Benzyl Bromide → 2-(Benzyloxy)-6-bromonaphthalene

HRID 2272813Notes

Reaction equation

HRID 2272813 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:5]=[C:6]2[C:11](=[CH:12][CH:13]=1)[CH:10]=[C:9]([OH:14])[CH:8]=[CH:7]2.[CH2:15](Br)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>CN(C)C=O.CCOC(C)=O.C([O-])(O)=O.[Na+]>[CH2:15]([O:14][C:9]1[CH:8]=[CH:7][C:6]2[C:11](=[CH:12][CH:13]=[C:4]([Br:3])[CH:5]=2)[CH:10]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

7

Reactant 3

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 271446-Bromo-2-naphthalenol

Product 1

HCID 6405952-(Benzyloxy)-6-bromonaphthaleneYield 90.3%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolventHCID 516892Sodium BicarbonateSolvent

Procedure

Sodium hydride (1.16 g, 29.12 mmol) was added to 6-bromo-2-naphthol (5.00 g, 22.41 mmol) in anhydrous N,N-dimethylformamide (162 mL) at 0° C. After 15 minutes, benzyl bromide (2.40 mL, 3.45 g, 20.18 mmol) was added and the reaction warmed to room temperature over 18 hours. The reaction was diluted with EtOAc (500 mL), saturated aqueous NaHCO3 (200 mL) was added, and the solution was extracted with EtOAc (3×500 mL). The combined organic layers were washed with water (3×1 L), saturated aqueous NaCl solution (1 L), dried (Na2SO4), filtered, and concentrated. The residue was purified via column chromatography (SiO2, 5:1 Hexanes:CH2Cl2) to give 36 as a colorless amorphous solid (5.71 g, 90%): 1H NMR (CDCl3, 500 MHz) δ 7.94 (d, J=1.9 Hz, 1H), 7.68 (d, J=9.0 Hz, 1H), 7.61 (d, J=8.7 Hz, 1H), 7.53-7.47 (m, 3H), 7.46-7.40 (m, 2H), 7.37 (m, 1H), 7.26 (dd, J=9.0, 2.5 Hz, 1H), 7.20 (d, J=2.5 Hz, 1H), 5.18 (s, 2H); 13C NMR (CDCl3, 125 MHz) δ 157.2, 136.8, 133.2, 130.3, 129.9, 129.9, 128.9 (2C), 128.8, 128.7, 128.4, 127.8 (2C), 120.3, 117.4, 107.3, 70.3; IR (film) νmax 1585, 1452, 1256, 1219, 1204, 1165, 1065, 997, 924, 852, 820, 800, 733, 698, 476 cm−1.

Workup

  1. additionwas added
  2. extractionthe solution was extracted with EtOAc (3×500 mL)
  3. washThe combined organic layers were washed with water (3×1 L), saturated aqueous NaCl solution (1 L)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified via column chromatography (SiO2, 5:1 Hexanes:CH2Cl2)

Sources & evidence

ORD record
ord-7b00b9146fb447cc8b5a12f93eb20cb7
Source dataset
uspto-grants-2015_09
Patent number
US09120774B2

Reaction notes

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