3-Methoxybenzyl bromide → HCID 68495693, compound

HRID 1944212Notes

Reaction equation

HRID 1944212 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH2:7][C:8]([CH3:15])([CH3:14])[NH:9][CH:10]2[CH3:13])=[CH:5][C:4]=1[O:16][Si:17]([CH:24]([CH3:26])[CH3:25])([CH:21]([CH3:23])[CH3:22])[CH:18]([CH3:20])[CH3:19].[Cs].[CH3:28][O:29][C:30]1[CH:31]=[C:32]([CH:35]=[CH:36][CH:37]=1)[CH2:33]Br>CC(C)=O.O>[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH2:7][C:8]([CH3:15])([CH3:14])[N:9]([CH2:33][C:32]3[CH:35]=[CH:36][CH:37]=[C:30]([O:29][CH3:28])[CH:31]=3)[CH:10]2[CH3:13])=[CH:5][C:4]=1[O:16][Si:17]([CH:24]([CH3:26])[CH3:25])([CH:21]([CH3:23])[CH3:22])[CH:18]([CH3:19])[CH3:20]

Participants

6

Reactant 3

HCID 40672073-Methoxybenzyl bromideHCID 5354618CesiumHCID 68492781HCID 68492781, compound

Product 1

HCID 68495693HCID 68495693, compoundYield 35.3%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

To a solution of 240 (170 mg, 0.45 mmol) in acetone (1.5 ml) was added cesium C(Ar)bonate (162 mg, 0.5 mmol) followed by 3-methoxy benzyl bromide (0.063 ml, 0.54 mmol). The reaction mixture was stirred at rt for 23 h. The resulting solution was diluted with water and extracted with ethyl acetate (3×). The combined organic phases were washed with brine, dried (MgSO4) and concentrated in vacuo. Purification (Flashmaster; 10 g, 100% hex to 95% hex:5% EtOAc over 25 min) afforded the title compound (79 mg, 35%) as a colourless oil. 1H NMR (270 MHz; CDCl3) 0.94 (3H, s, CH3), 1.07 (18H, d, J=6.7 Hz, 6×SiCHCH3), 1.09 (3H, s, CH3), 1.15-1.29 (3H, m, 3×CH), 1.20 (3H, d, J=6.2 Hz, CH3CH), 2.37 (1H, d, J=15.3 Hz, one of CH2), 2.94 (1H, d, J=15.3 Hz, one of CH2), 3.50 (1H, d, J=17.3 Hz, one of CH2), 3.71 (1H, q, J=6.2 Hz, CHCH3), 3.76 (3H, s, OCH3), 3.79 (3H, s, OCH3), 4.09 (1H, d, J=17.3 Hz, one of CH2), 6.48 (1H, s, CH), 6.59 (1H, s, CH), 6.71 (1H, dd, J=7.7, 2.2 Hz, CH), 7.0 (1H, d, J=7.7 Hz, CH), 7.09 (1H, brs, CH), 7.19 (1H, t, J=7.9 Hz, CH). 13C NMR (100 MHz; CDCl3) 12.85 (CH3), 17.92 (CH3), 18.69 (CH3), 24.35 (CH3), 30.03 (CH3), 44.29 (CH2), 53.29 (CH2), 53.72 (C), 55.08 (OCH), 55.47 (OCH3), 57.40 (OCH3), 111.06 (CH), 111.84 (CH), 112.92 (CH), 118.13 (CH), 119.34 (CH), 126.70 (C), 128.81 (CH), 132.34 (C), 143.23 (C), 146.35 (C), 148.81 (C), 159.46 (C). LC/MS (ES+) tr=7.09 min, m/z 498.42 (M++H). HPLC tr=7.03 min (>98%).

Workup

  1. extractionextracted with ethyl acetate (3×)
  2. washThe combined organic phases were washed with brine
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customPurification (Flashmaster; 10 g, 100% hex to 95% hex:5% EtOAc over 25 min)

Sources & evidence

ORD record
ord-16f5dc4a75cf49619c86fe9d8f1fee08
Source dataset
uspto-grants-2013_03
Patent number
US08394825B2

Reaction notes

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