Journal of Organic Chemistry p. 55 - 61 (1992)
Update date:2022-08-16
Topics:
Hogan, John C.
Gandour, Richard D.
Glymes, H-(CH2OCH2)n-H, GLM(n), catalyze butylaminolysis of 4-nitrophenyl acetate in chlorobenzene.Values of kcat/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 complexverifies 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 α,ω-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 kcat/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 kcat/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 kcat/Oxy for DME(2) exceeds the remaining DMEs by 3 - 3.6-fold, except for DME(8) and DME(10), which have values of kcat/Oxy only 1.7-fold slower.DME(8), the carba analogue of GLM(4), likely binds 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 stucture 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.
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