Triethylamine → 5-(3,3-Dimethyl-but-1-ynyl)-thiophene-2-carboxylic acid ethyl ester

HRID 336032Notes

Reaction equation

HRID 336032 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[S:7][C:8](Br)=[CH:9][CH:10]=1)=[O:5])[CH3:2].C(N(CC)CC)C.[CH3:19][C:20]([CH3:24])([CH3:23])[C:21]#[CH:22]>CN(C=O)C.[Cu](I)I.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:1]([O:3][C:4]([C:6]1[S:7][C:8]([C:22]#[C:21][C:20]([CH3:24])([CH3:23])[CH3:19])=[CH:9][CH:10]=1)=[O:5])[CH3:2]

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 135123,3-Dimethyl-1-butyneHCID 605723Ethyl 5-bromothiophene-2-carboxylate

Product 1

HCID 581141285-(3,3-Dimethyl-but-1-ynyl)-thiophene-2-carboxylic acid ethyl esterYield 97.3%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

A mixture of 5-Bromo-thiophene-2-carboxylic acid ethyl ester (7 g, 30 mmol), copper iodide (1.2 g, 6 mmol), triethylamine (20 mL) in DMF (100 mL) was degassed in a 350 mL pressure bottle. Then tris(dibenzylideneacetone)dipalladium(0) (2.1 g, 3 mmol) and 3,3-dimethyl-but-1-yne (18.3 mL, 150 mmol) were added and heated at 80 degree for 3 hours. The reaction mixture was filtered on celite and washed with ethyl acetate. The solution was diluted with water and extracted twice with ethyl acetate. The organic phases were combined and washed with water. After drying and concentration, the crude residue was purified by flash chromatography to yield 6.9 g (95%) of 5-(3,3-Dimethyl-but-1-ynyl)-thiophene-2-carboxylic acid ethyl ester as a yellow oil.

Workup

  1. customwas degassed in a 350 mL pressure bottle
  2. temperatureheated at 80 degree for 3 hours
  3. filtrationThe reaction mixture was filtered on celite
  4. washwashed with ethyl acetate
  5. additionThe solution was diluted with water
  6. extractionextracted twice with ethyl acetate
  7. washwashed with water
  8. customAfter drying
  9. concentrationconcentration
  10. customthe crude residue was purified by flash chromatography

Sources & evidence

ORD record
ord-9e3c5d8152d34b638911185df75aaf1f
Source dataset
uspto-grants-2014_11
Patent number
US08884030B2

Reaction notes

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