Thiophenols nitration

Thiophenol, 2,4,6-Trinitro (2,4.6-Trinitro-phenylmercaptan or Picrylmercaptan). C6H3N3S06 mw 245.18 N 17.14% OB to C02 —48.94% v small yel ndls with a bitter taste mp 114° v sol in acet, benz, chlf, ethanol and w insol in carbon disulfide and petr eth. Prepn is by reacting an ethanolic soln of K2S with an ethanolic soln of picryl chloride. The K salt formed is filtered off and dissolved in w and then hydrolyzed with hydrochloric acid to the free nitrate. The picryl compd explds with extreme violence at 115°. The salt, Potassium-2,4,6-Trinitro-Thiophenol KC6H2N3S06 mw 283.27 N 14.84% OB to C02 -48.94% reddish brn ndls v sol in ethanol and w difficultly sol in eth and w mp, explds with great violence at 140°... 

Thiophenol, see Benzenethiol, 2337 Thiophosphoryl chloride difluoride, 3974 Thiophosphoryl chloride, 4148 Thiophosphoryl fluoride, 4334 Thiotrithiazyl chloride, 4027 Thiotrithiazyl nitrate, 4762 Thiotrithiazyl perchlorate, 4026... 

Suzuki-Miyaura coupling of D with I smoothly afforded J, which was oxidized with ceric ammonium nitrate to give K. For the final demethylation of K, several methods were tried without success treatment of K with boron tribromide, 47% hydrobromic acid, lithium chloride in DMF, trimethylsilyl iodide, and potassium thiophenolate in diethylene glycol. Finally, clean demethylation of K was achieved with aluminum chloride in dichloromethane at room temperature to give diospyrin (58) as orange plates. The proposed structure 58 was thus confirmed by its synthesis.130... 

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