HCID 10192985, compound → HCID 10308259, compound

HRID 1835986Notes

Reaction equation

HRID 1835986 reaction equation
[CH2:1]([Li])CCC.[CH3:6][O:7][C:8]1[CH:9]=[C:10]([CH2:25]O)[C:11]2[O:15][C:14]([C:16]3[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=3)=[CH:13][C:12]=2[CH:24]=1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[CH3:6][O:7][C:8]1[CH:9]=[C:10]([CH:25]=[CH2:1])[C:11]2[O:15][C:14]([C:16]3[CH:17]=[CH:18][C:19]([O:22][CH3:23])=[CH:20][CH:21]=3)=[CH:13][C:12]=2[CH:24]=1

Participants

5

Reactant 2

HCID 10192985HCID 10192985, compoundHCID 178418339Butyllithium

Product 1

HCID 10308259HCID 10308259, compoundYield 71%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

Methyl triphenylphosphonium bromide (0.122 g, 0.334 mmole) was dissolved in 5 mL THF and placed in an acetone/dry ice bath at −78° C. n-Butyl lithium (0.131 mL, 0.328 mmole) was added and the mixture was allowed to stir for 30 minutes. To this solution was added aldehyde 3 (0.078 g, 0.278 mmole) in 3 mL THF. After stirring at room temperature for 4 hours, the reaction mixture was placed in an oil bath and allowed to stir overnight at 65° C. The solvent was evaporated and the residue was poured into water and extracted with ethyl acetate. The combined organic phases were washed with saturated sodium bicarbonate, water, brine, and dried with magnesium sulfate. The organic phases were concentrated and the residue was loaded on to silica gel and chromatographed with silica gel (hexanes:ethyl acetate, 95:5) to afford 0.055 g (71%) of 28 as a white solid: Mp=182-184° C.; 1H NMR (DMSO-d6) δ 7.87 (d, 2 H, J=8.4 Hz), 7.22 (s, 1 H), 7.08 (m, 3 H), 6.98 (m, 1 H), 6.96 (d, 1 H, J=2.3 Hz), 6.30 (d, 1 H, J=17.8 Hz), 5.59 (d, 1 H, J=11.4 Hz), 3.82 (s, 3 H), 3.80 (s, 3 H); MS 281 (M+H)+

Workup

  1. customplaced in an acetone/dry ice bath at −78° C.
  2. stirringAfter stirring at room temperature for 4 hours
  3. customthe reaction mixture was placed in an oil bath
  4. stirringto stir overnight at 65° C
  5. customThe solvent was evaporated
  6. additionthe residue was poured into water
  7. extractionextracted with ethyl acetate
  8. washThe combined organic phases were washed with saturated sodium bicarbonate, water, brine
  9. dry with materialdried with magnesium sulfate
  10. concentrationThe organic phases were concentrated
  11. customchromatographed with silica gel (hexanes:ethyl acetate, 95:5)

Sources & evidence

ORD record
ord-2626547d5b6d427191ace1bcefd22880
Source dataset
uspto-grants-2004_08
Patent number
US06774248B2

Reaction notes

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