Sodium hydride → 2-Bromo-6-(4-methoxy-phenyl)-4-(2-trimethylsilanyl-ethoxymethyl)-4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalene

HRID 532641Notes

Reaction equation

HRID 532641 reaction equation
[H-].[Na+].[Br:3][C:4]1[S:5][C:6]2[CH2:7][C:8]3[C:14]([C:15]4[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=4)=[N:13][NH:12][C:9]=3[C:10]=2[CH:11]=1.[CH3:23][Si:24]([CH2:27][CH2:28][O:29][CH2:30]Cl)([CH3:26])[CH3:25]>C1COCC1>[Br:3][C:4]1[S:5][C:6]2[CH2:7][C:8]3[C:14]([C:15]4[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=4)=[N:13][N:12]([CH2:30][O:29][CH2:28][CH2:27][Si:24]([CH3:26])([CH3:25])[CH3:23])[C:9]=3[C:10]=2[CH:11]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 27242712-Chloromethyl 2-(trimethylsilyl)ethyl etherHCID 718160142-Bromo-6-(4-methoxy-phenyl)-4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalene

Product 1

HCID 866992302-Bromo-6-(4-methoxy-phenyl)-4-(2-trimethylsilanyl-ethoxymethyl)-4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentaleneYield 75%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

At 0° C., NaH (60 percent, 1.3 g, 33 mmol) was added to a THF solution (40 mL) containing 2-Bromo-6-(4-methoxy-phenyl)-4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalene (8.3 g, 24.0 mmol). Then SEM-Cl (5.6 mL, 28.0 mmol) was added to the reaction mixture and the resulting mixture was stirred at 0° C. for 30 min, warmed up to 80° C. and stirred for 2 hr. The solution was cooled to room temperature and poured into ice water. The resulting mixture was extracted with ethyl acetate. The organic layer was collected and washed with saturated aqueous NH4Cl, dried over MgSO4(s), and concentrated under reduced pressure. The oily residue was purified by gravity column chromatography (20% ETOAc in hexane) to give 2-Bromo-6-(4-methoxy-phenyl)-4-(2-trimethylsilanyl-ethoxymethyl)-4,7-dihydro-1-thia-4,5-diaza-cyclopenta[a]pentalene (9.0 g, 18.0 mmol) as brown solid in 75% yield.

Workup

  1. temperaturewarmed up to 80° C.
  2. stirringstirred for 2 hr
  3. temperatureThe solution was cooled to room temperature
  4. extractionThe resulting mixture was extracted with ethyl acetate
  5. customThe organic layer was collected
  6. washwashed with saturated aqueous NH4Cl
  7. dry with materialdried over MgSO4(s)
  8. concentrationconcentrated under reduced pressure
  9. customThe oily residue was purified by gravity column chromatography (20% ETOAc in hexane)

Sources & evidence

ORD record
ord-18e26d6316f6475cb476c617ce0f49dd
Source dataset
uspto-grants-2014_10
Patent number
US08853207B2

Reaction notes

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