化合物 14a~14f 之合成

1-Ethoxy-2,3-difluorobenzene (9a) 1,2-Difluoro-3-propoxybenzene (9b) 1-Butoxy-2,3-difluorobenzene (9c)

以 9a 為例，將 2,3-difluorophenol ( 5.0 g，38.4 mmol )和 potasium carbonate (10.6 g， 76.9 mmol)放入 250 mL 之雙頸瓶中，與 75 mL 丙 酮混合後，在氮氣下加熱迴流30 分鐘，緩慢加入 bromoethane (8.4 g，

76.9 mmol)，繼續通氮氣加熱迴流反應 48 小時。反應結束後，降溫 並濃縮，以乙醚和蒸餾水進行萃取，以飽和氯化鈉水溶液清洗有機 層，並以無水硫酸鎂乾燥之，經濃縮後得淡黃色液體，6.0 g，產率 99%。9b，9c 的合成步驟和 9a 相同。

9a -產率 99%。MS (GC-MS) m/z:158。 ¹H NMR (CDCl₃, TMS, 300 MHz): δ 6.92~6.84 (m, 1H, aromatic proton), 6.70~6.61 (m, 2H, aromatic protons), 4.07~4.00 (q, 2H, -Ph-O-CH₂-CH₃), 1.37~1.34 (t, 3H, -Ph-O -CH2-CH3). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 153.98, 149.71, 142.46, 122.97, 109.19, 65.18, 14.55。

9b -產率 99%。MS (GC-MS) m/z:172。¹H NMR (CDCl3, TMS, 300 MHz): δ 6.98~6.90 (m, 1H, aromatic proton), 6.76~6.68 (m, 2H, aromatic protons), 4.00~3.95 (t, 2H, -Ph-O-CH2-CH2 -CH3), 1.89~1.77 (m, 2H, -Ph-O-CH₂-CH₂-CH₃), 1.06~1.01 (t, 3H, -Ph-O-CH₂-CH₂-CH₃). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 151.37, 149.77, 141.39, 123.05, 109.69,

9c -產率 99%。MS (GC-MS) m/z:186。 ¹H NMR (CDCl3, TMS, 300 MHz): δ 6.95~6.89 (m, 1H, aromatic proton), 6.76~6.68 (m, 2H, aromatic protons), 4.09~4.00 (t, 2H, -Ph-O-CH2-CH2 -CH3), 1.83~1.73 (m, -Ph-O-CH₂-CH₂-CH₂-CH₃), 1.52~1.45 (m, 2H, -Ph-O-CH₂-CH₂-CH₂ CH3), 0.99~0.94 (t, 3H, -Ph-O-CH2-CH2-CH2-CH3). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 149.90, 148.86, 141.43, 123.03, 109.74, 108.83, 69.49, 31.15, 19.08, 13.73。

1-Ethoxy-2,3-difluoro-4-iodobenzene (10a) 2,3-Difluoro-1-iodo-4-propoxybenzene (10b) 1-Butoxy-2,3-difluoro-4-iodobenzene (10c)

以 10a 為例，將 periodic acid (3.2 g，13.9 mmol)溶於 20 mL 之 methanol 中，在室溫下劇烈攪拌 20 分鐘後加入 iodine (7.1 g，27.8 mmol)，繼續攪拌 10 分鐘後再加入 1-Ethoxy-2,3-difluorobenzene (9a) (5.5 g，34.8 mmol)，在氮氣下加熱迴流 12 小時。反應結束後，經冷 卻濃縮，以乙醚和飽和硫代硫酸鈉水溶液進行萃取，以飽和氯化鈉水 溶液清洗有機層，並以無水硫酸鎂乾燥之，過濾濃縮後，得深棕色液 體，9.85 g，產率 99%。10b，10c 的合成步驟和 10a 相同。

10a -產率 99%。MS (GC-MS) m/z:285。 ¹H NMR (CDCl₃, TMS, 300 MHz): δ 7.37~7.31 (m, 1H, aromatic proton), 6.57~6.51 (m, 1H, aromatic proton), 4.11~4.04 (q, -Ph-O-CH₂-CH₃), 1.45~1.40 (t, 3H, -Ph-O-CH -CH ). ¹³C NMR (CDCl , TMS, 75 MHz): δ 150.98, 148.91,

141.16, 131.87, 111.38, 65.82, 15.60.

10b -產率為 99%。 MS (GC-MS) m/z:299。 ¹H NMR (CDCl₃, TMS, 300 MHz): δ 7.34~7.28 (m, 1H, aromatic proton), 6.56~6.49 (m, 1H, aromatic proton), 3.96~3.92 (t, 2H, -Ph-O-CH₂-CH₂-CH₃), 1.83~1.77 (m, 2H, -Ph-O-CH2-CH2-CH3), 1.02~0.98 (t, 3H, -Ph-O-CH2-CH2-CH3). ¹³C NMR (CDCl₃, TMS, 75 MHz): δ 150.82, 149.11, 141.04, 131.78, 111.33, 71.26, 70.44, 22.33, 10.21.

10c -產率為 99%。 MS (GC-MS) m/z:312。 ¹H NMR (CDCl3, TMS, 300 MHz): δ 7.34~7.30 (m, 1H, aromatic proton), 6.59~6.50 (m, 1H, aromatic proton), 4.01~3.97 (t, 2H, -Ph-O-CH2-CH2-CH3), 1.81~1.72 (m, -Ph-O-CH₂-CH₂-CH₂-CH₃,), 1.54~1.46 (m, 2H, -Ph-O-CH₂-CH₂-CH₂ -CH3), 0.98~0.93 (t, 3H, -Ph -O-CH2-CH2-CH2-CH3). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 150.83, 149.17, 141.10, 131.81, 111.35, 70.46, 69.58, 31.00, 19.03, 13.69.

4-Ethyl-4’-iodobiphenyl (11a) 4-Iodo-4’-propylbiphenyl (11b) 4-n-Butyl-4’-iodo biphenyl (11c) 4-Iodo-4’-n-pentyl biphenyl (11d) 4-n-Hexyl-4’-iodo biphenyl (11e)

以 11c為例，在 250 mL之雙頸瓶中放入iodic acid (16.3 g, 71.3 mmol)之冰醋酸(60.4 mL)中，於室溫下攪拌 20 分鐘，加入I2/H2O (27.1 g，107.0 mmol，蒸餾水 25 mL)，室溫下攪拌 15 分鐘後，依序加入濃

118.87 mmol，CCl4 5.6 mL)，在氮氣下加熱迴流 12 小時。反應結束 後，經濃縮冷卻後，以乙醚與飽和硫代硫酸鈉水溶液進行萃取，以飽 和氯化鈉水溶液清洗有機層，並以無水硫酸鎂乾燥之，過濾並濃縮，

以甲醇進行再沉澱。將溶液抽氣過濾，以冰甲醇洗固體，真空乾燥後 得白色固體，34.2 g，產率 86%。11a、11b、11d和 11e的合成步驟和 11c相同。

11a – 熔點：120 ^oC。率為 88%。MS (GC-MS) m/z:308。¹H NMR (CDCl₃, TMS, 300 MHz): δ 7.73~7.46 (d, 2H, aromatic protons), 7.76~7.48 (m, 2H, aromatic protons), 7.33~7.25 (m, 4H, aromatic protons), 2.73~2.64 (q, 2H, –Ph-CH₂-CH_3,), 1.30~1.24 (t, 3H, –Ph-CH2-CH3,). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 143.93, 140.67, 137.76, 137.40, 128.84, 128.42, 126.80, 92.59, 28.51, 15.54.

11b -熔點：132 ^oC。產率為 89%。MS (GC-MS) m/z:322。¹H NMR (CDCl3, TMS, 300 MHz): δ 7.76~7.48 (d, 2H, aromatic protons), 7.73~7.45 (m, 2H, aromatic protons), 7.34~7.23 (m, 4H, aromatic protons), 2.65~2.60 (t, 2H, –Ph-CH2-CH2-CH3), 1.72~1.59 (m, 2H, –Ph-CH₂-CH₂-CH₃), 1.00~0.95 (t, 3H, –Ph-CH₂-CH₃). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 142.37, 140.66, 137.75, 137.56, 129.01, 128.82, 126.68, 92.58, 37.67, 24.50, 13.85.

11c -熔點：144 ^oC。產率 86%。MS (GC-MS) m/z:336。 ¹H NMR (CDCl3, TMS, 300 MHz): δ 7.74~7.46 (d, 2H, aromatic protons), 7.72~7.43 (d, 2H, aromatic protons), 7.32~7.28 (m, 4H, aromatic protons),

2H, –Ph-CH₂-CH₂-CH₂ -CH₃), 1.42~1.32 (m, 2H, –Ph-CH₂-CH₂ CH2-CH3), 0.95~0.90 (t, 3H, –Ph-CH2-CH2-CH2-CH3). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 142.20, 140.08, 137.75, 136.88, 128.96, 128.83, 126.70, 92.60, 35.28, 33.59, 22.37, 13.95。

11d -熔點：155 ^oC。產率為 86%。MS (GC-MS) m/z:350。¹H NMR (CDCl3, TMS, 300 MHz): δ 7.77~7.46 (d, 2H, aromatic protons), 7.74~7.43 (d, 2H, aromatic protons), 7.35~7.21 (m, 4H, aromatic protons), 2.64~2.59 (t, 2H, –Ph-CH2-CH2-CH2–CH2-CH3), 1.62~1.53 (m, 2H, –Ph-CH₂-CH₂-CH₂-CH₂-CH₃), 1.34~1.30 (m, 4H, –Ph-CH₂-CH₂ (CH2)2-CH3), 0.92~0.88 (t, 3H, –Ph-CH2 -CH2-(CH2)2 -CH3). ¹³C NMR (CDCl₃, TMS, 75 MHz): δ 142.65, 140.66, 137.96, 137.74, 128.95, 128.82, 126.70, 92.57, 35.56, 31.51, 31.13, 22.53, 13.98。

11e -熔點：168 ^oC。產率為 87.2%。MS (GC-MS) m/z:364。¹H NMR (CDCl3, TMS, 300 MHz): δ 7.73~7.46 (d, 2H, aromatic protons), 7.71~7.44 (d, 2H, aromatic protons), 7.31~7.21 (m, 4H, aromatic protons), 2.64~2.59 (t, 2H, -Ph-CH2-CH2-(CH2)3-CH3,), 1.64~1.57 (m, 2H, -Ph-CH₂-CH₂-(CH₂)₃-CH₃), 1.37~1.26 (m, 6H, -Ph-CH₂-CH₂-(CH₂)₃ CH3), 0.92~0.85 (t, 3H, -Ph-CH2-CH2-(CH2)3-CH3). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 142.66, 140.68, 137.76, 137.31, 128.95, 128.83, 126.90, 92.57, 35.61, 31.72, 31.42, 29.01, 22.60, 14.09.

4-(4’-ethylbiphenyl-4-yl)-2-methylbut-3-yn-2-ol (12a) 2-Methyl-4-(4’-propylbiphenyl-4-yl)but-3-yn-2-ol (12b)

2-methyl-4-(4’-pentylbiphenyl-4-yl)but-3-yn-2-ol (12d) 4-(4’-hexylbiphenyl-4-yl)-2-methylbut-3-yn-2-ol (12e)

以 12c 為 例 ， 將 4-n-butyl-4’-iodobiphenyl (11c) (25 g ， 74.4 mmol)，triphenylphosphine (2.0 g， 7.4 mmol)，copper(I) iodide (1.4 g，

7.4 mmol)與Pd(PPh3)2Cl2 (5.2 g，7.4 mmol)加入裝有 240 mL acetonitrile 及 60 mL triethylamine (v/v=4:1) 之 雙 頸 瓶 中 ， 緩 慢 滴 入 2-methylbut-3-yn-2-ol (6.9 g，81.8 mmol)，於室溫下通氮氣反應 12 小 時。反應結束後，抽氣過濾分離固態鹽類得到澄清有機溶液，經濃縮 後以飽和氯化銨水溶液與乙醚進行萃取，以飽和氯化鈉水溶液清洗有 機層，並以無水硫酸鎂乾燥之。經濃縮後得到固體粗產物，再以管柱 層析(silica gel，EA/n-hexane＝1:10)為沖提液純化後，以n-hexane進行 再結晶，得到黃色固體，17.83 g，產率 82 %。12a、12b、12d和 12e 的合成步驟和12c相同。

12a -熔點：283 ^oC。產率為 85%。MS (GC-MS) m/z:278。 ¹H NMR (CDCl₃, TMS, 300 MHz): δ 7.55~7.45 (m, 6H, aromatic protons), 7.29~7.26 (d, 2H, aromatic protons), 2.74~2.66 (t, 2H, -Ph-CH2-CH3), 2.05 (br, 1H, -C(CH₃)₂ -OH), 1.64 (s, 6H, - C(CH₃)₂OH), 1.30~1.25 (t, 3H, -Ph-CH2 -CH3). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 143.87, 140.94, 137.66, 132.01, 128.37, 126.91, 126.72, 121.27, 94.23, 82.10, 65.68, 28.51, 15.55.

12b -熔點：299 ^oC。產率為 86%。MS (GC-MS) m/z:264。 ¹H NMR

(CDCl₃, TMS, 300 MHz): δ 7.54~7.45 (m, 6H, aromatic protons), 7.26~7.23 (d, 2H, aromatic protons), 2.65~2.60 (t, 2H, -Ph-CH₂-CH₂-CH₃), 2.05 (br, 1H, -C(CH₃)₂ -OH), 1.71~1.61 (m, 2H, -Ph-CH2-CH2-CH3), 1.64 (s, 6H, -C(CH3)2OH), 0.99~0.94 (t, 3H, -Ph-CH₂-CH₃). ¹³C NMR (CDCl₃, TMS, 75 MHz): δ 142.32, 140.95, 137.63, 132.01, 128.97, 127.00, 126.70, 121.26, 94.23, 82.10, 65.68, 37.68, 31.52, 24.52, 13.84.

12c -熔點：305 ^oC。產率 82 %。MS (GC-MS) m/z:292。 ¹H NMR MHz): δ 142.49, 140.87, 137.51, 132.29, 129.07, 126.76, 126.65, 94.23, 82.05, 65.63, 35.23, 33.55, 31.12, 30.98, 22.33, 13.91。

12d -熔點：321 ^oC。產率為 85%。MS (GC-MS) m/z:306。 ¹H NMR (CDCl3, TMS, 300 MHz): δ 7.54~7.42 (m, 6H, aromatic protons), 7.23~7.21 (d, 2H, aromatic protons), 2.64~2.59 (t, 2H, –Ph CH2-CH2-(CH2)2-CH3), 2.04 (br, 1H, -C(CH3)2OH), 1.67~1.51 (m, 2H, –Ph-CH₂-CH₂-(CH₂)₂-CH₃), 1.61 (s, 6H, -C(CH₃)₂OH), 1.34 ~1.30 (m, 4H, –Ph-CH2-CH2-(CH2)2-CH3), 0.90~0.86 (t, 3H, –Ph-CH2-CH2

-(CH₂)₂-CH₃). ¹³C NMR (CDCl₃, TMS, 75 MHz): δ 142.58, 140.96, 137.64, 132.33, 129.21, 127.06, 126.80, 94.07, 82.03, 65.68, 35.56.31.51, 31.14, 31.03, 26.57, 22.53, 14.02。

12e -熔點：331 ^oC。產率為 87%。MS (GC-MS) m/z:320。 ¹H NMR (CDCl₃, TMS, 300 MHz): δ 7.53~7.44 (m, 6H, aromatic protons), 7.24~7.22 (d, 2H, aromatic protons), 2.65~2.60 (t, 2H, -Ph-CH2

CH₂-(CH₂)₃-CH₃), 2.00 (br, 1H, -C(CH₃)₂OH), 1.64~1.57 (m, 6H for -C(CH₃)₂OH，and 2H for –Ph -CH₂-CH₂-(CH₂)₃-CH₃), 1.37~1.26 (m, 6H, -Ph-CH2-CH2-(CH2)3-CH3), 0.89~0.85 (t, 3H, -Ph-CH2-CH2-(CH2)3-CH3).

13C NMR (CDCl₃, TMS, 75 MHz): δ 142.60, 140.93, 137.56, 132.00, 128.91, 126.80, 126.70, 121.22, 94.19, 82.10, 65.68, 35.60, 31.72, 31.51, 31.44, 29.01, 22.61, 14,10。

4-Ethyl-4’-ethynylbiphenyl (13a) 4-Ethynyl-4’-propylbiphenyl (13b) 4-Butyl-4’-ethynylbiphenyl (13c) 4-Ethynyl-4’-pentylbiphenyl (13d) 4-Ethynyl-4’-hexylbiphenyl (13e)

以 13c 為 例 ， 於 乾 燥 的 250 mL 雙 頸 瓶 中 置 入 化 合 物 4- (4'-butylbiphenyl-4-yl)-2-methylbut-3-yn-2-ol (12c) (10.0 g，34.2 mmol )，potassium hydroxide (3.8 g，68.5 mmol) 與 130 mL 1,4-dioxane 混 合後架置Dean-Stark 裝置，在氮氣下加熱迴流 12 小時。反應結束後，

反應瓶降至室溫後過濾並濃縮，以乙醚與飽和食鹽水進行萃取，再對 移除的水層以乙醚做反萃取，有機層以無水硫酸鎂乾燥濃縮可得一固 體粗產物，再以管柱層析(silica gel，EA/n-hexane＝1:5)為沖提液純化

後得到黃色固體，7.26 g，產率 90 %。13a、13b、13d 和 13e 的合成 步驟和13c 相同。

13a -熔點：129 ^oC。產率為 90%。MS (GC-MS) m/z:206。¹H NMR (CDCl₃, TMS, 300 MHz): δ 7.51~7.40 (m, 6H, aromatic protons), 7.22~7.18 (d, 2H, aromatic protons), 3.04 (s, 1H, -C≡C-H), 2.66~2.59 (q, 2H, -Ph-CH₂ -CH₃), 1.23~1.18 (t, 3H, -Ph-CH₂-CH₃). ¹³C NMR (CDCl₃, TMS, 75 MHz): δ 143.97, 141.54, 137.59, 132.51, 128.40, 126.96, 126.80, 120.61, 83.63, 28.52, 15.54.

13b -熔點：141 ^oC。產率為 91.5%。MS (GC-MS) m/z:220。¹H NMR (CDCl3, TMS, 300 MHz): δ 7.55~7.49 (m, 6H, aromatic protons), 7.28~7.25 (d, 2H, aromatic protons), 3.12 (s, 1H, -C≡C-H), 2.66~2.61 (t, 2H, -Ph-CH2 -CH2-CH3,), 1.74~1.63 (m, 2H, -Ph-CH2 -CH2-CH2-CH3), 1.00~0.96 (t, 3H, -Ph-CH₂-CH₂-CH₂-CH₃). ¹³C NMR (CDCl₃, TMS, 75 MHz): δ 142.42, 141.53, 137.56, 132.50, 128.99, 126.81, 120.60, 83.63, 37.67, 24.50, 13.84.

13c -熔點：155 ^oC。產率 90 %。MS (GC-MS) m/z:234。 ¹H NMR (CDCl3, TMS, 300 MHz): δ 7.47~7.40 (m, 6H, aromatic protons), 7.20~7.17 (d, 2H, aromatic protons), 3.04 (s, 1H, -C≡C-H), 2.60~2.55 (t, 2H, -Ph-CH2 -CH2-CH3), 1.59~1.49 (m, 2H, -Ph-CH2-CH2-CH2-CH3), 1.35~1.21 (m, 2H, -Ph-CH₂-CH₂-CH₂-CH₃), 0.89~0.85 (t, 3H, -Ph-CH2-CH2-CH2-CH3). ¹³C NMR (CDCl3, TMS, 75 MHz): δ 142.65, 140.08, 137.51, 133.59, 128.69, 126.77, 120.58, 83.63, 77.49, 33.59, 32.72, 22.31, 13.95。

13d -熔點：169 ^oC。產率為 89%。MS (GC-MS) m/z:248。¹H NMR (CDCl₃, TMS, 300 MHz): δ 7.55~7.45 (m, 6H, aromatic protons), 7.25~7.17 (d, 2H, aromatic protons), 3.10 (s, 1H, -C≡C-H), 2.65~2.60 (t, 2H, –Ph-CH₂-CH₂-(CH₂)₂-CH₃), 1.64~1.60 (m, 2H, –Ph-CH₂-CH₂-(CH₂)₂ CH3), 1.35~1.27 (m, 4H, –Ph-CH2-CH2-(CH2)2-CH3), 0.90~0.86 (t, 3H, –Ph -CH₂-CH₂-(CH₂)₂-CH₃). ¹³C NMR (CDCl₃, TMS, 75 MHz): δ 142.54, 141.37, 137.34, 132.39, 128.60, 126.73, 120.51, 83.54. 77.59, 31.41, 31.02, 28.16, 22.44, 13.95。

13e -熔點：180 ^oC。產率為 90%。MS (GC-MS) m/z:262。¹H NMR (CDCl₃, TMS, 300 MHz): δ 7.50~7.41 (m, 6H, aromatic protons), 7.20~7.17 (d, 2H, aromatic protons), 3.04 (s, 1H, -C≡C-H), 2.60~2.54 (t, 2H, -Ph-CH₂-CH₂-(CH₂)₃-CH₃), 1.62~1.52 (m, 2H, -Ph-CH₂-CH₂-(CH₂)₃ CH3), 1.33~1.18 (m, 6H, -Ph-CH2-CH2-(CH2)3-CH), 0.84~0.80 (t, 3H, -Ph-CH₂-CH₂ -(CH₂)₃-CH₃). ¹³C NMR (CDCl₃, TMS, 75 MHz): δ 142.70, 141,53, 137.50, 132.49, 128.93, 126.85, 126.78, 120.57, 83.63, 77.56, 35.61, 31.72, 31.43, 29.69, 22.60, 14.09。

4-Butyl-4'-((4-ethoxy-2,3-difluorophenyl)ethynyl)biphenyl (14a)

11.2 mmol)，copper(I) iodide (0.4 g，2.2 mmol)與triphenylphosphine (0.6 g，2.2 mmol)置於 250mL之雙頸瓶中，以 5 mL acetonitrile與 60 mL triethylamine溶解後，在氮氣下快速加入Pd(PPh3)2Cl2 (1.6 g，2.2 mmol)，室溫下於氮氣中攪拌 20 分鐘後，緩慢滴入 4-Butyl-4'- ethynylbiphenyl (13c) (2.9 g，12.3 mmol)之acetonitrile溶液 10 mL，在 室溫下通氮氣反應 12 小時。反應結束後，將溶液抽氣過濾，以乙醚 清洗固體，濃縮濾液後，以乙醚和飽和氯化銨水溶液進行萃取，水層 再以乙醚作反萃取，有機層以飽和氯化鈉水溶液清洗有機層，並以無 水硫酸鎂乾燥之，過濾並濃縮後，進行管柱層析(silica gel，n-hexane)，

所得固體以n-hexane進行再結晶，過濾母液後得白色固體 14a，2.7 g，

產率61.8%。14b、14c、14d與 14e之實驗步驟與 14a相同。

14a -產率 61.8%。HRMS of C26H24OF2: calcd: 390.1795, found:

390.1795。¹H-NMR(CDCl3, TMS, 300 MHz): δ 7.57~7.24 (d, 2H, aromatic protons), 7.52~7.25 (m, 6H, aromatic protons), 7.21~7.16 (d, 1H, aromatic protons), 6.89~6.67 (m, 1H, aromatic proton), 4.17~4.10 (q, 2H, -Ph-O-CH₂-CH₃), 2.66~2.61 (t, 2H, -Ph-CH₂-CH₂-CH₂ -CH₃), 1.68~1.57 (m, 2H, -Ph-CH2-CH2 -CH2-CH3), 1.51~1.46 (t, 3H, -Ph-OCH2-CH3), 1.43~1.36 (m, 2H, -Ph-CH₂-CH₂-CH₂ -CH₃) , 0.95~0.90 (t, 3H, -Ph-CH2-CH2-CH2-CH3).¹³C-NMR(CDCl3, TMS, 75 MHz): δ 153.3, 150.0, 142.6, 141.2, 139.8, 132.9, 131.2, 128.9, 128.6, 127.0, 126.8,

14b -產率為 59%。HRMS of C28H28OF2: calcd: 418.2108, found:

418.2105。¹H-NMR(CDCl3, TMS, 300 MHz): δ 7.57~7.49 (m, 6H, aromatic protons), 7.26~7.24 (d, 2H, aromatic protons) , 7.21~7.16 (m, 1H, aromatic proton), 6.71~6.66 (m, 1H, aromatic proton) , 4.16~4.09 (q, 2H, -Ph-OCH₂-CH₃) , 2.66~2.61 (t, 2H, -Ph-CH₂-CH₂-(CH₂)₃-CH₃) , 1.66~1.59 (m, 2H, -Ph-CH2-CH2 -(CH2)3-CH3) , 1.46~1.41 (t, 3H, -Ph-OCH₂-CH₃) , 1.33~1.25 (m, 6H, -Ph -CH₂-CH₂-(CH₂)₃-CH₃), 0.91~0.87 (t, 3H, -Ph-CH2-CH2-(CH2)3-CH3). ¹³C-NMR(CDCl3, TMS, 75 MHz): δ153.3, 150.9, 142.9, 141.2, 137.5, 132.0, 127.1, 126.9, 121.3, 109.0, 105.6, 93.7, 65.4, 35.6, 31.7, 31.4, 29.0, 22.6, 14.6, 14.1.

14c -產率為 60%。HRMS of C27H26OF2: calcd: 404.1952, found:

404.1953。¹H-NMR(CDCl3, TMS, 300 MHz): δ 7.57~7.49 (m, 6H, aromatic protons), 7.26~7.24 (d, 2H, aromatic protons) , 7.21~7.15 (m, 1H, aromatic proton) , 6.72~6.66 (m, 1H, aromatic proton) , 4.04~3.99 (t, 2H, -Ph-OCH₂-CH₂-CH₃) , 2.66~2.13 (t, 2H, -Ph -CH₂-CH₂-CH₂-CH₃) , 1.91~1.79 (m ， 2H ， -Ph-OCH₂-CH₂ -CH₃), 1.67~1.57 (m, 2H, -Ph-CH2-CH2-CH2-CH3) , 1.46~1.31 (m, 2H, -Ph-CH2-CH2-CH2 C-H3) , 1.09~1.04 (t, 3H, -Ph-OCH₂-CH₂-CH₃) , 0.95~0.90 (t, 3H, -Ph-CH2-CH2-CH2-CH3). ¹³C -NMR(CDCl3, TMS, 75 MHz): δ 153.3, 150.9, 142.8, 141.9, 137.4, 132.9, 128.9, 127.1, 126.8, 121.4, 109.0, 103.1, 92.5, 66.2, 35.3, 33.6, 29.7, 22.4, 14.0.

14d -產率為 58%。HRMS of C29H30OF2: calcd: 432.2265, found:

432.2264。¹H-NMR(CDCl , TMS, 300 MHz): δ 7.58~7.44 (m, 6H,

aromatic protons), 7.20~7.19 (d, 2H, aromatic protons) , 7.16~7.10 (m, 1H, aromatic proton) , 6.67~6.61 (m, 1H, aromatic proton) , 3.98~3.94 (t, 2H, -Ph-OCH₂-CH₂-CH₃) , 2.60~2.55 (t, 2H, -Ph-CH₂-CH₂-(CH₂)₃-CH₃) , 1.83~1.74 (m, 2H, -Ph-OCH₂-CH₂ -CH₃) , 1.60~1.53 (m ， 2H, -Ph-CH2-CH2-(CH2)3 -CH3) , 1.30~1.09 (m, 6H, -Ph-CH2-CH2-(CH2)3

-CH₃) , 1.02~0.97 (t, 3H, -Ph-OCH₂-CH₂-CH₃) , 0.84~0.80 (t, 3H, -Ph-CH2-CH2 -(CH2)3-CH3). ¹³C-NMR(CDCl3, TMS, 75 MHz): δ149.2, 147.8, 142.7, 141.2, 137.6, 132.0, 128.9, 126.8, 123.1, 121.4, 109.1, 103.1, 92.5, 66.2, 35.6, 31.7, 31.4, 29.0, 22.6, 22.4, 14.1, 10.3.

14e - 產率為 57.3%。HRMS of C29H30OF2: calcd: 432.2265, found: 432.2265。¹H-NMR(CDCl3, TMS, 300 MHz): δ 7.51~7.44 (m, 6H, aromatic protons), 7.18~7.16 (d, 2H, aromatic protons), 7.116~7.10 (m, 1H, aromatic proton), 6.67~6.61 (m, 1H, aromatic proton), 4.02~3.98 (t, 2H，-Ph-OCH2-CH2-CH2-CH3), 2.60~2.55 (t, 2H, -Ph-CH2-CH2-(CH2)2 126.8, 121.3, 109.1, 92.8, 69.5, 35.6, 31.5, 31.2, 31.1, 29.7, 22.5, 19.1, 14.0, 13.8.

14f -產率為 58%。HRMS of C30H32OF2: calcd: 446.2421, found:

446.2424。¹H-NMR(CDCl₃, TMS, 300 MHz): δ 7.51~7.44 (m, 6H,

aromatic proton), 6.67~6.61 (m, 1H, aromatic proton), 4.02~3.98 (t, 2H, -Ph-OCH2-CH2-CH2-CH3), 2.60~2.55 (t, 2H, -Ph-CH2-CH2-(CH2)3-CH3), 1.78~1.70 (m, 2H, -Ph-OCH₂-CH₂ -CH₂-CH₃), 1.60~1.50 (m, 2H, -Ph-CH2-CH2-(CH2)2-CH3), 1.48~1.41 (m, 2H, -Ph-OCH2-CH2-CH2-CH3), 1.32~1.18 (m, 6H, -Ph-CH₂-CH₂-(CH₂)₃ -CH₃), 0.94~0.90 (t, 3H, -Ph-OCH2-CH2-CH2-CH3), 0.84~0.80 (t, 3H, -Ph-CH2-CH2-(CH2)3-CH3).

13C-NMR (CDCl₃, TMS, 75 MHz): δ142.7, 141.2, 137.5, 132.0, 128.9, 127.0, 126.8, 121.4, 109.1, 92.8, 69.5, 35.6, 31.7, 31.4, 31.1, 29.0, 22.6, 19.1, 14.1, 13.8.