Aluminium lithium hydride → (4-Phenylbicyclo[2.2.2]oct-1-yl)methanol

HRID 908126Notes

Reaction equation

HRID 908126 reaction equation
[C:1]1([C:7]23[CH2:14][CH2:13][C:10]([C:15](OCC)=[O:16])([CH2:11][CH2:12]2)[CH2:9][CH2:8]3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-]>C1COCC1>[C:1]1([C:7]23[CH2:14][CH2:13][C:10]([CH2:15][OH:16])([CH2:11][CH2:12]2)[CH2:9][CH2:8]3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 21627803Ethyl 4-phenylbicyclo[2.2.2]octane-1-carboxylate

Product 1

HCID 21675352(4-Phenylbicyclo[2.2.2]oct-1-yl)methanolYield 101.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
22.5 °C

Procedure

A solution of ethyl 4-phenylbicyclo[2.2.2]octane-1-carboxylate (207 g, 801 mmol) in THF (850 mL) was added to a stirred solution of lithium aluminium hydride (20 g, 527 mmol) in THF (1.25 L) under nitrogen, maintaining a temperature of 20-25° C. with an ice/water bath. The reaction mixture was stirred for 3 h, allowed to stand overnight, then quenched by addition to a mixture of water (900 mL) and ice (300 g). The mixture was acidified to pH 1-2 with concentrated hydrochloric acid then extracted with ethyl acetate (3×1 L). The combined organics were dried (MgSO4) and evaporated down to give the title compound as a brown solid (176 g; ˜100%). 1H NMR (CDCl3) 1.35 (1H, brd s), 1.40-1.52 (6H, m), 1.71-1.85 (6H, m), 3.25 (2H, s), 7.05-7.13 (1H, m), 7.17-7.30 4H, m).

Workup

  1. waitto stand overnight
  2. customquenched by addition to a mixture of water (900 mL) and ice (300 g)
  3. extractionthen extracted with ethyl acetate (3×1 L)
  4. dry with materialThe combined organics were dried (MgSO4)
  5. customevaporated down

Sources & evidence

ORD record
ord-dabeb87d7e2a46e18354f70429bc833c
Source dataset
uspto-grants-2011_09
Patent number
US08017603B2

Reaction notes

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