Dichloromethane → ethyl 4-(4-nitrophenyl)-1H-pyrrole-3-carboxylate

HRID 222569Notes

Reaction equation

HRID 222569 reaction equation
[CH2:1]([O:3][C:4](=[O:16])[CH:5]=[CH:6][C:7]1[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[CH:9][CH:8]=1)[CH3:2].CC1C=CC(S([CH2:27][N+:28]#[C-:29])(=O)=O)=CC=1.[H-].[Na+].C(Cl)Cl>CS(C)=O.CCOCC.CCOCC.[Cl-].[Na+].O>[CH2:1]([O:3][C:4]([C:5]1[C:6]([C:7]2[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[CH:9][CH:8]=2)=[CH:29][NH:28][CH:27]=1)=[O:16])[CH3:2]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 24758Sodium hydrideHCID 95370Ethyl 3-(4-nitrophenyl)-2-propenoateHCID 161915Tosylmethyl isocyanide

Product 1

HCID 53440113ethyl 4-(4-nitrophenyl)-1H-pyrrole-3-carboxylateYield 84%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 19869614Ether dimethylsulfoxideSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of 54 (3.74 g, 16.91 mmol) and TosMIC (3.30 g, 16.92 mmol) in DMSO/Et2O (1:2, 33 mL) was added via cannula to a vigorously stirred suspension of NaH (842 mg, 35.1 mmol) in Et2O (15 mL) under argon. Stirring was continued for 3 h. Brine and CH2Cl2 were added in small portions. The aqueous layer was extracted with CH2Cl2. The organic extract was washed with brine. The solvent was removed at reduced pressure, and the oily residue was chromatographed [silica, CH2Cl2/ethyl acetate (9:1)] to yield a brown solid (3.23 g, 84%): 1H NMR δ 1.23-1.29 (m, 3H), 4.20-4.27 (m, 2H), 6.88-6.90 (m, 1H), 7.53-7.55 (m, 1H), 7.64-7.67 (m, 2H), 8.18-8.21 (m, 2H), 8.78 (br, 1H).

Workup

  1. extractionThe aqueous layer was extracted with CH2Cl2
  2. extractionThe organic extract
  3. washwas washed with brine
  4. customThe solvent was removed at reduced pressure
  5. customthe oily residue was chromatographed [silica, CH2Cl2/ethyl acetate (9:1)]

Sources & evidence

ORD record
ord-de96c31730694fe89a71736960f15ef6
Source dataset
uspto-grants-2012_06
Patent number
US08207329B2

Reaction notes

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