Sodium hydride → HCID 59281701, compound

HRID 546369Notes

Reaction equation

HRID 546369 reaction equation
[C:1]([CH2:4][C:5](=[O:7])[CH3:6])(=[O:3])[CH3:2].[H-].[Na+].[Br:10][C:11]1[CH:18]=[CH:17][C:14]([CH2:15]Br)=[CH:13][CH:12]=1.[NH4+].[Cl-]>C1COCC1.CCOC(C)=O.CCCCCC>[Br:10][C:11]1[CH:18]=[CH:17][C:14]([CH2:15][CH:4]([C:5](=[O:7])[CH3:6])[C:1](=[O:3])[CH3:2])=[CH:13][CH:12]=1

Participants

7

Reactant 4

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 31261AcetylacetoneHCID 685274-Bromobenzyl bromide

Product 1

HCID 59281701HCID 59281701, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Conditions

Temperature
50 °C

Procedure

Acetylacetone (4.5 mL, 44 mmol) was added dropwise over 30 minutes to a cooled (ice/H2O bath) suspension of 95% NaH (0.95 g, 41 mmol) in anhydrous THF (150 mL). After H2 evolution had ceased, a solution of p-bromobenzyl bromide (10.2 g, 40.8 mmol) in anhydrous THF (20 mL) was added at once with stirring. The reaction mixture was heated to 50° C. (internal temperature) for 48 h, cooled to room temperature, and poured into saturated aqueous NH4Cl (250 mL). The organic phase was separated and the aqueous phase was extracted with EtOAc (3×125 mL). The combined organic extracts were dried (Na2SO4). The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure to give an oily residue. Flash column chromatography (EtOAc:hexane (1:8)) gave 4d as a clear amber oil which solidified upon standing at room temperature (9.01 g, 82%). 1H NMR (300 MHz, CDCl3): δ 7.42 (d, J=8.4 Hz, 2H, enol), 7.39 (d, J=8.4 Hz, 2H, keto), 7.03 (d, J=8.4 Hz, 2H, keto), 7.02 (d, J=8.4 Hz, 2H, enol), 3.95 (t, J=7.5 Hz, 1H, keto), 3.60 (s, 2H, enol), 3.10 (d, J=7.5 Hz, 2H, keto), 2.13 (s, 6H, keto), 2.05 (s, 6H, enol). 13C NMR (75 MHz, CDCl3): δ 203.3, 192.1, 138.9, 137.3, 132.0, 130.6, 129.4, 120.0, 120.9, 108.1, 70.0, 33.7, 32.6, 29.9, 23.5. IR (neat, cm−1): 3409, 3010, 3004, 2927, 1896, 1728, 1699, 1594, 1487, 1405, 1358, 1072, 1010. GC/MS (ET): m/z 268 (M+). Anal. Calcd. for C12H13BrO2: C, 53.55; H, 4.87; O, 11.89. Found: C, 53.27; H, 4.77; O, 11.61.

Workup

  1. temperaturea cooled
  2. temperaturecooled to room temperature
  3. customThe organic phase was separated
  4. extractionthe aqueous phase was extracted with EtOAc (3×125 mL)
  5. dry with materialThe combined organic extracts were dried (Na2SO4)
  6. customThe drying agent was removed by filtration
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customto give an oily residue

Sources & evidence

ORD record
ord-1454c73b21d84a3880d233aa10e8614c
Source dataset
uspto-grants-2011_05
Patent number
US07935847B2

Reaction notes

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