Diisopropylamine → Ethyl 3-hydroxy-3-(2-phenylethyl)hexanoate

HRID 1421659Notes

Reaction equation

HRID 1421659 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.CCCCCC.[C:19]([O:22][CH2:23][CH3:24])(=[O:21])[CH3:20].[C:25]1([CH2:31][CH2:32][C:33](=[O:37])[CH2:34][CH2:35][CH3:36])[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1>O1CCCC1>[CH2:23]([O:22][C:19](=[O:21])[CH2:20][C:33]([OH:37])([CH2:32][CH2:31][C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)[CH2:34][CH2:35][CH3:36])[CH3:24]

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 8058HexaneHCID 8857Ethyl AcetateHCID 1225021-Phenylhexan-3-oneHCID 178418339Butyllithium

Product 1

HCID 10149285Ethyl 3-hydroxy-3-(2-phenylethyl)hexanoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of diisopropylamine (32.2 ml, 230 mmol) in tetrahydrofuran (240 ml) at -58° is added 2.63 M n-butyl lithium in hexane (87.4 ml, 230 mmol) over one hour. Ethyl acetate (21.4 ml, 220 mmol) is then added and the reaction mixture stirred for 1 hour during which time the reaction mixture was cooled to -70°. 1-Phenyl-3-hexanone (I, 35.2 g, 200 mmol) is added slowly over 30 minutes and the reaction mixture stirred cold for 1 hour. The mixture was quenched with aqueous ammonium chloride (100 ml) and warmed to 20-25°. The mixture is then acidified with hydrochloric acid (4 M). The desired product is extracted into methyl t-butyl ether dried over magnesium sulfate and concentrated to give the title compound, TLC Rf =0.71 (ethyl acetate/hexane, 30/70); NNR (CDCl3) 7.28-7.12, 4.13, 3.60, 2.73-2.63, 2.50, 1.83-1.77, 1.58-1.53, 1.41-1.36, 1.24 and 0.93 δ; CMR (CDCl3) 173.0, 143.2, 128.5, 128.4, 128.3, 128.1, 125.8, 72.8, 60.6, 42.9, 41.3, 30.1, 17.0, 14.6 and 14.2 δ; MS (CI, ammonia) m/z (relative intensity) 282 (100), 264 (63), 247 (10), 194 (13), 172 (5), 159 (5).

Workup

  1. temperaturewas cooled to -70°
  2. stirringthe reaction mixture stirred cold for 1 hour
  3. customThe mixture was quenched with aqueous ammonium chloride (100 ml)
  4. temperaturewarmed to 20-25°
  5. extractionThe desired product is extracted into methyl t-butyl ether
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-b7130296bff7489b9475c30f02281b6a
Source dataset
uspto-grants-2000_06
Patent number
US06077963

Reaction notes

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