Chlorosulfonic acids

Chlorosulfonic acid [CSA] can be manufactured by using hydrrx hloric add and sulfur trioxide and the process varies depending on the mode of raw material available— whether liquid or gaseous. The reaction involved is S03+HQ=C1S020H 

Depending on the form in which the raw material is available, there are basically three known processes  

The entire system is under suction. The basic limitation of this process is high sulfate in the product (the general strength available is 98-99%) and a large quantity of effluent containing sulfuric as well as hydrochloric acids. 

Nissan independently developed this process using HCl gas obtained from reaction of sulfuric acid with chloride salts and SO3 gas by boiling oleum. 

4 Sulfonating Agents and Derivatives Based on Sulfuric Acid 

Chlorosulfonic acid was used to show the lamellar structure in both linear and branched PE and to study the effects of drawing and annealing [122, 136, 137]. Dlugosz et al [138] examined cryosections of drawn, rolled and annealed, bulk oriented PE which clearly showed a lamellar texture. Lamellae were shown to have two preferred orientations and to be arranged in 

A general method for staining PE with chlor-osulfonic acid is as follows. 

The stained lamellar texture is shown (Fig. 4.15) to result from the chlorosulfonation of linear PE crystallized isothermally from the melt [105]. Although large parts of the section show no detail, some regions do contain the parallel dark lines shown in this figure. These lines are a few hundred Angstroms apart, and they appear and 

Manufacture Chlorosulfonic acid is produced by the reaction of liquid sulfur trioxide with hydrogen chloride or by the gas phase reaction of sulfur trioxide, from catalyst tray contact in sulfuric acid plants, with an excess of dry hydrogen chloride at high temperatures. 

Applications Chlorosulfonic acid is mainly utilized as a dehydrating condensation agent in organic synthesis and in the sulfonation of long chain aliphatic alcohols. 70 10- t/a of chlorosulfonic acid is estimated to be currently produced in Western Europe. 

An important staining technique was developed by Kanig [114] for the enhanced contrast of polyethylene, a material which has been a model compound for fundamental polymer studies. PE crystals cannot be sectioned, nor are they stable in the electron beam, due to radiation damage. The chlorosulfonation procedure crosslinks. 

Staining was also applied (120°C) to the crystallization of PE [121,122]. The chlorosulfonation method has been applied to bulk polymers and high modulus fibers [123-125]. Smook et al. [125] studied the fracture process of ultrahigh strength PE fibers and used the method in a unique application to show the nature of the kink bands present. Highly oriented ultrahigh molecular weight PE fibers were shown to be preferentially attacked at these kink bands when exposed to the acid for 45 min at 80°C. 

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This simplified method gives 2-aminothiazole in good yield (50 to 70%) (311, 330), Other reactants can replace iodine, for example, chlorine, bromine, sulfuryl chloride, chlorosulfonic acid, or sulfur monochloride also give good results. 

Acetic acid Chromium(VI) oxide, chlorosulfonic acid, ethylene glycol, ethyleneimine, hydroxyl compounds, nitric acid, oleum, perchloric acid, peroxides, permanganates, potasssium r rf-butoxide, PCI3... 

Aniline Nitric acid, peroxides, oxidizing materials, acetic anhydride, chlorosulfonic acid, oleum, ozone... 

Chlorosulfonic acid Saturated and unsaturated acids, acid anhydrides, nitriles, acrolein, alcohols, ammonia, esters, HCl, HF, ketones, hydrogen peroxide, metal powders, nitric acid, organic materials, water... 

Hydrogen chloride Acetic anhydride, aluminum, 2-aminoethanol, ammonia, chlorosulfonic acid, ethylenediamine, fluorine, metal acetylides and carbides, oleum, perchloric acid, potassium permanganate, sodium, sulfuric acid... 

Mesityl oxide 2-Aminoethanol, chlorosulfonic acid, nitric acid, ethylenediamine, sulfuric acid... 

Nitric acid, fuming Organic matter, nonmetals, most metals, ammonia, chlorosulfonic acid, chromium trioxide, cyanides, dichromates, hydrazines, hydrides, HCN, HI, hydrogen sulflde, sulfur dioxide, sulfur halides, sulfuric acid, flammable liquids and gases... 

Nitropropane See under Nitromethane chlorosulfonic acid, oleum... 

A series of fiber-reactive dyes have been made by the reaction of Sulforhodamine B with chlorosulfonic acid, an appropriately substituted diamine, and cyanutic chloride to yield dyes, eg, a Sulforhodamine B derivative (34), with good hghtfastness (42). 

Alkylation. Ben2otrifluoride can also be alkylated, eg, chloromethyl methyl ether—chlorosulfonic acid forms 3-(trifluoromethyl)ben2yl chloride [705-29-3] (303,304), which can also be made from / -xylene by a chlorination—fluorination sequence (305). Exchange cyanation of this product in the presence of phase-transfer catalysts gives 3-(trifluoromethylphenyl)acetonitrile [2338-76-3] (304,305), a key intermediate to the herbicides flurtamone... 

Intermediate formation of formyl chloride is not necessary since the actual alkylating agent, HCO", can be produced by protonation of carbon monoxide or its complexes. However, it is difficult to obtain an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide. Suitable laboratory preparations involve the reaction of chlorosulfonic acid with formic acid or the reaction of ben2oyl chloride with formic acid ... 

Commercially, sulfonation is carried out by the classic method with sulfuric acid. Modem reactors are glass-lined older equipment was made from cast iron or coated with enamel Processes often use chlorosulfonic acid or sulfur trioxide to minimi2e the need of excess sulfuric acid. Improved analytical methods have contributed to the success of process optimi2ation (9—12). 

Sulfation and Sulfonation. a-Olefin reactions involving the introduction of sulfur-containing functional groups have commercial importance. As with many derivatives of olefins, several of these products have appHcations in the area of surfactants (qv) and detergents. Typical sulfur reagents utilized in these processes include sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide, and sodium bisulfite. 

Phthalocyanine sulfonic acids, which can be used as direct cotton dyes (1), are obtained by heating the metal phthalocyanines in oleum. One to four sulfo groups can be introduced in the 4-position by varying concentration, temperature, and reaction time (103). Sulfonyl chlorides, which are important intermediates, can be prepared from chlorosulfonic acid and phthalocyanines (104). The positions of the sulfonyl chloride groups are the same as those of the sulfonic acids (103). Other derivatives, eg, chlormethylphthalocyanines (105—107), / /f-butyl (108—111), amino (112), ethers (109,110,113—116), thioethers (117,118), carboxyl acids (119—122), esters (123), cyanides (112,124—127), and nitrocompounds (126), can be synthesized. 

Sulfonation. The main sulfonation product of quinoline at 220°C is 8-quinoHnesulfonic acid [85-48-3]-, at 300°C it rearranges to 6-quinolinesulfonic acid [65433-95-6] (10). Optimum conditions for sulfonation, 2 h at 140°C and a 1 4 quinoline/40% (wt) oleum ratio, produces 80% yield. The yield drops to 64% at 130°C with a 1 3 reactant ratio (11). Somewhat higher, but variable, yields of 8-quinoHnesulfonic acid hydrochloride [85-48-3] have been reported with chlorosulfonic acid (12). 

Reaction with cold nitric acid results primarily ia the formation of 5-nitrosahcyhc acid [96-97-9]. However, reaction with fuming nitric acid results ia decarboxylation as well as the formation of 2,4,6-trinitrophenol [88-89-1] (picric acid). Sulfonation with chlorosulfonic acid at 160°C yields 5-sulfosahcyhc acid [56507-30-3]. At higher temperatures (180°C) and with an excess of chlorosulfonic acid, 3,5-disulfosahcyhc acid forms. Sulfonation with hquid sulfur trioxide ia tetrachloroethylene leads to a nearly quantitative yield of 5-sulfosahcylc acid (1). 

Carbohydrates. Carbohydrates (240—244) of any form are easily sulfated in the presence of solvent, using sulfating reagents such as SO —pyridine, SO —triethjlamine, SO.—trimethyl amine, or chlorosulfonic acid—pyridine. As an example, starch (qv) is sulfated using SO.—trimethyl amine at 0 to 5°C in aqueous media (16). Sulfated carbohydrate products find some use in industry as thickening agents. 

An example of a sulfite ester made from thionyl chloride is the commercial iasecticide endosulfan [115-29-7]. A stepwise reaction of thionyl chloride with two different alcohols yields the commercial miticide, propaigite [2312-35-8] (189). Thionyl chloride also has appHcations as a co-reactant ia sulfonations and chlorosulfonations. A patent describes the use of thionyl chloride ia the preparation of a key iatermediate, bis(4-chlorophenyl) sulfone [80-07-9] which is used to make a commercial polysulfone engineering thermoplastic (see Polymers CONTAINING SULFUR, POLYSULFONe) (190). The sulfone group is derived from chlorosulfonic acid the thionyl chloride may be considered a co-reactant which removes water (see Sulfolanes and sulfones). 

The reaction of sulfuryl chloride with a stoichiometric amount of sulfuric acid produces chlorosulfuric acid [7790-94-5] (chlorosulfonic acid) ... 

This latter reaction is reversible. Sulfuryl chloride can be fractionally distilled from boiling chlorosulfonic acid ia the presence of a catalyst, eg, a mercuric salt. 

Because phenoHc compounds are easily sulfonated, their sulfation must be accompHshed with mil der sulfating agents, eg, complexes of sulfur thoxide or chlorosulfonic acid with trimethyl amine, dimethylform amide, pyhdine, or dim ethyl a n i1 in e, in anhydrous or aqueous medium below 100°C (86-89). 

SAMs of OH-terrninated alkanethiols have been used in many surface modification reactions (Fig. 14). These reacted with OTS to yield a weU-ordered bdayer (322), with octadecyldimethylchlorosilane (323,324), with POCI3 (325—327), with trifluoroacetic anhydride (328), epichlorohydrin (329), with alkyhsothiocyanate (330), with glutaric anhydride (331), and with chlorosulfonic acid (327). 

Toluenesulfonyl Chloride. Toluene reacts with chlorosulfonic acid to yield both ortho- and j )i7n7-toluenesulfonyl chlorides, of which Monsanto is the only producer. The ortho isomer is converted to saccharin. 

Sulfonation. Benzene is converted iato benzenesulfonic acid [98-11-3] C H SO, upon reaction with fuming sulfuric acid (oleum) or chlorosulfonic acid. y -Benzenedisulfonic acid [98-48-6] CgHgS20, is prepared by reaction of benzene-sulfonic acid with oleum for 8 h at 85°C. Often under these conditions, appreciable quantities ofT -benzenedisulfonic acid [31375-02-7] are produced. 1,3,5-Benzenetrisulfonic acid [617-99-2] C H S Og, is produced by heating the disulfonic acid with oleum at 230°C (21). 

A solution of sulfur trioxide [7446-11-9] dissolved in chlorosulfonic acid [7990-94-5] CISO H, has been used as a smoke (U.S. designation FS) but it is not a U.S. standard agent (see Chlorosulfuric acid Sulfuric acid and sulfur trioxide). When FS is atomized in air, the sulfur trioxide evaporates from the small droplets and reacts with atmospheric moisture to form sulfuric acid vapor. This vapor condenses into minute droplets that form a dense white cloud. FS produces its effect almost instantaneously upon mechanical atomization into the atmosphere, except at very low temperatures. At such temperatures, the small amount of moisture normally present in the atmosphere, requires that FS be thermally generated with the addition of steam to be effective. FS can be used as a fill for artillery and mortar shells and bombs and can be effectively dispersed from low performance aircraft spray tanks. FS is both corrosive and toxic in the presence of moisture, which imposes limitations on its storage, handling, and use. 

Chlorosulfonation of benzotrichloride with chlorosulfonic acid (28) or with sulfur trioxide (29) gives y -chlorosulfonyl benzoyl chloride [4052-92-0] in high yield. Nitration with nitronium fluoroborate in sulfolane gives 68% y -nitro-benzotrichloride [709-58-0] along with 13% of the ortho and 19% of the para isomers (30). 

Although chlorosulfuric acid [7790-94-5] CISO H, is the Chemicaly hstracts name, chlorosulfonic acid is the commercial designation by which this compound is more widely known. Other synonyms include sulfuric chlorohydrin, sulfuric acid chlorohydrin, monochlorosulfuric acid, chlorohydrated sulfuric acid, monochlorosulfonic acid, and chlorohydrosulfurous acid. 

In cases where a large excess of acid is undesirable, chlorosulfonic acid is employed. An excess of chlorosulfonic acid leads to the introduction of a chlorosulfonyl group which is a useful synthon for the preparation of sulfonamides and sulfonate esters. 

In the first case (22), almost stoichiometric amounts of sulfuric acid or chlorosulfonic acid are used. The amine sulfate or the amine chlorosulfate is, first, formed and heated to about 180 or 130°C, respectively, to rearrange the salt. The introduction of the sulfonic acid group occurs only in the ortho position, and an almost quantitative amount of l-aminoanthraquinone-2-sulfonic acid is obtained. On the other hand, the use of oleum (23) requires a large excess of SO to complete the reaction, and inevitably produces over-sulfonated compound such as l-amino-anthraquinone-2,4-disulfonic acid. Addition of sodium sulfate reduces the byproduct to a certain extent. Improved processes have been proposed to make the isolation of the intermediate (19) uimecessary (24,25). 

The hydrolysis of ethyl acetate, prepared by the reaction of ethylene with acetic acid under pressure (154), and the hydrolysis of the ethyl ester of chlorosulfonic acid (155) have been considered and found to be of Httie industrial importance. 

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