Hexane → HCID 14403837, compound

HRID 1194137Notes

Reaction equation

HRID 1194137 reaction equation
C([Li])CCC.CCCCCC.[CH3:12][C:13]1([CH3:34])[CH2:18][O:17][CH:16](/[CH:19]=[CH:20]/[C:21]2[C:26]([CH3:27])=[CH:25][C:24]([CH3:28])=[CH:23][C:22]=2[CH:29]([CH2:31][CH2:32][CH3:33])[OH:30])[O:15][CH2:14]1.[CH3:35][C:36]([CH3:42])([CH2:40][CH3:41])[C:37](Cl)=[O:38]>C1COCC1>[CH3:12][C:13]1([CH3:34])[CH2:14][O:15][CH:16](/[CH:19]=[CH:20]/[C:21]2[C:26]([CH3:27])=[CH:25][C:24]([CH3:28])=[CH:23][C:22]=2[CH:29]([O:30][C:37](=[O:38])[C:36]([CH3:42])([CH3:35])[CH2:40][CH3:41])[CH2:31][CH2:32][CH3:33])[O:17][CH2:18]1

Participants

6

Reactant 4

HCID 8058HexaneHCID 799582,2-Dimethylbutyryl chlorideHCID 14403836HCID 14403836, compoundHCID 178418339Butyllithium

Product 1

HCID 14403837HCID 14403837, compoundYield 43%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 1.4M solution of n-butyllithium in hexane (2.6 mL, 3.61 mmol) was added dropwise under a nitrogen atmosphere to a solution of (E)-2-[2-(5,5-dimethyl-1,3-dioxan-2-yl)ethenyl]-3,5-dimethyl-α-propylbenzenemethanol (956.8 mg, 3.01 mmol) in 100 mL of dry THF. After the addition, the solution was stirred at room temperature for 15 minutes. 2,2-Dimethylbutyryl chloride (500 μl, 3.61 mmol) was then added and the solution stirred at room temperature for 30 minutes. The reaction was partitioned between 1N HCl-EtoAc and extracted. The organic layer was washed with water (two times), dried (anh. K2CO3) and the solvent removed under reduced pressure. Purification of the residual oil on 250 g of silica gel (Merck, 230-400 mesh) using 3:2 CH2Cl2 -hexane as an eluent gave 2,2-dimethylbutanoic acid (E)-1-[2-[2-(5,5-dimethyl-1,3-dioxan-2-yl)ethenyl]-3,5-dimethylphenyl]butyl ester (534 mg, 43%) as an oil: IR (film) 2945, 2860, 1720 and 1605 cm-1 ; NMR (DMSO-d6) δ 0.68-0.80 (6H, m), 0.86 (3H, t, J=6 Hz), 1.07 (3H, s), 1.08 (3H, s), 1.12 (3H, s), 1.14-1.44 (2H, m), 1.46-1.66 (3H, m), 1.68-1.86 (1H, m), 1.18 (3H, s), 2.23 (3H, s), 3.54 (2H, d, J=10 Hz), 3.64 (2H, d, J=10 Hz), 5.09 (1H, d, J=5 Hz), 5.68 (1H, dd, J=5, 15 Hz), 5.74-5.86 (1H, m), 6.78 (1H, d, J=15 Hz), 6.98 (2H, s).

Workup

  1. additionAfter the addition
  2. stirringthe solution stirred at room temperature for 30 minutes
  3. customThe reaction was partitioned between 1N HCl-EtoAc
  4. extractionextracted
  5. washThe organic layer was washed with water (two times)
  6. dry with materialdried (anh. K2CO3)
  7. customthe solvent removed under reduced pressure
  8. customPurification of the residual oil on 250 g of silica gel (Merck, 230-400 mesh)

Sources & evidence

ORD record
ord-62946ff501bc4c509b785947bbb9a2a4
Source dataset
uspto-grants-1989_03
Patent number
US04812583

Reaction notes

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