All reactions were carried out under nitrogen when an inert atmosphere was needed. Syntheses that required dry and oxygen-free conditions were performed in a Glovebox MB Unilab or using Schlenk techniques under an atmosphere of purified nitrogen or argon, respectively. Dry, oxygen-free solvents (CH2Cl2, distilled from CaH2; THF, distilled from potassium) were employed. All distilled and deuterated solvents were stored over molecular sieves (4 Å). All glassware was oven-dried at 160 °C prior to use. Solvents and reagents were obtained from commercial suppliers and were of pure analytical grade. Purification of compounds was carried out using column chromatography with silica gel 40– 60 μM mesh or using a Biotage® Isolera™ (Uppsala, Sweden) flash purification system using Biotage® KP-Sil SNAP columns. Reaction progress was monitored by TLC using fluorescent pre-coated silica gel plates, and detection of the components was made by short UV light (λ = 254 nm).
3.1.2. General Procedures for Preparation of Compounds 5–28
A solution of compounds 1–4 (16.28 g, 47 mmol) in DMF (100 mL) was treated with K2CO3 (19.5 g, 141 mmol) and heated in an oil bath at 80 °C. The resulting suspension was treated with the appropriate commercially available base hydrochloride salt (51 mmol) portion-wise over a 2 h period and stirred for 16 h. The reaction mixture was cooled to room temperature. K2CO3 was filtered off, and DMF was removed under reduced pressure. The final product was purified by silica gel column chromatography or a Biotage® Isolera™ flash purification system using Biotage® KP-Sil SNAP columns (dichloromethane) to yield compounds (5–28).
E/Z-(3-{4-[1-(4-Chloro-phenyl)-2-phenyl-propenyl]-phenoxy}-propyl)-dimethyl-amine (5)
C26H28ClNO. Yield: 48%. Brown oil. Purity: 98%. 1H-NMR (400 MHz, CDCl3) δ: 7.30 (d, J = 8.4 Hz, 2H), 7.19–7.09 (m, 16H), 6.97 (d, J = 8.5 Hz, 2H), 6.86 (d, J = 8.6 Hz, 4H), 6.80–6.73 (m, 2H), 4.06 (t, J = 5.9 Hz, 2H), 3.91 (t, J = 5.9 Hz, 2H), 2.90 (m, 2H), 2.83 (m, 2H), 2.59 (s, 6H), 2.55 (s, 6H), 2.18–2.16 (dd, J = 9.6, 6.1 Hz, 2H), 2.14–2.08 (m, 8H). 13C-NMR (101 MHz, CDCl3) δ: 141.76, 135.78, 132.15, 131.97, 131.37, 131.23, 129.18, 129.16, 128.28, 128.00, 127.94, 127.55, 126.32, 126.22, 114.02, 113.38, 65.30, 56.11, 56.05, 44.18, 44.07, 25.95, 25.78, 23.48, 23.33. MS (ESI): m/z = 406.3 [M+H]+ (100%), m/z = 408.2 [M+H+2]+ (33%). Rf: 0.43 (9:1 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chloro-phenyl)-2-phenyl-propenyl]-phenoxy}-ethyl)-pyrrolidine (6)
C27H28ClNO. Yield: 44%. Faint brown oil. Purity: 95.84%. 1H-NMR (400 MHz, CDCl3) δ: 7.33–7.29 (m, J = 2.0 Hz, 2H), 7.20–7.08 (m, 14H), 6.99–6.96 (m, 2H), 6.91–6.87 (m, 2H), 6.81–6.73 (m, 4H), 6.68–6.57 (m, 2H), 4.23 (t, J = 5.6 Hz, 2H), 4.09 (t, J = 5.6 Hz, 2H), 3.09 (t, J = 5.6 Hz, 2H), 3.01 (t, J = 5.5 Hz, 2H), 2.85 (d, J = 18.8 Hz, 8H), 2.13 (s, 3H), 2.10 (s, 3H), 1.96–1.84 (m, 8H). 13C-NMR (101 MHz, CDCl3) δ: 157.17, 156.46, 143.84, 143.79, 142.13, 141.77, 137.52, 137.45, 136.14, 135.84, 135.51, 132.29, 132.18, 131.98, 131.48, 131.41, 131.23, 129.20, 129.17, 128.28, 128.01, 127.97, 127.56, 126.32, 126.25, 114.15, 113.51, 65.95, 65.65, 54.77, 54.69, 54.63, 54.58, 23.50, 23.39, 23.34. MS (ESI): m/z = 418.3 [M+H]+ (100%), m/z = 420.3 [M+H+2]+ (33%). Rf: 0.5 (9:1 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chloro-phenyl)-2-phenyl-propenyl]-phenoxy}-ethyl)-piperidine (7)
C28H30ClNO. Yield: 42%. Faint brown oil. Purity: 97.82%. 1H-NMR (400 MHz, CDCl3) δ: 7.32 (d, J = 2.0 Hz, 1H), 7.30 (d, J = 1.6 Hz, 1H), 7.20–7.09 (m, 14H), 6.98 (d, J = 1.9 Hz, 1H), 6.97 (d, J = 2.0 Hz, 1H), 6.89 (d, J = 2.0 Hz, 1H), 6.87 (d, J = 2.0 Hz, 1H), 6.80 (d, J = 2.0 Hz, 1H), 6.79 (d, J = 1.9 Hz, 1H), 6.76 (d, J = 2.0 Hz, 1H), 6.74 (d, J = 2.1 Hz, 1H), 6.56 (d, J = 2.1 Hz, 1H), 6.55 (d, J = 2.0 Hz, 1H), 4.20 (t, J = 5.8 Hz, 2H), 4.05 (t, J = 5.7 Hz, 2H), 2.91 (t, J = 5.7 Hz, 2H), 2.82 (t, J = 5.7 Hz, 2H), 2.72–2.55 (m, 8H), 2.14 (s, 3H), 2.10 (s, 3H), 1.72–1.64 (m, 8H), 1.52–1.44 (m, 4H). 13C-NMR (101 MHz, CDCl3) δ: 157.30, 156.61, 143.87, 143.80, 142.16, 141.79, 137.56, 137.49, 136.09, 135.69, 135.45, 135.34, 132.29, 132.18, 131.95, 131.48, 131.41, 131.21, 129.20, 129.18, 128.28, 128.01, 127.96, 127.56, 126.31, 126.23, 114.13, 113.52, 65.28, 65.03, 57.67, 57.58, 54.87, 54.80, 25.34, 25.23, 23.75, 23.68, 23.50, 23.33. MS (ESI): m/z = 432.3 [M+H]+ (100%), m/z = 434.3 [M+H+2]+ (33%). Rf: 0.37 (93:7 methylene chloride: methanol).
E/Z-4-(2-{4-[1-(4-Chloro-phenyl)-2-phenyl-propenyl]-phenoxy}-ethyl)-morpholine (8)
C27H28ClNO2. Yield: 48%. Orange oil. Purity: 100%. 1H-NMR (400 MHz, CDCl3) δ: 7.32 (d, J = 1.9 Hz, 1H), 7.31 (d, J = 2.0 Hz, 1H), 7.20–7.09 (m, 14H), 6.99 (d, J = 1.9 Hz, 1H), 6.97 (d, J = 2.0 Hz, 1H), 6.90 (d, J = 2.0 Hz, 1H), 6.88 (d, J = 2.0 Hz, 1H), 6.81 (d, J = 2.0 Hz, 1H), 6.79 (d, J = 1.9 Hz, 1H), 6.76 (d, J = 2.0 Hz, 1H), 6.75 (d, J = 2.1 Hz, 1H), 6.57 (d, J = 2.1 Hz, 1H), 6.56 (d, J = 2.0 Hz, 1H), 4.14 (t, J = 5.7 Hz, 2H), 4.00 (t, J = 5.7 Hz, 2H), 3.76 (m, 4H), 3.72 (m, 4H), 2.84 (t, J = 5.7 Hz, 2H), 2.74 (t, J = 5.7 Hz, 2H), 2.62 (m, 4H), 2.55 (m, 4H), 2.14 (s, 3H), 2.11 (s, 3H). 13C-NMR (101 MHz, CDCl3) δ: 157.44, 156.78, 143.90, 143.80, 142.17, 141.80, 137.57, 137.51, 136.09, 135.67, 135.44, 135.28, 132.30, 132.18, 131.93, 131.49, 131.40, 131.20, 129.20, 129.19, 128.29, 128.02, 127.95, 127.56, 126.32, 126.21, 114.14, 113.53, 66.85, 66.80, 65.62, 65.41, 57.66, 57.62, 54.06, 54.02, 23.50, 23.34. MS (ESI): m/z = 434.3 [M+H]+ (100%), m/z = 436.3 [M+H+2]+ (33%). Rf: 0.68 (95:5 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chloro-phenyl)-2-phenyl-propenyl]-phenoxy}-ethyl)-azepane (9)
C29H32ClNO. Yield: 40%. Brown oil. Purity: 95.34%. 1H-NMR (400 MHz, CDCl3) δ: 7.32 (d, J = 1.9 Hz, 1H), 7.30 (d, J = 1.9 Hz, 1H), 7.20–7.08 (m, 14H), 6.99–6.95 (m, 2H), 6.88 (dd, J = 6.7, 4.8 Hz, 2H), 6.80 (d, J = 1.9 Hz, 1H), 6.78 (d, J = 1.9 Hz, 1H), 6.76 (d, J = 2.0 Hz, 1H), 6.74 (d, J = 2.0 Hz, 1H), 6.56 (d, J = 1.9 Hz, 1H), 6.54 (d, J = 2.0 Hz, 1H), 4.21 (t, J = 5.7 Hz, 2H), 4.06 (t, J = 5.7 Hz, 2H), 3.12 (t, J = 5.7 Hz, 2H), 3.04 (t, J = 5.7 Hz, 2H), 3.00–2.89 (m, 8H), 2.14 (s, 3H), 2.10 (s, 3H), 1.80–1.58 (m, 16H). 13C-NMR (101 MHz, CDCl3) δ: 156.76, 156.25, 143.78, 141.76, 136.13, 132.17, 131.97, 131.48, 131.40, 131.23, 129.19, 129.17, 128.29, 128.01, 127.96, 127.56, 126.31, 126.24, 114.15, 113.52, 56.32, 56.20, 55.69, 55.61, 26.96, 26.92, 26.57, 23.50, 23.33. MS (ESI): m/z = 446.3 [M+H]+ (100%), m/z = 448.3 [M++H+2]+ (33%). Rf: 0.37 (93:7 methylene chloride: methanol).
E/Z-(3-{4-[1-(4-Chloro-phenyl)-2-(4-methoxy-phenyl)-propenyl]-phenoxy}-propyl)-dimethyl-amine (10)
C27H30ClNO2. Yield: 48%. Orange oil. Purity: 96.57%. 1H-NMR (400 MHz, CDCl3) δ: 7.30 (d, J = 1.9 Hz, 1H), 7.28 (d, J = 1.9 Hz, 1H), 7.16–6.96 (m, 12H), 6.87–6.68 (m, 8H), 6.56 (d, J = 2.1 Hz, 1H), 6.54 (d, J = 2.0 Hz, 1H), 4.05 (t, J = 6.0 Hz, 2H), 3.92 (t, J = 6.0 Hz, 2H), 3.75 (s, 6H), 2.84–2.73 (m, 4H), 2.51 (d, J = 10.2 Hz, 6H), 2.20–2.11 (m, 4H), 2.10 (s, 6H), 2.07 (s, 6H). 13C-NMR (101 MHz, CDCl3) δ: 157.96, 157.87, 157.32, 156.59, 142.39, 142.08, 136.96, 136.88, 136.05, 135.96, 135.93, 135.65, 135.54, 134.89, 132.21, 131.99, 131.42, 131.29, 131.24, 130.33, 130.31, 128.26, 127.60, 113.99, 113.43, 113.37, 113.31, 65.42, 65.16, 56.21, 56.16, 55.13, 53.44, 44.47, 44.35, 26.28, 26.13, 23.43, 23.28. MS (ESI): m/z = 436.3 [M+H]+ (100%), m/z = 438.3 [M+H+2]+ (33%). Rf: 0.45 (9:1 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chloro-phenyl)-2-(4-methoxy-phenyl)-propenyl]-phenoxy}-ethyl)-pyrrolidine (11)
C28H30ClNO2. Yield: 40%. Orange oil. Purity: 100%. 1H-NMR (400 MHz, CDCl3) δ: 7.31 (d, J = 1.9 Hz, 1H), 7.29 (d, J = 1.9 Hz, 1H), 7.17–6.96 (m, 12H), 6.89 (d, J = 2.0 Hz, 1H), 6.87 (d, J = 2.0 Hz, 1H), 6.82–6.74 (m, 4H), 6.72 (d, J = 2.1 Hz, 1H), 6.70 (d, J = 2.1 Hz, 1H), 6.59 (d, J = 2.1 Hz, 1H), 6.57 (d, J = 2.0 Hz, 1H), 4.24 (t, J = 5.6 Hz, 2H), 4.12 (t, J = 5.6 Hz, 2H), 3.76 (s, 6H), 3.09 (t, J = 5.5 Hz, 2H), 3.03 (t, J = 5.4 Hz, 2H), 2.88 (s, 8H), 2.11 (s, 3H), 2.07 (s, 3H), 1.95–1.89 (m, 8H). 13C-NMR (101 MHz, CDCl3) δ: 157.96, 157.89, 157.06, 142.06, 136.94, 136.12, 135.99, 135.94, 135.57, 132.22, 131.99, 131.43, 131.30, 131.25, 130.34, 130.31, 128.26, 127.61, 114.13, 113.56, 113.37, 113.33, 55.13, 54.78, 54.71, 54.64, 54.61, 23.44, 23.39, 23.35, 23.27. MS (ESI): m/z = 448.3 [M+H]+, m/z = 450.2 [M+H+2]+. Rf: 0.5 (9:1 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chloro-phenyl)-2-(4-methoxy-phenyl)-propenyl]-phenoxy}-ethyl)-piperidine (12)
C29H32ClNO2. Yield: 53%. Yellow oil. Purity: 100%. 1H-NMR (400 MHz, CDCl3) δ: 7.31 (d, J = 2.0 Hz, 1H), 7.29 (d, J = 2.1 Hz, 1H), 7.18–6.98 (m, 10H), 6.88 (d, J = 2.2 Hz, 1H), 6.87 (d, J = 2.1 Hz, 1H), 6.83–6.69 (m, 8H), 6.59 (d, J = 2.2 Hz, 1H), 6.57 (d, J = 2.1 Hz, 1H), 4.15 (t, J = 6.0 Hz, 2H), 4.03 (t, J = 6.0 Hz, 2H), 3.76 (s, 6H), 2.84 (t, J = 6.0 Hz, 2H), 2.76 (t, J = 6.0 Hz, 2H), 2.56 (d, J = 18.9 Hz, 8H), 2.11 (s, 3H), 2.08 (s, 2H), 1.64 (tt, J = 11.6, 5.6 Hz, 9H), 1.47 (dd, J = 13.2, 8.4 Hz, 4H). 13C-NMR (101 MHz, CDCl3) δ: 157.98, 157.89, 157.42, 156.73, 142.45, 142.12, 137.06, 136.97, 136.08, 136.00, 135.82, 135.49, 134.79, 132.21, 132.15, 131.91, 131.41, 131.30, 131.17, 130.33, 130.30, 128.25, 127.59, 114.15, 113.61, 113.38, 113.32, 65.65, 65.45, 57.86, 57.81, 55.12, 54.99, 54.95, 25.69, 25.62, 24.01, 23.95, 23.43, 23.25. MS (ESI): m/z = 462.3 [M+H]+ (100%), m/z = 464.2 [M+H+2]+ (33%). Rf: 0.37 (93:7 methylene chloride: methanol).
E/Z-4-(2-{4-[1-(4-Chloro-phenyl)-2-(4-methoxy-phenyl)-propenyl]-phenoxy}-ethyl)-morpholine (13)
C28H30ClNO3. Yield: 45%. Dark orange oil. Purity: 97.45%. 1H-NMR (400 MHz, CDCl3) δ 7.31 (d, J = 1.7 Hz, 1H), 7.29 (d, J = 2.0 Hz, 1H), 7.17–6.97 (m, 10H), 6.89 (d, J = 2.8 Hz, 1H), 6.87 (d, J = 2.0 Hz, 1H), 6.82–6.74 (m, 4H), 6.73–6.68 (m, 4H), 6.59 (d, J = 1.9 Hz, 1H), 6.57 (d, J = 2.0 Hz, 1H), 4.14 (t, J = 5.7 Hz, 2H), 4.01 (t, J = 5.7 Hz, 2H), 3.83–3.69 (m, 14H), 2.83 (t, J = 5.6 Hz, 2H), 2.75 (t, J = 5.6 Hz, 2H), 2.59 (d, J = 20.5 Hz, 8H), 2.11 (s, 3H), 2.08 (s, 3H). 13C-NMR (101 MHz, CDCl3) δ: 157.97, 157.87, 157.36, 156.68, 142.42, 142.10, 136.99, 136.92, 136.07, 135.94, 135.92, 135.59, 135.52, 134.85, 132.22, 132.16, 131.95, 131.43, 131.31, 131.21, 130.34, 130.32, 128.26, 127.61, 114.12, 113.58, 113.37, 113.31, 66.86, 65.61, 65.42, 57.67, 57.65, 55.13, 54.06, 54.04, 53.43, 23.44, 23.28. MS (ESI): m/z = 464.3 [M+H]+ (100%), m/z = 466.2 [M+H+2]+ (33%). Rf: 0.52 (95:5 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chloro-phenyl)-2-(4-methoxy-phenyl)-propenyl]-phenoxy}-ethyl)-azepane (14)
C30H34ClNO2. Yield: 43%. Orange oil. Purity: 95%. 1H-NMR (400 MHz, CDCl3) δ 7.32–7.25 (m, 2H), 7.17–7.08 (m, 4H), 7.06–6.97 (m, 6H), 6.87 (d, J = 8.7 Hz, 2H), 6.81–6.74 (m, 4H), 6.70 (d, J = 8.7 Hz, 4H), 6.59–6.55 (m, 2H), 4.19 (t, J = 5.6 Hz, 2H), 4.07 (t, J = 5.7 Hz, 2H), 3.76 (s, 6H), 3.09 (t, J = 5.6 Hz, 2H), 3.04–3.00 (m, 2H), 2.97–2.84 (m, 8H), 2.10 (s, 3H), 2.07 (s, 3H), 1.81–1.69 (m, 8H), 1.68–1.60 (m, 8H). 13C-NMR (101 MHz, CDCl3) δ 157.94, 142.40, 142.07, 135.56, 134.91, 132.19, 131.96, 131.51–131.06, 130.31, 128.26, 127.60, 114.16, 113.60, 113.36, 56.25, 55.62, 55.12, 26.97, 23.34. MS (ESI): m/z = 476.4 [M+H]+ (100%), m/z = 478.4 [M+H+2]+ (33%). Rf: 0.53 (9:1 methylene chloride: methanol).
E/Z-(3-{4-[1-(4-Chlorophenyl)-2-(3-fluoro-4-methoxyphenyl)-propenyl]-phenoxy}-propyl)-dimethyl-amine (15)
C27H29ClFNO2. Yield: 74%. Orange oil. Purity: 98.84%. 1H-NMR (400 MHz, CDCl3) δ 7.31–7.28 (m, 2H), 7.15–7.12 (m, 2H), 7.10–7.07 (m, 2H), 7.02–6.99 (m, 2H), 6.88 (s, 2H), 6.85 (d, J = 2.9 Hz, 2H), 6.82–6.79 (m, 3H), 6.77–6.73 (m, 5H), 6.58 (dd, J = 9.1, 2.3 Hz, 2H), 4.02 (t, J = 6.4 Hz, 2H), 3.91 (t, J = 6.4 Hz, 2H), 3.83 (s, 6H), 3.46–3.33 (m, 4H), 2.25 (dd, J = 12.1, 5.9 Hz, 10H), 2.10–2.04 (m, 12H). 13C-NMR: (101 MHz, CDCl3) δ 157.85, 157.27, 145.95 (d, J = 10.5 Hz), 145.92 (d, J = 10.5 Hz), 142.10, 141.75, 138.02, 137.95, 137.99, (d, J = 7.1 Hz), 135.18, 134.82, 134.29 (d, J = 1.4 Hz), 133.60 (d, J = 1.3 Hz), 132.32, 132.07, 131.78, 131.62, 131.30, 128.26, 127.71, 125.18 (d, J = 3.1 Hz), 125.08 (d, J = 3.1 Hz), 116.88 (d, J = 18.1 Hz), 116.83 (d, J = 18.3 Hz), 114.11, 113.66, 112.80 (d, J = 6.0 Hz), 112.78 (d, J = 5.9 Hz), 66.11, 65.93, 56.35 (d, J = 3.8 Hz), 56.10, 45.40, 45.35, 27.49, 27.41, 23.25, 23.06. MS (ESI): m/z = 454.30 [M+H]+, m/z = 456.30 [M+H+2]+ (100%). Rf: 0.41 (93:7 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chlorophenyl)-2-(3-fluoro-4-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-pyrrolidine (16)
C28H29ClFNO2. Yield: 61%. Orange oil. Purity: 100%. 1H-NMR (500 MHz, CDCl3) δ 7.31–7.27 (m, 2H), 7.15–7.10 (m, 2H), 7.10–7.06 (m, 2H), 7.02–6.98 (m, 2H), 6.88 (d, J = 2.1 Hz, 1H), 6.86 (t, J = 2.6 Hz, 2H), 6.84 (dd, J = 5.9, 3.5 Hz, 1H), 6.81–6.79 (m, 2H), 6.78 (t, J = 4.8 Hz, 2H), 6.76–6.71 (m, 4H), 6.62–6.57 (m, 2H), 4.15 (t, J = 5.9 Hz, 2H), 4.04 (t, J = 5.9 Hz, 2H), 3.82 (s, 6H), 2.65 (d, J = 20.4 Hz, 8H), 2.67–2.64 (m, 8H), 2.10 (s, 3H), 2.07 (s, 3H), 1.90–1.76 (m, 8H). 13C-NMR: (126 MHz, CDCl3) δ 157.64, 157.06, 151.86 (d, J = 245.2 Hz), 151.84 (d, J = 244.9 Hz), 145.93 (t, J = 11.1 Hz), 142.08, 141.74, 138.00, 137.93, 136.87 (d, J = 6.4 Hz), 136.80 (d, J = 6.3 Hz), 135.38, 135.03, 134.36 (d, J = 1.3 Hz), 133.70 (d, J = 1.3 Hz), 132.36, 132.09, 131.80, 131.66, 131.32, 131.09, 128.30, 127.74, 125.20 (d, J = 3.3 Hz), 125.14 (d, J = 3.3 Hz), 116.87 (d, J = 18.4 Hz), 116.85 (d, J = 18.4 Hz), 114.19, 113.76, 112.80 (d, J = 5.9 Hz), 112.79 (d, J = 5.9 Hz), 66.82, 66.63, 56.12, 55.02 (d, J = 5.1 Hz), 54.70, 54.68, 23.48, 23.45, 23.28, 23.08. MS (ESI): m/z = 466.40 [M+H]+ (100%), m/z = 468.00 [M+H+2]+. Rf: 0.34 (95:5 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chlorophenyl)-2-(3-fluoro-4-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-piperidine (17)
C29H31ClFNO2. Yield: 77%. Orange oil. Purity: 95.88%. 1H-NMR (400 MHz, CDCl3) δ 7.30–7.27 (m, 2H), 7.14–7.11 (m, 2H), 7.08 (d, J = 8.7 Hz, 2H), 7.02–6.98 (m, 2H), 6.88–6.84 (m, 4H), 6.82–6.77 (m, 4H), 6.76–6.73 (m, 4H), 6.60–6.56 (m, 2H), 4.12 (t, J = 6.0 Hz, 2H), 4.00 (t, J = 6.0 Hz, 2H), 3.82 (s, 6H), 2.79 (t, J = 6.0 Hz, 2H), 2.72 (t, J = 6.0 Hz, 2H), 2.58 (m, 8H), 2.07 (s, 3H), 2.05 (s, 3H), 1.60 (dd, J = 11.3, 5.6 Hz, 8H), 1.46–1.40 (m, 4H). 13C-NMR: (101 MHz, CDCl3) δ 157.65, 157.08, 151.87 (d, J = 245.2 Hz), 151.84 (d, J = 244.9 Hz), 145.97 (d, J = 10.8 Hz), 145.88 (d, J = 10.8 Hz), 142.08, 141.74, 138.01, 137.94, 136.88 (d, J = 8.5 Hz), 136.82 (d, J = 8.4 Hz), 135.34, 134.98, 134.35, 133.68, 132.36, 132.08, 131.79, 131.66, 131.31, 131.07, 128.30, 127.74, 125.19 (d, J = 3.4 Hz), 125.11 (d, J = 3.3 Hz), 116.88 (d, J = 18.4 Hz), 116.85 (d, J = 18.3 Hz) 114.20, 113.77, 112.82 (d, J = 5.0 Hz), 112.80 (d, J = 5.1 Hz), 65.72 (d, J = 17.0 Hz), 57.89 (d, J = 4.5 Hz), 56.12, 55.02, 54.99, 25.82, 25.76, 24.11, 24.07, 23.27, 23.08. MS (ESI): m/z = 480.01 [M+H]+, m/z = 482.01 [M+H+2]+ (100%). Rf: 0.30 (94:6 methylene chloride: methanol).
E/Z-4-(2-{4-[1-(4-Chlorophenyl)-2-(3-fluoro-4-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-morpholine (18)
C28H29ClFNO3. Yield: 65%. Brown oil. Purity: 100%. 1H-NMR (400 MHz, CDCl3) δ 7.32–7.25 (m, 3H), 7.16–7.07 (m, 4H), 7.03–6.99 (m, 2H), 6.90–6.73 (m, 11H), 6.62–6.57 (m, 2H), 4.11 (t, J = 5.6 Hz, 2H), 3.99–4.02 (t, J = 5.7 Hz, 2H), 3.84 (s, 6H), 3.77–3.70 (m, 8H), 2.80 (t, J = 5.6 Hz, 2H), 2.73 (t, J = 5.6 Hz, 2H), 2.64–2.50 (m, 8H), 2.09 (s, 3H), 2.06 (s, 3H).13C-NMR: (101 MHz, CDCl3) δ 157.51, 156.93, 151.82 (d, J = 245.2 Hz), 151.79 (d, J = 244.8 Hz), 145.87 (d, J = 10.3 Hz), 142.02, 141.69, 137.91, 137.85, 136.83 (d, J = 6.2 Hz), 136.71 (d, J = 6.2 Hz), 135.47, 135.11, 134.40 (d, J = 1.3 Hz), 133.76 (d, J = 1.3 Hz), 132.34, 132.04, 131.78, 131.63, 131.28, 131.07, 128.27, 127.71, 125.15 (d, J = 3.3 Hz), 125.04 (d, J = 3.4 Hz), 116.88 (d, J = 18.4 Hz), 116.80 (d, J = 18.5 Hz), 114.18, 113.75, 112.80 (d, J = 5.4 Hz), 112.78 (d, J = 5.5 Hz), 66.80, 66.76, 65.65, 65.48, 57.62, 57.58, 57.60 (d, J = 3.3 Hz), 54.03, 54.00, 53.51, 23.22, 23.04. MS (ESI): m/z = 482.00 [M+H]+ (100%), m/z = 484.00 [M+H+2]+. Rf: 0.58 (95:5 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chlorophenyl)-2-(3-fluoro-4-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-azepane (19)
C30H33ClFNO2. Yield: 54%. Brown oil. Purity: 100%. 1H-NMR (400 MHz, CDCl3) δ 7.30–7.27 (m, 2H), 7.14–7.05 (m, 4H), 7.02–6.98 (m, 2H), 6.88–6.82 (m, 4H), 6.81–6.77 (m, 4H), 6.76–6.71 (m, 4H), 6.61 (dd, J = 6.8, 4.8 Hz, 2H), 4.18 (t, J = 6.0 Hz, 2H), 4.04 (t, J = 6.0 Hz, 2H), 3.83 (s, 6H), 3.03 (t, J = 6.0 Hz, 2H), 2.97 (t, J = 6.0 Hz, 2H), 2.90–2.81 (m, 8H), 2.08 (d, J = 14.2 Hz, 8H), 1.72 (d, J = 4.7 Hz, 6H), 1.65–1.60 (m, 8H). 13C-NMR: (101 MHz, CDCl3) δ 158.79 (d, J =157.7 Hz), 157.56, 151.02, 150.83, 145.97, 144.90, 141.71, 136.39 (d, J = 6.2 Hz), 136.26 (d, J = 6.2 Hz), 135.71, 135.43, 134.38 (d, J = 1.3 Hz), 134.27 (d, J = 1.3 Hz), 132.37, 132.07, 131.81, 131.66, 131.30, 131.09, 128.29, 127.73, 125.18 (d, J = 3.1 Hz), 125.09 (d, J = 3.1 Hz), 116.93 (d, J = 18.4 Hz), 116.74 (d, J = 18.4 Hz), 114.21, 113.76, 112.82 (d, J = 5.7 Hz), 112.79 (d, J = 5.7 Hz), 66.06, 56.37, 56.11, 55.77 (d, J = 5.87 Hz), 53.41, 27.11, 27.01, 26.99, 26.90, 23.26, 23.07. MS (ESI): m/z = 494.04 [M+H]+ (100%), m/z = 496.04 [M+H+2]+. Rf: 0.34 (93:7 methylene chloride: methanol).
E/Z-(2-{4-[1-(4-Chlorophenyl)-2-(3-fluoro-4-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-dimethyl-amine (20)
C26H27ClFNO2. Yield: 55%. Reddish-brown oil. Purity: 98.69%. 1H-NMR (400 MHz, CDCl3) δ 7.32–7.28 (m, 2H), 7.16–7.12 (m, 2H), 7.11–7.07 (m, 2H), 7.03–6.99 (m, 2H), 6.91–6.87 (m, 3H), 6.86 (d, J = 1.9 Hz, 1H), 6.82 (d, J = 1.9 Hz, 1H), 6.79 (dd, J = 5.7, 2.9 Hz, 2H), 6.78–6.74 (m, 4H), 6.72 (dd, J = 8.5, 1.5 Hz, 1H), 6.64–6.59 (m, 2H), 4.10 (t, J = 5.7 Hz, 2H), 3.98 (t, J = 5.7 Hz, 2H), 3.84 (s, 6H), 2.77 (t, J = 5.7 Hz, 2H), 2.70 (t, J = 5.7 Hz, 2H), 2.37 (s, 6H), 2.33 (s, 6H), 2.09 (s, 3H), 2.06 (s, 3H). 13C-NMR: (101 MHz, CDCl3) δ 157.65, 157.07, 151.97 (d, J = 245.1 Hz), 151.94 (d, J = 244.9 Hz), 145.99 (d, J = 9.6 Hz), 142.07, 141.73, 138.01, 137.95, 136.81 (d, J = 6.7 Hz), 136.77 (d, J = 6.7 Hz),135.42, 135.07, 134.37 (d, J = 1.3 Hz), 133.72 (d, J = 1.6 Hz), 132.38, 132.09, 131.79, 131.68, 131.32, 131.09, 128.31, 127.76, 125.20 (d, J = 3.4 Hz), 125.13 (d, J = 3.4 Hz), 116.86 (d, J = 18.4 Hz), 116.98 (d, J = 18.3 Hz), 114.19, 113.75, 112.82 (d, J = 5.1 Hz), 112.80 (d, J = 5.2 Hz), 65.85, 65.64, 58.27, 58.22, 56.14, 45.83, 45.80, 23.29, 23.07. MS (ESI): m/z = 440.30 [M+H]+ (100%), m/z = 442.30 [M+2]+. Rf: 0.38 (92:8 methylene chloride: methanol).
E/Z-(2-{4-[1-(4-Chlorophenyl)-2-(3-fluoro-4-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-diethyl-amine (21)
C28H31ClFNO2. Yield: 51%. Yellow oil. Purity: 98.96%. 1H-NMR (500 MHz, CDCl3) δ 7.30 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H), 7.09 (d, J = 8.6 Hz, 2H), 7.02 (d, J = 8.5 Hz, 2H), 6.87 (dd, J = 11.8, 2.6 Hz, 4H), 6.80 (t, J = 8.0 Hz, 3H), 6.78–6.70 (m, 5H), 6.59 (d, J = 8.7 Hz, 2H), 4.10 (d, J = 5.4 Hz, 2H), 4.00 (s, 2H), 3.84 (s, 6H), 2.95 (d, J = 4.8 Hz, 2H), 2.88 (s, 2H), 2.78–2.57 (m, 8H), 2.09 (d, J = 7.5 Hz, 3H), 2.09 (d, J = 7.5 Hz, 3H), 1.14–1.04 (m, 12H). 13C-NMR: (126 MHz, CDCl3) δ 157.58, 156.96, 151.89 (d, J = 245.2 Hz), 151.85 (d, J = 244.8 Hz), 145.94 (t, J = 11.3 Hz), 142.07, 141.73, 137.99, 137.93, 136.89 (d, J = 6.2 Hz), 136.81 (d, J = 6.4 Hz), 135.43, 135.09, 134.38 (d, J = 1.1 Hz), 133.74 (d, J = 1.1 Hz), 132.39, 132.10, 131.84, 131.69, 131.33, 131.12, 128.32, 127.77, 125.21 (d, J = 3.3 Hz), 125.13 (d, J = 3.4 Hz), 116.91 (d, J = 18.4 Hz), 116.86 (d, J = 18.4 Hz), 114.15, 113.71, 112.81 (d, J = 5.9 Hz), 112.79 (d, J = 5.9 Hz), 66.12, 56.14, 53.42, 51.67, 51.54, 47.80, 47.77, 23.30, 23.09, 11.56. MS (ESI): m/z = 468.30 [M+H]+ (100%), m/z = 470.00 [M+H+2]+. Rf: 0.32 (93:7 methylene chloride: methanol).
E/Z-(3-{4-[1-(4-Chlorophenyl)-2-(4-fluoro-3-methoxyphenyl)-propenyl]-phenoxy}-propyl)-dimethyl-amine (22)
C27H29ClFNO2. Yield: 50%. Orange oil. Purity: 97.83%. 1H-NMR (500 MHz, CDCl3) δ 7.31 (d, J = 8.4 Hz, 1H), 7.16 (d, J = 8.3 Hz, 1H), 7.10 (t, J = 5.7 Hz, 3H), 7.02 (d, J = 8.4 Hz, 3H), 6.92–6.85 (m, 5H), 6.81 (t, J = 7.1 Hz, 3H), 6.75 (d, J = 8.7 Hz, 1H), 6.72–6.67 (m, 2H), 6.65 (dd, J = 8.4, 1.9 Hz, 1H), 6.63 (dd, J = 8.3, 1.9 Hz, 1H), 6.59 (d, J = 8.7 Hz, 1H), 4.04 (t, J = 6.3 Hz, 2H), 3.91 (t, J = 6.3 Hz, 2H), 3.62 (d, J = 2.0 Hz, 6H), 2.56 (dt, J = 27.7, 7.4 Hz, 4H), 2.37–2.31 (m, 12H), 2.11 (d, J = 17.4 Hz, 6H), 2.07–1.94 (m, 4H). 13C-NMR: (126 MHz, CDCl3) δ 157.79, 157.21, 150.97 (d, J = 245.6 Hz), 150.89 (d, J = 245.3 Hz), 146.89 (d, J = 10.8 Hz), 146.82 (d, J = 10.7 Hz), 141.93, 141.88, 140.08 (d, J = 4.0 Hz), 139.98 (d, J = 4.0 Hz), 138.09, 138.07, 135.19, 135.11, 135.02, 134.44, 132.44, 132.01, 131.75, 131.73, 131.33, 131.12, 128.34, 127.75, 121.42 (d, J = 6.6 Hz), 115.54 (d, J = 18.2 Hz), 115.43 (d, J = 18.2 Hz), 115.09, 114.13, 113.67, 65.94, 65.80, 56.37, 56.31, 56.03 (d, J = 2.6 Hz), 53.43, 45.17, 45.10, 27.16, 27.04, 23.24, 23.05.MS (ESI): m/z = 454.30 [M+H]+ (100%), m/z = 456.30 [M++H+2]+. Rf: 0.33 (91:9 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chlorophenyl)-2-(4-fluoro-3-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-pyrrolidine (23)
C28H29ClFNO2. Yield: 71%. Brown oil. Purity: 100%. 1H-NMR (400 MHz, CDCl3) δ 7.31 (d, J = 8.4 Hz, 2H), 7.16 (d, J = 8.4 Hz, 2H), 7.11 (d, J = 8.6 Hz, 2H), 7.02 (d, J = 8.4 Hz, 2H), 6.89 (dt, J = 8.2, 5.5 Hz, 4H), 6.81 (d, J = 8.4 Hz, 2H), 6.76 (d, J = 8.7 Hz, 2H), 6.72–6.67 (m, 3H), 6.64 (t, J = 2.0 Hz, 1H), 6.61 (d, J = 8.6 Hz, 2H), 4.18 (t, J = 5.8 Hz, 2H), 4.05 (t, J = 5.8 Hz, 2H), 3.62 (d, J = 2.8 Hz, 6H), 2.98 (t, J = 5.8 Hz, 2H), 2.90 (t, J = 5.8 Hz, 2H), 2.71 (d, J = 21.8 Hz, 8H), 2.13 (s, 3H), 2.09 (s, 3H), 1.89–1.80 (m, 8H). 13C-NMR: (101 MHz, CDCl3) δ 157.58, 157.01, 152.21, 152.16, 146.90 (d, J = 9.9 Hz), 146.89 (d, J = 9.8 Hz), 141.91, 141.86, 140.03 (d, J = 3.9 Hz), 139.97 (d, J = 4.1 Hz), 138.06, 138.03, 135.34, 135.25, 135.06, 134.47, 132.44, 132.00, 131.73, 131.31, 131.11, 128.33, 127.75, 121.45 (d, J = 6.0 Hz), 115.57 (d, J = 18.2 Hz), 115.39, (d, J = 18.3 Hz), 115.12 (d, J = 2.0 Hz), 115.11, 114.23, 113.79, 66.63, 66.50, 56.03 (d, J = 1.8 Hz), 54.99, 54.91, 54.69, 54.65, 23.48, 23.44, 23.22, 23.03. MS (ESI): m/z = 466.30 [M+H]+ (100%), m/z = 468.20 [M+H+2]+. Rf: 0.32 (94:6 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chlorophenyl)-2-(4-fluoro-3-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-piperidine (24)
C29H31ClFNO2. Yield: 42%. Orange oil. Purity: 95%. 1H-NMR (400 MHz, CDCl3)) δ 7.33 (d, J = 7.5 Hz, 2H), 7.16 (dd, J = 17.6, 7.6 Hz, 4H), 7.04 (d, J = 7.6 Hz, 2H), 6.91 (t, J = 9.5 Hz, 4H), 6.83 (d, J = 7.4 Hz, 2H), 6.77 (d, J = 7.7 Hz, 2H), 6.70 (d, J = 13.9 Hz, 3H), 6.62 (d, J = 8.6 Hz, 3H), 4.23 (s, 2H), 4.10 (s, 2H), 3.66 (s, 6H), 2.91 (dd, J = 30.7, 19.6 Hz, 4H), 2.63 (s, 6H), 2.13 (d, J = 13.6 Hz, 6H), 1.71 (s, 8H), 1.47 (d, J = 23.0 Hz, 6H). 13C-NMR: (101 MHz, CDCl3) δ 157.79, 157.21, 150.97, 150.89, 146.90 (d, J = 9.2 Hz), 146.81 (d, J = 9.0 Hz), 141.93, 141.88, 140.08 (d, J = 4.0 Hz), 139.98 (d, J = 4.0 Hz), 138.09, 138.07, 135.19, 135.11, 135.02, 134.44, 132.44, 132.01, 131.75, 131.73, 131.33, 131.12, 128.34, 127.75, 121.42 (t, J = 6.6 Hz), 115.56 (d, J = 13.4 Hz), 115.41 (d, J = 13.3 Hz), 115.09,114.33, 114.13, 113.67, 66.22, 57.98, 57.67, 56.04, 54.85 (d, J = 6.4 Hz), 53.40, 26.91, 25.63, 25.29, 23.72, 23.22, 23.04. MS (ESI): m/z = 480.01 [M+H]+ (100%), m/z = 482.01 [M+H+2]+. Rf: 0.40 (95:5 methylene chloride: methanol).
E/Z-4-(2-{4-[1-(4-Chlorophenyl)-2-(4-fluoro-3-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-morpholine (25)
C28H29ClFNO3. Yield: 61%. Orange oil. Purity: 97.07%. 1H-NMR (400 MHz, CDCl3) δ 7.31 (d, J = 8.4 Hz, 2H), 7.14 (dd, J = 15.7, 8.5 Hz, 4H), 7.02 (d, J = 8.4 Hz, 2H), 6.90 (t, J = 9.1 Hz, 4H), 6.81 (d, J = 8.4 Hz, 2H), 6.76 (d, J = 8.7 Hz, 2H), 6.73–6.65 (m, 3H), 6.64 (dd, = 5.4, 3.3 Hz, 1H), 6.61 (t, J = 6.2 Hz, 2H), 4.15 (t, J = 5.5 Hz, 2H), 4.03 (t, J = 5.5 Hz, 2H), 3.80–3.70 (m, 8H), 3.63 (s, 6H), 2.86 (t, J = 5.3 Hz, 2H), 2.77 (t, J = 5.3 Hz, 2H), 2.61 (d, J = 21.5 Hz, 8H), 2.13 (s, 3H), 2.10 (s, 3H). 13C-NMR: (101 MHz, CDCl3) δ 157.67, 157.09, 151.14 (d, J = 245.8 Hz), 151.06 (d, J = 245.2 Hz), 147.06 (d, J = 10.8 Hz), 146.99 (d, J = 10.8 Hz), 142.02, 141.98, 140.19 (d, J = 4.1 Hz), 140.06 (d, J = 4.0 Hz), 138.16, 138.14, 135.58, 135.49, 135.25, 134.70, 132.61, 132.13, 131.90, 131.44, 131.28, 128.49, 127.91, 121.57 (d, J = 5.1 Hz), 121.51 (d, J = 5.2 Hz), 115.69 (d, J = 18.2 Hz), 115.59 (d, J = 18.3 Hz), 115.27 (d, J = 1.4 Hz), 115.22 (d, J = 1.8 Hz), 115.12, 114.37, 113.93, 66.89, 65.70, 65.63, 57.76, 56.19, 54.19, 54.15, 53.56, 23.36, 23.19. MS (ESI): m/z = 482.30 [M+H]+ (100%), m/z = 484.20 [M+H+2]+. Rf: 0.35 (94:6 methylene chloride: methanol).
E/Z-1-(2-{4-[1-(4-Chlorophenyl)-2-(4-fluoro-3-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-azepane (26)
C30H33ClFNO2. Yield: 62%. Orange oil. Purity: 95%. 1H-NMR (400 MHz, CDCl3) δ 7.31 (d, J = 8.4 Hz, 2H), 7.16 (d, J = 8.4 Hz, 2H), 7.11 (d, J = 8.6 Hz, 2H), 7.02 (d, J = 8.5 Hz, 2H), 6.93–6.86 (m, 4H), 6.81 (d, J = 8.4 Hz, 2H), 6.76 (d, J = 8.7 Hz, 2H), 6.73–6.66 (m, 3H), 6.64 (s, 1H), 6.61 (t, J = 6.3 Hz, 2H), 4.13 (t, J = 6.0 Hz, 2H), 4.00 (t, J = 6.0 Hz, 2H), 3.62 (d, J = 3.2 Hz, 6H), 3.01 (t, J = 6.0 Hz, 2H), 2.93 (t, J = 6.0 Hz, 2H), 2.87–2.76 (m, 8H), 2.13 (s, 3H), 2.10 (s, 3H), 1.74–1.65 (m, 8H), 1.64–1.58 (m, 8H). 13C-NMR: (101 MHz, CDCl3) δ 157.68, 157.10, 150.98 (d, J = 245.8 Hz), 150.91 (d, J = 245.4 Hz), 146.90 (d, J = 10.6 Hz), 146.83 (d, J = 10.8 Hz), 141.93, 141.87, 140.05 (d, J = 4.0 Hz), 139.97 (d, J = 4.0 Hz), 138.08, 138.06, 135.26, 135.17, 135.04, 134.45, 132.44, 132.00, 131.73, 131.31, 131.10, 128.33, 127.75, 121.42 (d, J = 6.9 Hz), 121.31, 115.53 (d, J = 18.4 Hz), 115.43 (d, J = 18.3 Hz), 115.12, 114.24, 113.80,66.16, 66.00, 56.40, 56.30, 56.03 (d, J = 2.3 Hz), 55.83, 55.77, 27.51, 27.47, 27.04, 27.02, 23.23, 23.03. MS (ESI): m/z = 494.04 [M+H]+ (100%), m/z = 496.04 [M+2]+. Rf: 0.50 (95:5 methylene chloride: methanol).
E/Z-(2-{4-[1-(4-Chlorophenyl)-2-(4-fluoro-3-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-dimethyl-amine (27)
C26H27ClFNO2. Yield: 67%. Yellow oil. Purity: 100%. 1H-NMR (400 MHz, CDCl3) δ 7.31 (d, J = 8.4 Hz, 2H), 7.16 (d, J = 8.4 Hz, 2H), 7.11 (d, J = 8.6 Hz, 2H), 7.02 (d, J = 8.5 Hz, 2H), 6.92–6.86 (m, 4H), 6.81 (d, J = 8.5 Hz, 2H), 6.76 (d, J = 8.7 Hz, 2H), 6.73–6.65 (m, 3H), 6.62 (t, J = 7.5 Hz, 3H), 4.11 (t, J = 5.7 Hz, 2H), 3.98 (t, J = 5.7 Hz, 2H), 3.62 (d, J = 4.2 Hz, 6H), 2.78 (t, J = 5.7 Hz, 2H), 2.70 (t, J = 5.7 Hz, 2H), 2.38 (s, 6H), 2.33 (s, 6H), 2.13 (s, 3H), 2.09 (s, 3H). 13C-NMR: (101 MHz, CDCl3) δ 157.14, 156.57, 150.46 (d, J = 245.5 Hz), 150.38 (d, J = 245.3 Hz), 146.37 (d, J = 10.8 Hz), 146.31 (d, J = 10.8 Hz), 141.40, 141.34, 139.51 (d, J = 4.2 Hz), 139.45 (d, J = 4.0 Hz), 137.55, 137.52, 134.77, 134.68, 134.52, 133.93, 131.91, 131.48, 131.19, 130.79, 130.57, 127.81, 127.22, 120.90 (d, J = 6.8 Hz), 120.81 (d, J = 6.7 Hz), 115.04 (d, J = 10.6 Hz), 114.86, 114.81, 114.60, 113.69, 113.25, 65.83, 65.68, 58.25, 58.18, 56.03 (d, J = 3.1 Hz), 56.01, 45.82, 45.76, 23.23, 23.02. MS (ESI): m/z = 440.30 [M+H]+ (100%), m/z = 442.30 [M+H+2]+. Rf: 0.33 (94:6 methylene chloride: methanol).
E/Z-(2-{4-[1-(4-Chlorophenyl)-2-(4-fluoro-3-methoxyphenyl)-propenyl]-phenoxy}-ethyl)-diethyl-amine (28)
C28H31ClFNO2. Yield: 52%. Orange oil. Purity: 97.68%. 1H-NMR ((400 MHz, CDCl3) δ 7.31 (d, J = 7.0 Hz, 2H), 7.14 (dd, J = 16.5, 7.5 Hz, 4H), 7.02 (d, J = 7.2 Hz, 2H), 6.89 (t, J = 8.9 Hz, 4H), 6.81 (d, J = 7.5 Hz, 2H), 6.76 (d, J = 7.4 Hz, 2H), 6.73–6.65 (m, 3H), 6.65–6.57 (m, 3H), 4.17 (s, 2H), 4.04 (s, 2H), 3.63 (s, 6H), 2.97 (d, J = 30.6 Hz, 4H), 2.76 (d, J = 12.1 Hz, 8H), 2.13 (s, 3H), 2.10 (s, 3H), 1.19–1.08 (m, 12H). 13C-NMR: (101 MHz, CDCl3) δ 158.81, 158.37, 151.95, 151.76, 145.82 (d, J = 9.7 Hz), 145.80 (d, J = 9.6 Hz), 142.03, 141.98, 140.95, 140.69, 138.17, 135.25, 134.70, 134.56, 133.47, 132.62, 132.14, 131.92, 131.46, 131.29, 128.49, 127.91, 121.36 (d, J = 6.6 Hz), 117.43 (d, J = 13.6 Hz), 115.26 (d, J = 13.6 Hz), 115.23, 114.34, 113.88, 56.20, 53.56, 53.38, 51.73, 51.59, 47.87, 47.83, 23.38, 23.20, 11.39, 11.31. MS (ESI): m/z = 468.30 [M+H]+ (100%), m/z = 470.30 [M+H+2]+. Rf: 0.50 (93:7 methylene chloride: methanol).