Dimethylformamide → Ethyl ([1~2~,2~2~:2~5~,3~2~-terthiophen]-2~3~-yl)acetate

HRID 1770999Notes

Reaction equation

HRID 1770999 reaction equation
Br[C:2]1[S:3][C:4](Br)=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].C([Sn](CCCC)(CCCC)[C:19]1[S:20][CH:21]=[CH:22][CH:23]=1)CCC.CN(C)C=O>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[S:3]1[CH:4]=[CH:5][CH:6]=[C:2]1[C:2]1[S:3][C:4]([C:21]2[S:20][CH:19]=[CH:23][CH:22]=2)=[CH:5][C:6]=1[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9]

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 11209627HCID 11209627, compound

Product 1

HCID 58051793Ethyl ([1~2~,2~2~:2~5~,3~2~-terthiophen]-2~3~-yl)acetateYield 85%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

The procedure described by Taranekar et al30 was modified to synthesize G03TCOOR. Ethyl 2-(2,5-dibromothiophen-3-yl)acetate (6.4 g, 10 mmol) and 2-(tributylstannyl) thiophene (1.5 g, 20 mmol) were added to a 30 mL dry dimethylformamide (DMF) solution of dichlorobis(triphenylphosphine)palladium (Pd(dpp)Cl2) (1.3 g, 1.5 mmol). After three freeze thaw cycles, the mixture was heated at 100° C. for 48 hr. The mixture was cooled to room temperature and poured into a beaker containing 150 mL of water and subsequently extracted with CH2Cl2. The extracted CH2Cl2 mixture was dried with Na2SO4. After filtration and evaporation of the solvent, the crude product was purified by chromatography on silica gel using toluene as an eluent. The final product was obtained in 85% yield as pale yellow oil. The characterization of the compound was found in accordance with the literature.1 1H NMR (CDCl3): δ 6.8-7.2 (m, 7H), 4.19 (q, 2H, J=7.15 Hz), 3.72 (s, 2H), 1.27 (t, 41-1, J=7.14 Hz) as shown in FIG. 29.

Workup

  1. customto synthesize G03TCOOR
  2. temperatureThe mixture was cooled to room temperature
  3. additionpoured into a beaker
  4. extractionsubsequently extracted with CH2Cl2
  5. dry with materialThe extracted CH2Cl2 mixture was dried with Na2SO4
  6. filtrationAfter filtration and evaporation of the solvent
  7. customthe crude product was purified by chromatography on silica gel

Sources & evidence

ORD record
ord-3f0916e131f8431799dd22e2c35b12c2
Source dataset
uspto-grants-2016_02
Patent number
US09248467B2

Reaction notes

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