Water → HCID 59156565, compound

HRID 1694598Notes

Reaction equation

HRID 1694598 reaction equation
[H-].[Na+].[N+:3]([C:6]1[CH:20]=[CH:19][C:9]([CH2:10]P(=O)(OCC)OCC)=[CH:8][CH:7]=1)([O-:5])=[O:4].[Br:21][C:22]1[CH:23]=[C:24]([C:32]2([CH3:35])[CH2:34][CH2:33]2)[C:25]([O:30][CH3:31])=[C:26]([CH:29]=1)[CH:27]=O.O>C1COCC1.C1OCCOCCOCCOCCOC1>[Br:21][C:22]1[CH:29]=[C:26](/[CH:27]=[CH:10]/[C:9]2[CH:8]=[CH:7][C:6]([N+:3]([O-:5])=[O:4])=[CH:20][CH:19]=2)[C:25]([O:30][CH3:31])=[C:24]([C:32]2([CH3:35])[CH2:33][CH2:34]2)[CH:23]=1

Participants

7

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 256065Diethyl 4-nitrobenzylphosphonateHCID 86638343HCID 86638343, compound

Product 1

HCID 59156565HCID 59156565, compoundYield 101.5%

Reagents, catalysts & solvents 2

HCID 3633615-Crown-5CatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

Sodium hydride (60% dispersion, 0.10 g, 2.6 mmol) and 15-crown-5 (0.038 g, 0.17 mmol) were added to THF (5 mL) at 0° C. and stirred for 5 min. To the reaction mixture was then added dropwise over 5 min a solution of diethyl (4-nitrobenzyl)phosphonate (0.52 g, 1.9 mmol) in THF (5 mL), and stirring was continued at 0° C. for 5 min. To this reaction mixture was then added dropwise over 10 min a solution of 74b (0.47 g, 1.7 mmol) in THF (10 mL). The reaction mixture was stirred for 30 min at 0° C. then for 90 min at RT. Water was carefully added, and the mixture was partitioned between water and EtOAc. The EtOAc layer was washed sequentially with water and brine, dried (Na2SO4), filtered and concentrated. The crude residue was purified by SiO2 chromatography eluting with EtOAc/hexane to afford 0.67 g (94%) of 5-bromo-2-methoxy-1-(1-methylcyclopropyl)-3-[(E)-2-(4-nitrophenyl)vinyl]benzene (75) as a yellow solid (0.67 g, 94%).

Workup

  1. stirringstirring
  2. waitwas continued at 0° C. for 5 min
  3. stirringThe reaction mixture was stirred for 30 min at 0° C.
  4. waitfor 90 min at RT
  5. customthe mixture was partitioned between water and EtOAc
  6. washThe EtOAc layer was washed sequentially with water and brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude residue was purified by SiO2 chromatography
  11. washeluting with EtOAc/hexane

Sources & evidence

ORD record
ord-2eda3a1ef9a8408a8c392c0d0edaa376
Source dataset
uspto-grants-2012_04
Patent number
US08158803B2

Reaction notes

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