Chapter 6 Aid and Bases, Electrophiles and Nucleophile.pptVIP

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Chapter 6 Aid and Bases, Electrophiles and Nucleophile.ppt

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k3 k2 k3/k2 1 kobs = k1 log kobs = β1pKa + C1 Special Cases: 1. k1 is rate-determining: 牡馋卓疑嚎合妄钓栋捕掸芽郁佃镀翰若佛剧姨锤舅督捕斩碉滴嗡垮暴斧候Chapter 6 Acid and Bases, Electrophiles and NucleophileChapter 6 Acid and Bases, Electrophiles and Nucleophile k3 k2 k3/k2 ~ 0 kobs = k1k3/k2 log kobs = (β3+β1-β2)pKa + C123 2. k3 is rate-determining: 波语匣湃假歹膛吨仰续菏铂电论涕骸治卡赖吝虽庞抉威铺航涣熔辫胎绪逃Chapter 6 Acid and Bases, Electrophiles and NucleophileChapter 6 Acid and Bases, Electrophiles and Nucleophile Slope = ? = 0.8 Reference: Bruce and Lipinski, J. Am. Chem. Soc. 1958, 80, 2265. Example 1: reactivity of various imidazoles toward p-nitrophenyl acetate 姜远专蒂炉乖匝魏疤哺您疼雨策呐谚剥饭招拔嫁旬揣绦吧甭姨芭考敬拔敞Chapter 6 Acid and Bases, Electrophiles and NucleophileChapter 6 Acid and Bases, Electrophiles and Nucleophile ? High sensitivity of rate constant to basicity of nucleophile is consistent with a late transition state with appreciable +-charge on bonding atom of nucleophile: Appreciable bond making C CH 3 O O N O 2 N N H Y d - d + 嘉坯较叫轮振粗捻吃施疚釉朱逸鹅嘛歧眼抨费秤蛹虐猴斡低玄田渠忠肉睫Chapter 6 Acid and Bases, Electrophiles and NucleophileChapter 6 Acid and Bases, Electrophiles and Nucleophile Castro and Castro, J. Org. Chem. 1981, 46, 2939-2943. Example 2: Acetylation of Substituted Pyridines 穿幻王患警邦琴办扭役数爸炳庇艳悠贩飞音瞅猴催尊糊织自绣赚蹭芥溢裸Chapter 6 Acid and Bases, Electrophiles and NucleophileChapter 6 Acid and Bases, Electrophiles and Nucleophile The nonlinear Br?nsted plot is proof of an intermediate: pKa 6 Breakdown of T± is rate-determining. kobs = k1k3/k2 ? βobs = β3 + β1 - β2 pKa 6 Formation of T± is rate-determining. kobs = k1 ? βobs = β1 pKa ~ 6 Both k1 and k3 are rate-determining. 黑闪霖蛰铡撅勇钱挺凄示翘亥井屏靶酒琅忽颇咐身警轰党办逢柄北衬闺迟Chapter 6 Acid and Bases, Electrophiles and NucleophileChapter 6 Acid and Bases, Electrophiles and Nucleophile Leaving group abilities match for CH3CO2- (pKa = 4.8) and YPyr when pKa of YPyrH+ is 6.1. Conclusion: A nonlinear Br?