HCID 18971105, compound → HCID 22034350, compound

Participants

Reaction Steps

A TAIT mixture was prepared from an equimolar mixture of the four title ketones according to the procedure used for preparation of TMIT, using ammonium sulfide (136 mL, 0.4 moles, 20 wt % aqueous solution), sodium cyanide (14.7 g, 0.3 moles), ammonium chloride (16.1 g, 0.3 moles), water (80 mL), cyclohexanone (14.7 g, 0.15 moles), acetone (8.7 g, 0.15 moles) ethyl methyl ketone (10.8 g, 0.15 moles), and methyl isobutyl ketone (15.0 g, 0.15 moles) to obtain an oily layer at the end of the heating period. The oil layer was extracted into chloroform (350 mL), washed with water and dried with anhydrous potassium carbonate. Solvent evaporation yielded the product as a thick oil that slowly turned into a sticky gray solid (36 grams, yield: 55% for an average molecular weight of 219). IR: 3361, 2962, 2874, 1605, 1520, 1459 cm−1; 1H NMR (CDCl3, 500 MHz): δ 2.24 (d), 2.06 (s), 1.85-1.91 (m), 1.86-1.56 (m), 1.50-1.46 (m), 1.45-1.34 (m), 1.26-1.11 (bm), 1.39 (t), 0.99 (dd), 0.95-0.84 (m) ppm; 13C NMR (CDCl3, 125 MHz): δ 207.8, 207.62, 207.60, 207.43, 207.40, 207.01, 206.89, 206.68, 206.66, 81.6, 81.18, 81.14, 80.70, 80.65, 78.38, 78.31, 73.95, 73.30, 72.82, 70.79, 70.46, 70.18 and several peaks between 40-10 ppm. The average molecular weight of 219 was calculated by averaging the molecular weights of the acetone/cyclohexanone cross-product (198) and the methyl isobutyl ketone/cyclohexanone cross-product (240), these being the two predominant products among the 8-10 products detected by proton NMR.

Provenance & Evidence