알코올-물 혼합용매계에서 4-치환된 벤질 유도체의 반응성-선택성에 대한 반응속도 모델

다국어 초록 (Multilingual Abstract)

For solvolyses of various benzyl substrates in ethanol-water (EW) and methanol-water (MW) mixtures, product selectivities (S) are reported for chlorides at 75 ˚C defined as follows using molar concentrations: S = ([ether product]/[alcohol product]) x ([water]/[alcohol solvent]). The results support earlier evidence that solvolyses of 4-nitrobenzyl substrates are S_(N)2 processes, which are not susceptible to mechanistic changes over the whole range of solvents from water to alcohol. S values at 25 and/or 45 ˚C in EW and MW, and additional kinetic data including kinetic solvent isotope effects (KSIE) are reported for solvolyses of 4-nitrobenzyl mesylate and tosylate. A kinetic model, explaining both rates and product, is proposed; a general medium effect due to solvent polarity is combined in one parameter with solvent effects on the nucleophilicity of the water and alcohol molecules acting as nucleophiles in S_(N)2 reactions. According to this model, as alcohol is added to water the rate of reaction decreases due to a decrease in solvent polarity, but the nucleophilicity of water increases relative to alcohol. The availability of experimental rate and product data over the whole range of solvent compositions from alcohol to water, reveals limitations of alternative approaches using activities.

목차 (Table of Contents)

• Ⅰ. 서론 = 2
• II. 이론 = 6
• 1. Grunwald-Winstein 관계식 = 6
• 2. 생성물-선택성 관계 = 9
• 3. 반응속도론적 동위원소 효과 = 13
• Ⅱ. 실험 = 21
• 1. 시약 및 기기 = 21
• 2. 기질의 합성 = 22
• 3. 가용매분해반응 = 23
• 4. 생성물 연구 = 24
• Ⅲ. 결과 및 고찰 = 31
• 1. 기질의 선정 = 37
• 2. 반응속도-생성물 관계 = 38
• 3. 활동도의 역할 (Role of activities) = 47
• Ⅳ. 결론 = 51
• Ⅴ. 참고문헌 = 53
• VI. 부록 = 59