t-Butyl bromide → Tert-butyl 4-cyano-5-(methylthio)thiophene-2-carboxylate

HRID 448124Notes

Reaction equation

HRID 448124 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([C:10]([OH:12])=[O:11])[S:6][C:7]=1[S:8][CH3:9])#[N:2].[C:13](Br)([CH3:16])([CH3:15])[CH3:14].C(=O)([O-])[O-].[K+].[K+]>[Cl-].C([N+](C)(C)C)C1C=CC=CC=1.CC(N(C)C)=O.C(OCC)(=O)C>[C:1]([C:3]1[CH:4]=[C:5]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[S:6][C:7]=1[S:8][CH3:9])#[N:2]

Participants

7

Reactant 3

HCID 10485t-Butyl bromideHCID 11430Potassium CarbonateHCID 455943124-Cyano-5-methylsulfanylthiophene-2-carboxylic acid

Product 1

HCID 66785900Tert-butyl 4-cyano-5-(methylthio)thiophene-2-carboxylateYield 58.7%

Reagents, catalysts & solvents 3

HCID 5963Benzyltrimethylammonium chlorideCatalystHCID 8857Ethyl AcetateSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of 4-cyano-5-(methylthio)thiophene-2-carboxylic acid (2.0 g, 10 mmol), benzyltrimethylamonium chloride (2.25 g, 10 mmol), tertbutyl bromide (54 mL, 480 mmol) and anhydrous potassium carbonate (36 g, 260 mmol) in dimethylacetamide (100 mL) was stirred at 60° C. for 6 hours. After cooling, the mixture was diluted with ethyl acetate (400 mL) and washed with water. Organic layer was dried and evaporated under reduced pressure to give a residue which was purified by chromatography (eluent ethyl acetate/n-hexane 3:1) thus yielding 1.5 g of the title compound.

Workup

  1. temperatureAfter cooling
  2. washwashed with water
  3. customOrganic layer was dried
  4. customevaporated under reduced pressure
  5. customto give a residue which
  6. customwas purified by chromatography (eluent ethyl acetate/n-hexane 3:1)

Sources & evidence

ORD record
ord-e774d32a40ec4f16a4268d483dd9ab50
Source dataset
uspto-grants-2013_07
Patent number
US08481584B2

Reaction notes

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