HCID 18971105, compound → HCID 22719497, compound
Reaction equation
[CH3:1][C:2]([CH3:4])=[O:3].[C:5]1(=[O:11])[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]1.[CH2:12]([C:16]([CH3:18])=[O:17])[CH:13]([CH3:15])[CH3:14].C1(=O)CCCCC1>>[CH3:1][C:2]([CH3:4])=[O:3].[CH2:12]([C:16]([CH3:18])=[O:17])[CH:13]([CH3:15])[CH3:14].[C:5]1(=[O:11])[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]1Participants
Procedure
A TAIT mixture was prepared from an equimolar mixture of the three 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 (19.6 g, 0.2 moles), acetone (11.6 g, 0.2 moles) and methyl isobutyl ketone (20.3 g, 0.2 moles) to obtain a oily layer at the end of the heating period. The oil layer was extracted into chloroform (350 mL), washed with water and dried (anhydrous potassium carbonate). Solvent evaporation yielded the product as a thick oil that slowly turned into a sticky gray solid (20 grams, yield: 30% for an average molecular weight of 219). IR: 3533, 3137, 2925, 1599, 1516, 1450, 1379 cm−1; 1H NMR (CDCl3, 500 MHz): δ2.12 (d), 1.94 (s), 1.8 (m), 1.62-1.20 (m), 1.12-0.98 (broad m), 0.89 (dd), 0.82-0.76 (m), 0.72 (d) ppm; 13C NMR (CDCl3, 125 MHz): δ 208.6, 207.2, 206.9, 206.8, 206.6, 124.5, 123.7, 80.7, 80.3, 78.4, 77.9, 77.3, 76.9, 76.7, 73.1, 72.4, 70.3, 69.7, 52.1, 51.0, 49.5, 48.3, 39.3, 38.7, 38.2, 37.4, 36.9, 30.2, 29.5, 24.1, 22.4, 22.1, 21.6, 21.4 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 4-5 products detected by proton NMR.
Sources & evidence
- ORD record
- ord-adef4bd3f7114dedaff300c03ce93709
- Source dataset
- uspto-grants-2003_08
- Patent number
- US06602832B2
Reaction notes
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