2,2’-联吡啶桥连的双-4,4’-联吡啶哑铃型化合物的合成

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

二甘醇2与对甲苯磺酰氯在CH_2Cl_2中,0℃～r.t.及Et_3存在下反应得2-(羟乙氧基)乙醇对甲苯横酸酯(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-(对叔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-(对叙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 a,a’-二(溴甲基)-2,2’-联吡啶在乙腈中,油浴60℃反应36 h,得到标题化合物,产率为45％。

The reaction of di (ethylene glycol) with p-toluenesulfonate chloride in CH2Cl2 at 0 degreesC similar to r. t. in the presence of Et3N gave tosylate of 2-(hydroxyethoxy) ethanol (3) in 88% yield. Condensation of 3 with 4-tert-butylbenzoyl chloride in CH2Cl2 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 degreesC gave 2-(p-tert-butylbenzoyloxyethoxy)ethoxybenzylic 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 degreesC gave N-2-(p-tert-butylbenzoyloxyethoxy) ethoxybenzyl-4, 4'-bipyridinium hexafluorophosphate (7) in 85% yield, which reacted with alpha, alpha'-bis(bromomethyl)-2,2'-bipyridine in CH3CN at 60 degreesC for 36 h to obtain the title compounds in 45% yield.