Pinacolone → 3-[3-Methyl-4(2-hydroxy-3,3-dimethylbutoxy)phenyl]-3-[3-methyl-4-(3,3-dimethyl-2-oxobutoxy)phenyl]pentane

HRID 324604Notes

Reaction equation

HRID 324604 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:13]2[CH:18]=[CH:17][C:16]([O:19][CH2:20][CH:21]([OH:26])[C:22]([CH3:25])([CH3:24])[CH3:23])=[C:15]([CH3:27])[CH:14]=2)([CH2:11][CH3:12])[CH2:9][CH3:10])=[CH:4][C:3]=1[CH3:28].[H-].[Na+].[CH3:31][C:32](=[O:37])[C:33]([CH3:36])([CH3:35])[CH3:34].C(OCC)(=O)C>CN(C=O)C>[CH3:27][C:15]1[CH:14]=[C:13]([C:8]([C:5]2[CH:6]=[CH:7][C:2]([O:1][CH2:31][C:32](=[O:37])[C:33]([CH3:36])([CH3:35])[CH3:34])=[C:3]([CH3:28])[CH:4]=2)([CH2:9][CH3:10])[CH2:11][CH3:12])[CH:18]=[CH:17][C:16]=1[O:19][CH2:20][CH:21]([OH:26])[C:22]([CH3:23])([CH3:25])[CH3:24]

Participants

6

Reactant 4

HCID 6416PinacoloneHCID 8857Ethyl Acetate2×HCID 24758Sodium hydrideHCID 220048653-[4-Hydroxy-3-methylphenyl)-3-[3-methyl-4-(2-hydroxy-3,3-dimethylbutoxy)phenyl]pentane

Product 1

HCID 155213963-[3-Methyl-4(2-hydroxy-3,3-dimethylbutoxy)phenyl]-3-[3-methyl-4-(3,3-dimethyl-2-oxobutoxy)phenyl]pentaneYield 92.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of the compound of example 7 (100 mg, 0.26 mmol) in DMF (2.5 mL) was added NaH (7.0 mg, 0.29 mmol). The reaction mixture was stirred at ambient temperature for 30 min, then pinacolone (39 mg, 0.29 mmol) was added. The reaction was stirred at ambient temperature for I h or until judged complete by TLC (20% ethyl acetate in hexanes). The reaction mixture was quenched with water, and diluted with ethyl acetate. The organic fraction was separated, washed with water and brine, dried over MgSO4, and concentrated in vacuo. Chromatography (silica, 10% ethyl acetate in hexanes) afforded 117 mg (0.24 mmol, 92%) of 11. 1HNMR (CDCl3) δ: 6.91 (m, 4 H, Ar—H), 6.69 (d, J=8.3 Hz, 1 H, Ar—H), 6.49 (d, J=8.3 Hz, 1 H, Ar—H), 4.83 (s, 2 H, CH2), 4.09 (dd, J=11.3 Hz, J=3.3 Hz, 1 H, CH2), 3.85 (t, J=11.3 Hz, 1 H, CH2), 3.69 (d, J=11.3 Hz, 1 H, CH2), 2.23 (s, 3 H), Ar—CH3), 2.18 (s, 3 H, Ar—CH3), 2.00 (q, J=7.3 Hz, 4 H, CH2CH3), 1.24 (s, 9 H, t-Bu), 1.00 (s, 9 H, t-Bu), 0.58 (t, J=7.3 Hz, 6 H, CH2CH3).

Workup

  1. stirringThe reaction was stirred at ambient temperature for I
  2. customThe reaction mixture was quenched with water
  3. additiondiluted with ethyl acetate
  4. customThe organic fraction was separated
  5. washwashed with water and brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-84791007eff64aacb40e0d99f6f0e78f
Source dataset
uspto-grants-2001_04
Patent number
US06218430B1

Reaction notes

Loading…