PDF《第三章 实验部份》

H, 9.62.实际值:C, 75.62;

H, 9.73. 11-Bromoundecyl decyl sulfide (2) [94] 取一

50 mL 双颈瓶置入 1-undecene-11-bromide (10 g, 44.8 mmol) 以及 1-decanethiol (8 g, 44.8 mmol),於0℃低温下先搅拌五分钟,接下?以针筒 加入 9-BBN (9-borabicyclo[3.3.1]nonane , 0.5M 溶於 THF 之中 ) (1.8 mL,

13 mmol) ,於室温下搅拌

8 小时.待反应完成,先将溶液中的 THF 抽去,并 以正己烷(hexane)及水萃取,收集有机层用无水 MgSO4 乾燥后浓缩,可得 一淡黄色油?液体.此油?物以乙醇做再结晶可得白色固体 15.13 g,(37.17 mmol),产?

83 %,熔点:25~26 C.

1 H NMR(300M Hz, CDCl3, δ ppm): 3.41 (t, 2H, CH2Br), 2.49 (t, 4H, CH2S), 1.90-1.79 (m, 2H, CH2CH2Br),

31 1.45-1.18 (m, 32H, CH2), 0.89 (t, 3H, CH3).MS (EI-MS) m/z: 407. 2,7-Dibromo-9,9-di[11-(decylsulfanyl)undecyl]-fluorene (M3) 取一

100 mL 三颈瓶置入第三丁氧基钾( potassium tert-butoxide,5.2 g, 46.3 mmol )以提供碱性环境,11-Bromoundecyl decyl sulfide( 8.67 g, 21.3 mmol ),於氮气下搅拌

30 分钟.随后加入预先以

15 mL THF 溶解的 2,7-dibromofluorene (1) (

3 g , 9.26 mmol ),以加液?斗中缓慢滴入反应瓶内 并持续搅拌,加热至

70 ~80 ℃并通以氮气反应

12 小时,待反应结束,分别 用水及正己烷萃取,收集有机层用 MgSO4 乾燥后浓缩,再以乙酸乙酯(ethyl acetate):正己烷(hexane) = 1:10 为冲提液做管柱层析以纯化,得一白色结 晶产物 3.81 g,产?

88 %,熔点:41~42℃.1 H-NMR (300M Hz, CDCl3, δ ppm):7.50-7.41 (m, 6H, fluorene ring), 2.49-2.42 (t, 8H, CH2S), 1.90-1.85 (t, 4H, H-alkyl), 1.56-1.17 (m, 68H, CH2), 0.87 (s, 12H, CH3).13 C NMR (75 MHz, CDCl3, δ ppm):152.49, 139.02, 130.11, 126.14, 121.43, 121.08 (fluorene ring), 55.64 (C9, fluorene ring), 40.09, 32.15, 31.86, 29.79, 29.70, 29.53, 29.50, 29.42, 29.29, 29.23, 29.19, 29.12, 28.92, 28.90, 23.57, 22.65, 14.08 (C-alkyl).MS (Fab-MS) m/z: 977.2.元素分析(EA),C55H92Br2S2,??值: C, 67.6;

H, 9.49. 实际值:C, 67.72;

H, 9.53. N,N-Di(4-bromophenyl)-N-(4-pentylphenyl)amine (M4) 取一

250 mL 圆底瓶置入 1-bromo-4-iodobenzene ( 3.5 g , 21.4 mmol )、 4-pentylaniline ( 13.32 g ,

47 mmole ),以1,10-phenathroline ( 0.385 g , 2.14 mmole )和CuCl ( 0.212 g , 2.14 mmol )做为助催化剂 ,KOH ( 12g ,

214 mmol ) 提供碱性环境,并加入甲苯(Toluene)

120 mL 做为溶剂,加热回?

12 小时, 待反应结束,分别用水及乙酸乙酯萃取,收集有机层用 MgSO4 乾燥后浓缩, 再以乙酸乙酯:正己烷 = 1:5 为冲提液做管柱层析以纯化,得一白色结晶 产物 7.3 g ,产? 72.0 % ,熔点:57~60℃ .1 H-NMR (300M Hz, CDCl3, δ ppm): 6.86~7.32 (m, 12H, aromatic protons), 2.54(t, 2H, -CH2-(CH2)3-CH3),

32 1.23~1.59(m, 6H, -CH2-(CH2)3-CH3), 0.88(t, 3H, -CH3).13 C NMR (75 MHz, CDCl3, δ ppm):147.52, 144.40, 139.72, 132.59, 128.23, 124.21, 121.37, 114.28 (aromatic ring), 36.92, 31.66, 31.02, 22.43, 14.29, (C-alkyl). MS (EI-MS) m/z: 473.2.元素分析(EA),C23H23Br2N,??值: C, 58.37;

H, 4.9;

N, 2.96.实际 值:C, 58.67;

H, 5.06;

N, 2.90. 4,4'

-Bis[(N-p-bromophenyl)-N-phenylamino]biphenyl (M5) 此反应步骤同单体 M4.?同之处为药品采用 1-bromo-4-iodobenzene ( 9.25 g , 32.69 mmol )、N,N'

-diphenyl benzidine ( 5.00 g , 14.86 mmole ),以1,10-phenathroline ( 0.14 g , 0.74 mmole )和CuCl ( 0.08 g , 0.74 mmol )做为助 催化剂,KOH ( 6.67g , 118.88 mmol ).以乙酸乙酯:二氯乙烷(dichloroethane) = 1:6 为冲提液做管柱层析以纯化,可得一白色结晶产物 3.81 g,产? 40.0 %,熔点:57~60℃.1 H-NMR (300M Hz, CDCl3, δ ppm):7.43(d, 4H, aromatic protons), 7.34~7.24(m, 9H, aromatic protons), 7.11~7.04 (m, 9H, aromatic protons), 6.97(d, 4H, aromatic protons).13 C NMR (75 MHz, CDCl3, δ ppm): 147.16, 146.80, 146.32, 135.09, 132.18, 129.48, 127.45, 125.28, 124.52, 124.28, 123.38, 114.35 (aromatic ring).MS (EI-MS) m/z: 648.0.元素分析(EA), C36H26Br2N2 ,??值: C, 66.89;