Water → HCID 10673564, compound

HRID 1107640Notes

Reaction equation

HRID 1107640 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:18]=[C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:16]2[C:11](=[CH:12][C:13]([C:27]#[N:28])=[CH:14][CH:15]=2)[C:10]=1[Br:29])=[O:7])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].Br[CH2:33][CH:34]=[C:35]([CH3:37])[CH3:36].O>CN(C=O)C>[C:1]([O:5][C:6]([N:8]([C:9]1[CH:18]=[C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C:16]2[C:11](=[CH:12][C:13]([C:27]#[N:28])=[CH:14][CH:15]=2)[C:10]=1[Br:29])[CH2:33][CH:34]=[C:35]([CH3:37])[CH3:36])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 700922-Butene, 1-bromo-3-methyl-HCID 10742308HCID 10742308, compound

Product 1

HCID 10673564HCID 10673564, compoundYield 100.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 16 (1.77 g, 3.90 mmol) in anhydrous DMF (20 mL) under Ar was treated with NaH (206 mg, 5.1 mmol, 1.3 equiv, 60% oil dispersion) and the reaction mixture was stirred for 30 min. The mixture was cooled to 0° C. and 4-bromo-2-methyl-2-butene (1.35 mL, 11.7 mmol, 3 equiv) was added dropwise by cannula. The solution was stirred at 0° C. for 1 h before being allowed to warm to 25° C. and stirred overnight. Water (20 mL) was added and the aqueous phase was extracted with EtoAc (3×15 mL). The combined organic phases were washed with saturated aqueous NaCl (1×30 mL), dried (Na2SO4) and the solvent was removed under vacuum. Chromatography (SiO2, 4×20 cm, 10% EtOAc-hexane) afforded 17 (2.05 g, 2.03 g theoretical, >99%) as an amber oil: 1H NMR (CDCl3, 400 MHz) δ8.66 (d, 1H, J=0.5 Hz), 8.40 (d, 1H, J=8.6 Hz), 7.63 (d, 1H, J=8.6 Hz), 7.51-7.34 (m, 5H), 6.85 (s, 1H), 5.24 (d, 1H, J=9.5 Hz), 5.20 (d, 1H, J=11.7 Hz), 5.17 (d, 1H, J=11.7 Hz), 4.40 (dd, 1H, J=6.1, 14.5 Hz), 4.01 (dd, 1H, J=7.7, 14.9 Hz), 1.61 (s, 3H), 1.57 (s, 3H), 1.37 and 1.30 (two s, 9H); 13C NMR (CDCl3, 100 MHz) δ153.7, 140.9, 136.3, 135.8, 133.5, 128.8, 128.5, 127.3, 126.7, 124.1, 119.8, 119.5, 118.8, 111.7, 110.9, 81.0, 80.5, 70.8, 47.7, 46.3, 28.5, 28.2, 25.7; IR (film) vmax 3467 (br), 2928, 2229, 1701, 1676, 1596, 1503, 1438, 1387, 1335, 1255, 1164, 1090, 863, 738 cm-1.

Workup

  1. stirringThe solution was stirred at 0° C. for 1 h
  2. temperatureto warm to 25° C.
  3. stirringstirred overnight
  4. extractionthe aqueous phase was extracted with EtoAc (3×15 mL)
  5. washThe combined organic phases were washed with saturated aqueous NaCl (1×30 mL)
  6. dry with materialdried (Na2SO4)
  7. customthe solvent was removed under vacuum

Sources & evidence

ORD record
ord-e8229ec37ec14e9d89fe2c80daa9e48f
Source dataset
uspto-grants-2000_05
Patent number
US06060608

Reaction notes

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