N-bromobutanimide → Methyl 3-bromomethylthien-2-ylglyoxylate

HRID 1376512Notes

Reaction equation

HRID 1376512 reaction equation
[CH3:1][C:2]1[CH:6]=[CH:5][S:4][C:3]=1[C:7](=[O:12])[C:8]([O:10][CH3:11])=[O:9].[Br:13]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.N(C(C)(C)C#N)=NC(C)(C)C#N>[Br:13][CH2:1][C:2]1[CH:6]=[CH:5][S:4][C:3]=1[C:7](=[O:12])[C:8]([O:10][CH3:11])=[O:9]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 21843477Methyl 2-(3-methylthiophen-2-yl)-2-oxoacetate

Product 1

HCID 21843464Methyl 3-bromomethylthien-2-ylglyoxylateYield 52.1%

Reagents, catalysts & solvents 2

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

A solution of 135.7 g (0.73 mol) of methyl 3-methylthien-2-ylglyoxylate, 131.2 g (0.73 mol) of N-bromosuccinimide and 1.35 g of azobisisobutyronitrile in 1000 ml of carbon tetrachloride is refluxed for 3 hours. Thereafter, the mixture is filtered and the filtrate is evaporated down. The residue is taken up in diethyl ether and the solution is washed with water, dried and evaporated down. 166.4 g of crude product are obtained, which is recrystallized from methanol. 100 g of the abovementioned compound are obtained as a yellow solid. 1H--NMR (CDCl3 ; δ in ppm): 7.75 (d, 1 H, J=4 Hz, thienyl); 7.3 (d, 1 H, J=4 Hz, thienyl); 4.95 (s, 2 H, CH2 --Br); 4.0 (s, 3 H, O--CH3)

Workup

  1. filtrationThereafter, the mixture is filtered
  2. customthe filtrate is evaporated down
  3. washthe solution is washed with water
  4. customdried
  5. customevaporated down
  6. custom166.4 g of crude product are obtained
  7. customwhich is recrystallized from methanol

Sources & evidence

ORD record
ord-d4f0f0a0079347bf9c0af0aa0fcac913
Source dataset
uspto-grants-1997_09
Patent number
US05663185

Reaction notes

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