Chlorosulfonic acid chloride esters

Chlorosulfonic acid esters Sulfuric acid chloride esters 15 Fluorosulfonic acid esters... 

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. 

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). 

Methylpiperidine Stannous chloride dihydrate 2-Ethoxybenzoyl chloride 4-Dimethylaminopyridine Triethylamine Hydrogen peroxide Chlorosulfonic acid 5-carboxylic acid ethyl ester... 

Diketones are synthesized by Claisen condensation of appropriate acetyl methyl ketone and ethyl perfluoroalkyl carboxylate. For example, 4,4/-bis(l",l,/,l//,2//,2",3//,3//-heptafluoro-4//,6//-hexanedion-6"-yl)-chlorosulfo-o-terphenyl (BHHCT) was synthesized from o-terphenyl by three step reactions (scheme 3 (Yuan et al., 1998a, 1998b)). The o-ter-phenyl are acetylated by acetyl chloride with anhydrous aluminum chloride as a Lewis acid and 4,4 -diacetyl-e>-terphcnyl is obtained. Then, the 4,4/-diacetyl-o-terphenyl is reacted with perfluoropropionic acid ethyl ester with sodium methoxide as a base. Finally, 4,4,-bis(l", 1",l//,2,2,3,/,3"-heptafluoro-4//,6"-hexanedion-6//-yl)-o-terphenyl is chloro-sulfonylatcd by chlorosulfonic acid to form BHHCT. 

Sulfonation at C-4 can be accomplished with sulfur trioxide complexed with dioxane. Chlorosulfonic acid introduces the sulfonyl chloride group into the ring from which esters and sulfonamides can be made (79AP977,81AP470, 503). 

The HjC-O-Te bonds are remarkably stable no cis-trans isomerization was observed when the hydroxy methoxy tellurium tetrafluorides were kept at temperatures below 130°. The bonds are not cleaved by 65% oleum or chlorosulfonic acid at room temperature, instead, the sulfate esters HjCO-TeF tO-SOjH) were formed. These sulfate esters were transformed to HO-TeFiCO-SOjH) upon heating to 100°. Cesium chloride dissolved in an excess of cis- or /run.s-hydroxy methoxy tellurium tetrafluoride liberated hydrogen chloride with the formation of very hygroscopic cesium methoxo(oxo)letrafluorotellurates(VI). Trunj-hydroxy methoxy tellurium tetrafluoride reacts instantaneously with water with loss of fluoride. The cu-compound is stable toward hydrolysis at room temperature. ... 

A general route to acid fluorides, chlorides, bromides and iodides is provided by the reaction of enol esters, such as isopropenyl esters, with the appropriate hydrogen halide (equation 18). Phthalic acid dichloride in the presence of chlorosulfonic acid has been proposed as a reagent for the conversion of carboxylic esters to acid chlorides in high yield, as is shown in equation (19) for the cleavage of the ethyl ester of chlorofluoroacetic acid. °... 

Not only free cycloprop-2-enecarboxylic acids but also esters 5 were decarbonylated in oxidizing Bronsted acids, such as 25% sulfur trioxide in sulfuric acid, chlorosulfonic acid or fluorosulfuric acid, with evolution of carbon monoxide. Nearly quantitative formation of the corresponding cyclopropenylium ions 6 in solution was demonstrated by HNMR spectroscopy, and the hexachloroantimonate salts 7 were isolated when the solutions were treated with antimony(V) chloride in aeetyl chloride. ... 

Acid chlorides such as thionyl chloride, acetyl chloride, stearoyl chloride, and chloroformic esters have also proved to be very effective esterification catalysts, being superior to mineral acids for, in particular, heat-sensitive substances.811 Even acids that react sluggishly, such as 2-phenyl-4-quino-linecarboxylic acid, can be esterified in good yield by using chlorosulfonic acid, of which only small quantities are required (0.01-0.05 equivalent).812... 

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