ETHYL 8-(2-NAPHTHYL)-8-OXOOCTANOATE → HCID 11809077, compound

HRID 1182498Notes

Reaction equation

HRID 1182498 reaction equation
[CH2:1]([Li])CCC.[CH:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[C:16]([CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])=O>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[C:16](=[CH2:1])[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25]

Participants

5

Reactant 2

HCID 10881518ETHYL 8-(2-NAPHTHYL)-8-OXOOCTANOATEHCID 178418339Butyllithium

Product 1

HCID 11809077HCID 11809077, compoundYield 52.9%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of methyltriphenylphosphonium bromide (469 mg,1.31 mmol) in THF (6 mL) pre-cooled to 0° C. under nitrogen atmosphere was added dropwise n-butyllithium (1.42M solution in hexanes, 905 μL, 1.28 mmol) and stirred over 20 minutes. To this a THF (4mL) solution of 49g (82 mg, 0.262 mmol) was transferred via cannula. The yellow mixture was stirred over 30 minutes and quenched with a saturated aqueous solution of ammonium chloride, as the yellow color immediately disappeared. The solvent was removed by evaporation in vacuo and the aqueous residue was partitioned between water and ethyl acetate. The aqueous layer was then extracted with ethyl acetate and the combined organic layers were washed with brine, dried (MgSO4) and concentrated. The crude residue was purified by flash chromatography (5% to 8% diethyl ether in hexane) to afford the title compound 168 (43 mg) in 52% yield. 1H NMR: (CDCl3) δ: 7.85-7.78 (m, 4H), 7.58 (dd, J=8.8, 1.9 Hz, 1H), 7.48-7.44 (m, 2H), 5.42 (d, J=1.1 Hz, 1H), 5.16 (d, J=1.4 Hz, 1H), 4.12 (q, J=7.1 Hz, 2H), 2.62 (t, J=6.9 Hz, 2H), 2.28 (d, J=7.4 Hz, 2H), 1.64-1.49 (m, 4H), 1.39-1.33 (m, 4H), 1.25 (t, J=7.1 Hz, 3H). MS (ESI)=311 (MH+).

Workup

  1. stirringThe yellow mixture was stirred over 30 minutes
  2. customquenched with a saturated aqueous solution of ammonium chloride, as the yellow color
  3. customThe solvent was removed by evaporation in vacuo
  4. customthe aqueous residue was partitioned between water and ethyl acetate
  5. extractionThe aqueous layer was then extracted with ethyl acetate
  6. washthe combined organic layers were washed with brine
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. customThe crude residue was purified by flash chromatography (5% to 8% diethyl ether in hexane)

Sources & evidence

ORD record
ord-46c82fc5c5184a7ab25c95be43482b77
Source dataset
uspto-grants-2007_10
Patent number
US07288567B2

Reaction notes

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