4- benzene sulfonyl fluoride

Scheme 2. Synthesis of 4-(4-diethylamino-2-methyl-phenylazo)benzene sulfonyl fluoride...

In 1927 Steinkopf reported the preparation of several aromatic sulfonyl fluorides (287). For example, he obtained benzene sulfonyl fluoride, C6H6S02F, by the slow addition of fluorosulfonic acid to benzene at about 20°. The crude product was poured over ice and was then extracted in ether. After evaporating the ether, the benzene sulfonyl fluoride was refined by steam distillation. Another method for preparing aromatic sulfonyl fluorides is by the reaction of an aromatic sulfonic acid, such as C6H6S03H, with fluorosulfonic acid (202). By boiling a mixture of an aromatic sulfonyl chloride with a concentrated solution of potassium fluoride in water, the chloride is converted to a fluoride (62). 

The conversion of the sulfonyl chloride to the sulfonyl fluoride was carried out as follows. The sulfonyl chloride was removed from the filter by washing it with alcohol-free chloroform into a 5-ml round-bottom flask. The chloroform was then removed and 0.5 ml of acetonitrile and 167 mg of dry powdered sodium fluoride was added. The resulting mixture was magnetically stirred at 90°C for 6 hr, 2 ml of alcohol-free chloroform was then added and the mixture was filtered into a sublimation apparatus and the solvent was removed in a stream of nitrogen. The product sublimed readily at 45°C (0.3 mm) and could then be recrystallized from benzene-cyclohexane to yield crystals with m.p. 90-92°C. 

An alternate method of converting sulfonyl chlorides to sulfonyl fluorides has been reported by Sigler et al. (1966) in the synthesis of benzene sulfonylfluoride. Benzenesulfonyl chloride (18 g, 0.1 mole) was dissolved in 100 ml of acetone and then mixed vigorously at room temperature for 4 hr with 100 ml of aqueous 4 M potassium fluoride. On evaporation of the acetone, the pale yellow liquid product separates. It can be dried after dissolution in methylene chloride over anhydrous MgS04 and then distilled as a colorless oil (b.p. 63-67°C/6-7 mm). 

Organic polymers Polyethylene maleate Ethyl cellulose, fluoropolyol, phenoxy resin, poly(amidoxime), poly-1-butadiene, poly(epichloro-hydrin), polyethylene, poly-(ethylene m eate), poly(iso-prene), poly(methylmethacrylate), polystyrene, poly(vinyl chloride), poly(vinyl stearate), 1,1,1-tri-fluoroisopropyl methyl siloxane Cyclopentadiene [200 ppm-min] Benzene, 1-butanol, 2-buta-none, 1,2-dichloroethane, dichloropentane, methylacetamide, dimethyl-phosphite, dodecane, methane-sulfonyl fluoride, octane, a-pinene oxide, /-propyl-acetate, toluene, triamylphos-phite, tributylphosphate, water... 

Acetyl azide, 0771 A-Azidocarbonylazepinc, 2728 Azidocarbonyl fluoride, 0339 Azidocarbonylguanidine, 0820 4-Azidocarbonyl-1,2,3-thiadiazole, 1069 Azidodithioformic acid, 0386 Benzene-l,3-bis(sulfonyl azide), 2210 Benzenesulfinyl azide, 2273 Benzenesulfonyl azide, 2274 Benzoyl azide, 2698... 

A solution of morpholinosulfur trifluoride (1 equiv) was added to a stirred cooled solution of the sulfonyl or sulfinyl chloride (1 equiv) in Et20 (or benzene, hexane, or chlorobenzene). The mixture was stirred at 20 C for 10 min and a precipitation of morpholinosulfur chloride difluoride occurred. The precipitate was filtered off under anhydrous conditions, and the filtrate was evaporated and fractionated to give the sulfonyl or sulfinyl fluoride. 

The Friedel-Crafts sulfonylation of aromatics with alkane- and arenesulfonyl halides and anhydrides has been studied (Eq. 9) [23]. In the reaction of pentafluorobenzenesul-fonyl fluoride with pentafluorobenzene, decafluorodiphenyl sulfone is formed with deca-fluorodiphenyl [23c]. Certain phenylacetylenes react with SO2 and benzene in the presence of SbFs to form benzothiophene 5-oxide [24]. (Eq. 10). Sulfinyl fluoride reacts similarly with arenes under SbFs catalysis to give sulfoxides (Eq. 11) [25]. 

Kinetic studies of the acylation of imidazoles with benzoyl halides and sulfonyl halides have been carried out. In acetonitrile, benzoyl fluoride reacts with imidazole in a mixed third- and fourth-order reaction i.e., the rate-determining transition state contains the acid fluoride and two or three molecules of imidazole. With benzoyl chloride in benzene a second-order equation is followed similar to the aroylation of anilines ... 

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