Aluminium lithium hydride → 2,2-Bis(hexyloxy)propan-1-ol

HRID 1518170Notes

Reaction equation

HRID 1518170 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].[CH2:7]([O:13][C:14]([O:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])([CH3:24])[C:15](OCCCCCC)=[O:16])[CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]>CCOCC>[CH2:26]([O:25][C:14]([O:13][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12])([CH3:24])[CH2:15][OH:16])[CH2:27][CH2:28][CH2:29][CH2:30][CH3:31]

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 46945489Hexyl 2,2-bis(hexyloxy)propanoate

Product 1

HCID 469453022,2-Bis(hexyloxy)propan-1-olYield 96.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

To a mixture of LiAlH4 (3.44 g, 90.5 mmol) in Et2O (200 mL) is added a solution of ester 3 (29.5 g, 82.3 mmol) in Et2O (100 mL). After addition, the mixture is refluxed for 6 hours. The reaction mixture is cooled to 0° C. and quenched with ethyl acetate (20 mL) and H2O (20 mL). The mixture is added to saturated potassium sodium tartrate (300 mL) and stirred at 23° C. for 12 hours. The mixture is extracted with Et2O (2×200 mL) and the combined organic layers are dried over anhydrous sodium sulfate. The solvent is removed and the residue is purified by silica gel chromatography (1→10% ethyl acetate/hexane) to give 2,2-bis(hexyloxy)propan-1-ol 4 (20.6 g, 94%) as a colorless oil: Rf (15% EtOAc/hexane)=0.20; IR (thin film, cm−1) 3430, 2955, 2929, 2859, 1467, 1378, 1244, 1155, 1112, 1064, 876; 1H NMR (600 MHz, C6D6) δ 3.58 (d, J=6.6 Hz, 2H), 3.43 (t, J=6.6 Hz, 4H), 1.58 (t, J=6.6 Hz, 1H), 1.53 (m, 4H), 1.36 (s, 3H), 1.34-1.22 (m, 12H), 0.88 (t, J=7.2 Hz, 6H); 13C NMR (150 MHz, C6D6) δ 101.0, 66.2, 61.3, 32.5, 30.9, 26.8, 23.4, 21.3, 14.6.

Workup

  1. additionAfter addition
  2. temperaturethe mixture is refluxed for 6 hours
  3. customquenched with ethyl acetate (20 mL) and H2O (20 mL)
  4. additionThe mixture is added to saturated potassium sodium tartrate (300 mL)
  5. extractionThe mixture is extracted with Et2O (2×200 mL)
  6. dry with materialthe combined organic layers are dried over anhydrous sodium sulfate
  7. customThe solvent is removed
  8. customthe residue is purified by silica gel chromatography (1→10% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-e11bc10098b34d06b3899eed5fcfb5e0
Source dataset
uspto-grants-2012_07
Patent number
US08232423B2

Reaction notes

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