Sodium hydride → HCID 73990329, compound

HRID 2416404Notes

Reaction equation

HRID 2416404 reaction equation
[H-].[Na+].[CH:3]([C:5]1[CH:20]=[CH:19][C:8]([CH:9]=[CH:10][C:11]2[CH:18]=[CH:17][C:14]([CH:15]=O)=[CH:13][CH:12]=2)=[CH:7][CH:6]=1)=[CH2:4].[Br-].[C:22]([C:26]1[CH:51]=[CH:50][C:29]([CH2:30][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:28][CH:27]=1)([CH3:25])([CH3:24])[CH3:23]>>[C:22]([C:26]1[CH:27]=[CH:28][C:29]([CH:30]=[CH:15][C:14]2[CH:17]=[CH:18][C:11]([CH:10]=[CH:9][C:8]3[CH:7]=[CH:6][C:5]([CH:3]=[CH2:4])=[CH:20][CH:19]=3)=[CH:12][CH:13]=2)=[CH:50][CH:51]=1)([CH3:23])([CH3:24])[CH3:25]

Participants

4

Reactant 3

HCID 24758Sodium hydrideHCID 22630532[(4-tert-Butylphenyl)methyl](triphenyl)phosphanium bromideHCID 73990327HCID 73990327, compound

Product 1

HCID 73990329HCID 73990329, compound

Procedure

Solid NaH (396 mg, 16.5 mmol) was added in small portions into a suspension of 4-(4′vinylstyryl)benzaldehyde (703 g, 3.0 mmol) and 4-tert-butylbenzyltriphenylphosphonium bromide (1.61 g, 3.3 mmol). The reaction mixture was stirred under nitrogen at room temperature for 24 hours. The reaction was quenched slowly with water, extracted with CHCl3, washed with brine, and the solvent was evaporated under reduced pressure to dryness. To the residue, 100 mL of dry toluene was added and evaporated to dryness. The light yellow solid was triturated with ethanol, filtered to give light yellow solid (which is the all-trans isomer by NMR). The filtrate was concentrated and purified with silica gel chromatography (10-20% CHCl3/hexanes) to give another portion of product (a mixture of cis and trans isomers). Yield: 1.1 g (>99%). 1H NMR (CDCl3) of the all-trans isomer: δ 7.51 (s, 4H), 7.49, 7.47 (d, J=8.46 Hz, 4H), 7.41, 7.39 (d, J=8.45 Hz, 4H), 7.13, 7.07 (d, J=16.28 Hz, 2H), 7.11 (s, 2H), 6.72 (dd, J1=10.85 Hz, J2=17.55 Hz, 1H), 5.78 (d, J=17.55 Hz, 1H), 5.26 (d, J=10.85 Hz, 1H), 1.34 (s, 9H). The compound is too insoluble for 13C NMR spectroscopy.

Workup

  1. customThe reaction was quenched slowly with water
  2. extractionextracted with CHCl3
  3. washwashed with brine
  4. customthe solvent was evaporated under reduced pressure to dryness
  5. additionTo the residue, 100 mL of dry toluene was added
  6. customevaporated to dryness
  7. customThe light yellow solid was triturated with ethanol
  8. filtrationfiltered
  9. customto give light yellow solid (which
  10. concentrationThe filtrate was concentrated
  11. custompurified with silica gel chromatography (10-20% CHCl3/hexanes)
  12. customto give another portion of product (
  13. additiona mixture of cis and trans isomers)

Sources & evidence

ORD record
ord-3606d5f7f16446a6bda3c90782ce81f6
Source dataset
uspto-grants-2004_11
Patent number
US06824890B2

Reaction notes

Loading…