双二茂铁甲基碳正离子与乙酰乙酸乙酯的反应及其产物的晶体结构

Reaction of Diferrocenylmethyl Carbocation with Ethyl Acetoacetate and Crystal Structure of Its Product

双二茂铁甲醇与BF3?OEt2在CH2Cl2中作用形成稳定的双二茂铁甲基碳正离子,无需从溶液中分离,可直接与乙酰乙酸乙酯反应得到了较高产率的双二茂铁甲基乙酰乙酸乙酯.由苯重结晶得到的单晶经过X射线衍射测试发现,该化合物属于三斜晶系,空间群P-1,a=0.82554(8)nm,b=0.96962(10)nm,c=1.46662(14)nm,α=105.562(2)°,β=90.771(2)°,γ=96.727(2)°,V=1.2191(19)nm3,Dc=1.516g?cm-3,μ=1.320mm-1,F(000)=532,Z=2.

Diferrocenylmethanol was treated with BF3-OEt2 in CH2Cl2 to generate the diferrocenylmethyl carbocation. Without separation from the reaction mixture, the ion was reacted with ethyl acetoacetate to afford the ethyl a-diferrocenylmethylacetate in fairly high yield which was recrystallized from benzene to provide single crystal. By X-ray single crystal diffraction determination, it was found that the crystal belongs to tficlinic system with P1^-, a=0.82554（8） nm, b=0.96962（10） nm, c=1.46662（14） nm, α=105.562（2）°, β= 90.771（2）°,γ=96.727（2）°, V= 1.2191（19） nm^3, Dc= 1.516 g.cm^-3,μ= 1.320 nm^-1, F（000） = 532 and Z=2.