Sodium Cyanide → Isopropyl 4-cyano-5-methylthiophene-2-carboxylate

HRID 412969Notes

Reaction equation

HRID 412969 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]([O:10][CH:11]([CH3:13])[CH3:12])=[O:9])[S:5][C:6]=1[CH3:7].[Cu](C#N)[C:15]#[N:16].[C-]#N.[Na+]>CN(C)C=O>[C:15]([C:2]1[CH:3]=[C:4]([C:8]([O:10][CH:11]([CH3:13])[CH3:12])=[O:9])[S:5][C:6]=1[CH3:7])#[N:16]

Participants

5

Reactant 3

HCID 8929Sodium CyanideHCID 18537375Isopropyl 4-bromo-5-methylthiophene-2-carboxylateHCID 178418260HCID 178418260, compound

Product 1

HCID 18536841Isopropyl 4-cyano-5-methylthiophene-2-carboxylateYield 63%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Isopropyl 4-cyano-5-methylthiiophene-2-carboxylate: A stirred solution of 1.9 g (7.3 mmol) of isopropyl 4-bromo-5-methylthiophene-2-carboxylate was dissolved in dry dimethylformamide (30 mL) and refluxed with copper cyanide (785 mg, 8.8 mmol) for 16 hours. The cooled solution was poured into 0.1 M aqueous sodium cyanide solution (300 mL) and extracted with diethyl ether (4×40 mL). The organic layers were washed with brine (2×40 mL), dried over anhydrous sodium sulfate, and the solvents removed in vacuo. Column chromatography on silica gel eluting with hexanes:ethyl acetate 9/1 (v:v), gave isopropyl 4-cyano-5-methylthiophene-2-carboxylate (960 mg, 63%) as a yellow crystalline solid 1H-NMR (DMSO-d6; 300 MHz) δ 8.01 (s, 1H), 5.09 (septet, 1H, J=6.2 Hz), 2.67 (s, 31H), 1.29 (d, 6H, J=6.2 Hz).

Workup

  1. extractionextracted with diethyl ether (4×40 mL)
  2. washThe organic layers were washed with brine (2×40 mL)
  3. dry with materialdried over anhydrous sodium sulfate
  4. customthe solvents removed in vacuo

Sources & evidence

ORD record
ord-c880a72d148b4f008ea51a5b09a8ab6f
Source dataset
uspto-grants-2003_05
Patent number
US06562840B1

Reaction notes

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