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Mechanism of the Chromic Acid Oxidation of Alcohols

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Mechanism of the Chromic Acid Oxidation of Alcohols MECHANISM OF THE CHROMIC ACID OXIDATION OF ALCOHOLS by DONALD GARRY LEE B.A., University of Saskatchewan, 195# M.A., University of Saskatchewan, I960 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in the Department of CHEMISTRY We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH. COLUMBIA March, 1963 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agr.ee that per• mission for extensive copying of this thesis for scholarly purposes may be granted by the -Head of my Department or by his representatives» It is understood that copying.'or publi• cation of this thesis for financial gain shall not be allowed without my written permission. Department of C^^^^yyvNui^^^Tc^ The University of British Columbia,. Vancouver 8, Canada. Date 1y^&-i£ 1 / & 3 The University of British Columbia FACULTY OF GRADUATE STUDIES PROGRAMME OF THE " FINAL ORAL EXAMINATION FOR THE DEGREE OF DOCTOR OF PHILOSOPHY of DONALD GARRY LEE PUBLICATIONS B.A. , The University of Saskatchewan, 1958 M.A. , The University of Saskatchewan, 1960 Rearrangement Studies with C^4, X. Ethanol- 2-C14 from the Irradiation of ethanol-1-C14 MONDAY. APRIL ,29th^ 1963, AT 9s30 A.M. 60 2315 with Co Gamma Rays. Can. J. Chem. 38. IN ROOM 261, CHEMISTRY BUILDING (1960) C.C. Lee and D.G. Lee 2-Phenylethyl-Iodide from the Irradiation 14 COMMITTEE IN CHARGE of 2-Phenylethyl-l-C Iodide with Cobalt-60 Gamma Rays. Radiation Research 17, 536 (1962) Chairman: F.H. Soward C.C.. Lee, D.G. Lee, and I.S. Bhardwaj 14 W.A. Bryce R.E. Pincock Rearrangement Studies with C , XIII. The W.R. Cullen R. Stewart Thermal Decomposition of l-C^4-2-Butyl Chloro- C.A. McDowell D.S. Scott sulphite. Tetrahedron 18, 1395 (1962) C.C. Lee J.W. Clayton, D.G. Lee and A.J. Finlayson External ExaminerF.H. Westheimer Harvard University MECHANISM OF THE CHROMIC ACID OXIDATION OF ALCOHOLS A spectroscopic investigation of the variation of the pKa of chromic acid with changes in the identity of the mineral acid solvents was made, and the re- ABSTRACT suits were applied to explain observed variations in the rate of oxidation of isopropyl alcohol in solu• The relative rates of chromic acid oxidation of tions of' different mineral acids all having the same eight aryltrifluoromethylcarbinols were determined acidity. in 77.27o acetic acid medium. The primary deuterium isotope effects of these alcohols ranged from 7.40 The results are best explained in terms of a uni- jD for -tolyltri;fluoromethylcarbinol to 12.93 for 3.5 molecular decomposition of a chromate ester via a dinitrophenyltrifluoromethylcarbinol at 25° . The cyclic transition state. rates fitted a Hammett plot best when modified <T + substituent values were used and a modified "rho" value of -1.01 was observed. The rates of oxidation of several halogenated-2- propanols as well as their corresponding 2-d ana• logues were also determined in 77.27, acetic acid and GRADUATE STUDIES in 50.17, sulfuric acid. Results indicated that whil the isotope effect varied with changes in the nature of the alcohol being oxidized, it was constant for a particular alcohol in solutions of varying acidity. Field of Study: Physical Organic Chemistry The thermodynamic parameters for the oxidation of Topics in Physical Chemistry R.F. Snider- two different alcohols under a variety of conditions J.A.R. Coope were determined and found to be approximately the Topics in Organic Chemistry R„A. Bonnett same, A H# = 9 kcal/mole, AS# = -40 cal/mole deg. R, Stewart J. Kutney An extensive investigation of the oxidation of Physical Organic Chemistry R. Stewart alcohols in sulfuric acid solutions ranging from 5 R.E„ Pincock to 957o was conducted and a spectroscopic study was Inorganic Reaction Mechanisms J. Halpern made of the behaviour of chromium VI in this entire Organic Reaction Mechanisms R.E, Pincock region. A Q-* value was obtained for the CF3 group and this was used to determine the "true rate constant", Related Studies: = K r k k0bs/ > f° the chromic acid oxidation of a series of primary alcohols,, A Taft (j* - p* plot Differential Equations S.A. Jennings then yielded a p* value of -0,92 for the rate de• Light J.J. Veit termining step of this reaction. (ii) ABSTRACT The relative rates of chromic acid oxidation of eight aryltrifluoromethylcarbinols were determined in 77.2$ acetic acid medium. The primary deuterium isotope effects for these alcohols ranged "from 7.40 for £-tolyltrifluoromethylcarbinol to 12.93 for 3,5- dinitrophenyltrifluoromethylcarbinol at 25°. The rates fitted a Hammett plot best when modified <5N+ substituent values were used and a modified wrhott value of -1.01 was observed. The rates of oxidation of several halogenated- 2-propanols as well as their corresponding 2-d analogttas were also determined in 77.2$ acetic acid and in 50.1$ sulfuric acid. Results indicated that while the' isotope effect varied with changes in the nature of the alcohol being oxidized, it was constant for a particular alcohol in solutions of varying acidity. The thermodynamic parameters for the oxidation of two different alcohols under a variety of conditions were determined and found to be approximately the same, = 9 kcal/mole, = -40 cal/mole deg. An extensive investigation of the oxidation of alcohols in sulfuric acid solutions ranging from 5 to 95$ was conducted and a spectroscopic study was made (iii) of the behavior of chromium VI in this entire region,, A <5~* value was obtained for the CF^ group and this was used to determine the "true rate constant", k = kQlD5/K, for the chromic acid oxidation of a •if- $ series of primary alcohols. A Taft - 6 plot then yielded a £ value of -0.92 for the rate determining step of this reaction. A spectroscopic investigation of the variation of the pKa of chromic acid with changes in the identity of the mineral acid solvents was made, and the results were applied to explain observed variations in the rate of oxidation of isopropyl alcohol in solutions of different mineral acids all having the same acidity. N The HQ acidity function for nitric and phosphoric acid systems with a 1:1 molar ratio of sodium perchlorate was also determined. ACKNOWLEDGMENTS The author wishes to express his sincere appreciation to Dr. Ross Stewart for his guidance during the course of this research and for his constructive criticism during the preparation of this thesis. Grateful acknowledgment is also made to the University of British Columbia for the award of two Teaching Assistantships (1960-61 and 1961-62), and to the National Research Council of Canada for the award of a Student• ship (1961-62). (v) TABLE OF CONTENTS Page I. HISTORICAL INTRODUCTION 1. Chromic Acid^Oxidation of Organic Compounds 1 2. Chromic'Acid Oxidation of Alcohols 3 3. Primary Kinetic Isotope Effects 24 II. SCOPE OF THE PRESENT INVESTIGATION 36 III. EXPERIMENTAL 39 1. Materials (i) Alcohols 39 (ii) Inorganic Reagents 53 (iii) Indicators 54 2. Kinetic Methods 55 (i) Iodometric Method 56 (ii) Spectrophotometric Method 64 3. Consideration of the Acid Chromate- Bichromate Equilibrium 64 4. Product Analysis 65 5. Determination of pKa Values for HgCrO^ 67 6. Acidity Function for the Phosphoric Acid- Sodium Perchlorate System 72 7. Acidity Function for the Nitric Acid- Sodium Perchlorate System 79 Determination of the Chromate Ester Equilibrium Constant for 2-Methoxy- 1 ethanol and 2,2,2-Trifluoroethanol 80 (vi) Page IV. RESULTS AND DISCUSSION 1. Oxidation of Fluoro Alcohols in 77.2$ Acetic Acid 85 2. Oxidation of some Halogenated 2-propanols in 50.1% Sulfuric Acid 101 i 3. Variation in the Magnitude of Isotope 107 Effects with Changes in Acidity 109 4» Thermodynamic Parameters 5. Oxidation in Concentrated Sulfuric Acid 113 Solutions 6. Determination of the 6 Value for the CF^ Group 136 7. Determination of the "True Rate Constant", k2 = kobs/K* for the Chromic Acid Oxidation of some Primary Alcohols 138 8. Acidity Functions for Nitric and Phosphoric Acid Solutions with Added Sodium Perchlorate 143 9. Variation in the pKa of Chromic Acid with Changes in the Identity of the Mineral Acid Solvent 149 10. Variation in Rate of Chromic Acid Oxidations with Changes in the Identity of the Mineral Acid Solvent 166 V. CONCLUSION 175 VI„ SUGGESTIONS FOR FURTHER RESEARCH 181 VII. APPENDIX 133 VIII. BIBLIOGRAPHY 134 (vii) TABLES I. Variation in Theoretical Isotope Effects 28 with Temperature Hi Data for Rate Plots 59 III. Acidity of Solutions Containing a 1:1 Molar Ratio of H3.P04 to NaClO^ 74 IV. Acidity of Solutions Containing a 1:1 Molar Ratio of HNO^ to NaClO^ 75 V. Data for Figure 10 84 VI. Oxidation of Fluoro alcohols, in 77.2% Acetic Acid 86 VII. Variation in Rate of Oxidation of Phenyltrifluoromethylcarbinols in 77.2$ Acetic with HQ 101 VIII. Rates of Oxidation of Substituted 2-Propanols in 50.1$ Sulfuric Acid 104 IX. Deuterium Isotope Effects for the Oxidation of Isopropyl Alcohol in Perchloric Acid Solutions of,Varying Acidities 108 X. Heats and Entropies of Activation for the Oxidation of Substituted 2-Propanols Under Various Conditions 110 XI. Rates Used in Calculation of Thermodynamic Parameters 111 XII. Extinction Coefficients of Chromium VI in Sulfuric Acid Solutions 117 XIII. Oxidation of CF^CROHCH^ by Chromium VI in Sulfuric Acid Solutions at 25.0°C. 123 XIV. Oxidation of CH3CROHCH3 in Sulfuric Acid Solutions 124 XV. Oxidation of 1,1,1,3,3,3-hexafluoro-2- propanol in Sulfuric Acid Solutions 125 (viii) XVI.
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