Nitromethane → 1-allyl-4-formyl-1H-pyrrole-2-carbonitrile

HRID 244439Notes

Reaction equation

[Al+3].[Cl-].[Cl-].[Cl-].[N+](C)([O-])=O.[CH2:9]([N:12]1[CH:16]=[CH:15][CH:14]=[C:13]1[C:17]#[N:18])[CH:10]=[CH2:11].[CH3:19][O:20]C(Cl)Cl>C(Cl)Cl>[CH2:9]([N:12]1[CH:16]=[C:15]([CH:19]=[O:20])[CH:14]=[C:13]1[C:17]#[N:18])[CH:10]=[CH2:11]

Participants

Conditions

Temperature: 0 °C

Procedure

To a 100 mL flask charged with AlCl3 (3.3 g, 25 mmol, 2.5 equiv.) and 35 mL of dry CH2Cl2 was added 2 mL of nitromethane. The mixture was cooled to 0° C. and a solution of 1-allyl-1H-pyrrole-2-carbonitrile (1.3 g, 10 mmol, 1 equiv.) in 5 mL of CH2Cl2 was added followed by a solution of dichloromethyl methyl ether in 10 mL of CH2Cl2 dropwise. After 30 minutes, the reaction was warmed to room temperature, stirred for 1.5 hours, poured over 100 mL of ice water, and the organic layer was separated. The organic layers were washed with 30 mL of 3M HCl, 30 mL of water, 18% aqueous sodium sulfite, filtered through CELITE® filter aid and concentrated in vacuo. The residue was purified by flash chromatography eluting with EtOAc-hexanes (5-40% gradient) to provide 1.25 g (78%) of 1-allyl-4-formyl-1H-pyrrole-2-carbonitrile as a yellow oil.

Workup

temperaturethe reaction was warmed to room temperature
customthe organic layer was separated
washThe organic layers were washed with 30 mL of 3M HCl, 30 mL of water, 18% aqueous sodium sulfite
filtrationfiltered through CELITE®
filtrationfilter aid
concentrationconcentrated in vacuo
customThe residue was purified by flash chromatography
washeluting with EtOAc-hexanes (5-40% gradient)

Sources & evidence

ORD record: ord-ba697181718e4dc79e994a64d024d890
Source dataset: uspto-grants-2014_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08658637B2

Reaction notes

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