Hydroxylamine → N-2-Thiabicyclo[2.2.2]oct-5-en-3-ylidenehydroxylamine

Participants

Reaction Steps

Thiophosgene (296 g of 85% , 2.19 m) was added dropwise to a stirred solution of 167 g (2.08 m) of 1,3-cyclohexadiene in 500 ml of chloroform. The exothermic reaction caused the temperature to rise from 25° C. to 68° C. with refluxing of the solvent. After 45 minutes, the reaction mixture was cooled and added in portions over four hours to a stirred solution of hydroxylamine (prepared from 480 g (6.9 m) of hydroxylamine hydrochloride in 175 ml water by dropwise addition at 0° C. of a solution of 434 g of 89% potassium hydroxide (6.9 m) in 250 ml of water) at -15° C. After being stirred overnight, the reaction mixture was filtered and the filter cake washed with methylene chloride. The combined filtrate and washings were separated and the organic layer dried (MgSO4) and reduced in volume at about 20 Torr. After addition of carbon tetrachloride to the residue, distillation of solvent was continued at atmospheric pressure until a pot temperature of 75° C. was attained. The hot mixture was filtered. Cooling of the gave a solid which was recrystallized from carbon tetrachloride to yield 271 g of the title compound.

Provenance & Evidence