α,α,α‐Trichloroacetanilide

Abstract

α,α,α‐Trichloroacetanilide product: α,α,α‐Trichloroacetanilide reactant: 265 g. (1 mole) of hexachloroacetone

Competitive Pseudopericyclic [3,3]- and [3,5]-Sigmatropic Rearrangements of Trichloroacetimidates

“…This (200 mg) was reduced using H 2 and 10% Pd/C to yield the corresponding amino phenol (143 mg, 89%) . The aminophenol (80 mg, 0.65 mmol) was then treated with hexachloroacetone in hexane and the reaction mixture was refluxed for 6 h, to yield the desired trichloroacetamide 10 as a white solid (141.06 mg, 86%): 1 H NMR (400 MHz, CDCl 3 ) δ 8.94 (bs, 1H), 7.71 (d, J = 6.8 Hz, 1H), 7.03 (d, J = 6.8 Hz, 1H), 6.91 (t, J = 7.8 Hz, 1H), 5.72 (bs, 1H), 2.31 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159.9, 144.9, 128.3, 125.4, 124.4, 121.3, 119.2, 92.17, 29.8,16.0; EIMS m / z (relative abundance) 269 (4), 267 (4), 150 (100), 122 (24); HRMS (ESI) calcd for [C 9 H 8 Cl 3 NO 2 + H] + 267.9693 found 267.9688.…”

“…Compound 12 was synthesized by treating commercially available 4-amino- o -cresol (100 mg, 0.812 mmol) with hexachloroacetone in hexane at 65–70 °C for about 4 h and was obtained as a white solid (189 mg, 92%): 1 H NMR (400 MHz, CDCl 3 ) δ 8.20 (bs, 1H), 7.33 (d, J = 2.6 Hz, 1H), 7.28 (d, J = 2.8 Hz, 1H), 6.79 (d, J = 8.7 Hz, 1H), 4.77 (bs, 1H), 2.27 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159.4, 152.1, 128.9, 125.0, 123.8, 119.9, 115.5, 93.0, 16.0; EIMS m / z (relative abundance) 271(6), 269 (18), 267 (18), 150 (30), 122 (100). Anal.…”

“…2,2,2-Trichloro-N-(2-hydroxy-3,4,6-trimethylphenyl)acetamide 25. Compound 25 was synthesized according to the general procedure described in the literature 52 The aminophenol 32 (150 mg, 0.99 mmol) was taken up in hexane, and hexachloroacetone (166 μL, 1.09 mmol) was added to it at room temperature. The mixture was then heated at 65−70 °C for about 6 h. TLC showed the disappearance of the starting aminophenol 32 and formation of a new less polar spot.…”