SULPHONIC ACIDS

This article appears in Volume V26, Page 61 of the Encyclopedia Britannica.

Encyclopedia Britannica - Main :: STE-SUS

SULPHONIC ACIDS , in organic

chemistry

, a group of compounds of the type RS03H, where R is an alkyl or an aryl group.
Aliphatic Sulphonic Acids.The members of this class may be prepared by the direct sulphonation of some paraffins (I. Worstall, Amer. Chem. Journ., 1898, 20, p. 664) , by the oxidation of mercaptans with concentrated nitric acid (H. Kopp, Ann., 1840, 35, p. 346); in the form of their salts from the alkyl halides and alkaline sulphites, and as esters from the alkyl halides and silver sulphite. They are colourless oils or crystalline solids which are extremely hygroscopic, very soluble in water and have a strongly acid reaction. They are unaffected by

heating

HEATING

with aqueous alkalis or acids and are

stable

STABLE

towards concentrated nitric acid. Phosphorus pentachloride converts them into the corresponding acid chlorides, RSO2C1, which are decomposed slowly by water. These chlorides, on reduction by zinc and sulphuric acid, pass readily into the mercaptans, whilst if zinc dust and alcohol be used they are converted into the sulphinic acids, RS02H.
Methyl sulphonic acid, CH3SO3H, was obtained by H.

Kolbe

KOLBE, ADOLPHE WILHELM HERMANN (1818–1884)

(Ann., 1845, 54, p. 174) by reducing trichloromethyl sulphonic chloride (formed from chlorine and carbon bisulphide in the presence of water :CS2+5C12+2H2O=CC13SO2C1+4HC1+SCl2) with sodium amalgam. It is a colourless syrup which decomposes when heated above 13o C. The corresponding acid chloride is an extremely

stable

STABLE

solid which melts at 135 C. It is formed by the action of carbon bisulphide on potassium bichromate in the presence of nitric and hydrochloric acids (Loew, Zeit. f. Chem., 1869, p. 82). When heated under pressure it decomposes with the final production of carbonyl and thionyl chlorides: CC13SO2C1=CCla+SO2= COC12+SOC12. Ethyl sulphonic acid,

C2H6

C2H6

.SO3H, is a crystalline deliquescent solid formed by oxidizing ethyl mercaptan or by reducing vinyl sulphonic acid, CH2:CHSO3H (Kohler, Amer. Chem. Journ., 1898, 20, p. 687).
Thiosulphonic acids of the type RSO2SH are formed by the action of the sulphochlorides on a concentrated solution of potassium sulphide: RSO2CI + K2S = RSO2K+S+KCl=KCI+RSO2SK: or by the action of the salt of a sulphinic acid on an alkaline sulphide in the presence of iodine (Otto, Ber., 1891, 24, p. 144).
Aromatic Sulphonic Acids.The acids of this group are very similar to the corresponding aliphatic sulphonic acids and are usually obtained by the direct

heating

HEATING

of an aromatic hydro-carbon with concentrated sulphuric acid, fuming sulphuric acid or

sulphur

SULPHUR

chlorhydrin. After the action is completed they may frequently be " salted out " by adding common salt to the acid solution until no more dissolves, when the sodium salt of the acid separates (L. Gattermann, Ber., 1891, 24, p. 2121). They are also formed by oxidizing thiophenols or by decomposing diazonium salts with sulphurous acid. The free acids are usually hygroscopic, crystalline solids which are readily soluble in water. When heated under pressure with concentrated hydrochloric acid to about 15o C. they yield hydrocarbons and sulphuric acid. The salts usually crystallize well, and those of the alkali metals are employed in the preparation of phenols, into which they pass when fused with the

caustic

CAUSTIC (Gr. rcavvraubs, burning)

alkalis. When distilled with potassium

cyanide

CYANIDE

they yield the aromatic nitriles. The sulphonic acids with phosphorus pentachloride are converted into sulphochlorides which are stable to cold water, but with ammonia they yield sulphonamides, RS02NH2, and with

alcohols

esters of the sulphonic acids.
Benzene sulphonic acid, C6H5SO3H,1H2O, crystallizes in small plates and is very deliquescent. Benzene sulphochloride, C6H5-SO2CI, is a colourless fuming liquid which boils at 120 C. (io mm.). The aminobenzene sulphonic acids, particularly the meta and para compounds, are of importance owing to their employment in the colour industry. The direct sulphonation of aniline yields the para acid, sulphanilic acid, C6H4(NH2)(SO3H), which crystallizes in small plates and is sparingly soluble in cold water. When fused with

caustic

CAUSTIC (Gr. rcavvraubs, burning)

potash it yields aniline, whilst oxidation with chromic acid yields benzoquinone. In constitution it is probably to be regarded
/NH3N
as a cyclic ammonium salt, C3H4
SO3/. When diazotized in
~
acid solution and coupled with dimethyl aniline it yields helianthine,
the sodium salt of which is used as an indicator (q.v.). Metanilic acid C6H,(NH2) (SO2H) [1.3], which crystallizes in prisms, is formed by the reduction of meta-nitrobenzene sulphonic acid and is used In the preparation of various azo dyes.
Sulphinic acids, RS02H, are formed by reducing sulpho= chlorides with zinc dust; by the action of

sulphur

SULPHUR

dioxide on the zinc alkyls (Hobson, Ann, 1857, 102, p. 72; 1858, Io6, p. 287) ; by the action of sulphochlorides on mercaptans in alkaline solution; and by the action of the Grignard reagent on sulphur dioxide or thionyl chloride (Rosenheim, Ber., 1904, 37, p. 2152; Oddo, R. Accad. Lin., 1905 (5), 14 (i.), p. 169). The free acids are unstable. They are readily oxidized to sulphonic acids and reduced to mercaptans.. Their alkali salts on treatment with the alkyl halides yield sulphones, R2S02. Ethyl sulphinic acid, C2H5SO2H, is a colourless syrup. Benzene sulphinic acid, C6H5S02H, crystallizes in large prisms and acts as .a reducing agent. It decomposes when heated with water under pressure: 3C6H5SO2H=C6H5S02H+C6H5S02SC6H5+H20. The potassium salt when fused with caustic potash yields benzene and potassium sulphite.

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