Sodium hydride → 2-(4-Nitrobenzoyl)-1-(2-trimethylsilylethoxymethyl)pyrrole

HRID 279052Notes

Reaction equation

HRID 279052 reaction equation
[N+:1]([C:4]1[CH:16]=[CH:15][C:7]([C:8]([C:10]2[NH:11][CH:12]=[CH:13][CH:14]=2)=[O:9])=[CH:6][CH:5]=1)([O-:3])=[O:2].[H-].[Na+].[CH3:19][Si:20]([CH3:27])([CH3:26])[CH2:21][CH2:22][O:23][CH2:24]Cl>CN(C=O)C>[N+:1]([C:4]1[CH:16]=[CH:15][C:7]([C:8]([C:10]2[N:11]([CH2:24][O:23][CH2:22][CH2:21][Si:20]([CH3:27])([CH3:26])[CH3:19])[CH:12]=[CH:13][CH:14]=2)=[O:9])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 27242712-Chloromethyl 2-(trimethylsilyl)ethyl etherHCID 42684372-(4-nitrobenzoyl) pyrrole

Product 1

HCID 226242202-(4-Nitrobenzoyl)-1-(2-trimethylsilylethoxymethyl)pyrrole

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
5 °C

Procedure

A solution of 2-(4-nitrobenzoyl) pyrrole (White et al., J. Org. Chem., 42 4284 [1977]; 2 g. 9.26 mM) in DMF (5 ml) was added dropwise to a stirred suspension of sodium hydride (0.42 g of a 60% dispersion in mineral oil, 1.05 mM) in DMF (15 ml). After 10 minutes, the mixture was cooled to 5° C. and 2-trimethylsilylethoxymethyl chloride (1.7 ml) was added dropwise and the mixture stirred for 10 minutes. The cooling bath was removed and stirring continued for 1.5 hours. The mixture was poured into aqueous sodium carbonate solution and extracted into EtOAc. The organic layer was washed with water, dried (MgSO4) and evaporated. The residue was purified by column chromatography in dichloromethane, eluting with a gradient increasing in polarity from 2% to 5% MeOH/dichloromethane to give 2-(4-nitrobenzoyl)-1-(2-trimethylsilylethoxymethyl)pyrrole as an oil (2.3 g). MS: 347 (MH+) NMR: −0.1 (9H, s); 0.82 (2H, t) 3.5 (2H, t); 5.71(2H, s); 6.28 (1H, m); 6.84 (1H, m); 7.52 (1H, m), 7.92 (2H, d); 8.36 (2H, d).

Workup

  1. customThe cooling bath was removed
  2. stirringstirring
  3. waitcontinued for 1.5 hours
  4. additionThe mixture was poured into aqueous sodium carbonate solution
  5. extractionextracted into EtOAc
  6. washThe organic layer was washed with water
  7. dry with materialdried (MgSO4)
  8. customevaporated
  9. customThe residue was purified by column chromatography in dichloromethane
  10. washeluting with
  11. temperaturea gradient increasing in polarity from 2% to 5% MeOH/dichloromethane

Sources & evidence

ORD record
ord-9150fa43fd6747d2b55cc83236714c1d
Source dataset
uspto-grants-2002_03
Patent number
US06362191B1

Reaction notes

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