Chlorotrimethylsilane → 1-ethyl-4-fluoro-2-naphthalen-1-yl-5-trimethylsilanyl-1H-imidazole

HRID 12466

Reaction equation

HRID 12466 reaction equation
Br[C:2]1[N:3]=[C:4]([C:10]2[C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH:13]=[CH:12][CH:11]=2)[N:5]([CH2:8][CH3:9])[C:6]=1Br.[Li]CCCC.CCCCCC.[CH3:31][Si:32](Cl)([CH3:34])[CH3:33].C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:46])(=O)=O)=CC=1>C1COCC1.O>[CH2:8]([N:5]1[C:6]([Si:32]([CH3:34])([CH3:33])[CH3:31])=[C:2]([F:46])[N:3]=[C:4]1[C:10]1[C:19]2[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH:13]=[CH:12][CH:11]=1)[CH3:9]

Participants

8

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 8058Hexane2×HCID 588007N-FluorobenzenesulfonimideHCID 534259994,5-Dibromo-1-ethyl-2-(naphthalen-1-yl)-1H-imidazoleHCID 178418339Butyllithium2×

Product 1

HCID 686294501-ethyl-4-fluoro-2-naphthalen-1-yl-5-trimethylsilanyl-1H-imidazole

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 4,5-dibromo-1-ethyl-2-naphthalen-1-yl-1H-imidazole (6.55 g, 17.2 mmol) in anhydrous THF (150 ml) at −78° C. under nitrogen is added a solution of n-BuLi in hexane (1.6 M, 11.8 ml, 19 mmol, 1.1 eq.) dropwise. The resulting mixture is stirred at −78° C. for 1 hr, and TMSCl (2.05 g, 19 mmol, 1.1 eq.) is added. The resulting solution is stirred at −78° C. After 1 hr, n-BuLi in hexane (1.6 M, 11.8 ml, 19 mmol, 1.1 eq.) is added dropwise. The resulting mixture is stirred at −78° C. for 1 hr, and N-fluorobenzenesulfonimide (5.99 g, 19 mmol, 1.1 eq.) is added. The resulting solution is stirred at −78° C. for 2 hr, warmed to rt slowly, and then stirred at rt overnight. Water (50 ml) is added to quench the reaction, and THF is evaporated. The residue is extracted with EtOAc (75 ml×2) and the combined organic layers are washed with water and brine, dried and concentrated to give crude 1-ethyl-4-fluoro-2-naphthalen-1-yl-5-trimethylsilanyl-1H-imidazole as a yellow oil. LCMS 313 (M+1).

Workup

  1. stirringThe resulting solution is stirred at −78° C
  2. waitAfter 1 hr
  3. stirringThe resulting mixture is stirred at −78° C. for 1 hr
  4. stirringThe resulting solution is stirred at −78° C. for 2 hr
  5. temperaturewarmed to rt slowly
  6. stirringstirred at rt overnight
  7. customto quench
  8. customthe reaction, and THF
  9. customis evaporated
  10. extractionThe residue is extracted with EtOAc (75 ml×2)
  11. washthe combined organic layers are washed with water and brine
  12. customdried
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-063302fd527f4632a4a26455de7386ac
Source dataset
uspto-grants-2010_06
Patent number
US07728009B1

Linked notes

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