Sodium hydride → 6-Geranyloxycoumarin

HRID 1051035Notes

Reaction equation

HRID 1051035 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][C:7](=[O:12])[CH:6]=[CH:5]2.[H-].[Na+].[CH2:15](Br)/[CH:16]=[C:17](/[CH2:19][CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])\[CH3:18]>CN(C=O)C>[CH3:18]/[C:17](/[CH2:19][CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])=[CH:16]\[CH2:15][O:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][C:7](=[O:12])[CH:6]=[CH:5]2

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 994776-hydroxy-2H-chromen-2-oneHCID 53658672,6-Octadiene, 1-bromo-3,7-dimethyl-, (2E)-

Product 1

HCID 468412096-Geranyloxycoumarin

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

An oven-dried 50 mL round bottom flask was prepared with a magnetic stirring bar, a rubber septum cover, and a nitrogen inlet. 6-hydroxycoumarin (1) (114 mg, 0.7 mmol) and 4 mL of anhydrous DMF were added to the round bottom flask. The solution was stirred and cooled to 0° C. in a salt-ice bath. Sodium hydride (28 mg of 60% mineral oil suspension, 0.7 mmol) was added to the flask and the solution was kept stirring at 0° C. for 30 minutes. Geranyl bromide (329 μL, 1.66 mmol) in 1 mL of anhydrous DMF was cooled to 0° C. and added dropwise to the flask through the rubber septum using a syringe. The reaction mixture was left stirring under nitrogen at room temperature for 14 hours. The desired product was isolated by column chromatography using a solvent system of 100% Hexanes, 20:1 Hexanes:Ethyl acetate, 15:1 Hexanes:Ethyl acetate, 10:1 Hexanes:Ethyl acetate, 7:3 Hexanes:Ethyl acetate, and 2:1 Hexanes:Ethyl acetate. The purified product was characterized by NMR spectroscopy (1H-NMR, 13C-NMR) and high-resolution mass spectrometry (HRMS). 1H-NMR (300 MHz, CDCl3): ∂ 1.61-1.84 (9H), 2.13 (m, 4H), 4.57 (d, 2H, J=6 Hz), 5.1 (m, 1H), 5.48 (t, 1H), 6.43 (d, 1H, J=9 Hz), 6.93-7.67 (4H); 13C-NMR (75 MHz, CDCl3): ∂ 18.0, 18.2, 26.25, 26.38, 39.06, 65.20, 111.08, 117.01, 117.83, 118.89, 119.14, 119.70, 123.88, 131.94, 141.44, 143.27, 148.41, 155.33, 161.06. HRMS (CI) Calcd. for C19H23O3: 299.16473. found: 299.16377.

Workup

  1. customAn oven-dried 50 mL round bottom flask was prepared with a magnetic stirring bar
  2. stirringthe solution was kept stirring at 0° C. for 30 minutes
  3. additionadded dropwise to the flask through the rubber septum
  4. waitThe reaction mixture was left
  5. stirringstirring under nitrogen at room temperature for 14 hours

Sources & evidence

ORD record
ord-a5dbfd7da839487aa4af311939e10fa1
Source dataset
uspto-grants-2016_07
Patent number
US09388155B1

Reaction notes

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