Sodium hydride → HCID 14876208, compound

HRID 1709310Notes

Reaction equation

HRID 1709310 reaction equation
[H-].[Na+].[CH2:3]([N:5]([C:8]1[CH:15]=[CH:14][C:11]([CH:12]=O)=[C:10]([OH:16])[CH:9]=1)[CH2:6][CH3:7])[CH3:4].Br[CH2:18][C:19]([O:21][CH3:22])=[O:20]>O1CCCC1>[CH2:3]([N:5]([C:8]1[CH:15]=[CH:14][C:11]2[CH:12]=[C:18]([C:19]([O:21][CH3:22])=[O:20])[O:16][C:10]=2[CH:9]=1)[CH2:6][CH3:7])[CH3:4]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 60984Methyl bromoacetateHCID 872934-(Diethylamino)-2-hydroxybenzaldehyde

Product 1

HCID 14876208HCID 14876208, compoundYield 45.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a 250 mL three necked, round bottom flask equipped with a mechanical stirrer, reflux condenser, and Y-tube with a rubber septum and nitrogen inlet was added 1.8 gm (45 mmol) of 60% sodium hydride in mineral oil. After washing twice with 20 mL of hexanes, 150 mL of THF was added, followed by the rapid dropwise addition via transfer syringe of 3.86 gm (20 mmol) of 4-(N,N diethylamino)-2-hydroxybenzaldehyde, dissolved in 50 mL of tetrahydrofuran (THF). The flask was placed in an 80° C. oil bath and stirred vigorously for 5 minutes, at which time 2.08 mL (20 mmol) of methyl bromoacetate was added in one portion. Sodium bromide precipitated from solution and vigorous stirring had to be maintained throughout. The suspension was refluxed for 80 minutes, allowed to cool to room temperature, and diluted with 75 mL of diethyl ether. The reaction was quenched by the slow dropwise addition of 50 mL of dilute aqueous ammonium chloride. The phases were separated and the aqueous phase extracted with 100 mL of diethyl ether (Et2O). The combined organic phases were washed with 20 mL 1N NaOH and 20 mL water. After drying (MgSO4), the solvent was removed by rotary evaporation and the residual oil purified by flash chromatography (CH2Cl2 ; SiO2, 11/2×15") to yield 2.23 gm (45.3%) of the product as a colorless oil. Field desorption mass spectrum: m/e 247 (M+). Anal. calcd. for C14H17NO3 : C, 68.0., H, 6.9; N, 5.7. Found: C, 67.9; H, 6.8; N, 5.8. 1H 270 NMR (CDCl3): δ 6.7 (m, 2H, ArHa,b), 7.4 (m, 2H, ArHc,d).

Workup

  1. temperaturereflux condenser
  2. washAfter washing twice with 20 mL of hexanes, 150 mL of THF
  3. additionwas added
  4. customwas placed in an 80° C.
  5. additionwas added in one portion
  6. customSodium bromide precipitated from solution
  7. temperatureto be maintained throughout
  8. temperatureThe suspension was refluxed for 80 minutes
  9. additiondiluted with 75 mL of diethyl ether
  10. customThe reaction was quenched by the slow dropwise addition of 50 mL of dilute aqueous ammonium chloride
  11. customThe phases were separated
  12. extractionthe aqueous phase extracted with 100 mL of diethyl ether (Et2O)
  13. washThe combined organic phases were washed with 20 mL 1N NaOH and 20 mL water
  14. dry with materialAfter drying (MgSO4)
  15. customthe solvent was removed by rotary evaporation
  16. customthe residual oil purified by flash chromatography (CH2Cl2 ; SiO2, 11/2×15")

Sources & evidence

ORD record
ord-e7202d5d3600454a8a1604428f56da46
Source dataset
uspto-grants-1990_08
Patent number
US04948893

Reaction notes

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