2-Propen-1-yl 4-bromo-3,5-bis(2-propen-1-yloxy)benzoate → HCID 6709793, compound

HRID 1008243Notes

Reaction equation

HRID 1008243 reaction equation
C([O:4][C:5](=O)[C:6]1[CH:11]=[C:10]([O:12][CH2:13][CH:14]=[CH2:15])[C:9]([Br:16])=[C:8]([O:17][CH2:18][CH:19]=[CH2:20])[CH:7]=1)C=C.[H-].[Al+3].[Li+].[H-].[H-].[H-].C(C(C(C([O-])=O)O)O)([O-])=O.[Na+].[K+]>C1COCC1>[CH2:18]([O:17][C:8]1[CH:7]=[C:6]([CH2:5][OH:4])[CH:11]=[C:10]([O:12][CH2:13][CH:14]=[CH2:15])[C:9]=1[Br:16])[CH:19]=[CH2:20]

Participants

5

Reactant 3

HCID 67097922-Propen-1-yl 4-bromo-3,5-bis(2-propen-1-yloxy)benzoateHCID 9855836Potassium sodium tartarateHCID 21226445Aluminium lithium hydride

Product 1

HCID 6709793HCID 6709793, compoundYield 47%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 16 (30 g, 85 mmol) in THF (600 ml) at 0° C. was added lithium aluminum hydride (1.0M in THF, 175 mL, 2 equiv) dropwise over 45 minutes. The reaction was stirred at 0° C. for 2 hours, after which time saturated aqueous potassium sodium tartrate was added dropwise until bubbling ceased (25 mL, over 45 minutes). To the suspension was added ether (100 mL) and additional saturated aqueous potassium sodium tartrate (30 mL). The suspension was filtered through celite, the THF and ether were removed under reduced pressure, and water (250 mL) was added. The aqueous suspension was extracted into EtOAc (4×250 mL). The organic layer was washed with brine, dried over MgSO4, filtered, and concentrated. Purification by flash chromatography (20→75% EtOAc/hexane) afforded 17 (11.93 g, 47%) as a white oil. Rf=0.39 (50% EtOAc/hexane); FTIR (neat, cm−1) 3363, 2924, 2869, 1587, 1435, 817; 1H NMR (400 MHz, CDCl3) δ, 6.56 (s, 2H), 6.10-6.00 (m, 2H), 5.48 (dd, J=17.4, 1.6 Hz, 2H), 5.29 (dd, J=10.6, 1.6 Hz, 2H), 4.62 (s, 2H), 4.60 (d, J=5.2 Hz, 4H); 13C NMR (100 MHz, CDCl3) δ156.2, 141.4, 132.6, 117.6, 104.5, 100.9, 69.8, 65.0; MS EI+ calculated for C13H15BrO3 (M−H)+: 298, found: 298.

Workup

  1. customuntil bubbling
  2. custom(25 mL, over 45 minutes)
  3. additionTo the suspension was added ether (100 mL) and additional saturated aqueous potassium sodium tartrate (30 mL)
  4. filtrationThe suspension was filtered through celite
  5. customthe THF and ether were removed under reduced pressure, and water (250 mL)
  6. additionwas added
  7. extractionThe aqueous suspension was extracted into EtOAc (4×250 mL)
  8. washThe organic layer was washed with brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by flash chromatography (20→75% EtOAc/hexane)

Sources & evidence

ORD record
ord-c25a2db38abc4c4995d7cb7d85a26ebc
Source dataset
uspto-grants-2004_09
Patent number
US06797819B1

Reaction notes

Loading…