4.1 General
Merck silica gel (70-230 mesh) was used in column chromatography. Mixed solvent was used as eluent and recorded in volume ratio of polar to less polar solvents. Merck Art. 5544 precoated sheets were used in thin-layer chromatography (TLC) and visualized by UV lamp.
Melting points were measured with a Fargo MP-1D melting point determination apparatus and were not calibrated. 1H and 13C nuclear magnetic resonance (NMR) spectra were recorded on a Varian 400 Unity plus (400 MHz) at ambient temperature. Proton chemical shifts () were reported as parts per million (ppm) downfield from tetramethylsilane and coupling constants (J) were reported in unit of hertz (Hz). 1H NMR data were reported in this order: chemical shift;
multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad); coupling constant(s); number of protons. 13C chemical shifts were reported in ppm using CDCl3 calibrated at 77.00 ppm as the internal standard. Samples for 1H and 13C NMR measurement were dissolved in CDCl3. All 13C NMR spectra were recorded with the proton completely decoupled.
Infrared spectra (IR) were obtained by using a Thermo Nicolet iS5 FT-IR spectrometer, and configured with EZ OMNIC software. Liquid or oil samples were dropped on a KBr window and solid samples were mixed with KBr and tableted into transparent windows before measurement. The spectral data were recorded in unit of wavenumber (cm-1). Electron-Impact (EI) mass spectra were recorded on Jeol SX-102A with an electron beam energy of 70 eV. Mass spectroscopy data were reported as m/z. High resolution mass spectroscopy (HRMS) was obtained using Jeol SX-102A spectrometer. FAB-mass spectroscopy were collected on a JMS-700 double focusing mass spectrometer (JEOL, Tokyo, Japan) with a resolution of 8000 and 3000 for HR and LR FAB-mass spectra, respectively (5% valley definition). MALDI-mass spectra were conducted on an Applied Biosystems 4800 Proteomics Analyzer (Applied Biosystem, Foster City) equipped with an Nd/YAG laser (335nm) operating at a repetition rate of 200 Hz.
43 4.2 Synthesis
3-Methyl-1,5-bis(trimethylsilyl)penta-1,4-diyn-3-ol (12a)
Under N2 atmosphere, to a solution of trimethylsilylacetylene (8.05 g, 82 mmol) in THF (250 mL) at -78oC, was added n-butyllithium (1.6 M in hexanes, 50 mL, 80 mmol dropwise over 2 min and the mixture was stirred at -78oC for 30 min before a solution of ethyl acetate (4.1 mL, 3.7 g, 82 mmol) in THF (20 mL) was added in one portion. The mixture was gradually warmed to rt and stirred for 2 h, then poured onto an ice-cold saturated NH4Cl. Diethyl ether (200 mL) was added and the organic layer was washed with saturated NH4Cl, water, brine and passed through a thin pad of silica gel. The solution was and dried (MgSO4) and filtered and the filtrate was evaporated in vacuo to afford 12a (9.18 g, 96%) as a white solid: mp 54-56 oC (MeOH-H2O) (lit.22 41-42 oC). 1H NMR (CDCl3, 400 MHz) 0.18 (s, 18 H), 1.74 (s, 3 H), 2.47 (br, 1 H); 13C NMR (CDCl3, 100 MHz) -0.3, 24.6, 39.9, 71.2, 88.7, 104.6; IR (KBr) 3476, 2959, 2901, 2176, 1366, 1254, 1182, 1140, 956, 935, 839, 761, 698 cm-1; HRMS(APCI) (M + H) calcd for C12H23OSi2: 239.1287; Found: 239.1288.
3-Ethoxycarbonylmethoxy-3-methyl-1,5-bis(trimethylsilyl)penta-1,4-diyne (18a)
Under N2 atmosphere, NaH (60% mineral oil suspension, 670 mg, 16.8 mmol) was washed with THF (2 mL x 3). THF (10 mL) was introduced and the slurry was cooled to 0 oC. A solution of 12a (2.00 g, 8.39 mmol) in THF (5 mL) was added and the mixture was allowed to warm to rt over 2 h. The solution was transferred to an addition funnel and added dropwise into ethyl bromoacetate (2.04 mL, 3.08 g, 18.5 mmol) and DMAP (5 mg, 41 mol) in THF (20 mL) at 0 oC. The reaction mixture turned opaque while warming to rt and was further stirred for 4 h before being poured onto a solution of saturated NH4Cl (200 mL). Diethyl ether (200 mL) was added and the organic layer was washed with saturated NH4Cl, water and brine, dried
44
(MgSO4) and filtered. The filtrate was evaporated in vacuo to give a yellow oil which was chromatographed on silica gel (hexanes/EA = 93/7) to afford 18a as a colorless oil (1.25 g, 46%):
bp 78 – 82 oC (0.05 mmHg), 1H NMR (CDCl3, 400 MHz) 0.18 (s, 18 H), 1.30 (t, J = 7.2Hz, 3 H), 1.79 (s, 3 H), 4.23 (q, J = 7.2 Hz, 2 H), 4.31 (s, 2 H); 13C NMR (CDCl3, 100 MHz) -0.3, 14.2, 30.6, 60.8, 63.86, 66.89, 89.5, 102.7, 169.9; IR (KBr) 2962, 2174, 1768, 1739, 1379, 1252, 1189, 1109, 1035, 960, 844, 761, 700 cm-1; HRMS(ESI) (M + Na) calcd. for C16H28O3NaSi2: 347.1475; Found: 347.1479.
3-(2-Hydroxyethoxy)-3-methyl-1,5-bis(trimethylsilyl)penta-1,4-diyne (19a)
To a solution of 18a (200 mg, 0.62 mmol) in THF (10 mL) was added lithium borohydride (4 M in THF, 1.5 mL, 6.0 mmol) and the mixture was stirred for 8 h at rt then poured onto saturated NH4Cl(50 mL). Diethyl ether (50 mL) was added and the organic layer was washed with saturated NH4Cl (20 mL x 2), water (20 mL x 2) and brine (5 mL), dried (MgSO4) and pushed through a pad of silica gel (2 cm) then evaporated in vacuo to afford 19a as a colorless oil (145 mg, 83%): 1H NMR (CDCl3, 400 MHz) 0.20 (s, 18 H), 1.73 (s, 3 H), 1.91 (br, 1 H), 3.79-3.82 (m, 4 H); 13C NMR (CDCl3, 100 MHz) -0.1, 30.9, 62.0 66.4, 67.1, 88.8, 103.6; IR (KBr) 2961, 2172, 1251, 1186, 1098, 958, 844, 760 cm-1; HRMS(EI) (M) calcd for C14H26O2Si2: 282.1471; Found: 282.1469.
2-Acetoxyethyl 3-methyl-1,5-bis(trimethylsilyl)penta-1,4-diyn-3-yl ether (13a)
A THF solution (10 mL) of 19a (200 mg, 0.708 mmol), DMAP (2 mg, 0.02 mmol) and acetic anhydride (0.5 mL, 5 mmol) was stirred at rt for 4 h before being poured onto saturated NaHCO3
(50 mL). Hexanes (20 mL) were added and the organic layer was washed with saturated NaHCO3 (20 mL x 3), water (10 mL), brine (5 mL), dried (MgSO4), filtered and the filtrate was evaporated in vacuo to obtain the crude product which was chromatographed on silica gel (5:95
45
ether/pentane) to give 13a (218 mg, 94%) as a colorless oil: bp 68-71 oC (0.3 mmHg); 1H NMR (CDCl3, 400 MHz) 0.18 (s, 18 H), 1.72 (s, 3 H), 2.08 (s, 3 H), 3.88 (t, J = 4.8 Hz, 3 H), 4.26 (t, J = 4.8 Hz, 3 H); 13C NMR (CDCl3, 100 MHz) -0.3, 21.0, 30.7, 63.7, 63.9, 66.5, 88.7, 103.5, 171.1; IR (KBr) 2998, 2960, 2917, 2848, 2174, 1745, 1458, 1375, 1099, 958, 844, 761 cm-1; HRMS(EI) (M + Na) calcd for C16H28O3NaSi2: 347.1475; Found: 347.1479.
3-(2-Acetoxyethoxy)-1,5-bis(4-(2-(2-hydroxyprop-2-yl)ethynyl)-2,5-dihexylphenyl)-3-methylpenta-1,4-diyne (15a)
A mixture of 12a (22.9 mg, 0.0706 mmol), 1,4-dihexyl-2,5-diiodobenzene (352 mg, 0.700 mmol), Pd(PPh3)4 (16.2 mg, 0.014 mmol), copper(I) iodide (1.00 mg, 0.005 mmol), TBAF (1 M in THF, 0.35 mL, 0.35 mmol), diisopropylamine (0.5 mL) and THF (1 mL) in a Schlenk tube underwent three freeze-pump-thaw degas cycles. After warming to rt, the reaction mixture was refluxed under N2 for 24 h before being evaporated in vacuo to afford a residue which was chromatographed on silica gel (hexanes/EA = 9/1) to remove the excess 1,4-dihexyl-2,5-diiodobenzene and the corresponding diiodo compound (21.7 mg) was collected and directly used for the next transformation.
A mixture of the diiodo compound (21.7 mg, 0.0236 mmol), 2-methylbut-3-yn-2-ol (85 mg, 1.0 mmol), Pd2(dba)3CHCl3 (5.6 mg, 0.0054 mmol), triphenylphosphine (8.50 mg, 0.032 mmol), copper(I) iodide (1.00 mg, 0.005 mmol), and triethylamine (1 mL) was refluxed under N2 for 6 h before being evaporated in vacuo to afford a crude mixture which was chromatographed on silica gel (hexanes/EA = 8.5/1) to give 15a (18 mg, 30%) as a pale yellow oil: 1H NMR (CDCl3, 400 MHz) 0.75-0.83 (m, 12 H), 1.18-1.25 (m, 24 H), 1.53-1.56 (m, 20 H), 1.89 (s, 3 H), 1.96 (s, 2 H), 1.99 (s, 3 H), 2.58-2.63 (m, 8 H), 3.99 (t, J = 4.8 Hz, 2 H), 4.25 (t, J = 4.8 Hz, 2 H), 7.15 (s, 2 H), 7.17 (s, 2 H); 13C NMR (CDCl3, 100 MHz) 14.05, 14.07, 20.9, 22.6, 29.2, 29.3,
46
30.61, 30.64, 30.9, 31.5, 31.7, 34.06, 34.1, 63.7, 64.2, 65.7, 67.2, 80.8, 83.1, 92.0, 98.3, 121.3, 122.4, 132.3, 132.4, 142.2, 142.4, 171.0; IR (KBr) 3433, 2924, 2852, 2224, 1744, 1466, 1377, 1260, 1099, 901, 804, 722 cm-1; HRMS(ESI) (M + Na) calcd for C56H80O5Na: 855.5903; Found:
855.5897.
3-(tert-butyl)-1,5-bis(trimethylsilyl)penta-1,4-diyn-3-ol (12b)
Under N2 atmosphere to a solution of trimethylsilylacetylene (4.03 g, 41 mmol) in THF (100 mL) at -78oC, n-butyllithium (1.6 M in hexanes, 25 mL, 40 mmol) was added dropwise over 2 min and the mixture was stirred for 30 min before a solution of methyl pivalate (5.3 mL, 4.7 g, 40 mmol) in THF (20 mL) was added in one portion. The mixture was warmed to rt and poured onto an ice-cold saturated NH4Cl. Diethyl ether (200 mL) the organic layer was washed with saturated NH4Cl, H2O, brine and passed through a thin pad of silica gel. The solution was dried (MgSO4) and filtered and the filtrate was evaporated in vacuo to afford 12b (5.3 g, 47%) as a white solid: mp 40-41 oC (EtOH-H2O), 1H NMR (CDCl3, 400 MHz) 0.19 (s, 18 H), 1.11 (s, 9 H), 2.30 (s, 1 H); 13C NMR (CDCl3, 100 MHz) -0.3, 24.6, 39.9, 71.2, 88.7, 104.6; IR (KBr)
3540, 2965, 2832, 2902, 2164, 1482, 1461, 1392, 1364, 1327, 1307, 1250, 1221, 1118, 1071, 1006, 977, 844, 760, 701, 678 cm-1; HRMS(ESI) (M + Na) calcd for C19H34O3NaSi2: 389.1944;
Found: 389.1942.
3-Ethoxycarbonylmethoxy-3-(tert-butyl)-1,5-bis(trimethylsilyl)penta-1,4-diyne (18b)
Under N2 atmosphere, NaH (60% mineral oil suspension, 1100 mg, 27.5 mmol) was washed with THF (2 mL x 3). THF (10 mL) was introduced and the slurry was cooled to 0oC. A solution of 12b (3.50 g, 12.5 mmol) in THF (10 mL) was added and the solution was allowed to warm to rt over 2 h. The solution was transferred to an addition funnel and added dropwise into ethyl bromoacetate (3.20 mL, 4.83 g, 28.9 mmol) and DMAP (5 mg, 41 mol) in THF (20 mL) at
47
0oC. The reaction mixture turned opaque while warming to rt and was further stirred for 4 h before being poured into a solution of saturated NH4Cl (200 mL) and extracted with diethyl ether (200 mL). The organic layer was washed with saturated NH4Cl, water and brine, dried (MgSO4) and filtered. The filtrate was evaporated in vacuo to give a yellow oil which was chromatographed on silica gel (hexanes/EA = 95/5) to afford 18b as a white wax-like solid (3.08 g, 67%): mp 71-72 oC, 1H NMR (CDCl3, 400 MHz) 0.17 (s, 18 H), 1.12 (s, 9 H), 1.29 (t, J = 7.2 Hz, 3H), 4.20 (q, J = 7.2 Hz, 2 H), 4.30 (s, 2 H); 13C NMR (CDCl3, 100 MHz) -0.3, 14.1, 24.9, 40.0, 60.5, 78.1, 90.8, 101.8, 170.4; IR (KBr) 2963, 2904, 2168, 1765, 1251, 1204, 1119, 1077, 846, 762 cm-1; HRMS(ESI) (M + Na) calcd for C19H34O3NaSi2: 389.1944; Found:
389.1942.
3-(2-Hydroxyethoxy)-3-(tert-butyl)-1,5-bis(trimethylsilyl)penta-1,4-diyne (19b)
To a solution of 18b (420 mg, 1.15 mmol) in THF (25 mL) was added lithium borohydride (4 M in THF, , 2.5 mL, 10 mmol) and the mixture was stirred for 8 h at rt then poured into saturated NH4Cl (100 mL) and extracted with diethyl ether (100 mL) and the organic layer was washed with saturated NH4Cl (50 mL x 2), water (50 mL x 2), brine (20 mL), dried (MgSO4), filtered and the filtrate was evaporated in vacuo to afford the crude product which was chromatographed on silica gel (hexanes/EA = 93/7) to give 19b (344 mg, 1.06 mmol, 92%) as a wax-like solid: mp 45-46oC; 1H NMR (CDCl3, 400 MHz) 0.17 (s, 18 H), 1.08 (s, 3 H), 1.95 (br, 1 H), 3.75-3.81 (m, 4H); 13C NMR (CDCl3, 100 MHz) -0.2, 24.9, 40.0, 62.1, 67.2, 77.5, 90.3, 102.5; IR (KBr) 3428, 2958, 2920, 2850, 2166, 1464, 1377, 1250, 1119, 1053, 845, 761cm-1; HRMS(ESI) (M + Na) calcd for C17H32O2Si2Na: 347.1839; Found: 347.1838.
3-(2-Acetoxyethoxy)-3-(tert-butyl)-1,5-bis(trimethylsilyl)penta-1,4-diyne (13b)
A THF solution (10 mL) of 19b (120 mg, 0.370 mmol), DMAP(2 mg, 0.02 mmol) and acetic
48
anhydride (0.5 mL, 5 mmol) was stirred at rt for 4 h before being poured into saturated NaHCO3
(50 mL) and extracted with hexanes (20 mL). The organic layer was washed with saturated NaHCO3 (20 mL x 3), water (10 mL), brine (5 mL) and dried (MgSO4) before being filtered and the filtrate was evaporated in vacuo to afford the crude product which was chromatographed on silica gel (hexanes/EA = 95/5) to give 12b (132 mg, 97%) as a colorless oil: bp 66-68 oC (0.04 mmHg); 1H NMR (CDCl3, 400 MHz) 0.18 (s, 18 H), 1.07 (s, 9 H), 2.06 (s, 3 H), 3.86 (t, J = 4.8 Hz, 2 H), 4.25 ( t, J = 4.8 Hz, 2 H); 13C NMR (CDCl3, 100 MHz) -0.2, 20.9, 24.8, 40.0, 63.5, 63.9, 77.5, 90.1, 102.5; IR (KBr) 2960, 2916, 2850, 2168, 1745, 1251, 1233, 1115, 1055, 1014, 844, 761 cm-1; HRMS(ESI) (M + Na) calcd for C19H34O3Si2Na: 389.1946; Found:
389.1944.
3-(2-Acetoxyethoxy)-3-(tert-butyl)-1,5-bis(4-(2-(2-hydroxyprop-2-yl)ethynyl)-2,5-dihexylphenyl)penta-1,4-diyne (15b)
A mixture of 12b (96.3 mg, 0.262 mmol), 1,4-dihexyl-2,5-diiodobenzene (1.00 g, 2.00 mmol), Pd2(dba)3CHCl3 (5.6 mg, 0.0054 mmol), triphenylphosphine (8.50 mg, 0.032 mmol), copper(I) iodide (1.00 mg, 0.005 mmol), TBAF (1 M in THF, 1.2 mL, 1.2 mmol), diisopropylamine (0.5 mL) and THF (1 mL) in a Schlenk tube underwent three freeze-pump-thaw degas cycles. After warming to rt, the reaction mixture was refluxed under N2 for 24 h before being evaporated in vaco to afford a residue which was chromatographed on silica gel (hexanes/EA = 9/1) to remove the excess 1,4-dihexyl-2,5-diiodobenzeneand the corresponding diiodo compound (54.1 mg) was collected and directly used for the next transformation.
A mixture of the diiodo compound (54.1 mg, 0.0562 mmol), 2-methylbut-3-yn-2-ol (170 mg, 2.02 mmol), Pd2(dba)3CHCl3 (11.2 mg, 0.011 mmol), triphenylphosphine (17 mg, 0.065 mmol), copper(I) iodide (2 mg, 0.01 mmol), and triethylamine (1 mL) was refluxed under N2 for 6 h
49
before being evaporated in vacuo to afford a crude mixture which was chromatographed on silica gel (hexanes/EA = 10/1) to give 15b as a pale yellow oil (43 mg, 19%): 1H NMR (CDCl3, 400 MHz) 0.74-0.83 (m, 12 H), 1.16-1.25 (m, 33 H), 1.52-1.56 (m, 20 H), 1.96-1.97 (m, 5 H), 2.58-2.64 (m, 8 H), 3.98 (t, J = 5 Hz, 2 H), 4.25 (t, J = 5 Hz, 2H), 7.14 (s, 2 H), 7.16 (s, 2 H);
13C NMR (CDCl3, 100 MHz) 14.05, 14.08, 22.57, 22.62, 25.3, 29.2, 29.3, 30.9, 31.50, 31.74, 31.78, 40.7, 63.5, 64.0, 65.7, 78.3, 80.9,84.7, 90.9, 98.2, 121.7, 122.2, 132.3, 132.6, 142.2, 142.3, 171.0; IR (KBr) 3423, 2958, 2928, 2857, 2224, 1746, 1458, 1376, 1246, 1127, 1049, 958, 900, 723 cm-1; HRMS(ESI) (M + Na) calcd for C59H86O5Na: 897.6373; Found: 897.6365.
1,4-bis(2-(2-hydroxyprop-2-yl)-ethynyl)-2,5-dihexylbenzene (14)
A mixture of 1,4-dihexyl-2,5-diiodobenzene (500 mg, 1.00 mmol), 2-methylbut-3-yn-2-ol (252 mg, 3.00 mmol), PdCl2(dppf) (10 mg, 0.013 mmol), CuI (10 mg, 0.052 mmol) and triethylamine (15 mL) were refluxed under N2 for 6 h. The reaction mixture was evaporated in vacuo and chromatographed on silica gel (hexanes/EA = 9/1) to afford 14 (349 mg, 85%) as a white solid: mp 95-97 oC; 1H NMR (CDCl3, 400 MHz) 0.81 (t, J = 6.6 Hz, 6 H), 1.22-1.26 (m, 12 H), 1.49-1.55 (m, 16 H), 2.09 (br, 2 H), 2.56-2.60 (m, 4 H), 7.12 (s, 2 H); 13C NMR (CDCl3, 100 MHz) 14.1, 22.6, 29.2, 30.5, 31.5, 31.7, 34.0, 65.7, 80.9, 98.1, 121.9, 132.2, 142.1; IR (KBr) 3284, 2979, 2957, 2925, 2856, 2155, 1654, 1493, 1458, 1400, 1378, 1364, 1250, 1162, 957, 920, 864, 840, 761, 724; HRMS(ESI) (M + Na) calcd for C28H42O2Na: 433.3803; Found:
433.3801.
General procedure for the synthesis of polymers (11a) and (11b), demonstrating with the synthesis of polymer 11b1:
A Schlenk reaction tube containing the bis-silane 12b (70.0 mg, 0.19 mmol), 1,4-dihexyl-2,5-diiodobenzene (95.12 mg, 0.19 mmol, 1 eq), Pd2(dba)3(CHCl3) (4.94 mg, 0.0048 mmol, 0.025 eq), CuI (3.64 mg, 0.019 mmol, 0.1 eq), diisopropylamine (0.5 mL) and THF (1 mL) was capped with a meld Schlenk tube containing triphenylphosphine (7.51 mg, 0.029 mmol, 0.15 eq) and TBAF (1 M in THF, 0.57 mL, 3 eq). Both ends of the apparatus were brought to -78 oC and the system was degassed by three freeze-pump-thaw cycles, with the pumping times being 5 min, 5 min and 30 min. After degassing, the apparatus was warmed to rt and reagents in the
50
meld Schlenk tube was transfered into the Schlenk reaction tube. The reaction mixture was refluxed for 5 days. The reaction was traced by GPC to monitor the molecular weight distribution and the consumption of 1,4-dihexyl-2,5-diiodobenzene. Additional THF solution (0.2 mL) of dihexyl-2,5-diiodobenzene (10 mg, 0.02 mmol, 0.1 eq) was then added and the mixture was refluxed for another 12 h before being evaporated in vacuo to remove most volatile components. The residue was taken up in diethyl ether (20 mL) and was washed with saturated NH4Cl (50 mL x 3), dried (MgSO4) then filtered through a pad of celite. The filtrate was evaporated in vacuo to give a residue which was chromatographed on silica gel (1.5 cm diameter, 7 cm length, eleuent: CHCl3). Fractions were monitored by TLC. Those with Rf = 0.3 were collected to afford 11b1 (25 mg, 27%) as a yellow solid: Mn = 5000, PDI = 1.11; 1H NMR (CDCl3, 400 MHz) 0.80-0.89 (br, 6 H), 1.18-1.26 (br, 21 H), 1.58-1.60 (br, 4 H), 2.03-2.05 (br, 3 H), 2.68-2.72 (br, 4 H), 4.05-4.06 (br, 2 H), 4.30-4.33 (br, 2 H), 7.25-7.27 (br, 2 H); 13C NMR (CDCl3, 100 MHz) 14.0, 20.9, 22.6, 25.2, 29.3, 29.7, 31.1, 31.7, 31.8, 34.4, 40.7, 63.5, 64.1, 78.3, 84.6, 91.0, 122.0, 132.7, 142.4, 171.0; IR (KBr) 2956, 2924, 2854, 2156, 1748, 1653, 1559, 1541, 1491, 1458, 1376, 1234, 1084, 1054, 1000, 899, 844, 759, 723 cm-1.
11b2
In a manner similar to that described in the general procedure for polymer synthesis, the bis-silane 12b (40 mg, 0.11 mmol) was used. Chromatographic fractions with Rf = 0.1 were collected to obtain 11b2 (5.3 mg, 10%) as an yellow solid: Mn = 9300, PDI = 1.18; 1H NMR (CDCl3, 400 MHz) 0.80-0.86 (br, 6 H), 1.18-1.26 (br, 21 H), 1.58 (br, 4 H), 2.03-2.05 (br, 3 H), 2.68-2.72 (br, 4 H), 4.01-4.05 (br, 2 H), 4.31-4.32 (br, 2 H), 7.25-7.26 (br, 2 H); 13C NMR (CDCl3, 100 MHz) 14.0, 20.9, 22.6, 25.2, 29.3, 31.1, 31.8, 34.4, 40.8, 63.5, 64.1, 78.3, 84.6, 91.0, 122.0, 132.7, 142.4, 171.0; IR (KBr) 2956, 2922, 2854, 2222, 2155, 1747, 1611, 1492, 1462, 1376, 1234, 1164, 1084, 1054, 1000, 939, 899, 845, 804, 722 cm-1.
11a1
In a manner similar to that described in the general procedure for polymer synthesis, bis-silane 12a (87 mg, 0.27 mmol) was used. Chromatographic fractions with Rf = 0.3 were collected to obtain 11a1 (12.2 mg, 11%): Mn = 6200, PDI = 1.19; 1H NMR (CDCl3, 400 MHz)
51
0.80-0.86 (br, 6 H), 1.18-1.26 (br, 21 H), 1.58 (br, 4 H), 2.03-2.05 (br, 3 H), 4.01-4.05 (br, 2 H), 4.31-4.32 (br, 2 H); 13C NMR (CDCl3, 100 MHz) 14.1, 20.9, 22.6, 29.3, 30.7, 31.6, 31.7, 34.2, 40.2, 62.0, 63.4, 63.6, 64.3, 64.5, 66.9, 67.2, 68.0, 82.7, 83.0, 91.7, 92.2, 101.4, 121.5, 121.8, 132.4, 132.5, 134.4, 139.5, 142.6, 142.9, 144.3, 171.0; IR (KBr) 2956, 2928, 2857, 2224, 2154, 1748, 1729, 1634, 1459, 1379, 1365, 1360, 1233, 1148, 1101, 1053, 983, 907, 864, 845, 761, 723, 699 cm-1.
11a2
In a manner similar to that described in the general procedure for polymer synthesis, the bis-silane 12a (100 mg, 0.308 mmol) was used. Chromatographic fractions with Rf < 0.1 were collected to obtain 11a2 (2.6 mg, 1.9%): Mn = 19000, PDI = 1.29; 1H NMR (CDCl3, 400 MHz)
0.80-0.83 (br, 6 H), 1.22-1.31 (br, 12 H), 1.59 (br, 4 H), 1.94 (br, 3 H), 2.04 (br, 3 H), 2.66-2.70 (br, 4 H), 4.04-4.05 (br, 2 H), 4.29-4.31 (br, 2 H), 7.17-7.24 (br, 2 H); 13C NMR (CDCl3, 100 MHz) 14.0, 20.9, 22.6, 29.2, 30.7, 31.0, 31.7, 34.2, 62.0, 63.6, 64.2, 67.2, 76.7, 77.0, 77.3, 83.0, 92.2, 121.8, 132.5, 142.5, 171.0; IR (KBr) 2925, 2856, 2224, 1745, 1492, 1458, 1403, 1376, 1236, 1147, 1098, 1054, 979, 899, 725 cm-1.
52 4.3 Steady State Photophysical measurements
Absorption spectra were measured on a Hitachi U-3310 spectrophotometer, and fluorescence spectra were measured on a Hitachi F-4500 fluorescence spectrophotometer. A 1 cm x 1 cm quartz cuvette was used. Absorption spectra were measured with the absorbance kept below 0.1.
Sample solutions satisfying the same criteria were then used to measure the fluorescence spectra and fluorescence excitation spectra.
Fluorescence quantum yield was measured using p-terphenyl in cyclohexane ( = 0.93) as a standard. 10-5 M solution of the sample was prepared and its absorbance at 280 nm ( ) was measured. A standard solution was prepared with its absorbance at 280 nm ( ) comparable with that of the sample solution (within 10%). Their fluorescence spectra were measured and the area under their emission profiles were calculated for the sample solution ( ) and standard solution ( ). The quantum yield was then obtained by:
0.93
53
4.4 Time Resolved Fluorescence Measurements.
Picosecond time-resolved fluorescence measurements were performed with time-correlated single-photon counting (TCSPC). The light source was a femtosecond mode-locked Ti:sapphire laser (Spectra-Physics, Mai Tai) pumped with a Nd:YVO4 laser (5 W CW, 532 nm, Spectra-Physics, Millennia type). This laser outputs a pulse train (82 MHz, 800 nm) with an average power ∼400 mW. The third-harmonic pulses at 266 nm were generated with two nonlinear crystals (BBO, type I) and were focused with a lens (focal length 50 mm) for excitation. Samples were operated under the same condition as for the steady state measurements. The fluorescence was filtered with a bandpass filter and detected with a multichannel plate photomultiplier (MCP-PMT). The instrument response function was 30 ps at fwhm. Fluorescence intensities were fitted with a multiexponential decay model:
,
where stands for the fluorescence intensity over time, stands for the signal baseline, represents the relative weight between components of various lifetime and were the corresponding lifetimes. Measurement and fitting results were plotted in Figures S1-S7, with the fitting lines being white curves. All fittings converged with R2 > 0.97.
54
Chapter 5: References
1. (a) Colvin, E. W. Silicon Reagents in Organic Synthesis; Academic: San Diego, USA, 1988;
pp 1 – 5. (b) Corey, J. Y. Historical overview and comparison of silicon with carbon. In The Chemistry of Organic Silicon Compounds, Volume 1; Patai, S; Rappoport, Z., Ed.; John Wiley
& Sons, Ltd, Chichester, UK, 1989; pp 1–101. (c) Cartledge, R. K. Journal of Organometallic Chemistry, 1982, 225, 131–139.
2. For reviews: (a) Miller, R. D.; Michl, J. Chem. Rev. 1989, 89, 1359–1410. (b) Raabe, G.;
Michl, J. Chem. Rev. 1985, 85, 419–509. (c) West, R.; West, R. Polyhedron 2002, 21, 467–
472. (d) Tokitoh, N. and Okazaki, R. Recent Advances in the Chemistry of Silicon–
Heteroatom Multiple Bonds. In The Chemistry of Organic Silicon Compounds, Volume 2;
Rappoport, Z.; Apeloig, Y., Ed.; John Wiley & Sons, Ltd: Chichester, UK, 1998; pp 1063 - 1103.
3. (a) West, R.; Fink, M. J.; Michl, J. Science 1981, 214, 1343–1344. (b) Sekiguchi, A.; Kinjo, R.; Ichinohe, M. Science 2004, 305, 1755–1757. (c) Wiberg, N.; Finger, C. M. M.; Polborn, K. Angew. Chem., Int. Ed. Engl. 1993, 32, 1054-1056. (d) Kipping, F. S. J. Chem. Soc., Trans., 1921, 119, 647-653 (e) Ishida, S.; Iwamoto, T.; Kabuto, C.; Kira, M. Nature 2003, 421, 725 - 727.
4. Fleming, I.; Dunoguès, J.; Smithers, R. The Electrophilic Substitution of Allylsilanes and Vinylsilanes In Organic Reactions; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2004; pp 57–575.
5. (a) West, R.; David, L. D.; Djurovich, P. I.; Stearley, K. L.; Srinivasan, K. S. V; Yu, H. J. Am.
Chem. Soc. 1981, 103, 7352–7354. (b) Sakurai, H.; Kira, M.; Uchida, T. J. Am. Chem. Soc.
1973, 95, 6826-6827. (c) Chicart, P.; Corriu, R. J. P.; Moreau, J. J. E.; Garnier, F.; Yassar, A.
Chem. Mater. 1991, 3, 8-10. (d) Ohshita, J.; Kanaya, D.; Ishikawa, M.; Koike, T.; Yamanaka, T. Macromolecules 1991, 24, 2106-2107. (e) Sakurai, H.; Sakamoto, K.; Kira, M. Chemistry Letters, 1984, 1213–1214. (f) Sakurai, H.; Sakamoto, K.; Kira, M. Chemistry Letters, 1984, 1213–1214. (g) Corriu, R. J. P.; Guerin, C.; Henner, B.; Kuhlmann, T. Organometallics 1990, 351–352. (h) Ijadi-Maghsoodi, S.; Barton, T. J. Macromolecules 1990, 23, 4485–4486.
55
6. (a) Shizuka, H.; Obuchi, H.; Ishikawa, M.; Kumada, M. J. Chem. Soc. Chem. Commun. 1981, 405. (b) Sakurai, H.; Sugiyama, H.; Kira, M. J. Phys. Chem. 1990, 94, 1837–1843. (c) Fang, M.; Watanabe, A.; Matsuda, M. Macromolecules 1996, 29, 6807–6813. (d) Kwak, G.;
Masuda, T. Macromolecules 2002, 35, 4138–4142. (e) Brown, A. E.; Eichler, B. E.
Tetrahedron Lett. 2011, 52, 1960–1963. (f) Shimizu, M.; Kawaguchi, T.; Oda, K.; Hiyama, T. Chem. Lett. 2007, 36, 412–413.
7. (a) Sakurai, H.; Kira, M.; Uchida, T. J. Am. Chem. Soc. 1973, 95, 6826–6827. (b) Ishikawa, M.; Hatano, T.; Hasegawa, Y.; Horio, T.; Kunai, A.; Miyai, A.; Ishida, T.; Tsukihara, T.;
Yamanaka, T. Organometallics 1992, 11, 1604 - 1618. (c) Oshita, J.; Takada, A.; Kunai, A.;
Komaguchi, K.; Shiotani, M.; Adachi, A.; Sakamaki, K.; Okita, K.; Harima, Y.; Konugi, Y.;
Yamashita K.; Ishikawa, M. Organometallics 2000, 19, 4492-4498. (d) Fang, M.; Watanabe, A.; Matsuda, M. Macromolecules 1996, 29 , 6807 - 6813. (e) Kwak, G.; Masuda, T.
Macromolecules 2002, 35, 4138 - 4142. (f) Kwak, G.; Masuda, T. Macromol. Rapid Commun.
2001, 22, 846 - 849.
8. (a) van Walree, C. A.; Roest, M. R.; Schuddeboom, W.; Jejnneskens, L. W.; Verhoeven, J.
W.; Warman, J. M.; Kooijman, H.; Spek, A. L. J. Am. Chem. Soc. 1996, 118, 8395-8407. (b) Van Walree, C. A.; Kooijman, H.; Spek, A. L.; Zwikker, J. W.; Jenneskens, L. W. J. Chem.
Soc. Chem. Commun. 1995, No. 1, 35. (c) Zehnacker, A.; Lahmani, F.; van Walree, C. A.;
Jenneskens, L. W. J. Phys. Chem. A 2000, 104, 1377–1387.
9. (a) Burroughes, J. H.; Bradley, D. D. C.; Brown, a. R.; Marks, R. N.; Mackay, K.; Friend, R.
H.; Burns, P. L.; Holmes, a. B. Nature 1990, 347, 539–541. (b) Grimsdale, A. C.; Chan, K.
L.; Martin, R. E.; Jokisz, P. G.; Holmes, A. B. Chem. Rev. 2009, 109, 897–1091. (c) Bunz, U.
H. F. Chem. Rev. 2000, 100, 1605–1644. (d) Martin, R. E.; Diederich, F. Angew. Chemie Int.
Ed. 1999, 38, 1350–1377.
10. (a) Brouwer, H. J.; Krasnikov, V. V; Hilberer, a; Hadziioannou, G. Adv. Mater. 1996, 8, 935–937. (b) Kim, H. K.; Ryu, M.; Lee, S. Macromolecules 1997, 30, 1236–1239. (c) Gao, Z.; Lee, C. S.; Bello, I.; Lee, S. T.; Chen, R.-M.; Luh, T.-Y.; Shi, J.; Tang, C. W. Appl. Phys.
Lett. 1999, 74, 865.
56
11. (a) Chen, R.-M.; Chien, K.-M.; Wong, K.-T.; Jin, B.-Y.; Luh, T.-Y.; Hsu, J.-H.; Fann, W. J.
Am. Chem. Soc. 1997, 119, 11321-11322. (b) Chen, R.-M.; Luh, T.-Y. Tetrahedron 1998, 54, 1197–1206. (c) Yeh, M.-Y.; Lin, H.-C.; Lee, S.-L.; Chen, C.-H.; Lim, T.-S.; Fann, W.; Luh, T.-Y. Chem. Commun. 2007, 3459-3461.
12. (a) Cheng, Y.-J.; Hwu, T.-Y.; Hsu, J.-H.; Luh, T.-Y. Chem. Commun. 2002, 1978–1979. (b) Cheng, Y.-J.; Luh, T.-Y. Chem. Eur. J. 2004, 10, 5361–5368. (c) Luh, T.-Y.; Cheng, Y.-J.
Chem. Commun. 2006, 4669–4678. (d) Cheng, Y.-J.; Basu, S.; Luo, S.-J.; Luh, T.-Y.
Macromolecules 2005, 38, 1442–1446.
13. (a) Yeh, M. Y.; Lin, H. C.; Lim, T. S.; Lee, S. L.; Chen, C. H.; Fann, W.; Luh, T. Y.
Macromolecules 2007, 40, 9238–9243. (b) Chen, C.-H.; Huang, Y.-C.; Liao, W.-C.; Lim, T.-S.; Liu, K.-L.; Chen, I.-C.; Luh, T.-Y. Chem. Eur. J. 2012, 18, 334–346. (c) Liao, W.-C.; Chen, W.-H.; Chen, C.-H.; Lim, T.-S.; Luh, T.-Y. Macromolecules 2013, 46, 1305-1311. (d) Chen, C.-H.; Chen, W.-H.; Liu, Y.-H.; Lim, T.-S.; Luh, T.-Y. Chem. Eur. J. 2012, 18, 347–354.
14. For reviews, see: (a) Jung, M. E.; Piizi, G. Chem. Rev. 2005, 105, 1735-1766. (b) Sammes, P. G.; Weller, D. J. Synthesis 1995, 1205-1222. (c) Galli, C.; Mandolini, L. Eur. J. Org. Chem.
2000, 3117-3125 (d) Luh, T.-Y.; Hu, Z. Dalton Trans. 2010, 39, 9185-9192. (e) Toniolo, C.;
Crisma, M.; Formaggio, F.; Peggion, C. Biopolymers 2001, 60, 396-419.
15. (a) Beesley, R. M.; Ingold, C. K.; Thorpe, J. F. J. Chem. Soc. Trans. 1915, 107, 1080. (b) Ingold, C. K.; Sako, S.; Thorpe, J. F. J. Chem. Soc. Trans. 1922, 121, 1177.
16. (a) Kirby, A. J.; Lancaster, P. W. J. Chem. Soc. Perkin Trans. 2 1972, 1206-1214. (b) Kirby, A. J.; Lloyd, G. J. J. Chem. Soc. Perkin Trans. 2 1976, 1753-1761. (c) Jager, J.; Graafland, T.; Schenk, H.; Kirby, A. J.; Engberts, J. B. F. N. J. Am. Chem. Soc. 1984, 106, 139-143. (d) Kirby, A. J. Adv. Phys. Org. Chem. 1994, 29, 87-183.
17. (a) Sternbach, D. D.; Rossana, D. M. Tetrahedron Lett. 1982, 23, 303–306. (b) Sternbach, D. D.; Rossana, D. M.; Onan, K. D. Tetrahedron Lett. 1985, 26, 591–594.
18. Bunz, U. H. F. Top. Curr. Chem. 1999, 201, 131–161.
19. Bothner-By, A.A.; Colin, C. N.; Günther, H. J. Am. Chem. Soc. 1962, 84, 2748-2751.
20. 葉美鈺，國立臺灣大學化學所博士論文，2007.
57
21. (a) Tsuji, J. Palladium Reagents and Catalysts: New Perspectives for the 21st Century;
John Wiley & Sons, Ltd: Chichester, UK, 2005; pp. 543-563.(b) Elsevier, C. J.; Kleijn, H.; Ruitenberg, K.; Vermeer, P. J. Chem. Soc. Chem. Commun. 1983, 1529-1530.
22. Alberts, A. H. J. Am. Chem. Soc. 1989, 111, 3093-3094.
58