Phenylcyclopropane 유도체들의 lanthanide shift reagent-substrate 평형과 bound shift에 미치는 영향

다국어 초록 (Multilingual Abstract)

trans-2-phenylcyclopropyl methyl ketone, trans-2-phenylcyclopropyl amine, t-butyl trans-2-phenylcyclypropane carboxylate를 합성하고, gas chromatography로 분리 정제하였다.
Eu(fod)₃을 가지고 위 3가지 화합물의 Lanthanide Induced Shift(LIS)을 C_6D_6에서 측정하였다. cyclopropane ring에 있는 수소들은 chemical shift와 LIS로 해석하엿다.
L+S□LS의 equilibrium constant와 4개의 cyclopropane ring proton들의 bound shift는 computer program으로 계산했다.
Eu(fod)₃와 화합물간의 equilibrium constant는 trans-amine>trans-methyl ketone>trans-t-butyl ester의 순으로 감소하는 경향을 나타내고, bound shift는 trans-methyl ketone□trans-t-butylester>trans-amine의 순으로 감소하는 것으로 나타났다. Eu(fod)₃-substrate의 착화합물에서 cyclopropane ring수소들의 bound shift 값들은 모든 화합물에서 동일한 경향으로 H_D>H_C>H_B>H_A의 순서로 감소를 나타낸다.
equilibrium constant와 bound shift들은 화합물의 염기도에 주로 기인됨을 보여준다.

다국어 초록 (Multilingual Abstract)

Trans-2-phenylcyclopropyl methyl ketone, trans-2-phenylcyclo- propyl amine, t-butyl trans-2-phenylcyclopropane carbaxylate were synthesized and purified by gas chromatography.
Lanthanide induced shift of above three compounds with Eu(fod)?in C_6 D_6 have been measured. All protons in cyclopropane ring are assigned with chemical shifts and lanthanide induced shifts. The equilibrium constant of L+S□S and bound shifts of the four protons in cyclopropane ring were computed with aid of computer program.
The equilibrium constant between Eu(fod)?and substrate is decreased in this order trans-amine> trans-methyl ketone > trans-t-butyl ester and the bound shift of four protons in cyclopropane ring is decreased in this order trans-methyl ketone □ trans-t- butyl ester> trans-amine. The. bound shift of four protons in cyclopropane ring is same trend like H_D>H_C>H_B>H_A in all three compounds.

목차 (Table of Contents)

• 목차
• I. 서론 = 1
• II. 이론 및 계산 = 7
• III. 실험 = 11
• 1. LIS 측정 = 11
• 2. 합성 = 11
• (1) methyleneaminoacetonitrile = 12
• (2) Glycine ethyl ester hydrochloride = 12
• (3) ethyldiazoacetate = 13
• (4) Ethyl cis and trans-2-phenylcyclopropane carboxylate = 14
• (5) cis and trans-2-phenylcyclopropane carboxylic = 15
• (6) cis and trans-2-phenylcyclopropane carboxylic acid chloride = 16
• (7) t-butyl cis and trans-2-phenylcyclopropane car boxylate = 17
• (8) trans-2-phenylcyclopropyl methyl ketone = 18
• (9) trans-2-phenylcyclopropyl amine = 19
• IV. 결과 및 고찰 = 21
• V. 결론 = 36
• VI. 요약 = 38
• VII. 참고문헌 = 39
• VIII. Abstract = 43