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化学学报
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化学学报 ›› 1988, Vol. 46 ›› Issue (3): 234-238. 上一篇    下一篇

研究论文

α'-三氟甲基-含氟β-二酮镧系螯合物的合成及其用作位移试剂的研究

黄维垣;张龙庆   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1988-03-15

Study on the synthesis of the lanthanide chelates of α -trifluoro-methyl-polyfluoroalkyl β-diketones and their application as H NMR shift reagents

HUANG WEIYUAN;ZHANG LONGQING   

  • Published:1988-03-15

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579

被引次数

5

本文合成了α'-三氟甲基-含氟β-二酮镧系螯合物Ln{CF3CF2[CF2OCF(CF3)]nCOCHCOC(CH3)3}3[n=1; Ln=Eu(1a), Pr(1b), Nd(1c),Sm(1d), Gd(1e), Tb(1f), Dy(1g), Er(1h). n=2; Ln=Eu(2a), Pr(2b), Nd(2c),Sm(2d), Gd(2e), Tb(2f), Dy(2g), Er(2h)], 并研究了它们的位移性能. 1a、1b、2a和2b在用作位移试剂时, 不仅具备Ln(fod)3(Ln=Eu, Pr)的所有优点, 而且还有另外两个优点: (1)在底物存在时, 试剂自身的叔丁基峰明显向高场迁移, 特别是在醇类化合物存在下, δ-Bu^t接近于0ppm, 因此, 1a和2a的t-Bu峰总是处于底物ω-甲基的高场, 不干扰图谱的解析. (2)1b和2b虽为镨类螯合物, 但与1a与2a一样, 都能得到非常清晰的一级图谱. c、f和g均使谱峰向高场迁移, 而h却使谱峰向低场迁移. c的位移能力略低于b. f、g和h的位移能力极强.

关键词: 红外分光光度法, 质子磁共振谱法, 有机氟化合物, 镧络合物, 位移试剂, β双酮类

The preparation of Ln{CF3CF2[CF2OCF(CF3)]nCOCHCOC(CH3)3}3 [I; n = 1, 2; Ln = Eu, Pr, Nd, Sm, Gd, Tb, Dy, Er] is reported. The 1H NMR shift properties were studied using alcohol, ketone, ether and amine as substrates. I (Ln = Eu, Pr) induce shifts similar to those induced by LnL3 (Ln = Eu, Pr; HL = fod). However, I (Ln = Eu) are superior to EuL3, because their 1H signal shifts to higher field in the presence of substrate than that of EuL3 does. For example, dH for I (Ln = Eu) is close to 0 ppm in the presence of alcohol Very satisfactory 1st order spectra can be obtained using I (Ln = Eu, Pr) as 1H NMR shift reagents. I (Ln = Nd, Tb, Dy) produce upfield shifts, and I (Ln = Er) produce downfield shifts. I (Ln = Nd) induce shifts smaller than those of I (Ln = Pr) whereas I (Ln = Tb, Dy, Er) induce very large shifts.

Key words: INFRARED SPECTROPHOTOMETRY, PROTON MAGNETIC RESONANCE SPECTROMETRY, ORGANO FLUORINE COMPOUNDS, LANTHANUM COMPLEX, SHIFT REAGENT, BETA DIKETONES

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