Dichloromethane → Ethyl 5-(2-trimethylsilyl-ethyn-1-yl)-thiophene-2-carboxylate

HRID 2174704Notes

Reaction equation

HRID 2174704 reaction equation
Br[C:2]1[S:6][C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:4][CH:3]=1.[CH3:12][Si:13]([CH3:17])([CH3:16])[C:14]#[CH:15].C(Cl)Cl>C(#N)C.C1COCC1.[Cu]I.Cl[Pd]Cl>[CH3:12][Si:13]([C:14]#[C:15][C:2]1[S:6][C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:4][CH:3]=1)([CH3:17])[CH3:16]

Participants

8

Reactant 3

HCID 6344DichloromethaneHCID 66111TrimethylsilylacetyleneHCID 605723Ethyl 5-bromothiophene-2-carboxylate

Product 1

HCID 66974178Ethyl 5-(2-trimethylsilyl-ethyn-1-yl)-thiophene-2-carboxylate

Reagents, catalysts & solvents 4

HCID 24290Palladium ChlorideCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Procedure

Under an argon atmosphere a solution of 32.5 g (138.0 mmol) ethyl 5-bromo-thiophene-2-carboxylate in 320 ml acetonitrile and 640 ml THF is combined with 1.3 g (7.0 mmol) copper-(I)-iodide and 39.0 g (276.0 mmol) trimethyl-silylacetylene with stirring, the mixture is stirred for 5 min and then 5.6 g (7.0 mmol) 1,1-bis-(diphenylphosphino)-ferrocene-dichloropalladium(II))-PdCl2 in a complex with CH2Cl2 1/1 and 57.4 ml (414.0 mmol) TEA are added. The reaction mixture is stirred overnight at room temperature, evaporated down i. vac., the residue is combined with ethyl acetate and washed with ammonia solution (5%) and water. The organic phase is dried on sodium sulphate and evaporated to dryness i. vac. The residue is combined with diethyl ether, the precipitate is suction filtered and dried.

Workup

  1. stirringthe mixture is stirred for 5 min
  2. stirringThe reaction mixture is stirred overnight at room temperature
  3. customevaporated down i
  4. washwashed with ammonia solution (5%) and water
  5. customThe organic phase is dried on sodium sulphate
  6. customevaporated to dryness i
  7. filtrationfiltered
  8. customdried

Sources & evidence

ORD record
ord-bfe2ffccfdeb45aa80c437e28df87d49
Source dataset
uspto-grants-2015_06
Patent number
US09062034B2

Reaction notes

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