Molecules 2003, 8
321
cream colored solid melting at 133○C {lit. [2] mp 132-133○C}. yield: 19.0 g (96%); 1H-NMR δ(ppm):
2.7 (s; 3H); 7.5 (d; 1H); 8.1 (d; 1H); 8.5 (s;1H). MS (EI): m/z: 217 (M+); 200; 182; 135; 105; 89; 30.
Preparation of 4,4'-dinitrostilbene-2,2'-disulfonic acid (3) using diethylene glycol as the solvent.
A mixture of sodium hypochlorite (50 mL, 5% available chlorine) and a solution of sodium
hydroxide (6g) in water (8 mL) was slowly added with stirring to a warm (40-45○C) solution of
compound 2 (5g) in diethylene glycol (30 mL). Stirring was continued and the temperature raised to
85○C. After about ten minutes the reaction was complete (as indicated by starch-iodide paper). Upon
cooling and filtration the sodium salt of 4,4'-dinitrostilbene-2,2'-disulfonic acid (5.6 g) was obtained.
Treatment of this salt with hydrochloric acid afforded the free acid 3 (5.1 g, 93% yield), m.p. 266○C
(lit. [6] m.p. 266○C); 1H-NMR δ (ppm): 7.9 (d; 1H); 8.3 (d; 1H); 8.4 (s; 2H); 8.6 (s; 1H); FTIR (cm-1):
2800, 3400, 1475, 1590, 1350, 1520, 1140, 1200; MS (EI): m/z: 430 (M+); 349; 214; 165; 75.
References
1. Venkatraman K. The Chemistry of Synthetic Dyes, Academic Press: New York, 1952; Vol. 1, pp.
628-629.
2. Lee J.G. et al, Process for the Production of p-Nitrotoluene-2-sulfonic Acid, U. S. Pat. 3840591,
1974.
3. Furniss B.S.; Hannaford, A.J.; Smith, P.W.G.; Tetcheu, A. R. Vogel’s Textbook of Practical
Organic Chemistry; 5th Ed. Longman Scientific & Technical: UK, 1991.
4. Bermes, R. et al, Preparation of Amine Salts of 4-Nitrotoluene-2-sulfonic Acid, U. S. Pat. 5892105,
1999.
5. Inukai K.; Maki Y., Fluorescent Bleaching Agent of Stilbene Series, I. Influence of Alkali and
Sodium Hypochlorite in the Preparation of Dinitrostilbenedisulfonic Acid, Repts. Govt. Ind. Res.
Inst., Nagoya, 1952, 1, 98-100, [Chem. Abstr. 1956, 50, 3347].
6. Kmonickova S.; Drabek J.; Cermak. J.; Mudroch J. Method of preparation of the 4, 4'-
Dinitrostilbene-2,2'-disulpho Acid, C. S. Pat. 216126, 1984. [Chem. Abstr. 1985, 102, 5933].
7. Bulliger H.R.; McGilvary J.R.N.; Smith, G., Process for the Industrial Manufacture of
Dinitrostilbene Disulphonic Acid, G. B. Pat. 1381730, 1975.
8. Hein, D.W.; Pierce, E.S. Optical Bleaching Agents. I. Derivatives of Dichlorodiaminostilbene
disulfonic Acid, J. Am. Chem. Soc., 1954, 76, 2725-2731.
9. Farris, R.E. In Kirk-Othmer, Encyclopedia of Chemical Technology, Wiley-Interscience: New
York, 1983; Vol. 21, pp. 729-746.
10. Baker R.L. Fluorescent Whitening Agents, Its Preparation and Use, U. S. Pat. 6165973, 2000.
Sample Availability: Samples of compounds 2 and 3 are available from the authors.