Ethyl Acetate → HCID 22022391, compound

HRID 352153Notes

Reaction equation

HRID 352153 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.[Li]CCCC.[CH3:13][Si:14]([CH3:27])([CH3:26])[CH2:15][CH2:16][O:17][CH2:18][N:19]1[CH:23]=[C:22]([CH:24]=[O:25])[N:21]=[CH:20]1.C(OCC)(=O)C>CCOCC>[N:4]1[CH:5]=[CH:6][CH:7]=[C:2]([CH:24]([C:22]2[N:21]=[CH:20][N:19]([CH2:18][O:17][CH2:16][CH2:15][Si:14]([CH3:27])([CH3:26])[CH3:13])[CH:23]=2)[OH:25])[CH:3]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 122863-BromopyridineHCID 119910021-(2-Trimethylsilanylethoxymethyl)-1H -imidazole-4-carbaldehydeHCID 178418339Butyllithium

Product 1

HCID 22022391HCID 22022391, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A solution of 3-bromopyridine (1.0 g, 6.33×10−3 mol) was cooled to −78° in a dry ice/acetone bath. To this solution, BuLi (3.48 mL, 6.96×10−3 mol, 2M solution in cyclohexane) was added dropwise and the reaction was stirred for 15 minutes. A solution of 1-(2-trimethylsilanylethoxymethyl)-1H-imidazole-4-carbaldehyde (0.955 g, 4.22×10−3 mol) in ether (5 mL) was added dropwise to the reaction and the solution was stirred for 1 hour at −78 C. The reaction was quenched with sat. NaHCO3 (10 mL) and allowed to warm to room temperature. Ethyl acetate was added (100 mL) and the organic layer was washed with water (3×50 mL), dried over MgSO4, filtered and solvent was removed under reduced pressure. The crude product was purified by silcagel column chromatography eluting with a gradient of ethyl acetate:hexane (1:3) to ethyl acetate to ethyl acetate:methanol (9:1). The pure product was isolated as a mixture of isomers (yellow oil, yield 778 mg, 40%). Rf 0.5 (ethyl acetate); 1H-NMR (CDCl3) δ−0.09-0.11 (m, 9H), 0.86-0.99 (m, 2H), 3.41-3.57 (m, 2H), 5.22 & 5.26 (2×s, 2H), 5.89 & 6.05 (2×s, 1H), 6.63 & 6.80 (2×s, 1H), 7.25-7.39 (m, 1H), 7.53 & 7.58 (2×s, 1H), 7.79-7.90 (m, 1H), 8.53 & 8.57 (d, 1H), 8.64 & 8.69 (2×s, 1H); ESMS Calcd (C10H18N2O2Si): 226.11, found 227.1 (M+H)+.

Workup

  1. stirringthe solution was stirred for 1 hour at −78 C
  2. customThe reaction was quenched with sat. NaHCO3 (10 mL)
  3. additionEthyl acetate was added (100 mL)
  4. washthe organic layer was washed with water (3×50 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customsolvent was removed under reduced pressure
  8. customThe crude product was purified by silcagel column chromatography
  9. washeluting with a gradient of ethyl acetate:hexane (1:3) to ethyl acetate to ethyl acetate:methanol (9:1)
  10. customThe pure product was isolated as a mixture of isomers (yellow oil, yield 778 mg, 40%)

Sources & evidence

ORD record
ord-9fa7f4729b224bf99b86d2b6d0dc5454
Source dataset
uspto-grants-2004_06
Patent number
US06743919B2

Reaction notes

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