Benzene sulfonic anhydride

Conversion of the carboxylic acid to the diethyl amide interestingly leads to an agent that exhibits the properties of a respiratory stimulant. One synthesis of this agent starts with the preparation of the mixed anhydride of nicotinic and benzene-sulfonic acid (4). An exchange reaction between the anhydride and diethyl benzenesulfonamide affords nikethemide (5). ... 

The acetylium ion is the strongest acid species in the acetic anhydride system, and acetyl fluoborate, which is a good conductor in liquid sulfur dioxide, is a strong acid in acetic anhydride. Acetyl fluoborate, chloride, thiocyanate, and benzene sulfonate may all be titrated as acids in acetic anhydride using sodium acetate, a strong base in that system. 08 The neutralization reaction is ... 

Uses Manufacture of ethylbenzene (preparation of styrene monomer), dodecylbenzene (for detergents), cyclohexane (for nylon), nitrobenzene, aniline, maleic anhydride, biphenyl, benzene hexachloride, benzene sulfonic acid, phenol, dichlorobenzenes, insecticides, pesticides, fumigants, explosives, aviation fuel, flavors, perfume, medicine, dyes, and many other organic chemicals paints, coatings, plastics and resins food processing photographic chemicals nylon intermediates paint removers rubber cement antiknock gasoline solvent for fats, waxes, resins, inks, oils, paints, plastics, and rubber. 

Proton acids can be used as catalysts when the reagent is a carboxylic acid. The mixed carboxylic sulfonic anhydrides RCOOSO2CF3 are extremely reactive acylating agents and can smoothly acylate benzene without a catalyst.265 With active substrates (e.g., aryl ethers, fused-ring systems, thiophenes), Friedel-Crafts acylation can be carried out with very small amounts of catalyst, often just a trace, or even sometimes with no catalyst at all. Ferric chloride, iodine, zinc chloride, and iron are the most common catalysts when the reactions is carried out in this manner.266... 

In a model study for erythronolide B, White et al. [43] synthesized lactone 72 from hydroxy acid 71 via a mixed sulfonic anhydride. Thus, as shown in Scheme 23, exposure of 71 to p-toluenesulfonyl chloride and triethylamine in benzene followed by chromatography afforded 72 in 52% yield. 

Benzenediazomum-2-carboxylate, 46,1194 Benzenediazonium chloride, 394, 838 Benzenediazonium fluoroborate, 394 Benzenediazonium nitrate, 328 Benzenediazonium sulfonate, 713 Benzene-maleic anhydride 1 2 adduct, 557 Benzenesulfinyl fluoride, 849 Benzenesulfonamides, 46-47, 48... 

Use Manufacturing of ethylbenzene (for styrene monomer), dodecylbenzene (for detergents), cyclohexane (for nylon), phenol, nitrobenzene (for aniline), maleic anhydride, chlorobenzene, diphenyl, benzene hexachloride, benzene-sulfonic acid, and as a solvent. 

ISOPROPYLAMINE DODECYL-BENZENE SULFONATE (42504-46-1) C11H39NO4S Combustible solid (flash point, liquid >300°F/>149°C cc). A weak organic base. Incompatible with oxidizers, strong acids, organic anhydrides, acrylates, alcohols, aldehydes, alkylene oxides, substituted allyls, cresols, caprolactam solution, epichlorohydrin, ethylene dichloride, glycols, isocyanates, ketones, maleic anhydride, nitrates, nitromethane, phenols, vinyl acetate. 

Inhibiting Side Reactions. As stated in a preceding section, undesired by-product sulfone formation is pronounced in the mono- and disulfonation of ai matic hydrocarbons such as benzene, toluene, or xylene with SO or strong oleum. The addition of acetic acid (about 5 per cent by weight of the hydrocarbon) inhibits, but does not eliminate, sulfone formation. Sodium sulfate and sodium benzenesulfonate are also said to inhibit sulfone formation from benzene. In sul nating dodecylbenzene detergent alkylate with SO3, sulfone formation does not occur as it does with benzene or toluene, but sulfonic anhydride formation does occur. This objection-... 

Bismuth(III) trifluoromethanesulfonate D3i(OTf)3] has been established as an efficient catalyst (0.05 molar equiv.) for the sulfonylation of a range of substituted benzenes by sulfonyl chlorides and sulfonic anhydrides. With the former, ligand exchange is believed to lead to the formation of a mixed sulfonic anhydride (RS020Tf) which is the reactive sulfonylating species. 

Maleic acid anhydride and methyl-p-nitro-benzene sulfonate are also alkylating agents ... 

A vigorous stream of acetylene passed for 2 hrs. through a soln. of benzene-sulfonic acid and yellow HgO in dioxane-acetic anhydride with efficient stirring and cooling below 37 vinyl benzenesulfonate. Y 48%.—Benzene may be used as a diluent. F. e. s. H. Hopff and H. Lussi, Helv. 42, 2742 (1959). 

The major aromatics (organics having at least one ring structure with six carbon atoms) manufactured include benzene, toluene, xylene, and naphthalene. Other aromatics manufactured include phenol, chlorobenzene, styrene, phthalic and maleic anhydride, nitrobenzene, and aniline. Benzene is generally recovered from cracker streams at petrochemical plants and is used for the manufacture of phenol, styrene, aniline, nitrobenzene, sulfonated detergents, pesticides such as hexachlorobenzene, cyclohexane (an important intermediate in synthetic fiber manufacture), and caprolactam, used in the manufacture of nylon. Benzene is also used as a general purpose solvent. 

Tnfluoroacetic anhydnde in a mixture with sulfuric acid is an efficient reagent for the sulfonylation of aromatic compounds [44] The reaction of benzene with this system in nitromethane at room temperature gives diphenyl sulfone in 61% yield Alkyl and alkoxy benzenes under similar conditions form the corresponding diaryl sulfones in almost quantitative yield, whereas yields of sulfones from deactivated arenes such as chlorobenzene are substantially lower [44] The same reagent (tnfluoroacetic anhydride-sulfunc acid) reacts with adamantane and its derivatives with formation of isomeric adamantanols, adamantanones, and cyclic sultones [45]... 

A heterocyclic ring may be used in place of one of the benzene rings without loss of biologic activity. The first step in the synthesis of such an agent starts by Friedel-Crafts-like acylation rather than displacement. Thus, reaction of sulfenyl chloride, 222, with 2-aminothiazole (223) in the presence of acetic anhydride affords the sulfide, 224. The amine is then protected as the amide (225). Oxidation with hydrogen peroxide leads to the corresponding sulfone (226) hydrolysis followed by reduction of the nitro group then affords thiazosulfone (227). ... 

Figure 10-5. Cumarone, hydroxypropyl acrylate, Indene, maleic anhydride, styrene sulfonate, 0-dimethyl benzene.

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

Selective sulfonylation of 1 A/i -tri-O-tritylsucrose (activated by Bu2SnO) with methanesulfonyl chloride in benzene afforded the 3-mesylated derivative, whereas the same process performed in toluene surprisingly provided the 4-mesylate in 50% yield. If triflic anhydride is used as the sulfonating reagent, the 4-triflate was obtained in 40% yield (Scheme 12).153... 

The production of anthraquinone dyes generally proceeds from a few key products generated by electrophilic substitution of unsubstituted anthraquinone or by synthesis of the nucleus. The major methods employed to prepare anthraquinone derivatives substituted in the a-position are sulfonation and nitration. Preparation of b-substituted anthraquinones and of quinizarin (1,4-dihydroxyan-thraquinone) generally is accomplished by synthesis of the nucleus starting from phthalic anhydride and a benzene derivative. 

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]. 

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