Chlorosulfonates

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). 

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

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... 

Many cellular plastics that have not reached significant commercial use have been introduced or their manufacture described in Hterature. Examples of such polymers are chlorinated or chlorosulfonated polyethylene, a copolymer of vinyUdene fluoride and hexafluoropropylene, polyamides (4), polytetrafluoroethylene (5), styrene—acrylonitrile copolymers (6,7), polyimides (8), and ethylene—propylene copolymers (9). 

Most elastomers can be made iato either opea-ceUed or closed-ceUed materials. Natural mbber, SBR, nitrile mbber, polychloroprene, chlorosulfonated polyethylene, ethylene—propylene terpolymers, butyl mbbers, and polyacrylates have been successfuUy used (4,111,112). 

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. 

The use of TAG as a curing agent continues to grow for polyolefins and olefin copolymer plastics and mbbers. Examples include polyethylene (109), chlorosulfonated polyethylene (110), polypropylene (111), ethylene—vinyl acetate (112), ethylene—propylene copolymer (113), acrylonitrile copolymers (114), and methylstyrene polymers (115). In ethylene—propylene copolymer mbber compositions. TAG has been used for injection molding of fenders (116). Unsaturated elastomers, such as EPDM, cross link with TAG by hydrogen abstraction and addition to double bonds in the presence of peroxyketal catalysts (117) (see Elastol rs, synthetic). 

The resulting acetyl compound is usually hydrolyzed with aqueous alkaU to give the free amine. Other A/-acyl derivatives may be used, particularly for the less soluble succinyl and phthaloyl products. The use of -nitrobenzenesulfonyl chloride, followed by reduction of the nitro to an amino function, is much more expensive and is rarely used. A/-Acetylsulfanilyl chloride [121 -60-8] is obtained by the chlorosulfonation of acetanilide [103-84-4] which is the basic material for most of the sulfonamides. 

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