Bromoacetonitrile → ethyl 1-(cyanomethyl)-5-methyl-1H-pyrrole-2-carboxylate

HRID 77363

Reaction equation

HRID 77363 reaction equation
[CH3:1][C:2]1[NH:6][C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:4][CH:3]=1.[H-].[Na+].Br[CH2:15][C:16]#[N:17]>CN(C)C=O.C(OCC)(=O)C>[C:16]([CH2:15][N:6]1[C:2]([CH3:1])=[CH:3][CH:4]=[C:5]1[C:7]([O:9][CH2:10][CH3:11])=[O:8])#[N:17]

Participants

6

Reactant 3

HCID 11534BromoacetonitrileHCID 24758Sodium hydrideHCID 965981H-Pyrrole-2-carboxylic acid, 5-methyl-, ethyl ester

Product 1

HCID 86706662ethyl 1-(cyanomethyl)-5-methyl-1H-pyrrole-2-carboxylateYield 39.8%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of ethyl 5-methyl-1H-pyrrole-2-carboxylate (1 g, 6.53 mmol) in anhydrous N,N-dimethylformamide (20 mL) under nitrogen at 0° C. was treated with a 60% dispersion of sodium hydride in mineral oil (392 mg, 9.79 mmol). After effervescence ceased, the reaction was treated with a solution of 2-bromoacetonitrile (1.17 g, 9.79 mmol) in N,N-dimethylformamide (2 mL). The resulting mixture was allowed to warm to room temperature and was stirred at room temperature for 30 min. At this time, the reaction was diluted with ethyl acetate (200 mL), washed with water (2×100 mL) and a saturated aqueous sodium chloride solution (2×100 mL), dried over sodium sulfate, filtered and concentrated in vacuo. Flash chromatography (80 g silica gel column, 0-20% ethyl acetate/hexanes) afforded ethyl 1-(cyanomethyl)-5-methyl-1H-pyrrole-2-carboxylate (0.5 g, 39.8%). LC-MS calcd. for C10H13N2O2 [(M+H+] 193, obsd. 193.1.

Workup

  1. washwashed with water (2×100 mL)
  2. dry with materiala saturated aqueous sodium chloride solution (2×100 mL), dried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-a8e6857b07574fe5b2a7a3e665fe38ee
Source dataset
uspto-grants-2014_09
Patent number
US08841299B2

Linked notes

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