第七章 實驗部分
Scheme 5- 7 閉環機制的比較
在本反應系統中，目前已觀察到腈正離子-烯烴環化反應的發生，但仍無法達 成目標分子 Aristoteline 的合成，未來仍然需要繼續嘗試。除此之外，此一方向之 研究也需要開發更多能應用腈正離子-烯烴環化反應的分子骨架設計，除了在本研 究中所提出的喹啉、螺環與[3,3,1]壬烯產物之外，應仍有可合成之結構，未來還有 很長的路要走。
第六章 結論
根據腈正離子-烯烴環化反應，本研究中也提出合成天然物的應用，雖然到目 前為止在測試中僅能得到副產物，但在反應過程中，確實能觀察到腈正離子與烯烴 的環化，此結果展現出此一策略具有可行性，除了此一應用外，也期待未來能將腈 正離子-烯烴環化合成策略應用於其他分子骨架的合成。
第七章 實驗部分
7.1 實驗儀器
1. 核磁共振光譜(nuclear magnetic resonance spectroscopy)
本 篇 論 文 中 所 提 及 的 核 磁 共 振 氫 譜 (1H NMR) 是 以 Bruker AVANCE-400 (400.13MHz)所測得，化學位移(chemical shift, δ)以 ppm 為單位，以溶劑訊號或 四甲基矽烷(tetramethylsilane, TMS)之δ= 0 作為核磁共振儀的內標值；核磁共 振碳譜(13C NMR)，是以 Bruker AVANCE-400 (100.62 MHz)所測得，化學位移 以 ppm 為單位，耦合常數(coupling constant)以 J 來表示，其單位為 Hz，而分裂 形式(splitting pattern)定義如下：s，單峰(singlet)；d，雙峰(doublet)；t，三重峰 (triplet)；q，四重峰(quartet)；m，多重峰(multiplet)；br，寬峰(broad)。
2. 質譜分析(mass spectrum analysis)
ESI-Mass 之機型為 Water LCT Premier XE，將待測樣品溶於乙腈，注入量測管 柱內鑑定有機物之荷質比。
3. 管柱色層分析(column chromatography)
一般有機物的重力管柱層析以 Merck Silica gel 60 (40 – 63 μM)填充。
4. 薄層色層分析(thin layer chromatography, TLC)
將樣品以毛細管點於 Merck Art. 5544 precoated sheet 薄片後至於展開液中，再 以 254 nm 紫外光燈檢視。
7.2 試劑來源與前處理
1. 溶劑之純化
(a) 無水乙腈：加入氫化鈣(calcium hydride)，加熱回流數小時後於氮氣下蒸餾 純化，並保存於活化過之 3Å 分子篩中。
(b) 無水二氯甲烷：取自 MBRAUN Solvent Purification Systems (MB-SPS-800) ， 並保存於活化過之 3Å 分子篩中。
(c) 無水甲苯：取自 MBRAUN Solvent Purification Systems (MB-SPS-800)，並保 存於活化過之 3Å 分子篩中。
2. 試劑來源
其他溶劑與試劑一般是直接由藥品供應商(Sigma-Aldrich Co., Acros Organic Co., Alfa Aesar Co., Merck Co. and TCI Co.)所供應之試藥級藥品、溶劑級藥品，如藥 品需要進一步純化或乾燥，則依標準方式處理純化。
7.3 實驗步驟與數據
7.3.1 3,4-氫化喹啉之合成與鑑定
3,4-氫化喹啉的三成分一鍋化合成之反應步驟；
將 aryldiazonium tetrafluoroborate 2 (0.52 mmol)、styrene derivative 3 置於 10 mL 之密封管內，打入無水 nitrile 4 (2 mL)，在 80°C 下反應 2 小時，反應結束後冷卻置
13C NMR (100 MHz, CD3CN): 189.25, 141.84, 133.20, 132.66, 131.39, 130.51, 130.34, 130.11, 129.28, 129.16, 121.80, 38.72, 38.67, 25.72 ppm.
HRMS (ESI-TOF) calcd. for C16H16N(M - BF4) m/z = 222.1283; found: 222.1281.
6-(tert-butyl)-2-methyl-4-phenyl-3,4-dihydroquinolinium tetrafluoroborate (5caa)
得黃色固體 101 mg，產率 68%。mp: 190–191 °C
1H NMR (400 MHz, CD3CN): δ 7.53 – 7.50 (m, 1H, Ar-H), 7.44 – 7.37 (m, 3H, Ar-H), 7.20 – 7.18 (m, 2H, Ar-H), 7.14 (s, 1H, Ar-H), 4.48 (t, J = 8.4 Hz, 1H, -CH), 3.47 – 3.30 (m, 2H, -CH2), 2.62 (s, 3H, -CH3), 1.22 (s, 9H, -C(CH3)3) ppm.
13C NMR (100 MHz, CD3CN): 187.54, 158.18, 141.93, 130.74, 130.59, 130.24, 128.83, 127.43, 126.82, 121.20, 38.68, 38.59, 35.86, 31.21, 25.40 ppm.
HRMS (ESI-TOF) calcd. for C20H24N(M - BF4) m/z = 278.1903; found 278.1914.
13C NMR (100 MHz, CD3CN): 192.42, 140.76, 135.59, 133.20, 132.87, 132.59, 130.48, 129.29, 129.13, 127.18, 127.13, 127.11, 127.07, 125.80, 123.10, 122.48, 38.50, 38.36, 25.89 ppm.
4-(4-Bromophenyl)-2-methyl-3,4-dihydroquinolinium tetrafluoroborate (5aba)
得橘色固體 162 mg，產率 80%。mp: 145-147 °C
1H NMR (400 MHz, CD3CN): δ 12.44 (br, 1H, N-H), 7.56 – 7.42 (m, 5H, Ar-H), 7.16-7.13 (m, 2H, Ar-H), 7.02 (d, J = 7.4 Hz, 1H, Ar-H), 4.50 (t, J = 8.8 Hz, 1H, -CH), 3.47 – 3.29 (m, 2H, -CH2), 2.65 (s, 3H, -CH3) ppm.
13C NMR (100 MHz, CD3CN): 188.70, 140.77, 133.01, 132.77, 132.31, 131.03, 130.32, 129.87, 122.06, 121.45, 38.06, 37.76, 25.31 ppm.
HRMS (ESI-TOF) calcd. for C16H15N79Br(M-BF4): m/z = 300.0388; found: 300.0379.
13C NMR (100 MHz, CD3CN): 188.66, 140.30, 134.00, 132.82, 132.34, 130.72, 130.43, 130.04, 129.92, 129.46, 121.46, 38.16, 37.71, 25.31 ppm.
HRMS (ESI-TOF) calcd. for C16H15N35Cl(M - BF4) m/z = 256.0893; found: 256.0897.
HRMS (ESI-TOF) calcd. for C16H15N37Cl(M - BF4) m/z = 302.0367; found: 302.0369.
4-(4-(chloromethyl)phenyl)-2-methyl-3,4-dihydroquinolinium tetrafluoroborate
13C NMR (100 MHz, CD3CN): 188.71, 141.75, 138.49, 132.73, 132.29, 130.63, 130.42, 129.92, 129.30, 121.42, 46.53, 38.13, 37.99, 25.30 ppm.
HRMS (ESI-TOF) calcd. for C17H17N35Cl((M - BF4): = 270.1050; found: 270.1050.
HRMS (ESI-TOF) calcd. for C17H17N37Cl((M - BF4): = 272.1015; found: 272.1058.
2,4-dimethyl-4-phenyl-3,4-dihydroquinolinium tetrafluoroborate (5aea)
得白色固體 white solid (60 mg, 49%).
1H NMR (400 MHz, CD3CN): δ 7.55 – 7.51 (m, 3H, Ar-H), 7.37 – 7.29 (m, 4H, Ar-H), 7.21 – 7.19 (m, 2H, Ar-H), 3.71 – 3.66 (d, J = 18.8 Hz, 1H, -CHa(Hb)), 3.23 – 3.19 (d, J
= 18.8 Hz, 1H, -C(Ha)Hb), 2.63 (s, 3H, -CH3), 1.72 (s, 3H, -CH3) ppm.
13C NMR (100 MHz, CD3CN): 188.33, 144.81, 135.89, 132.53, 132.44, 129.74, 129.68, 128.65, 128.39, 127.36, 121.70, 44.85, 40.02, 27.39, 25.47 ppm.
mp: 171-172°C
HRMS (ESI-TOF) calcd. for C17H18N((M - BF4): = 236.1439; found: 236.1442.
7.3.2 3-羥基喹啉之合成與鑑定
3,4-氫化喹啉氧化生成 3-羥基喹啉或喹啉酮之反應步驟；
將 3,4-dihydroquinolinium tetrafluoroborate 5 (0.3 mmol)加入飽和碳酸氫鈉水溶 液(5 mL)，以 DCM(5 mL x 3)萃取，合併有機層並加入過量無水硫酸鎂除去有機層 的水分，加入 sodium carbonate (3.0 mmol, 318 mg)在室溫下反應 72 小時，反應結 束後加入飽和 NH4Cl(aq)(5 mL)，以 DCM(10 mL x 2)萃取，合併有機層並加入過量 無水硫酸鎂除去有機層的水分，將溶液旋乾後以管柱層析分離純化(silica gel, 20-40% EtOAc in hexane)，可得相對應的 3-羥基喹啉產物 7 或喹啉酮 8。
3-羥基喹啉的三成分一鍋化合成之反應步驟；
將 aryldiazonium tetrafluoroborate 2 (0.52 mmol)、styrene derivative 3 置於 10 mL 之密封管內，打入無水 nitrile 4 (2 mL)，在 80°C 下反應 2 小時，反應結束後冷卻 置室溫，加入飽和碳酸氫鈉水溶液(5 mL)，以 DCM(5 mL x 3)萃取，合併有機層並 加入過量無水硫酸鎂除去有機層的水分，加入 sodium carbonate (3.0 mmol, 318 mg) 在室溫下反應 72 小時，反應結束後加入飽和 NH4Cl(aq)(5 mL)，以 DCM(10 mL x 2) 萃取，合併有機層，加入過量無水硫酸鎂除水，將溶液旋乾後以管柱層析分離純化 (silica gel, 20-40% EtOAc in hexane)，可得相對應的 3-羥基喹啉產物 7。
2-methyl-4-phenylquinolin-3-ol (7aaa) 128.50, 128.21, 127.85, 127.50, 125.79, 125.74, 124.13, 21.24 ppm.
HRMS (ESI-TOF) calcd. for C16H13NO(M+H+): = 236.1075; found: 236.1074.
4-(4-chlorophenyl)-2-methylquinolin-3-ol (7aca) 128.29, 127.28, 127.19, 125.96, 125.85, 123.88, 21.24 ppm.
HRMS (ESI-TOF) calcd. for C16H1335ClNO(M+H+): = 270.0680; found: 270.0695. 128.99, 128.25, 128.19, 127.38, 125.84, 124.02, 46.00, 21.25 ppm.
HRMS (ESI-TOF) calcd. for C17H1435ClNO(M+H+): = 284.0842; found: 284.0840.
HRMS (ESI-TOF) calcd. for C17H1437ClNO(M+H+): = 286.0813; found: 286.0807.
2,4-diphenylquinolin-3-ol (7aab) 129.1, 128.4, 127.6, 126.8, 124.5 ppm.
HRMS (ESI-TOF) calcd. for C21H16NO(M+H+): = 298.1232; found: 298.1242. 128.4, 126.6, 126.3, 125.6, 124.3, 11.9, 9.5 ppm.
HRMS (ESI-TOF) calcd. for C18H16NO(M+H+): = 262.1232; found 262.1232.
2,6-dimethyl-4-phenylquinolin-3-ol (7baa) 128.50, 128.28, 127.86, 127.79, 127.45, 122.93, 21.34, 21.10 ppm.
HRMS (ESI-TOF) calcd. for C17H16NO(M+H+): = 250.1232; found 250.1239.
2,4-dimethyl-4-phenylquinolin-3(4H)-one (8aea)
得黃色油狀物 52 mg，70%。
1H NMR (400 MHz, CDCl3): δ 7.60 (d, J = 7.2 Hz, 1H, H), 7.46 – 7.42 (m, 1H, Ar-H), 7.46 (m, 1H, Ar-Ar-H), 7.37 – 7.33 (m, 1H, Ar-Ar-H), 7.29 – 7.23(m, 4H, Ar-Ar-H), 7.03 – 7.01 (m, 2H, - Ar-H), 2.28 (s, 3H, -CH3), 1.89 (s, 3H, -CH3) ppm.
13C NMR (100 MHz, CDCl3): δ 196.44, 160.66, 140.69, 140.58, 136.82, 129.40, 128.77, 128.73, 127.85, 127.59, 127.17, 53.56, 23.26, 20.01 ppm.
HRMS (ESI-TOF) calcd. for C17H14NO(M+H+): = 250.1232; found: 250.1243.
7.3.3 高烯丙基醇與松油醇的合成 9-(2-methylallyl)-9H-fluoren-9-ol (11)
將 magnesium turnings (1.5 g, 60 mmol)置於經烘箱除水的 100 mL 雙頸瓶中，
抽灌氮氣數次後，打入無水乙醚(10 mL)。在 0 °C 下逐滴加入 methylallyl chloride (5.54 g, 60 mmol)，慢慢以熱水加熱直到 Grignard 試劑被起始為止，將反應溶液立 即以冰浴降至 0 °C，逐滴加入 fluorenone (3.6 g, 20 mmol)的無水乙醚(30 mL)溶液，
移除冰浴，在室溫下反應 12 小時後，逐滴加入 NH4Cl(aq) (5 mL)淬息反應，用乙醚 (40 mL x 2)萃取後，合併有機層並以無水硫酸鎂乾燥，將溶液旋乾後以管柱層析分 離純化(silica gel, 10% EtOAc in hexane)即可得白色固體 11(4.7 g, 98%)。
1H NMR (400 MHz, CDCl3): δ7.61 (d, J = 7.2 Hz, 2H, Ar-H), 7.52 (d, J = 7.2 Hz, 2H, H), 7.37 (ddd, J = 7.2, 7.2, 1.2 Hz, 2H, H), 7.31 (ddd, J = 7.2, 7.2, 1.2 Hz, 2H, Ar-H), 4.65 (m, 1H, allyl-Ar-H), 4.42 (m, 1H, allyl-Ar-H), 2.86 (s, 2H, -C-CH2C), 2.32 (br, 1H, -OH), 1.41 (s, 3H, -CH3) ppm.
13C NMR (100 MHz, CDCl3): δ 148.4, 140.8, 139.4, 128.8, 127.6, 124.1, 119.8, 115.3,
82.0, 46.9, 24.0 ppm.
methyl 4-methylcyclohex-3-ene-1-carboxylate (15)
取 3-methyl-1,2-butadiene (6.0 mL, 60 mmol)與 methyl acrylate(2.7 mL,30 mmol) 置入 50 mL 單頸瓶中，加入 AlCl3 (402 mg, 3 mmol)在 0 °C 下反應 6 小時後，以二
取 mthyl 4-methylcyclohex-3-ene-1-carboxylate 15 (2.3 g, 15 mmol) 置入 50 mL 單 頸 瓶 中 ， 抽灌 氮 氣數 次 後 ， 打 入無 水 乙醚 (10 mL) ， 在 0 °C 下 逐 滴 加 入 methylmagnesium bromide solution 3.0 M in dibutyl ether (10 mL, 30 mmol)，在室溫 下反應 12 小時後，逐滴加入 NH4Cl(aq) (5 mL)淬息反應，用乙醚(40 mL x 2)萃取後，
7.3.4 高烯丙基醇與松油醇之腈正離子-烯烴環化產物
N-(4',6'-dimethyl-4',5'-dihydro-3'H-spiro[fluorene-9,2'-pyridin]-4'-yl)acetamide (12)
將 9-(2-methylallyl)-9H-fluoren-9-ol 11 (100 mg, 0.42 mmol) 置入 4 mL 反應管 中，抽灌氮氣數次後，打入無水乙腈(1 mL)和無水甲苯(1 mL)。將 trifluoroborate etherate(60 mg, 0.42 mmol)於無水甲苯(1 mL)的溶液緩慢滴入反應管中。在室溫下 反應 12 小時後，滴入數滴甲醇淬息反應，以 DCM (10 mL x 2)與 NaHCO3 (2 mL) 萃取，合併有機層並以無水硫酸鎂乾燥，將溶液旋乾後以管柱層析分離純化(silica gel, EtOAc:hexane:triethylamine = 50:49:1)得到白色固體 (72.8 mg, 54%).
1H NMR (400 MHz, CDCl3): δ 7.73 - 7.69 (m, 2H, Ar-H), 7.38 – 7.32 (m, 4H, Ar-H), 7.26 – 7.22 (m, 2H, Ar-H), 5.60 (br, 1H, N-H), 3.63 - 3.58 (m, 1H, AB-H), 2.36 - 2.32 (m, 1H, AB-H), 2.14 (s, 3H, -CH3), 2.08 – 2.02 (m, 2H, AB-H), 1.96 (s, 3H, -CH3), 1.49 (s, 3H, -CH3) ppm.
13C NMR (100 MHz, CDCl3): δ 169.7, 168.7, 152.3, 149.7, 140.8, 139.6, 128.4, 128.2, 128.0, 126.9, 125.0, 123.6, 120.5, 120.0, 70.6, 50.5, 43.3, 38.8, 28.7, 28.2, 24.6 ppm.
HRMS (ESI-TOF) calcd. for C21H23N2O(M+H+): = 319.1805; found: 319.1812.
N-((1S,5S)-4-benzyl-2,2,6-trimethyl-3-azabicyclo[3.3.1]non-3-en-6-yl)-2-phenylacetamide (21)
將α-terpineol 16 (100 mg, 0.65 mmol) 置入 4 mL 反應管中 ，抽灌氮氣數次後，
打入無水苯乙腈(1 mL)和無水甲苯(1 mL)。將 trifluoroborate etherate(92 mg, 0.65 mmol)於無水甲苯(1 mL)的溶液緩慢滴入反應管中。在室溫下反應 12 小時後，滴入 數滴甲醇淬息反應，以 DCM (10 mL x 2)與 NaHCO3 (2 mL)萃取，合併有機層並以 無水硫酸鎂乾燥，將溶液旋乾後以管柱層析分離純化(silica gel, EtOAc : hexane : triethylamine = 50:49:1)得到白色固體 (191 mg, 73%).
1H NMR (400 MHz, CDCl3): δ 7.37 – 7.20 (m, 10H, Ar-H), 5.37 – 3.59 (m, 2H), 3.51 (s, 2H), 5.60 (br, 1H, N-H), 3.06 (m, 1H), 1.66 – 1.32 (m, 8H), 1.28 (s, 6H, 2 x -CH3), 1.16 (m, 4H) ppm.
13C NMR (100 MHz, CDCl3): δ 170.2, 168.4, 137.6, 135.2, 129.1, 129.0, 128.4, 127.3, 126.4, 58.4, 55.7, 48.8, 44.9, 37.5, 33.8, 32.4, 31.5, 27.2, 26.1, 24.4, 24.3 ppm.
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附錄
化合物之光譜資料
1H NMR spectrum of compound 5aaa (400 MHz, CD3CN)
13C NMR spectrum of compound 5aaa (100 MHz, CD3CN)
1H NMR spectrum of compound 5caa (400 MHz, CD3CN)
13C NMR spectrum of compound 5caa (100 MHz, CD3CN)
1H NMR spectrum of compound 5daa (400 MHz, CD3CN)
13C NMR spectrum of compound 5daa (100 MHz, CD3CN)
1H NMR spectrum of compound 5aba (400 MHz, CD3CN)
13C NMR spectrum of compound 5aba (100 MHz, CD3CN)
1H NMR spectrum of compound 5aca (400 MHz, CD3CN)
13C NMR spectrum of compound 5aca (100 MHz, CD3CN)
1H NMR spectrum of compound 5ada (400 MHz, CD3CN)
13C NMR spectrum of compound 5ada (100 MHz, CD3CN)
1H NMR spectrum of compound 5aea (400 MHz, CD3CN)
13C NMR spectrum of compound 5aea (100 MHz, CD3CN)
1H NMR spectrum of compound 7aaa (400 MHz, DMSO-d6)
13C NMR spectrum of compound 7aaa (100 MHz, DMSO-d6)
1H NMR spectrum of compound 7aca (400 MHz, DMSO-d6)
13C NMR spectrum of compound 7aca (100 MHz, DMSO-d6)
1H NMR spectrum of compound 7ada (400 MHz, DMSO-d6)
13C NMR spectrum of compound 7ada (100 MHz, DMSO-d6)
1H NMR spectrum of compound 7aab (400 MHz, CDCl3)
13C NMR spectrum of compound 7aab (100 MHz, CDCl3)
1H NMR spectrum of compound 7aac (400 MHz, CDCl3)
13C NMR spectrum of compound 7aac (100 MHz, CDCl3)
1H NMR spectrum of compound 7baa (400 MHz, DMSO-d6)
1H NMR spectrum of compound 7baa (100 MHz, DMSO-d6)
1H NMR spectrum of compound 7daa (400 MHz, DMSO-d6)
19F NMR spectrum of compound 7daa (376 MHz, DMSO-d6)
1H NMR spectrum of compound 8aea (400 MHz, CDCl3)
13C NMR spectrum of compound 8aea (100 MHz, CDCl3)
1H NMR spectrum of compound 11 (400 MHz, CDCl3)
13C NMR spectrum of compound 8aea (100 MHz, CDCl3)
1H NMR spectrum of compound 15 (400 MHz, CDCl3)
13C NMR spectrum of compound 15 (100 MHz, CDCl3)
1H NMR spectrum of compound 16 (400 MHz, CDCl3)
13C NMR spectrum of compound 16 (100 MHz, CDCl3)
1H NMR spectrum of compound 12 (400 MHz, CDCl3)
13C NMR spectrum of compound 12 (100 MHz, CDCl3)
1H NMR spectrum of compound 12’ (400 MHz, DMSO-d6)
13C NMR spectrum of compound 12’ (100 MHz, DMSO-d6)
13C + DEPT NMR spectrum of compound 12’ (100 MHz, DMSO-d6)
HMQC spectrum of compound 12’
HMBC spectrum of compound 12’
1H NMR spectrum of compound 21 (400 MHz, CDCl3)
13C NMR spectrum of compound 21 (100 MHz, CDCl3)
13C + DEPT NMR spectrum of compound 21 (100 MHz, CDCl3)
HMQC spectrum of compound 21
HMBC spectrum of compound 21
Mass spectrum of compound 7aaa
Mass spectrum of compound 12