is for polystyrene at the same conditions. Also, sulfur dioxide swells polystyrene. The polymer can be sulfonated in this medium with sulfur trioxide or with chlorosulfonic acid. Polystyrene, sulfonated in CS2 with aluminum chloride catalyst, is water insoluble in a free acid form. ... 

In pyridine and with a suitably blocked derivative, the same reagent can be used selectively to introduce sulfate acid ester groups thus, 1,2 5,6-di-O-isopropylidene-D-glucose can be sulfated, and, on removal of the cyclic acetal groups, D-glucose 3-sulfate can be obtained as a suitable salt. Sulfur trioxide or chlorosulfonic acid in liquid sulfur dioxide, and sulfur trioxide in halogenated hydrocarbon solvents, pyridine, or iV,A -dimethylforma-mide, can also be employed for sulfation. 

Chloro-2-fluoronitrobenzene 105 was treated with excess chlorosulfonic acid (five equivalents) at room temperature (30 minutes) and the mixture was then heated at 120-130 °C (3 hours) to give 2-chloro-4-fluoro-5-nitrobenzenesulfonyl chloride 106 (Equation 34). Sulfonation occurred in the expected position (0/p to the halogens and m to the nitro group). The sulfonyl chloride 106 could be reduced, by reaction with tin(ii) chloride, to the corresponding thiol 107 which is used as a herbicide intermediate. ... 

Sulfation of alcohols with chlorosulfonic acid (Eq. 2) has been used in the laboratory and on an industrial scale to prepare sodium alkyl sulfates. The reaction is usually rapid in the presence or absence of solvents at 25-30°C and gives a product with little color. Unreactive solvents such as ether, dioxane, and halogenated hydrocarbons are commonly used in the sulfation reaction. Acetic acid has also been reported as a solvent for the sulfation of C5-C19 long-chain secondary alcohols. Table I gives several examples of the type of alcohols sulfated with chlorosulfonic acid. 

Modification reactions of PP aiming at producing suitably functionalized resins with enhanced affinity towards polar polymers are summarized in [1-3]. Important functionalization reactions involve the incorporation of reactive groups through, for example, halogenation, chlorosulfonation or peroxidation, reaction with azidosulfonyl benzoic acid and monomer grafting (e.g. maleic anhydride, acrylic add) through the action of peroxides. Such modified materials are used to provide blends with enhanced properties. 

Several rubbers may be crosslinked using divalent metal oxides, usually zinc oxide. There are a limited number of polymers that utilise this method, which is used with halogenated polymers such as polychloroprene [8], chloro- and bromobutyl, and chlorosulfonated polyethylene and carboxylated nitrile rubbers. The system may utilise the metal oxide alone or in combination with the organic accelerators used with sulfur-curing systems. In the case of halogenated polymers, magnesium oxide may be added to act as an acid scavenger. 

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