机构地区: 绵阳师范学院化学与化学工程学院化学与化学工程系
出 处: 《武汉大学学报(理学版)》 2008年第4期396-400,共5页
摘 要: 通过亲核反应合成了芳氧功能化的氮杂环卡宾前体[HO-4,6-di-C(CH3)3-C6H2-2-CH2{CH(NCH-CHN)CH3}]Cl(1),1再与正丁基锂(n-BuLi)按照摩尔比2∶1常温反应生成芳氧功能化的氮杂环卡宾迁移产物[O-4,6-dit-Bu-C6H2-2-CH2{C(MeNCHCHNH)}]2Li2(THF)2(2).化合物1和2均通过核磁、元素分析和X射线衍射表征.晶体结构显示化合物1属单斜晶系,空间群为C2/c,化学式为C19H29ClN2O,晶胞参数a=3.203 4(14)nm,b=0.863 0(4)nm,c=1.469 5(7)nm,α=90°,β=106.305(10)°,γ=90°,V=3.899(3)nm3,Z=8,R=0.170 5,wR=0.176 6.化合物2也属三斜晶系P1,a=0.942 64(13)nm,b=0.987 21(15)nm,c=1.405 58(16)nm,α=79.040(10)°,β=73.928(9)°,γ=85.804(11)°,V=1.233 7(3)nm3,Z=1,Dc=1.116 mg/m3,μ=0.070 mm-1,F(000)=452.同时,发现温度是影响氮杂环卡宾迁移的主要原因. Abstract: Phenoxo functionalized-NHC predecessor [HO-4,6-di-C(CH3)2-C6H2-2-CH2{CH(NCHCHN)CH3}]Cl(1) has been synthesized by nucleophilic reaction. The reaction of 1 with n-BuLi in molar ratio 2:1 at the room temperature gives the first N-heterocyclic carbenes (NHC) benzyl migration product functionalized by phenoxo [O-4,6-di-^t Bu-C6H2-2-CH2{C(MeNCHCHNH)}]2Li2(THF)2(2), The complexes 1 and 2 have been characterized by the 1HNMR and X-ray diffraction. The results show the crystal of complex 1 belongs to Monoclinic system with the empirical formula:C19 H29C1N2O,a=3. 203 4(14) nm, b =0.863 0(4) nm, c=1.469 5(7) nm,α=90°,β=106.305(10) ° γ=90°, V=3.899(3) nm^3, Z=8, R= 0.170 5, wR=0. 176 6. And the complex belongs to Triclinic system with a=0. 942 64(13)nm, b= 0. 987 21(15)nm, c=1. 405 58(16)nm, α=79. 040(10)°, β=73. 928(9)°, γ=85. 804(11)°, V=1. 233 7(3) nm^3 , Z=1, Dc=1. 116 mg/m^3 , μ=0. 070 mm 1 , F(000)= 452. The main reason for the N-heterocyclic carbenes (NHC)benzyl migration is temperature.