HCID 10192985, compound → HCID 10308259, compound

HRID 1794483Notes

Reaction equation

HRID 1794483 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
  5. customat 65° C
  6. customThe solvent was evaporated
  7. additionthe residue was poured into water
  8. extractionextracted with ethyl acetate
  9. washThe combined organic phases were washed with saturated sodium bicarbonate, water, brine
  10. dry with materialdried with magnesium sulfate
  11. concentrationThe organic phases were concentrated
  12. customchromatographed with silica gel (hexanes:ethyl acetate, 95:5)

Sources & evidence

ORD record
ord-fa99a722b14c4e9196661f70c4815003
Source dataset
uspto-grants-2006_04
Patent number
US07022733B2

Reaction notes

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