📜1,6-己二醇置于吡啶,Sodium Methylate体系中,用 二氯甲烷 用作溶剂,化学反应 0.33H,反应生成1,6-二甲氧基己烷
参考文献:Fingerprinting A Transition-Structure Guest By A Building-Block Approach With An Incremental Series Of Catalytic Hosts. Structural Requirements For Glyme And .Alpha.,.Omega.-Dimethoxyalkane Catalyses In N-Methylbutylaminolysis And Butylaminolysis Of 4-Nitrophenyl Acetate In Chlorobenzene
标题:Fingerprinting A Transition-Structure Guest By A Building-Block Approach With An Incremental Series Of Catalytic Hosts. Structural Requirements For Glyme And .Alpha.,.Omega.-Dimethoxyalkane Catalyses In N-Methylbutylaminolysis And Butylaminolysis Of 4-Nitrophenyl Acetate In Chlorobenzene
摘要:Glymes,H-(Ch2och2)N-H,Glm(N),Catalyze Butylaminolysis Of 4-Nitrophenyl Acetate In Chlorobenzene. Values Of K(Cat)/oxy,Where Oxy Is The Number Of Oxygens In The Catalyst,Increase With Oligomer Length Up To Triglyme,Glm(4),And Then Plateau. Optimal Catalysis On A Per Oxygen Basis Requires A-(Ch2och2)4-Fragment,Which Suggests A Four-Point Recognition Of The Secondary Ammonium Ion Of The Zwitterionic Tetrahedral Intermediate (Ti) (J. Org. Chem. 1991,56,2821-2826). Dissection Of Individual Structural Components And Reassembly To The Same Structure Of The Complex Verifies This Model. The Following Kinetic Studies Of 4-Nitrophenyl Acetate In Chlorobenzene Have Accomplished The Task: (A) Methylbutylaminolysis Catalyzed By Glm(N),N = 2-4; (B) Methylbutylaminolysis Catalyzed By Alpha,Omega-Dimethoxyalkanes,Ch3O-(Ch2)N-och3,Dme(N),N = 2-10 And 12; And (C) Butylaminolysis Catalyzed By Dme(N),N = 2-10 And 12. Experiment A Has Revealed That K(Cat)/oxy Is The Same For Glm(2)-Glm(4). Optimal Catalysis For Breakdown Of A Zwitterionic Ti With One Ammonium Proton Only Requires A-(Ch2och2)2-Fragment. Experiment B Has Shown That K(Cat)/oxy Is Largest For Dme(2) With The Values For The Remaining Dmes 2-2.5-Fold Lower. A-Ch2Ch2-Is The Best Spacer Between The Two Oxygens. Thus,Bifurcated Hydrogen-Bond Formation Between The Two Oxygens And The One Ammonium Proton Enhances Catalysis. Experiment C Has Revealed That K(Cat)/oxy For Dme(2) Exceeds The Remaining Dmes By 3-3.6-Fold,Except For Dme(8) And Dme(10),Which Have Values Of K(Cat)/oxy Only 1.7-Fold Slower. Dme(8),The Carba Analogue Of Glm(4),Likely Binds To The Two Ammonium Protons Individually With The Two Oxygens. Dme(10) Behaves Similarly. Glm(4) Catalysis Of Butylaminolysis Identifies-(Ch2och2)4-As An Optimal Size. Dme(8) Catalysis Confirms This Size,Although The Two Catalysts Stabilize The Two-Proton Ammonium Ion Differently. Glm(4) Catalyzes Butylaminolysis By Forming Two Bifurcated Hydrogen Bonds. This Suggested Structure Defines The Size Of The Ammonium Ion,Which Agrees With X-Ray Structural Studies Of Polyether-Ammonium Complexes. Mechanistic Proposals Of Butylaminolysis Of Aryl Esters Require Such An Ion. The Results Of This Study Confirm The Structure Of The Ion In The Rate-Limiting Step. This Building-Block Approach Is A Method For ''Fingerprinting'' Ammonium Ions In Transition Structures Of Ionogenic Reactions.
Doi:10.1021/jo00027A014