General. Chemicals were purchased from Fluka and Aldrich companies and used without further purification. The known products were characterized by comparing their spectral and physical data with those reported in the literature. 1H NMR (250 MHz) and 13C NMR (62.5 MHz), spectra were recorded on a Brucker (250 MHz) Avance DRX. FT-IR spectroscopy (Shimadzu FT-IR 8300 spectrophotometer), were employed for the characterization of the products. Melting points were determined in open capillary tubes in a Buchi melting point B-545. The reaction monitoring was accomplished by TLC on silica gel PolyGram SILG/UV254 plates. Column chromatography was carried out on columns of silica gel 60 (70−230 mesh).
Procedure for the synthesis of compounds ASDSB and AADSB
1-(Methylsulfonyl)-4-(4-vinylstyryl)benzene (C). A sealed Schlenk tube was charged with1-bromo-4-methanesulfonyl-benzene (A; 5 mmol, 1.17 g), and K2CO3 (10.0 mmol, 1.4 g), Pd(OAc)2 (1.2 mol%, 14 mg), DPEPhos ligand (2.4 mol%, 65 mg) and it was evacuated and backfilled with argon. Then 1,4-divinyl-benzene (B; 5 mmol, 0.6 mL) and 5 mL of dry DMF was added to the reaction mixture under fellow of argon and tube was sealed with a screw-cap and the resulting mixture was heated in an oil bath at 120°C for 6h. To obtain the pure product its was purified by column chromatography (hexane/ethyl acetate: 10/1) (1.04g, 73%). Yellow solid; mp 182.7°C. IR (KBr): 3448, 3016, 1589, 1412, 1311, 1149, 957, 833, 764, 448 cm-1. 1H-NMR (250 MHz, CDCl3/TMS) δ (ppm): 3.07 (s, 3H), 5.29 (d, J = 11.0 Hz, 1H), 5.80 (d, J = 17.5 Hz, 1H), 6.73 (dd, J = 17.6, 10.7 Hz, 1H), 7.12 (d, J = 16.5, 1H), 7.24 (d, J = 16.5 Hz, 1H), 7.43 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 8.2 Hz, 2H), 7.67 (d, J = 8.5 Hz, 2H), 7.92 (d, J = 8.5 Hz, 2H). 13C-NMR (62.5 MHz, CDCl3/TMS) δ (ppm): 44.6, 114.5, 126.3, 126.7, 127.0, 127.1, 127.9, 132.2, 135.7, 136.2, 137.9, 142.8. Anal. Cal. C17H16O2S (284.4): C, 71.80; H, 5.67; O, 11.25; S, 11.28; found: C, 71.85; H, 5.71.
2-4- 2-{Ethyl-[4-(2-{4-[2-(4-methanesulfonyl-phenyl)-vinyl]-phenyl}-vinyl)-phenyl]-amino}-ethanol (ASDSB). A sealed Schlenk tube was charged with compound C (1 mmol, 0.29 g), 2-[Ethyl-(4-iodo-phenyl)-amino]-ethanol (D; 1 mmol, 0.29 g), and K2CO3 (2.5 mmol, 0.35 g), Pd(OAc)2 (1.2 mol%, 2.7 mg), DPEPhos ligand (2.4 mol%, 13 mg) and it was evacuated and backfilled with argon. Then 5 mL of dry DMF was added to the reaction mixture under fellow of argon and tube was sealed with a screw-cap and the resulting mixture was heated in an oil bath at 120°C for 12h. After completion of the reaction, the mixture was filtered (in hot form) and the remaining solid was washed with DMF (2 mL) in order to separate the catalyst. Subsequently, water (10 mL) was added to the solution in order to precipitate product. The obtained solid was purified by column chromatography (hexane/ethyl acetate: 10/2) to obtain the pure product (0.4g, 90%). Orange solid; mp 275.5°C.1 IR (KBr): 3300, 3000, 1600, 1590, 1510, 1400, 1350, 1290, 1180, 1130, 1080, 1060, 830, 820, 760, 550 cm-1. 1H-NMR (250 MHz, DMSO-d6/TMS) δ (ppm): 1.07 (t, J = 6.8 Hz, 3H), 3.20 (s, 3H), 3.32-3.51 (m, 6H), 4.72 (s, 1H), 6.66 (d, J = 8.6 Hz, 2H), 6.93 (d, J = 16.4 Hz, 2H), 7.15 (d, J = 16.4 Hz, 2H), 7.36-7.42 (m, 2H), 7.48-7.62 (m, 6H), 7.81-7.90 (m, 2H). Anal. Cal. C27H29NO3S (447.6): C, 72.45; H, 6.53; N, 3.13; O, 10.72; S, 7.16; found: C, 72.51; H, 6.58; N, 3.19.
2-[Ethyl-(4-{2-[4-(2-{4-[ethyl-(2-hydroxy-ethyl)-amino]-phenyl}-vinyl)-phenyl]-vinyl}-phenyl)-amino]-ethanol (AADSB). A sealed Schlenk tube was charged with 2-[Ethyl-(4-iodo-phenyl)-amino]-ethanol (D; 2 mmol, 0.60 g), K2CO3 (5 mmol, 0.68 g), Pd(OAc)2 (1.2 mol%, 5.5 mg), DPEPhos ligand (2.4 mol%, 26 mg) and it was evacuated and backfilled with argon. Then 1,4-divinyl-benzene (B; 1 mmol, 0.12 mL) and 6 mL of dry DMF wereadded to the reaction mixture under the argon atmosphere. The tube was sealed with a screw-cap, and the resulting mixture was heated in an oil bath at 120°C for 6h. The reaction was followed by TLC. After completion of the reaction, the mixture was cooled down to room temperature and filtered. The remaining solid was washed with dichloromethane (3 x 5 mL) to separate the catalyst. After the extraction of dichloromethane from water, the organic extract was dried over Na2SO4. The products were purified by column chromatography (hexane/ethyl acetate: 10/2) to obtain the pure product (0.4g, 88%). Yellow solid; mp 216.5°C. IR (KBr): 3389, 2922, 1601, 1520, 1360, 1267, 1180, 1051, 964, 823, 550 cm-1. 1H-NMR (250 MHz, DMSO-d6) )δppm): 1.04-1.14 (m, 6H), 3.31-3.53 (m, 12H), 4.70 (m, 2H), 6.55-6.67 (m, 4H), 6.85-7.10 (m, 8H), 7.22-7.66 (m, 4H). M/z (%): 456 (94.5%, (M)+). Anal. Cal. C30H36N2O2 (456.6): C, 78.91; H, 7.95; N, 6.13; O, 7.01; found: C, 78.98; H, 7.99; N, 6.18.
Theoretical calculations
The geometry of the molecules in the ground state was optimized by the first-principles density functional theory (DFT). The calculations carried byB3LYP functional63 and 6-311+g(2d,p)as the basis set. The most stable geometry was found by examining different isomers and configurations and examining vibrational frequency calculation. The excited state of the molecules was simulated by time-dependent density functional theory(TD-DFT). The model was the Coulomb attenuating employing the B3LYP hybrid functional (CAM-B3LYP)64 and the same basis-set as the DFT method. The Polarizable Continuum Model with the integral equation formalism (IEFPCM)was chosen to model the dichloromethane (DCM) as solvent. Calculations were carried out using Gaussian 09.65