Iodine → 5-Bromo-[2,2']bithiophenyl

Participants

Reaction Steps

A solution of 2-bromothiophene (4.967 g, 24.92 mmol) in 5 ml dry THF was added dropwise to a mixture of Mg-turnings (752 mg, 30.94 mmol) and a small iodine crystal in 25 ml dry THF. After addition of about 1 ml of the bromothiophene solution, the reaction started and the mixture heated to reflux. The rest of the bromothiophene solution was added dropwise to the reaction, and the mixture was stirred for 1 hour at reflux. The reaction mixture was then transferred with a syringe into an addition funnel and was added slowly during 3 hours to an ice-cooled mixture of 2,5-dibromothiophene (8.206 g, 33.91 mmol) and PdCl2 (dppf)2 (250 mg, 0.306 mmol, complex with CH2Cl2 1:1) in 50 ml dry THF. This mixture was stirred for 2 hours at 0° C. and for 16 hours at room temperature. The solvent was evaporated in vacuo and the residue was suspended in EtOAc and washed with saturated NaHCO3 solution and brine. The aqueous layers were extracted with EtOAc and the organic layers were dried (MgSO4). Evaporation of the solvent and purification by FC (hexanes) gave 4.229 g 5-bromo-2,2′-bithiophene (6, FIG. 3) (17.25 mmol, 57%) and 1.216 g 2,2′:5′,2″-terthiophene (7, FIG. 3) (4.896 mmol, 16%) as yellow solids. 6:1H-NMR: 7.22 (dd, J=5.2, 0.8, 1 H), 7.11 (dd, J=3.6, 0.8, 1 H), 7.00 (dd, J=5.2, 3.6, 1 H), 6.96 (d, J=3.9, 1 H), 6.91 (d, J=3.9, 1 H). 13C-NMR: 138.9, 136.4 (2s), 130.6, 127.8, 124.8 (3d), 124.3 (s), 124.0, 123.8 (2d). EI-MS: 246 (100, [M]+, 81Br), 244 (88, [M]+, 79Br), 165 (39), 121 (53).

Provenance & Evidence