Chlorotrimethylsilane → 1-Bromo-4-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)benzene

Participants

Reaction Conditions

Reaction Steps

To a 250 mL three-neck flask equipped with dropping funnel was added zinc powder (9.50 g, 146.2 mmol) and dry THF (20 mL) under argon. 1,2-Dibromoethane (0.5 mL) was added and the mixture was heated at 65° C. for 2 min. The mixture was then cooled to room temperature. Chlorotrimethylsilane (0.5 mL) was added and the mixture was stirred at room temperature for 20 min. A solution of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl iodide (57.8 g, 126.6 mmol) in dry THF (100 mL) was added dropwise to keep the temperature of the solution at room temperature. The reaction mixture was stirred at room temperature for 12 h. The colorless solution was then transferred via canula to a solution of 1-bromo-4-iodobenzene (35.8 g, 126.6 mmol) and tetrakis(triphenylphosphine) palladium(0) (5.0 g, 4.3 mmol) in THF (60 mL). After 24 h at 45° C., the solvent was removed under vacuum. The residue was dissolved in methylene chloride (50 mL), extracted with FC-72 (50 mL) six times. The combined FC-72 layers were concentrated. Vacuum distillation of the residue gave 8 (34.3 g, 56%) as a colorless liquid. b.p. 79.1-80.9° C./0.03 mmHg; 1H NMR (300 MHz, CDCl3) δ2.36 (tt, J=18.3, 9.1 Hz, 2H), 2.86-2.92 (m, 2H), 7.11 (d, J=8.4 Hz, 2H), 7.45 (d, J=8.4 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ26.1, 32.9 (t, JFC=22.1 Hz), 105.5-123.2 (m, C6F13), 120.7, 130.1, 132.1, 138.3; 19F NMR (282.4 MHz, CDCl3) δ−125.6 (2F), −122.9 (2F), −121.7 (2F), −120.7 (2F), −113.4 (2F), −79.6 (3F); IR (CHCl3) 3065, 2954, 2879, 1490, 1237, 1145, 1013, 810 cm−1; EIMS m/z 502/504 (M+), 423, 169/171 (M—C6F13CH2)+.

Provenance & Evidence