Ammonia → HCID 14692992, compound

HRID 1608075Notes

Reaction equation

HRID 1608075 reaction equation
[Li].[CH3:2][C:3]1([CH3:18])[CH:8]=[C:7]([CH3:9])[CH2:6][C:5]([CH3:11])([CH3:10])[CH:4]1[C:12]([CH3:17])=[CH:13][C:14](=[O:16])[CH3:15].N.[Cl-].[NH4+]>C(O)C.CCOCC>[CH3:15][CH:14]([OH:16])[CH2:13][CH:12]([CH3:17])[CH:4]1[C:5]([CH3:11])([CH3:10])[CH2:6][C:7]([CH3:9])=[CH:8][C:3]1([CH3:18])[CH3:2]

Participants

7

Reactant 4

HCID 222Ammonia2×HCID 25517Ammonium ChlorideHCID 3028194LithiumHCID 56998058HCID 56998058, compound

Product 1

HCID 14692992HCID 14692992, compoundYield 78%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 3283Diethyl EtherSolvent

Procedure

Lithium shot (0.5 g, 0.071 mol) was added portionwise over a 40 min. period to a cold (-30° to -40° C.) mixture of 4-(2,2,4,6,6-pentamethyl-3-cyclohexen-1-yl)-3-penten-2-one (1.08 g, 0.0046 mol), ether (20 mL), ethanol (20 mL) and ammonia (80 mL). Ammonium chloride (8.0 g) was added to the blue colored reaction mixture. The ammonia was allowed to evaporate. Ether (100 mL) and water (200 mL) were added to the residue. The aqueous layer was extracted with ether (100 mL). The combined organic extracts were washed with 0.5N HCl (2×100 mL), saturated sodium bicarbonate solution (100 mL) and dried. Evaporation of solvents, chromatography of the residue and kugelrohr distillation provided 0.850 g (78% yield) of α,γ,2,2,4,6,6-heptamethyl-3-cyclohexene-1-propanol. GLC analysis shows 4 isomers of 4.1%, 12.8% and 82.3% (two peaks incompletely resolved). 1H-NMR (60 MHz, CDCl3) δ0.98 and 1.05 (12H, 2s), 1.12 (3H, d, J=6 Hz), 1.25 (3H, d, J=4 Hz), 1.60 (3H, s), 1.0-2.5 (7H, m), 3.6-4.1 (1H, m), 5.00 (1H, broad s). IR (film) vmax 3320, 2950, 1640, 1470, 1450, 1380, 1360 cm-1 ; Ms m/e 238, 223, 180, 151, 109, 96.

Workup

  1. customto evaporate
  2. additionEther (100 mL) and water (200 mL) were added to the residue
  3. extractionThe aqueous layer was extracted with ether (100 mL)
  4. washThe combined organic extracts were washed with 0.5N HCl (2×100 mL), saturated sodium bicarbonate solution (100 mL)
  5. customdried
  6. customEvaporation of solvents, chromatography of the residue and kugelrohr distillation

Sources & evidence

ORD record
ord-46cb0013f49a429bb02e7192df2847d6
Source dataset
uspto-grants-1989_09
Patent number
US04868339

Reaction notes

Loading…