Aluminium lithium hydride → HCID 86698785, compound

HRID 338452Notes

Reaction equation

HRID 338452 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].C([O:9][C:10](=O)[C:11]([CH2:24][O:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)([C:17]1[CH:22]=[CH:21][C:20]([Br:23])=[CH:19][CH:18]=1)[C:12](OCC)=[O:13])C>C(OCC)C>[CH2:26]([O:25][CH2:24][C:11]([C:17]1[CH:18]=[CH:19][C:20]([Br:23])=[CH:21][CH:22]=1)([CH2:10][OH:9])[CH2:12][OH:13])[C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 86698786HCID 86698786, compound

Product 1

HCID 86698785HCID 86698785, compoundYield 36%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To a 0° C. suspension of LAH (444 mg, 11.1 mmol) in diethyl ether (10 mL) was added a solution of 2-Benzyloxymethyl-2-(4-bromo-phenyl)-malonic acid diethyl ester (1.67 g, 3.84 mmol) in diethyl ether (10 mL) dropwise via addition funnel. The reaction mixture was warmed to room temperature and stirred for 22 hours. The reaction was quenched with water (1.5 mL), 15% NaOH (1.5 mL), and water (3 mL) added sequentially. The white slurry was stirred for 30 minutes, diluted with ethyl acetate and filtered to remove the aluminum salts. The filtrate was concentrated in vacuo to afford a green semisolid, which was purified by flash chromatography (40 g silica, 30-82% ethyl acetate/heptane, 10 column volumes). Product fractions were combined and concentrated in vacuo to afford the title compound as a colorless oil (482 mg, 36% yield). 1H NMR (500 MHz, CD3OD) δ ppm 7.45 (d, J=8.54 Hz, 2H), 7.35 (d, J=8.78 Hz, 2H), 7.22-7.33 (m, 5H), 4.51 (s, 2H), 3.92 (s, 4H), 3.82 (s, 2H).

Workup

  1. additiondropwise via addition funnel
  2. customThe reaction was quenched with water (1.5 mL), 15% NaOH (1.5 mL), and water (3 mL)
  3. additionadded sequentially
  4. stirringThe white slurry was stirred for 30 minutes
  5. additiondiluted with ethyl acetate
  6. filtrationfiltered
  7. customto remove the aluminum salts
  8. concentrationThe filtrate was concentrated in vacuo
  9. customto afford a green semisolid, which
  10. customwas purified by flash chromatography (40 g silica, 30-82% ethyl acetate/heptane, 10 column volumes)
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a2e21fb28af7408d9f987ee08d6bdeea
Source dataset
uspto-grants-2014_11
Patent number
US08889730B2

Reaction notes

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