Disulfonic acid anhydride

Behr, RE. Cyclic perfluoro aliphatic disulfonic acid anhydrides. (Minnesota Mining and Manufacturing Co., USA.) US Patent 4,329,478, 1982. 

A series of water-soluble fiber-reactive xanthene dyes has been prepared from the reaction of ben2oxanthenedicatboxylic acid anhydride disulfonic acid with, for example, 3-aminophenyl-P-hydtoxyethyl sulfone to yield dyes, with high brilliance and good fastness properties for dyeing of or printing on leather, wool, sHk, or ceUulosic fibers (53). 

Dichloroanthraquinone [82-46-2] (46) is an important iatermediate for vat dyes and disperse blue dyes. Examples are Cl Vat Violet 13 [4424-87-7] (170), Cl Vat Orange 15 [2379-78-4] (154), and Cl Disperse Blue 56 [31810-89-6] (11). 1,5-DichloroantliraquiQone is prepared by the reaction of anthraquiQone-l,5-disulfonic acid with NaClO iu hot hydrochloric acid solution. Alternative methods from 1,5-dinitroanthraquiaone (49) by reaction of chlorine at high temperature ia the presence of phthaUc anhydride have been proposed (66). 

Bls(Chollne)-Naphthalene-1 JS-Disulfonate Lactic Acid Anhydride Diacetate... 

Anhydride and sulfone formation are not the only side reactions. Other side reactions lead to colored products (excess S03, high temperatures), traces of disulfonic acid, olefins, and oxidation products. 

In a similar manner to the preparation of 1,3,2-dioxathiolane 2-oxide from 1,2-dihydroxyethane and thionyl chloride, 1,2,3-oxadithiolane 2-oxide was prepared from 2-mercaptoethanol and thionyl choride <75ACS(A)414>. 1,2,5-Oxadithiolane 2,5-dioxide (66), the cyclic anhydride of ethane-1,2-disulfinic acid, was obtained by controlled hydrolysis of ethanebis(disulfinyl) chloride <76CRV747>. The corresponding 2,2,5,5-tetroxide (67) was obtained by treatment of ethane-1,2-disulfonic acid with thionyl chloride <(66HC(2l-i)l>. 

Ferrocene can readily be sulfonated by either sulfuric acid or chlorosulfonic acid in acetic anhydride (43, 123). The products, ferrocenesulfonic acid (XXV) and ferrocene-l,l -disulfonic acid (XXVI), are obtained together with products resulting from oxidation. 

There is surprisingly little reliable information on the sulfonation of benzo[6]thiophene or its derivatives. Benzo[6]thiophene is more readily sulfonated than naphthalene.699 Reaction with concentrated sulfuric acid at 80° gives a mixture of mono-, di-, and trisulfonic acids, reaction with 70% sulfuric acid at 80° gives a monosulfonic acid,699 and reaction with 18% oleum gives a disulfonic acid 86 in each case the orientation of the products is unknown. Treatment of benzo[6]thiophene with concentrated sulfuric acid in acetic anhydride at 20° gives 3-acetylbenzo[6]thiophene (ca. 10%) and a sulfonation product (isolated as the potassium salt), which was believed to be the 3-sulfonic acid.660 Recently, the sulfonation product has been shown to contain the 2- (8%) and 3-isomer (92%), by conversion into the sulfonyl chlorides and reduction to a separable mixture of 2- and 3-mercaptobenzo[6]thiophene.84... 

Bis(choline)-naphthalene-1,5-disulfonate Lactic acid anhydride diacetate... 

In place of sodium hydroxide, sodium acetate may be added to the mixture of diazonium salt solution and the aromatic liquid.6 Another variation, introduced by Hodgson and Marsden,6 consists in converting the aryldiazonium chloride to a stabilized diazonium salt by treatment wi,th naphthalene-l-sulfonic acid, naphthalene-1,5-disulfonic acid, or zinc chloride the dried salt is then suspended in an aromatic liquid and treated with sodium acetate and acetic anhydride. 

Being the cyclic anhydride of ethane-1,2-disulfinic acid, 1,2,5-oxadithiolane 2,5-dioxide (99) hydrolyzed to the parent acid in an almost quantitative fashion on boiling for 1 minute in water (76CRV747). In an analogous manner, 1,2,5-oxadithiolane 2,2,5,5-tetroxide (100) and its benzo-, naphtho- and thieno-fused derivatives were hydrolyzed by water or, more rapidly, by hot alkali to the corresponding 1,2-disulfonic acids or their salts, respectively (66HC(21-l)l). 

Most compounds of this type are cyclic sulfite and sulfate esters of aromatic 1,2-diols as well as anhydrides of aromatic 1,2-disulfonic acids. The simplest representatives with unsubstituted benzene rings are 1,3,2-benzodioxathiole 2-oxide (48) (catechol sulfite), the corresponding 2,2-dioxide (156) (catechol sulfate) and 2,1,3-benzoxadithiole 1,1,3,3-tetroxide (158) (1,2-benzenedisulfonic anhydride). Compound (48) was synthesized by refluxing catechol with thionyl chloride in the presence of pyridine. In a similar fashion, from 2-mercaptophenol 1,2,3-benzoxadithiole 2-oxide was prepared (81AG603). The dioxide (156) was obtained in two steps by reaction of catechol monosodium salt with sulfuryl chloride in benzene at 0-10 °C and subsequent reflux of the intermediate (155) in the presence of pyridine. 

The benzenedisulfonic acids are of little interest, except that benzene-1,3-disulfonic acid is a source of 1,3-dihydroxybenzene (see Chapter 4). The benzene dicarboxylic acids are more important. Benzene-1,2-dicarboxylic acid (phthalic acid, 8) can be converted into phthalic anhydride (9), which is a typical acid anhydride, reacting with amines and alcohols and also taking part in Friedel-Crafts reactions. Phthalimide (10), produced by reaction of the anhydride with ammonia, is weakly acidic and forms a potassium salt with ethanolic potassium hydroxide. 

Sulfophthalic anhydride is formed on sulfonation of phthalic anhydride by oleum, but presence of mercury(i) sulfate leads to the 3,5-disulfonic acid.162 The catalytic effect of mercury and mercury salts is also applied to the conversion of 4-methylpyridine into 4-methyl-3-pyridinesulfonic acid163 and of... 

Chlorination of fiiran at -40°C yields 2-chlorofuran and 2,5-dichlorofuran. Bromination with the di-oxane-Br2 complex at -5°C gives 2-bromofuran. Nitration is best carried out with fuming nitric acid in acetic anhydride at -10° to -20°C, and yields 2-nitrofuran. Pyridine-S03 or dioxane-S03 complex converts furan into furan-2-sulfonic acid and then further into furan-2,5-disulfonic acid. Alkylation and acylation are also possible. The action of mercury(II) chloride and sodium acetate in aqueous ethanol brings about mercuration of furan ... 

Perfluorinated disulfonic acids are readily available through the hydrolysis of the corresponding disulfonyl fluorides, which are prepared by ECF. Several cyclic derivatives of disulfonic acid are known. The preparation of cyclic anhydrides of the perfluorinated disulfonic acid is disclosed in patent hterature. The process includes the hydrolysis of the corresponding sulfonyl fluorides by KOH, acidification of the salt and the cyclization of diacid under the action of P2O5 (Fig. 9.18). 

FIGURE 9.18 Preparation of cyclic anhydrides of perfluorinated disulfonic acids. 

CAS 129-17-9 EINECS/ELINCS 204-934-1 Synonyms Ammonium, (4-(a-(p-(diethylamino) phenyl)-2,4-disulfobenzylidene)-2,5-cyclohexadien-1-ylidene) diethyl-, hydroxide, monosodium salt Anhydro-4,4 -bis (diethylamino) triphenylmethanol-2, 4"-disulfonic acid, monosodium salt Cl 42045 4,4 -Di (diethylamino)-4, 6 -disulfotriphenylmethanol anhydride, sodium salt N-[4-[[4-(Diethylamino) phenyl] (2,4-disulfophenyl) methylene]-2,5-cyclohexadien-... 

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