Chlorosulfonic acid, reaction

EXPLOSION and FIRE CONCERNS flammable liquid when exposed to heat, flame, or oxidants NFPA rating Health 2, Flammability 2, Reactivity 0 dangerous explosion hazard reacts vigorously with oleum and chlorosulfonic acid reaction with water or steam produces toxic and corrosive fumes formation of peroxides may occur in containers that have been opened and remain in storage incompatible with strong oxidizers decomposes in the presence of moisture to form hydrochloric acid use dry ehemical, foam, carbon dioxide, or water spray for firefighting purposes. 

A monosulfate is formed when sulfuric [reaction (25)] or chlorosulfonic acid [reaction (26)] reacts with an alcohol ... 

Studies of the reaction of benzene with chlorosulfonic acid (one molar equivalent) showed that the major product was benzenesulfonic acid (Equation 21) with a little diphenyl sulfone. When an excess of chlorosulfonic acid was used benzenesulfonyl chloride was obtained (Equation 22). Spryskov and Kuz mina demonstrated the reversibility of Equation 22 and measured the equilibrium constants for several different aromatic substrates. In the benzene-chlorosulfonic acid reaction, the quantity of diphenyl sulfone produced was increased by addition of anhydrous benzenesulfonic acid, but not by benzenesulfonyl chloride. The sulfone therefore apparently derived from reaction of benzenesulfonic acid and benzene under the influence of chlorosulfonic acid. Sulfone formation appeared to be relatively favoured at low temperatures and this may be due to the formation of an intermediate pyrosulfuric acid (Equations 23,24). 

Chitosan was sulfonated by treatment with chlorosulfonic acid-formamide, in which the ratio of chitosan to formamide was 1 g 10 ml. Studies were made of the effects of the addition of chlorosulfonic acid, reaction temperature and time. The optimum conditions for the sulfonation were 4 ml of chlorosulfonic acid for 1 g of chitosan and a reaction temperature of 68 °C for 4 hours (see Chapter 5, Section 3.2). 

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). 

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 ... 

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. 

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). 

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. 

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). 

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). 

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. 

Bischloromethyl ether has been prepared by saturation of formalin with dry hydrogen chloride by the reaction of paraformaldehyde with phosphorus trichloride or phosphorus oxychloride, by solution of paraformaldehyde in concentrated sulfuric acid and treatment with ammonium chloride or dry hydrogen chloride, and by suspension of paraformaldehyde in seventy or eighty percent sulfuric acid and treatment with chlorosulfonic acid. It is formed together with the asymmetrical isomer when methyl ether is chlorinated and when paraformaldehyde is treated with chlorosulfonic acid. The present method has been published. ... 

Other direct methods for the sulfonation of the higher fatty acids are by the use of sulfur trioxide vapor or by the use of chlorosulfonic acid. Indirect methods are also available for the preparation of a-sulfo fatty acids and their salts from an a-bromo fatty acid made by the Hell-Volhard-Zelinsky reaction. The bromo compound may be converted directly to the sodium salt of a sulfonic acid through the Strecker reaction or may be converted to the mercaptan and oxidized to the sulfonate. Sulfonation of the lower fatty acids has been studied by Backer and co-workers. ... 

The next major bonded phase project was the development of the GBR resin, which stands for modified glucose bonded on both the backbone and the ring of basic PDVB gels. The manufacture of this product was ultimately achieved, as outlined later. The gel is first brominated, which places bromine atoms on both tertiary hydrogens of the PDVB. The brominated gel is then reacted with chlorosulfonic acid, and a specially treated reduced D-glucosamine is coupled to the gel. This process has the potential to covalently bond up to three sugar residues to each available divinylbenzene residue in the PDVB polymer. The exact reaction conditions used are proprietary however, the surface of the finished product is believed to look similar to Figs. 13.11 and 13.12. 

Aj Preparation of 5-Trifluoromethylaniline-2,4-Disulfonylchloride— H ml of chlorosulfonic acid Is cooled in an ice bath, and to the acid is added dropwise while stirring 26.6 grams of a,a,a-trifluoro-m-toluidine. 105 grams of sodium chloride is added during 1-2 hours, whereafter the temperature of the reaction mixture is raised slowly to 150°-160°C which temperature is maintained for three hours. After cooling the mixture, ice-cooled water is added, whereby 5-trifluoromethylaniline-2,4-disulfonyl chloride separates out from the mixture. 

Chilled 3-trifluoromethylaniline (32.2 g) is added dropwise over a 45-minute period to 150 ml of chlorosulfonic acid with stirring and cooling. The ice bath is removed and 140 g of sodium chloride is added over 3 hours. The mixture is heated on a water bath for 30 minutes, then gradually up to 160°C over 6 hours. The cooled reaction mixture is diluted with 500 ml of an ice water slurry and taken into ether. The ether is dried and evaporated to leave 5-triflu oromethylamine-2A-disulfonyl chloride. 

B) Preparation of 4-Amino-2-Chloro-5-(Methylsulfamyl)Benzenesulfonamide The 5-sub-stituted-2,4-dlsulfamyl anilines may be prepared by procedures described in the literature, for example, the general procedures in Monatsch. Chem. vol. 48, p 87 (1927), which involves the treatment of a m-substituted aniline with from 10 to 20 parts by weight of chlorosulfonic acid followed by the gradual addition of from about 90 to 170 parts by weight of sodium chloride. The resultant mixture is heated at approximately 150°C for about 2 hours after which the reaction mixture is poured into water and the resultant 5-substituted aniline-2,4-disulfonyl chloride is filtered and is then treated with concentrated ammonium hydroxide or suitable amine by standard procedures to obtain the corresponding disulfonamide. 

Quentin may have been the first to sulfonate (arylene ether sulfone).168 In this patent, it was demonstrated that the bisphenol A polysulfone could be sulfonated by chlorosulfonic acid to produce a sulfonated polyfarylene ether sulfone), which was used for desalination via reverse osmosis. However, the chlorosulfonic acid may be capable of cleaving the bisphenol A polysulfone partially at the iso-propylidene link or it might induce branching and crosslinking reactions by... 

Years ago sulfation with chlorosulfonic acid was the most significant industrial method to obtain alcohol sulfates because it offers multiple advantages over sulfation with sulfuric acid. The reaction proceeds with evolution of hydrogen chloride as follows ... 

Although widely used in the past and still used in special cases, the industrial sulfation with chlorosulfonic acid presents several problems which have caused the decline of this technique in favor of the more advantageous sulfation method with sulfur trioxide. These problems consist of evolution of the highly corrosive hydrogen chloride, heat transfer characteristics of the reaction, and the comparatively high level of chloride ion in the sulfated product compared with alcohol and alcohol ether sulfates obtained with sulfur trioxide. 

A published account of laboratory batch sulfations of Alfol 1214 SP, Alfol 1216 SP, and natural coconut alcohol using chlorosulfonic acid at atmospheric pressure and 16 L/min dry air sparged through the reaction mixture to remove HC1 is available [42], The optimal conditions and the characteristics of the triethanolamine alcohol sulfates obtained are shown in Table 1. 

Thirty percent of the weight of the chlorosulfonic acid fed is lost as HC1, which must be recovered by absorption or disposed of after neutralization. Neither process is financially attractive. An interesting alternative was suggested [43] consisting of the in situ production of chlorosulfonic acid by direct reaction of the spent HC1 with S03 in a packed tower precharged with chlorosulfonic acid. 

Chlorosulfonic acid, particularly with batch operation, is best suited for production of a range of products on a relatively small scale. Chlorosulfonic acid is still used for the sulfonation of fatty alcohols, fatty alcohol/ethoxylates, and related detergent raw materials with OH groups available for the attachment of an S03H group. For example, the reaction of lauryl alcohol with chlorosulfonic acid illustrates for example the chemistry involved ... 

Bozzetto (Bergamo, Italy) offers a continuous chlorosulfonic acid sulfona-tion process which comprises two water-jacketed glass vessels for sulfonation and neutralization, and an HC1 absorption column. Organic feedstock and chlorosulfonic acid are mixed on a rotating disk. Under the centrifugal action of the disk, the reaction mixture is sprayed as a thin film onto the wall of the reaction vessel. The acid product falls to the base of the reactor and then onto a similar rotating disk system, where it is mixed with alkali and sprayed onto the wall of the neutralization vessel. The unit is operated under slightly reduced pressure to remove HC1 gas. 

A 4 1 0.04 molar ratio of carboxylic acid, chlorosulfonic acid, and chloranil was used. A 2 1 mixture of chlorine and oxygen was passed into the reaction for 3 hours. 

---