69103-65-7Relevant articles and documents
Aromatic Sulphonation. Part 92. Sulphonation of the Three Methylphenols and the Six Dimethylphenols in Concentrated Aqueous Sulphuric Acid; and the Isomerization of Some of the Resulting Sulphonic Acids and of m-Xylene-2- and o-Xylene-3-sulphonic Acid
Lambrechts, Hans J. A.,Schaasberg-Nienhuis, Zwaan R. H.,Cerfontain, Hans
, p. 669 - 676 (2007/10/02)
The isomer distributions for the mono- and di-sulphonation of the three methylphenols in 81.6-90.0percent sulphuric acid and of the six dimethylphenols in 84.9percent sulphuric acid at 35 deg C have been determined by means of 1H n.m.r. spectroscopy.Products that would result from demethylation, disproportionation, or ipso-substitution have not been observed.The monosulphonation isomer distribution of each of the three methylphenols is independent of the sulphuric acid concentration. 2,4-Dimethylphenol in 84.9percent H2SO4 yields 19percent 5- and 79percent 6-sulphonic acid, and 2,6-dimethylphenol yields 28percent 3- and 72percent 4-sulphonic acid.With the phenols (2), (3), (5),and (7), which have positions both ortho and para to the -OH substituent available for sulphodeprotonation, the yield of ortho-substitution is relatively high, viz. 44, 45, 36, and 27percent, respectively.The mono- and di-sulphonic acids of which the sulpho group is between the -OH and an -Me group are unstable under the reaction conditions employed, with the exception of the 3,5-dimethylphenol-2-sulphonic acid.It is proposed that their isomerization proceeds by protiodesulphonation followed by resulphonation to yield the more stable sulphonic acid isomer(s).From a kinetic analysis of the calculated first-order rate coefficients for protiodesulphonation, it is concluded that the unprotonated substrate species is the entity undergoing the protiodesulphonation.
