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General Procedure for Fluorine Replacement
A Schlenk flask was charged with the ethynyl derivative and anhyd THF. A solution of EtMgBr (1 M in THF) was then added dropwise and the mixture was stirred at 50 °C for 2 h. The mixture was then added at 25 °C via a cannula to a solution of 4a-c in anhyd THF. The mixture was stirred at 70 °C for 16 h and the solvent was removed by rotary evaporation. The residue was treated with H2O and extracted with CH2Cl2. The organic extracts were washed with H2O, and dried over MgSO4. The solvent was removed, and the residue was purified by chromatography.
Compound 5a
Prepared following general procedure from 4a (100 mg, 0.22 mmol), 1-ethynyltoluene (104 mg, 0.9 mmol), EtMgBr (0.41 mL, 0.41 mmol, 1 M in THF), THF (8 mL). Chromatography (silica gel, CH2Cl2-cyclohexane, 30:70 to 50:50) gave 5a as a blue crystalline powder (60 mg, 42%). 1H NMR (CDCl3, 300 MHz): δ = 8.20 (d, 4 H, J = 6.6 Hz), 7.96 (d, 4 H, J = 6.0 Hz), 7.92 (s, 1 H), 7.61-7.39 (m, 11 H), 7.22-7.18 (m, 1 H), 6.88 (AB system, 8 H, J
AB = 8.0 Hz, ΔδAB = 24.3 Hz), 2.27 (s, 6 H). 13C NMR (CDCl3, 75 MHz): δ = 151.2, 136.8, 133.7, 132.4, 131.3, 130.9, 130.3, 128.3, 128.1, 127.7, 127.6, 124.6, 123.0, 122.4, 121.7, 118.4, 115.8, 98.6, 21.3. 11B NMR (CDCl3, 128 MHz): δ = -7.14 (s). UV/Vis (CH2Cl2): λ (ε, M-1 cm-1) = 632 (82500), 588 (27000, sh), 269 (12000) nm. MS (ES): m/z (nature of the peak, relative intensity) = 637.1 (100) [M + H]+. Anal. Calcd for C47H33BN2: C, 88.68; H, 5.23; N, 4.40. Found: C, 88.40; H, 4.95; N, 4.18.
17 Crystal Data for 4a at 293 K: C29H19BF2N2, M = 444.27, triclinic, space group P-1, a = 7.310 (5) Å, b = 11.771 (5) Å, c = 13.336 (5) Å, α = 86.84 (0)°, β = 79.14 (0)°, γ = 89.79 (0)°, V = 1125.2 (10) Å3, Z = 2, λ = 0.7107 Å, D
c = 1.311 g cm-3, µ = 0.057 mm-1, 24014 reflections collected with θ £ 26.0°, 4363 unique, R(int) = 0.0202, and 3343 observed reflections [ I ³ 2σ(I)], 308 parameters, R1 = 0.0396, wR2 = 0.1012 refined on F
2. CCDC 637684.
18 Crystal Data for 5a at 293 K: C47H33BN2, M = 636.56, triclinic, space group P-1, a = 11.119 (4) Å, b = 11.674 (3) Å, c = 15.572 (4) Å, α = 78.73 (2)°, β = 73.51 (2)°, γ = 66.73 (2)°, V = 1772.5 (9) Å3, Z = 2, λ = 0.7107 Å, D
c = 1.193 g cm-3, µ = 0.068 mm-1, 12226 reflections collected with θ < 27.5°, 8071 unique, R(int) = 0.0241, and 5025 observed reflections [ I ³ 2σ(I)], 453 parameters, R1 = 0.0571, wR2 = 0.1438 refined on F
2. CCDC 623954.
19 Crystal Data for 6a at 293 K: [C49H33BN2, 0.5 × (C6H12, C2H3N)], M = 723.19, triclinic, space group P-1, a = 11.294 (4) Å, b = 13.299 (3) Å, c = 14.735 (4) Å, α = 101.78 (2)°, β = 110.03 (2)°, γ = 102.17 (2)°, V = 1938.4 (10) Å3, Z = 2, λ = 0.7107 Å, D
c = 1.239 g cm-3, µ = 0.071 mm-1, 10488 reflections collected with θ < 22.4°, 4585 unique, R(int) = 0.0351, and 3135 observed reflections [ I ³ 2σ(I)], 470 parameters, R1 = 0.0649, wR2 = 0.1879 refined on F
2. SQUEEZE macro within PLATON was used to take disordered solvent molecules (half a molecule of cyclohexane and half a molecule of MeCN in the asymmetric unit) into account during the structure refinement process. CCDC 623955.
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