2,4,6-тринитробензолсульфоновая кислота (TNBS)

[Ximeg]

Господа!
Помогите, пожалуйста, найти методику получения 2,4,6-тринитробензолсульфоновой кислоты. В принципе понятно, что нужно либо нуклеофильно замещать пикрилхлорид сульфитом, либо сначала сульфидом, а потом окислять. Но конкретных методик нет, тк вещество сварено, видимо, достаточно давно. Делать наобум не хочется, ибо TNBS явно может все окислить или пойти в пикринку.

[Serty]

Из Pettitt, D.J.; Helmkamp,G.K.; JOCEAH; Journal of Organic Chemistry; English; 29; 1964; 2702 - 2706; ISSN: 0022-3263.:

2,4,6-Trinitrobenzenesulfonic Acid.-The preparation of the acid was based.on that of Golumbic and Bergman.l6 To 100 g.(0.40 mole) of picryl chloride in 1000 ml. of absolute ethanol was added 100 g. (0.53 mole) of anhydrous sodium metabisulfiie. The mixture was heated under reflux with vigorous stirring for 3hr. and then cooled to below 5 and filtered. The crude sodium salt was washed with 100-ml. portions of cold, absolute ethanol until the wash solution was colorless.
After the tan solid was air-dried for 15 min., it was mixed with 300 ml. of reagent grade acetone; then 100 ml. of concentrated hydrochloric acid was added with swirling over a 5-min. period. The precipitated sodium chloride was removed by filtration and washed with 50 ml. of acetone. The acetone solvent and excess water were removed at reduced pressure with gentle heating on a water bath. At this point the light yellow product contained water of crystallization. Further heating a t reduced pressure gave 102 g. (87%) of the anhydrous acid as a chalk-white solid, m.p. 193-195. Although the anhydrous acid could be recrystallized from acetone-chloroform, a more satisfactory procedure was available for the dihydrate. The entire product from the synthesis was dissolved in 50-55 ml. of hot acetone and 50ml. of chloroform was added. The dihydrate, which crystallized as long needles, was separated by filtration of the cold mixture, washed with 100 ml. of chloroform, and air-dried, melting a t 85-87 with resolidification a t 125-135 and remelting a t 193-195. The anhydrous acid was obtained by heating the hydrate for 2-3 hr. at 80 and 1-mm. pressure over phosphorus pentoxide, yield 94 g., 80%, m.p. 193-195.

[Ximeg]

Спасибо огромное!

[Briy]

Я тоже спасибо скажу,
делал эту штуку без методики, но похожим образом.
Только выход был меньше.