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有机化学
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有机化学 ›› 2003, Vol. 23 ›› Issue (7): 682-685. 上一篇    下一篇

研究论文

2,2'－联吡啶桥连的双－4,4'-联吡啶哑铃型化合物的合成

许新华;卢锐亮;黄荣新;张秋林;陈雄   

  1. 湖南大学化学化工学院
  • 发布日期:2003-07-25

Synthesis of Dumbell-Shaped Compound of Bis-4,4'-bipyridinie Bridged by 2,2'-Bipyridine

Xu Xinhua;Lu Ruiliang;Huang Rongxin;Zhang Qiulin;Chen Xiong   

  1. College of Chemistry and Chemical Engineering, Hunan University
  • Published:2003-07-25

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753

被引次数

6

二甘醇2与对甲苯磺酰氯在CH_2Cl_2中，0 ℃～r.t.及Et_3N存在下反应得2－ （羟乙氧基）乙醇对甲苯磺酸酯（3），收率88％。化合物3与对叔丁基苯甲酰氯在 CH_2Cl_2中0～5 ℃及吡啶存在下反应得2－（对叔丁基苯甲酰氧基乙氧基）乙醇对 甲苯磺酸酯（4），收率96％。4与对羟苯甲醇在乙腈中及CsF/K_2CO_3存在下70 ℃ 反应得2－（对叔丁基苯甲酰氧基乙氧基）乙氧苄醇（5），收率98％。5与NBS及 PPh_3在THF中，室温下反应得化合物2－（对 丁基苯甲酰氧基乙氧基）乙氧苄溴 （6），收率95％。6与4,4'－联吡啶在乙腈中，60 ℃反应1h得N－[2－（对叔丁基 苯甲酰氧基乙氧基）乙氧苄基]－4,4'－联吡啶六氟磷酸盐（7），收率85％。7与 α,α－二（溴甲基）－2,2'－联吡啶在乙腈中，油浴60 ℃反应36h，得到标题化 合物，产率为45％。

关键词: 联吡啶, 冠式化合物, 磷酸盐, 甘醇, 酰氯, 乙腈

The reaction of di(ethylene glycol) with p-toluenesulfonate chloride in CH2C12 at 0 °C ~ r. t. in the presence of Et3N gave tosylate of 2-(hydroxyethoxy) ethanol (3) in 88% yield. Condensation of 3 with A-tert-butylbenzoyl chloride in CH2C12 at room temperature in the presence of pyridine afforded tosylate of 2-(p-tert- butylbenzoyloxyethoxy)ethanol (4) in 96% yield. Substitution of 4 with 4-hydroxybenzylmethanol in CH3CN and in the presence of CsF/K2CO3 at 70 °C gave 2-(j3-tert-butylbenzoyloxyethoxy)ethoxyben2ylic alcohol (5) in 98% yield. Bromination of 5 using NBS and PPh3 in THF at room temperature resulted in the formation of 2-( p-tert- butylbenzoyloxyethoxy)ethoxybenzylic bromide (6) in 95% yield. The reaction of 6 with 4,4'-bipyridine in CH3CN at 60 °C gave iV-2-(p- tert-butylbenzoyloxyethoxy) ethoxybenzyl-4, 4'-bipyridinium hexafluorophosphate (7) in 85% yield, which reacted with a, a'-bis (bromomethyl)-2,2'-bipyridine in CH3CN at 60 T! for 36 h to obtain the title compounds in 45% yield.

Key words: BIPYRIDINE;CROWN ETHER COMPOUNDS;PHOSPHATE;GLYCEROL;ACYL CHLORIDES P, ACETONITRILE

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