2-Bromothiophene → 2,2'-Bithiophene

HRID 1917589Notes

Reaction equation

HRID 1917589 reaction equation
Br[C:2]1[S:3][CH:4]=[CH:5][CH:6]=1.[Mg]>CCOCC.Cl[Ni]1(Cl)[P](C2C=CC=CC=2)(C2C=CC=CC=2)CCC[P]1(C1C=CC=CC=1)C1C=CC=CC=1>[S:3]1[CH:4]=[CH:5][CH:6]=[C:2]1[C:2]1[S:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 2

HCID 138512-Bromothiophene2×HCID 5462224Magnesium2×

Product 1

HCID 681202,2'-Bithiophene

Reagents, catalysts & solvents 2

HCID 178418745HCID 178418745, compoundCatalystHCID 3283Diethyl EtherSolvent

Procedure

Gringard reagent 2-thiophenylmanesium bromide was prepared from 60 g of 2-bromothiophene (0.368 mole) and magnesium (9.7 g, 0.404 mole). Magnesium was slowly added to a mixture of 2-bromothiophene (50 g, 0.307 mole), Ni(dppp)Cl2 (1.66 g, 3 mmol) in 150 mL dry ether at 0° C. The mixture was warmed to RT for 20 h before being quenched by diluted HCl. The aqueous layer was extracted with ether and all organic layers were combined. The solvent was evaporated after drying over MgSO4. The crude liquid product was redistilled under reduced pressure to afford 40 g (80%) of a low melting solid of the tilled compound. Mp 32-33° C. 1H-NMR (300 MHz, CDCl3) δ 7.19 (dd, 4H), 7.04 (t, 2H).

Workup

  1. custombefore being quenched by diluted HCl
  2. extractionThe aqueous layer was extracted with ether
  3. customThe solvent was evaporated
  4. dry with materialafter drying over MgSO4
  5. distillationThe crude liquid product was redistilled under reduced pressure
  6. customto afford 40 g (80%) of a low melting solid of the tilled compound

Sources & evidence

ORD record
ord-be9ddd4eba4f4782b54d72c827343e90
Source dataset
uspto-grants-2013_12
Patent number
US08618298B2

Reaction notes

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