第 6 章 附錄
CDCl 3 )
1.02–1.26 (m, 8H), 0.53–0.65 (m, 4H).
F1 之合成
Under nitrogen atmosphere, 2-bromo-9,9′-bis(6-bromohexyl)fluorene (1.6 g, 2.8 mmol) was added to a THF (15 mL) solution of trimethylamine (3 mL, 12.6 mmol, 4.2 M in ethanol). The mixture was stirred overnight at 40 oC. After removal of the solvent, the residue was washed with chloroform and dichloromethane to furnish F1 as a white powder (1.44 g, 75%).
1H NMR (400 MHz, d6-DMSO) δ: 7.82–7.87 (m, 1H), 7.76–7.80 (m, 1H), 7.69–7.71 (m, 1H), 7.51–7.55 (m, 1H), 7.43–7.48 (m, 1H), 7.33–7.38 (m, 2H), 3.09– 3.15 (m, 4H), 2.94–
2.98 (s, 18H), 1.93–2.09 (m, 4H), 1.39–1.52 (m, 4H), 0.94–1.12 (m, 8H), 0.43–0.53 (m, 4H).
13C NMR (125 MHz, d6-DMSO) δ: 152.56, 149.61, 139.96, 139.52, 129.99, 127.83, 127.20, 125.93, 122.87, 121.87, 120.49, 120.27, 65.15, 55.04, 52.10, 28.59, 25.38, 23.23, 21.87.
F2 之合成
To a stirred mixture of 2-bromofluorene (2 g, 8.16 mmol) and 35 ml of dimethylsulfoxide (DMSO) under nitrogen were added tetrabutylammoium bromide (110 mg) and a 50 wt%
aqueous solution (8 ml) of sodium hydroxide. A DMSO (10 ml) solution of 1,4-butanesultone (2.68 g, 19.7 mmol) was added dropwise to the mixture. The reaction mixture was stirred at room temperature for 4 h and dropped slowly into 500 ml of acetone to induce precipitation. The precipitate was collected by filtration, washed with ethanol, and recrystallized from acetone/H2O to yield ivory solid (2.75 g, 60%).
1H NMR (400 MHz, D2O) δ: 7.77–7.75 (m, 1H), 7.67 (d, J=8.1 Hz, 1H), 7.63 (d, J=1.52 Hz, 1H), 7.51 (dd, J=8.1, 1.6 Hz, 1H), 7.46–7.43 (m, 1H) 7.38–7.36 (m, 2H), 2.56–2.52 (m, 4H), 2.04–1.98 (m, 4H), 1.42 (quin, J=7.8 Hz, 4H), 0.60–0.53 (m, 4H).
13C NMR (100 MHz, D2O) δ: 152.46, 149.82, 139.81, 139.68, 130.08, 127.76, 127.23, 126.33, 123.29, 121.27, 120.75, 119.81, 54.83, 50.68, 38.62, 24.16, 22.36.
2-(2-bromothiophen-3-yl)ethanol 之合成
To a solution of 2-(3-thienyl)ethanol (1 g, 7.8 mmol) in CH2Cl2 (50 mL), 1.667g (9.36
mmol) of NBS was added. The reaction mixture was sonicated for 90 min at 40 °C and cooled to room temperature. The mixture was washed with saturated NaHCO3 solution, water, and brine consecutively and dried over MgSO4. The residue was purified by column chromatography on silica gel (ethyl acetate : hexane 2:8 v/v) to give 2-(2-bromothiophen-3-yl)ethanol as a yellow oil (1.45 g, 90%).
1H NMR (400 MHz, CDCl3) δ: 7.24 (d, J=5.6 Hz, 1H), 6.87 (d, J=5.6 Hz, 1H), 3.82–3.87 (m, 2H), 2.87 (t, J=6.56 Hz, 2H), 1.42 (t, J=5.6 Hz, 1H).
13C NMR (100 MHz, CDCl3) δ: 137.86, 128.45, 125.64, 110.30, 62.03, 32.72.
2-bromo-3-(2-(6-bromohexyloxy)ethyl)thiophene 之合成
Under nitrogen, to a solution of 2-(2-bromothiophen-3-yl)ethanol (1 g, 4.83 mmol) in 40 mL of dried THF was slowly added sodium hydride (60% in mineral oil, 0.3 g, 7.5 mmol) with vigorous stirring. The reaction mixture was stirred for 30 min at room temperature.
1,6-dibromohexane (5.98 g, 24.53 mmol) was then added and the mixture was stirred for 1 h at room temperature and for 15 h at 80 °C. The reaction was quenched with water.
The organic phase was extracted with diethyl ether and dried over MgSO4. The solvent was evaporated and the excess amount of 1,6-dibromohexane was removed under high vacuum. After removal of the solvent, the residue was purified by silica gel chromatography (ethyl acetate ： hexane 1:9 v/v) to afford 2-bromo-3-(2-(6-bromohexyloxy)ethyl)thiophene as a pale yellow oil (0.31 g, 17%).
1H NMR (400 MHz, CDCl3) δ: 7.19 (d, J=5.6 Hz, 1H), 6.86 (d, J=5.6 Hz, 1H), 3.59 (t, J=6.96 Hz, 2H), 3.43 (t, J=6.3 Hz, 2H), 3.40 (t, J=6.72 Hz, 2H), 2.85 (t, J=6.96 Hz, 2H), 1.89–1.82 (m, 2H), 1.61–1.54 (m, 2H), 1.46–1.34 (m, 4H).
13C NMR (100 MHz, CDCl3) δ: 138.40, 128.56, 125.17, 109.79, 70.64, 69.64, 33.78, 32.65, 29.92, 29.41, 27.87, 25.27.
T1 之合成
Under nitrogen atmosphere, 3-(2-(6-bromohexyloxy)ethyl)thiophene (370 mg, 1 mmol) was added to a dried THF (0.5 ml) solution of trimethylamine (3ml, 12.6 mmol, 4.2 M in ethanol). The mixture was stirred overnight at 40 °C. After removal of the solvent, the residue was washed with hexane to furnish T1 as a white solid (0.382 g, 89%).
1H NMR (400 MHz, D2O) δ: 7.43 (d, J=5.6 Hz, 1H), 6.99 (d, J=5.6 Hz, 1H), 3.77 (t, J=6.4 Hz, 2H), 3.53 (t, J=6.44 Hz, 2H), 3.28 (m, 2H), 3.11 (s, 9H), 2.89 (t, J=6.34 Hz, 2H), 1.76 (m, 2H), 1.55 (m, 2H), 1.33 (m, 4H).
13C NMR (125 MHz, D2O) δ: 138.49, 128.83, 126.16, 109.48, 70.43, 69.21, 66.48, 52.79, 29.25, 28.50, 25.31, 24.95, 22.30.
T2 之合成
To a toluene solution (35 ml) of 2-(2-bromothiophen-3-yl)ethanol (1 g, 4.83 mmol), sodium hydride (60% in mineral oil, 0.46 g, 11.59 mmol) was added slowly. The mixture was stirred at room temperature for 30 min, followed by adding 1,4-butanesultone (0.92 g, 6.76 mmol) drop-wise, and then refluxed for 2 h under nitrogen. The precipitate was collected by filtration, washed with toluene, and dried under vacuum to furnish a pale yellow solid (1.24 g, 70%).
1H NMR (400 MHz, D2O) δ: 7.40 (d, J=5.6 Hz, 1H), 6.97 (d, J=5.6 Hz, 1H), 3.75 (t, J=6.4 Hz, 2H), 3.54 (t, J=6.2 Hz, 2H), 2.89−2.84 (m, 4H), 1.70−1.61 (m, 4H).
13C NMR (100 MHz, D2O) δ: 138.40, 128.44, 126.25, 125.56, 69.82, 69.17, 50.60, 28.86, 27.41, 20.76.
2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene 之合成
An aqueous (100 mL) solution of KOH (50 g, 891.3 mmol) was heated to 80 °C. 2,7-dibromofluorene (1.62 g, 5.0 mmol), 1,6-dibromohexane (12.2 g, 50 mmol), and tetrabutylammonium bromide (0.16 g 0.49 mmol) were added. The reaction mixture was
with dichloromethane. The organic layer was collected, washed with dilute hydrochloric acid (100 mL), water (100 mL) and brine (100 mL) sequentially, and dried over MgSO4. After removal of solvent, the residue was heated at 70 °C under 0.03 mbar to remove excess 1,6-dibromohexane and purified by column chromatography (silica gel, chloroform : hexane = 1 : 9) to give 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene as a white solid (1.72 g, 53%).
1H NMR (400 MHz, CDCl3) δ: 7.53 (d, J = 8.0 Hz, 2H), 7.46 (dd, J = 8.0, 1.7 Hz, 2H), 7.44 (d, J = 1.7 Hz, 2H), 3.29 (t, J = 6.8 Hz, 4H), 1.91-1.95 (m, 4H), 1.64-1.71 (m, 4H), 1.24-1.12 (m, 4H), 1.05-1.10 (m, 4H), 0.56-0.63 (m, 4H).
13C NMR (100 MHz, CDCl3) δ: 152.32, 139.22, 130.49, 126.24, 121.72, 121.38, 55.71, 40.19, 34.00, 32.76, 29.10, 27.90, 23.61.
SPF 之合成
A mixture of 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene (0.7 g, 1.08 mmol), bis(pinacolato)diboron (273 mg, 1.08 mmol), Pd2(dba)2 (20.0 mg, 0.022 mmol), tricyclohexyl phosphonium tetrafluoroborate(23.4 mg, 0.064 mmol), cesium fluoride (1.11 g, 7.3 mmol), and anhydrous toluene (36 mL) was bubbled with nitrogen for 15 minutes and stirred at 80 ℃ for 24 hours under nitrogen atmosphere. Tetra-n-butylammonium bromide (69.9 mg, 0.22 mmol) was then introduced. The reaction mixture was stirred for further 24 hours, cooled to room temperature, and evaporated in
acetone sequentially. The mixture was filtered with a nylon membrane to afford SPF as a yellow solid. (323 mg, 57%)
SPF1 之合成
A mixture of SPF (100 mg), trimethylamine (300 mg), and tetrahydrofuran (5.0 mL), was heated to 40 ℃ in a sealed Schlenk tube for 24 hours, cooled to room temperature, and evaporated under vacuum. The residue was washed with chloroform and dichloromethane sequentially. The insoluble fraction was evaporated under vacuum to furnish SPF1 (92.3 mg, 75%).
嘧啶(pyrimidine)配位基鈀催化劑之合成
A mixture of 2-amino-4,6-dihydroxypyrimidine (26 mg, 0.2 mmol) and 4 mL of 0.1 M NaOH was heated to 65 ˚Cwith stirring. To the mixture, palladium(II) acetate (22 mg, 0.1 mmol) was added and it was stirredat 65 ˚C for 30 minutes. The stir bar was then removed, and the solution was allowed to cool to room temperature. After cooling, the solution was removed to a 10 mL volumetric flask and diluted to 10 mL with water.
高分子一般聚合條件：
以 m-TPPTs 作為鈀金屬配位基
Under nitrogen atmosphere, a mixture of monomer (50 mg), pivalic acid, Cs2CO3, Pd(OAc)2, m-TPPTs, and deionized water (2.5 mL) was stirred at 80 °C for 72 hours, cooled to room temperature, filtrated, transferred into Spectrum standard RC dialysis membrane, and dialyzed (2 × 12 h). Removal of water furnished polymer.
以pyrimidine 作為鈀金屬配位基
Under nitrogen atmosphere, a mixture of monomer (50 mg), pivalic acid, Cs2CO3, Pd-pyrimidine solution, and deionized water (2.5 mL) was stirred at 80 °C for 72 hours, cooled to room temperature, filtrated, transferred into Spectrum standard RC dialysis membrane, and dialyzed (2 × 12 h). Removal of water furnished polymer.
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第6章 附錄
圖 60 2-bromo-9,9′-bis(6-bromohexyl)fluorene 1H NMR 光譜圖(400 MHz, CDCl3)
圖 62 F1 1H NMR 光譜圖(400 MHz, d6-DMSO)
圖 63 F1 13C NMR 光譜圖(125 MHz, d6-DMSO)
圖 64 F2 1H NMR 光譜圖(400 MHz, D2O)
圖 65 F2 13C NMR 光譜圖(100 MHz, D2O)
圖 66 2-(2-bromothiophen-3-yl)ethanol 1H NMR 光譜圖(400 MHz, CDCl3)
圖 67 2-(2-bromothiophen-3-yl)ethanol 13C NMR 光譜圖(100 MHz, CDCl3)
圖 68 2-bromo-3-(2-(6-bromohexyloxy)ethyl)thiophene 1H NMR 光譜圖(400 MHz, CDCl3)
圖 69 2-bromo-3-(2-(6-bromohexyloxy)ethyl)thiophene 13C NMR 光譜圖(100 MHz, CDCl3)
圖 70 T1 1H NMR 光譜圖(400 MHz, D2O)
圖 71 T1 13C NMR 光譜圖(100 MHz, D2O)
圖 72 T2 1H NMR 光譜圖(400 MHz, D2O)
圖 73 T2 13C NMR 光譜圖(100 MHz, D2O)
圖 74 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene 1H NMR 光譜圖(400 MHz, CDCl3)
圖 75 2,7-dibromo-9,9-bis(6-bromohexyl)-9H-fluorene 13C NMR 光譜圖(100 MHz, CDCl3)
圖 76 聚合產物 PF1 (m-TPPTs) 1H NMR 光譜圖(400 MHz, D2O)
圖 77 聚合產物 PF1 (pyrimidine) 1H NMR 光譜圖(400 MHz, D2O)
圖 78 聚合產物 PF2 (m-TPPTs) 1H NMR 光譜圖(400 MHz, D2O)
圖 79 聚合產物 PF2 (pyrimidine) 1H NMR 光譜圖(400 MHz, D2O)
圖 80 聚合產物 PT1 (m-TPPTs) 1H NMR 光譜圖(400 MHz, D2O)
圖 81 聚合產物 PT1 (pyrimidine) 1H NMR 光譜圖(400 MHz, D2O)
圖 82 聚合產物 PT2 (m-TPPTs) 1H NMR 光譜圖(400 MHz, D2O)
圖 83 聚合產物 PT2 (pyrimidine) 1H NMR 光譜圖(400 MHz, D2O)
圖 84 SPF 1H NMR 光譜圖(400 MHz, CDCl3)
圖 85 SPF1 1H NMR 光譜圖(400 MHz, D2O)
圖 86 F1 之高解析質譜圖(HRESI-MS)
圖 87 F2 之高解析質譜圖(HRESI-MS)
圖 88 T1 之高解析質譜圖(HRESI-MS)
圖 89 T2 之高解析質譜圖(HRESI-MS)
Cartesian coordinates (Å) of the Gaussian wb97xd/6-311G(d,p)/SMD=water optimized structure:
4 thiophene units with sulfonate functional groups
C -2.70743000 -1.82538900 6.23744300
C 1.35405600 6.05615700 1.13119500
C -6.16316200 -4.84543700 2.85279200
H 6.16693400 3.81287900 -3.12928800