Lanthanide chemical shift reagent들의 NMR induced chemical shift에 관한 연구 : phenylcyclopropane 유도체들의 입체적 구조 및 염기도가 Lanthanide induced shift에 미치는 영향 = Study on NMR induced chemical shift by lanthanide chemical shift reagent : effect on structure and basicity of phenylcyclopropane derivatives on lanthanide induced shift

다국어 초록 (Multilingual Abstract)

Methyl-_cis and _trans-2-phenylcyclopropanecarboxylate, ethyl-_cis and _trans-2-phenylcyclopropanecarboxamide were synthesized and purified by gas chromatography.
Lanthanide induced shifts (LIS) of above six compounds have been measured with Eu(fod). All protons in cyclopropane ring are assigned with chemicall shifts and lanthanide induced shifts. The trend of lanthanide induced shifts of the protons in cyclopropane ring is H_D>H_B>H_C>H_A in cis compounds. The geometric isomer can be determined by the trend of the lanthanide induced shifts of the protons in cyclopropane ring.
The lanthanide induced shift of H_B in cis compounds are much smaller than those of trans compounds in consequence of the steric hinderance of phenyl grop for the formation fo lanthanide shift reagent-substrate complexes. The basicity of amino group in phenylcyclopropanecarboxamide cannot much contribute to the change of the lanthanide induced shifg, comparing to the steric factor.
This explanation can be supported by the different formation constant of methyl-_trans-2-phenycyclopropanecarboxylate-Eu (fod)_3 complexes (K=33±17), methyl-_cis-2-phenycyclopropanecarboxylate-Eu (fod)_3 complexes(K=15?5) and N,N-dimethyl-_trans-2-phenylcyclopopanecarboxamide-Eu(fod)_3 complexes(K=18±2)
* A thesis submitted to committee of the Graduate School of Chungnam National University in partial fulfillment of the requirements for the degree of Master of Science in january, 1983.

목차 (Table of Contents)

• 목차
• I. 서론 = 1
• II. 이론 = 8
• 1. LIS의 mechanism= 8
• 2. LIS의 정량적 해석 = 13
• III. 실험 = 15
• 1. 합성 = 15
• 1) methyleneaminoacetonitrile = 15
• 2) glycine ethyl ester hydrochlroide = 16
• 3) ethyldiazoacetate = 16
• 4) ethyl-cis and trans-2-phenylcyclopropanecarboxylate = 17
• 5) cis and trans-2-phenylcyclopropanecardoxylicacid = 19
• 6) cis and trans-2-phenylcyclopropanecardoxylicacid chloride = 20
• 7) methyl-cis and trans-2-phenylcyclopropanecardoxylate = 21
• 8) N, N-d imethiy-cis and trans-2-phenylcyclopropanecardoxamide = 23
• 2. LIS의 측정 = 24
• IV. 결과 = 26
• V. 고찰 = 55
• VI. 결론 = 60
• VII. 요약 = 61
• VIII. RETERANCES = 62
• IX. ABSTRACT