基于萘基新型冠醚的合成、晶体结构及其对联吡啶盐的络合性能研究

Novel Naphthalene-Based Crown Ether:Synthsis,Crystal Structure and Its Complexation with Paraquat Derivatives

以2,7-二羟基萘为起始原料,经与8-(对甲苯磺酰氧基)-3,6-二氧-1-辛醇醚化,再与对甲苯磺酰氯酯化得7,7最后与2,7-二羟基萘在碳酸铯为碱作用下得基于2,7-二羟基萘基块新型的冠醚,三步总收率为35%.利用单晶X衍射研究其结构,晶体为三斜晶系,P-1空间群,a=8.165(3),b=13.435(4),c=14.083(3),γ=64.11(2)°,β=80.40(3)°,γ=88.19(3)°,V=1368.9(7)3,Z=2,Dc=1.331 g/cm3,λ=0.071070 nm,μ(Mo Kα)=1.331 mm-1,Mr=353.22,F(000)=584.在1的晶体结构中,两个萘基块通过二缩三乙二醇醚键相连形成1个二萘并[30]-冠-8大环结构,空腔大小为8.2×12.0,分子呈Z型结构.通过核磁研究了主体分子1对联吡啶盐在溶液中的相互络合作用.

Abstract A Novel naphthalene-based crown ether has been synthesized by the etherification of 2,7-dihydroxyhaphthalene with 8-tosyloxy-3,6-dioxaoctanol in the presence of K2CO3, followed by reaction with p-toluenesufonyl chloride to give 7. Compound 7 was further reacted with 2,7-dihydroxynaphthalene in the presence of cesium carbonate to give 1 in 38% total yield. Its crystal structure was determined by X-ray diffraction method. The crystal is of triclinic, space group P-1 with aa=8.165（3）A,6=13.435（4）A,c=14.083（3）A,7=64.11（2）°,β=80.40（3）°,γ=88.19（3）°,V=1368.9（7）A3,Z=2,D,=1.33lg/cm3,A=0.071070nm,,u（MoKa）=1.331mm-2,Mr=353.22,F（000）=584. The crystal structure of 1 shows that two nap- thalene units are linked two tri（ethylene glycol） bridges to form dinapthalzo[30]crown-8 cavity and one Z-like central cavity with size of ca. 8.2 A× 12.0 A. The host 4 was proved to be a efficient host for the complexation with paraquat derivatives in solution by IH NMR.