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This Dissertation Has Been 64—3179 Microfilmed Exactly As Received BASE-CATALYZED HYDROLYSIS OF PYRIDINIUM SALTS Item Type text; Dissertation-Reproduction (electronic) Authors Moss, Ernest Kent, 1938- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 29/09/2021 13:55:45 Link to Item http://hdl.handle.net/10150/284499 This dissertation has been 64—3179 microfilmed exactly as received MOSS, Ernest Kent, 1938- BASE-CATALYZED HYDROLYSIS OF PYRIDINIUM SALTS. University of Arizona, Ph.D., 1963 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan BASE-CATALYZED HYDROLYSIS OF PYRIDINIUM SALTS by Ernest K. Moss A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 19 6 3 " THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by ~rn::-' !""t K . TToss be accepted as fulfilling the dissertation requirement of the degree of ___n_ o~c _t_o_r__ o__ f __ n _.n_; ,_· __l _o_2_- o_~_h_.,,_r ____________________________ After inspection of the dissertation, the following members of the Final Examination Committee concur in its approval and recommend its acceptance :* *This approval and acceptance is contingent on the candidate's adequate performance and defense of this dissertation at the final oral examination. The inclusion of this sheet bound into the library copy of the -dissertation is evidenceof satisfactory performance at the final examination. STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the Univer­ sity Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allow­ able without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or reproduction of this manu­ script in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED. )C VMao* ACKNOWLEDGMENT The author wishes to express his sincere appre­ ciation and thanks to Dr. Alec E. Kelley for his contri­ butions and helpful advice during the course of this research. iii TABLE OF CONTENTS Page LIST OF TABLES . vii LIST OF FIGURES ix ABSTRACT xi INTRODUCTION 1 STATEMENT OF PROBLEM 13 EXPERIMENTAL 14 Materials 14 Solutions 17 Identification of Intermediates and Products .... 18 Reaction Products from N~(2,4-Dinitrophenyl)- pyridinium Chloride and Sodium Hydroxide ... 18 5-(2,4-Dinitroanilino)-2,4-pentadienal ... 18 Sodium Glutacondialdehyde Enolate 19 2,4-Dinitroaniline 20 2,4-Dinitrophenol 22 Condensation Products 22 5-Hydroxy-2-pentenoic Acid . 26 Dissociation Constant for Glutacondialdehyde .... 28 Kinetic Methods 29 Apparatus 29 Procedure 30 N-(2,4-Dinitrophenyl)pyridinium Chloride and Sodium Hydroxide 30 5-(2,4-Dinitroanilino)-2,4-pentadienal and Sodium Hydroxide 31 Sodium Enolate of Glutacondialdehyde and Sodium Hydroxide 34 iv Page Calculations 34 Rate Constants ....... 35 Equilibrium Constant for Glutacondialdehyde ... 37 Energy of Activation ......... 38 Entropy of Activation 38 Mechanisms . 39 Mechanism for Reaction of N-(2,4-Dinitro- phenyl)pyridinium Chloride with Sodium Hydroxide 39 Mechanism for Reaction of Sodium Enolate of Glutacondialdehyde with Water and Sodium Hydroxide 43 RESULTS AND DISCUSSION 50 Kinetics and Reaction of N-(2,4-Dinitrophenyl)- pyridinium Chloride and Sodium Hydroxide 50 Irreversibility of Initial Ring-opening Reaction 50 Comparison of Rates for N-(2,4-Dinitrophenyl)- . pyridinium Chloride and 5-( 2,4-Dinitroanilino)- 2,4-pentadienal 51 Effect of Ionic Strength on Rate Constant .... 51 Experimental Rate Constant as a Function of Pyridinium Salt and Sodium Hydroxide Concentrations 52 Change in Concentration of N-(2,4-Dinitro- phenyl)pyridinium Chloride 52 Change in Concentration of Sodium Hydroxide . 54 Energy of Activation for Decrease of 530 ny Peak . 61 Entropy of Activation for Decrease of 530 mji Peak 61 v Page Comparison of Rate Constants for N-Picryl- pyridinium and N-Picryl-3-picolinium Chloride with N-(2,4-Dinitrophenyl)pyridin- ium Chloride 63 N-Picrylpyridinium Chloride and N-(2,4- Dinitrophenyl)pyridinium Chloride ... 63 N-Picryl-0-picolinium Chloride and N- Picrylpyridinium Chloride 63 Kinetics and Reaction of 5-(2,4-Dinitroanilino)- 2,4-pentadienal 65 Effect of Ionic Strength on Rate Constant . 65 Experimental Rate Constant as a Function of Sodium Hydroxide Concentration 65 Kinetics and Reactions of Glutacondialdehyde and Its Sodium Enolate 68 Effect of Ionic Strength on Rate Constant . 68 Equilibrium Constant for Glutacondialdehyde . 71 Kinetic Proof that Sodium Glutacondialdehyde Corresponds to 365 mp. Peak 72 Kinetic Results at Various Sodium Hydroxide Concentrations 73 Rate Constant as a Function of Sodium Hydroxide Concentration between pH 13-14 73 Energy of Activation at pH 13-14 74 Entropy of Activation at pH 13-14 .... 74 Rate Constants as a Function of Sodium Hydroxide Concentration between pH 11-12 78 SUMMARY 84 LIST OF REFERENCES 90 vi LIST OF TABLES Table Page 1 Experimental Kinetic Data for Decrease of 530 mn Peak 33 2 Comparison of Rate Constants for N-(2,4- Dinitrophenyl)pyridinium Chloride and 5-(2,4-Dinitroanilino)-2,4-pentadienal . 53 3 Effect of N-(2,4-Dinitrophenyl)pyridinium Chloride Concentration on Rate Constant at 30° 53 4 Effect of Sodium Hydroxide Concentration on Rate Constant for Decrease of 530 m|i Peak . 55 5 Slopes, Intercepts, and Their Ratio From (OH") vs k' Plot of Data for N-(2,4-Dinitrophenyl) pyridinium Chloride 57 6 Activation Energies for Decrease of 530 mn Peak 57 7 Entropy of Activation for Decrease of 530 mp. Peak at 0.10 M Sodium Hydroxide Concentra­ tion . .— 57 8 Comparison of Kinetic Results for N-Picryl- pyridinium, N-Picryl-P-picolinium, and N-(2,4-Dinitrophenyl)pyridinium Chlorides . 64 9 Effect of Ionic Strength on Rate Constant for Hydrolysis of 5-(2,4-Dinitroanilino)- 2,4-pentadienal 67 10 Effect of Ionic Strength on Rate Constant for Reaction of Sodium Glutacondialdehyde Enolate and Sodium Hydroxide *69 11 Peak Height Measurements of Sodium Gluta­ condialdehyde Enolate at Various pH Values 69 VI1 Table Page 12 Entropy of Activation for Reaction of Glutacondialdehyde Enolate and Sodium Hydroxide 77 13 Rate Constant for Reaction of GJLutacondi- aldehyde Enolate and Sodium Hydroxide at pH 11-12 77 viii LIST OF FIGURES Figure Page 1 Solutions of 5-(2,4-Dinitroanilino)-2,4- pentadienal: Visible and Ultraviolet Spectra 9 2 Experiment 61. Visible Spectrum Showing Changes of 530 and 365 m|i Peaks with Time . 32 3 Experiment 61. Guggenheim Plot for Decrease of 530 m|i teak and Increase of 365 m^i Peak at 0.24 M Sodium Hydroxide and 20° .... 36 4 Rate Constant as Function of Sodium Hydrox­ ide Concentration for Decrease of 530 mn Peak at 20° ... 56 5 Correlation of Slopes for Rate Data Obtained for 530 m^i Peak 59 6 Correlation of Intercepts for Rate Data Obtained for 530 m|i Peak 60 7 Activation Energy for Decrease of 530 m|i Peak at 0.10 M Sodium Hydroxide 62 8 Experiment 143. First Order Rate Plot for Decrease of 425 m|i Peak at 5 x 10-3 M Sodium Hydroxide and 50° 66 9 Experiment 192. First Order Plot for Decrease of 365 mp. Peak at 70° 70 10 Rate Constant as a Function of Sodium Hydrox­ ide Concentration for Decrease of 365 mpi Peak . 75 11 Activation Energy for Decrease of 365 mn Peak at 0.3 M Sodium Hydroxide 76 12 Experiment 216. Rate Plot for Mixed Order Reaction for Decrease of 365 mp. Peak ... 79 ix Figure Page 13 Correlation of Data for Combination Mechanism for Decrease of 365 mp. Peak at pH 11-12; kj vs 1/(0H") Plot 81 14 Correlation of Data for Combination Mechanism for Decrease of 365 rrp Peak at pH 11-12; kj(OH~) vs (OH") Plot 82 15 Complete Mechanism for Reaction of N-(2,4- Dinitrophenyl)pyridinium Chloride with Sodium Hydroxide 89 x ABSTRACT The mechanism of reaction of N-(2,4-dinitrophenyl) pyridinium chloride with sodium hydroxide in aqueous solu­ tion was studied via spectrophotometry methods. The intermediates in this reaction, 5-(2,4-dinitroanilino)- 2,4-pentadienal and its enolate, glutacondialdehyde and its enolate, and 2,4-dinitroaniline, were identified by chemical and physical methods. Glutacondialdehyde sodium enolate and 5-(2,4- dinitroanilino)-2,4-pentadienal were synthesized and the kinetics of their reactions with hydroxide were also studied. The kinetics of basic hydrolysis of the mono- anil and its enolate agree with a proposed mechanism vrfiich involves two parallel pathways. The products of this hydrolysis are 2,4-dinitroaniline and glutacondialdehyde or its enolate. The amine reacts further with hydroxide to give 2,4-dinitrophenol. Glutacondialdehyde enolate is converted to 5-hydroxy-2-pentenoic acid via a Cannizzaro reaction at high base concentrations (pH 13-14) and con­ denses with itself or glutacondialdehyde in aldol-type reactions at low base concentrations (pH 10 or lower). At base concentrations between pH 11-12, both Cannizzaro and aldol-type reactions occur. xi At pH 13-14, the reaction of glutacondialdehyde enolate with sodium hydroxide follows first order kinetics with respect to both enolate and hydroxide concentrations. A positive salt effect was also observed. The rate- controlling step in this reaction was assumed to be a hydride ion transfer via a cyclic transition state complex.
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