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In Presenting the Dissertation As a Partial Fulfillment of The "In presenting the dissertation as a partial fulfillment of the requirements for an advanced degree from the Georgia Institute of Technology, I agree that the Library of the Institution shall make it available for inspection and circulation in accordance with its regulations governing materials of this type. I agree that permission to copy from, or to publish from, this dissertation may be granted•by the professor under whose direction it was written, or, in his absence, by the dean of the Graduate Division when such copying or publication is solely for scholarly purposes and does not involve potential financial gain. It is understood that any copying from, or publication of, this dissertation which involves potential financial gain will not be allowed without written permission. SOME STUDIES ON THE HALIDES OF METHANE PART I 'WE EFFECT OF HALOGEN ATOMS UPON THE SN2 REACTIVITY OF OTHER HALOGEN ATOMS ATTACHED TO 1HE SAME CARBON ATOM PART II AN EMPIRICAL METHOD FOR PREDICTION OF THE BOILING POINTS OF THE HALOMETHANES PART III A CORRELATION OF REACTIVITIES IN THE BASIC SOLVOLYSIS OF HALOFORMS A THESIS Presented to the Faculty of the Graduate Division By Stanton Jay Ehrenson In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry Georgia Institute of Technology' June 1957 SOME STUDTES ON HALIDES OF METHANE PART I TKE 0TECT OF HALOGEN ATOMS UPON THE 2 REACTIVITY OF OTHER HALOGEN ATOMS ATT BED TO TEE SAME CARBON ATOM PART II AN EMPIRICAL METHOD FOR PREDICTION OF TAE BOILING POINTS OF TEE HALOMETHANES PART III A'CORRELATION OF REACTIVITIES IN THE BASIC SOLVOLYSIS OF HALOFORMS Approved: L 77. / Date approved by Chairman:, Fai, ud ii J ACENOWLEDGEMENTS My sincerest thanks are to be expressed initially to Dr. Jack Hine whose continued interest and guidance served as invaluable and stimulating aids during the course of this investigation. To the National Science Foundation, the Tennessee Eastman Corporation and the Office of Ordnance Research my gratitude is also due for the grants that supported the work. I am likewise appreciative of the time and helpful information concerning use of the electronic computer provided by Drs. W. F. Atchison and J. C. Currie. iii TABLE OF CONTENTS Page ACKNOWLEDGEMENTS iii LIST OF TABLES vi LIST OF ILLUSTRATIONS ix SUMMARY PART I Chapter I INTRODUCTION 2 II PROCEDURE 4 Experimental 4 Preparation and Purification of Reagents 6 III RESULTS 11 IV DISCUSSION AND CONCLUSIONS 23 V RECOMMENDATIONS 32 APPENDIX - TABLES 33 BIBLIOGRAPHY 44 PART II Chapter I INTRODUCTION 48 II PROCEDURE 51 The Correlation Equation 51 Data Survey 53 Least Squares Treatment 57 Computer Calculations 57 iv Chapter Page III RESULTS 6o IV DISCUSSION AND CONCLUSIONS 61 V RECOMMENDATIONS 63 BIBLIOGRAPHY PART III Chapter I INTRODUCTION 68 II PROCEDURE 71 Experimental 71 Preparation and Purification of Reagents 75 III RESULTS 77 IV DISCUSSION AND CONCLUSIONS 86 The Correlation Equation 86 Hydrolysis Reactions in Pure Aqueous Solution 91 Hydrolysis Reactions in Aqueous Dioxane 96 Methanolysis Reactions 102 General Conclusions 103 V RECOMMENDATIONS 105 APPENDIX - TABLES 107 BIBLIOGRAPHY 123 VITA 125 V LIST OF TABLES PART I Table Page 1. Kinetic Constants for Reactions of Methylene Halides with Sodium Thiophenolate in Methanol 14 2. CH2C1Br + C 6H5SNa in Absolute Methanol at 40°C. 19 1 3. Relative Rates of Chloride Displacement by Iodide Ion in Acetone at 50 °C. 30 4 and 5. CH2I2 + C6H5SNa in Absolute Methanol at 0 and 410c. 34 6 and 7. CH2BrI + C 6H5SNa in Absolute Methanol at 0 and 40 °C. 35 8 and 9. CH2C1I + C 6H5SNa in Absolute Methanol at 0 and 40°C. 36 10 and 11. CH2FI + C 6H5SNa in Absolute Methanol at 0 and 50 °C. 37 12 and 13. CH 2 Br2 + C6Ho 5SNa in Absolute Methanol at 0 and 40°C. 38 14. CH C1Br • C 2 6H5SNa in Absolute Methanol at 0 °C. 39 15. CH2FBr + C 6H5SNa in Absolute Methanol at 0°C. 39 16. CH2FBr + C6H5SNa in Absolute Methanol at 40 °C. 40 17. CH2C12 + C6H5SNa in Absolute Methanol at 20.35°C. 40 18. CH2 Cl2 + C6Ho 5SNa in Absolute Methanol at 40°C. 41 19. c2H5Br + KI in Acetone at 20°C. 4-1 20. C H 2 5Br + KI in Acetone at 0 °C. 42 21. Kinetic Constants for Reactions with Iodide Ion in Acetone 1 3 22. Kinetic Constants for Reactions with Sodium Methoxide in Methanol 43 vi PART II Table Page 1. Normal Boiling Points of the Halomethanes Assigned Double Weight- in•the Correlation 54 2.. Normal Boiling Points of the Halomethanes Assigned Single Weight in the Correlation 55 3. Predicted and Observed Boiling Points of Some Halomethanes 63_ PART III 1. CHC1I 2 + NaOH in Two-Thirds Aqueous Dioxane at 50°C. 79 2. Haloform Hydrolysis Rates in Aqueous Dioxane at 35 °C. 79 3. Haloform Hydrolysis Rates in Water, Two-Thirds Dioxane and Rates of Methanolysis 8o 4. CHC1Br + NaOH in Water at 2 50°C. 85 5. Kinetic Constants for the Basic Hydrolysis of, and the Proton Removal from, Haloforms in Aqueous Solution at Zero Degrees 92 6. Kinetic Constants for the Basic Hydrolysis of Haloforms in Two-Thirds Aqueous Dioxane at 35°C. 100 7 and 8. CHC1 + NaOH in 78 and 18 Per Cent Aqueous Dioxane at 35 °C 3. 108 9 and 10. CHC13 + NaOH in 48 and 66 2/3 Per Cent Aqueous Dioxane at 35 °C. 109 11 and 12. CHC13 + NaOH in 72 and 60 Per Cent Aqueous Dioxane at 35°C. 110 13 and 14. CHC12Br F NaOH in 60 and 50 Per Cent Aqueous Dioxane at 35 °C. 111 15 and 16. CHC12Br NaOH in 66 2/3 and 29.4 Per Cent Aqueous Dioxane at 35°C. 112 17 and 18. CHC12Br + NaOH in 40 and 75 Per Cent Aqueous Dioxane at 35°C. 113 vii Table Page 19 and 20. CHBr3 + NaOH in 36.4 and 50 Per Cent Aqueous Dioxane 114 at 35 °C. 21. CHBr3 + NaOH in 66 2/3 Per Cent Aqueous Dioxane at 35°C. 115 22. CHC11, + NaOH in 66 2/3 Per Cent Aqueous Dioxane at 50°C. 115 23. CHC1I2 + NaOH in 66 2/3 Per Cent Aqueous Dioxane at 67.1°C. 116 24. CHC13 + NaOCH3 in Absolute Methanol at 50°C. 116 25 and 26. CHC12Br and CHC1Br2 + NaOCH 3 in Absolute Methanol at 50 °C. 117 27. CHC12Br + NaOH in Water at 50°C. 118 28. CHBr3 + NaOH in Water at 25°C. 118 29 and 30. CHBr3 + NaOH in Water at 35 and 50°C. 119 31 and 32. CHC12I + NaOH in Water at 25 and 50°C. 120 33. CHC1I2 + NaOH in Water at 50°C. 121 II 34. CHC1I2 + NaOH in Water at 67.1 °C. 122 35. CHBr3 + NaOH in Water at 35 °C. 122 If viii LIST OF ILLUSTRATIONS PART Figure Page 1. Parameter A versus the Time Parameter T 18 PART II 1. Log Factor of Equation (2) versus Time for CHC1Br + NaOH in 2 Water at 50°C. 8 it. 2. The Relative Rates of Hydrolysis of Chloroform, Dichloro- bromomethane and Bromoform versus Dioxane Concentration at 35°C. 101 ix SUMMARY Part I Information on the effects of halogen substitution for hydrogen in the methyl halides had previously been obtained by kinetic studies of the SN2 reactions with methoxide ion in Methanol and iodide ion in acetone. While the deactivation effects of the halogens as substituents were qual- itatively similar for the reactions with both these nucleophiles, differ- ences in magnitude were evident, In order to provide a wider perspective on the subject and in an attempt to uncover the reasons for the quantita- tive differences noted, the reactions of the methylene halides with the strongly nucleophilic thiophenolate ion in methanol were studied. All the methylene halides examined with the exception of those con- taining fluorine react by the mechanism k 1 C + CH rr H SCH Y + X 6 5 - 6 5 k 2 C H + SCH,Y---,(C6 H5 S) 2cH2 Y 6 5' o5 d. with k2>>kl . The fluoromethyl halides undergo the initial displacement; the resulting fluoromethyl phenyl thioether is resistant to further at- tack. Experimentally following the reactions by titration of the unre- acted thiophenol with standard methanolic iodine allowed calculation of the rate constants (k ) and the heats and entropies of activation that appear in Table 1. Table 1. - Kinetic Constants for 'Reactions of Methylene Halides with Sodium Thiophenolate in Methanol 10k (1./m.s.) 1 Ma a Halide 0.0° 40 ° lc.cal.. e.u. ICH2I 1 1.19 ± .01 108 ± 2 18.6 ± 0.1 -8.5 ± o.4 Brall 0.811 ± .018 79.8 ± 1.6 18.9 ± 0.2 -7.9 ± 0.6 2 1 1.83 ± .,03 149 ± 3 C1CR2I 18.1 ± 0.2 -9.2 ± 0.7 47.9 ± .9 964 ± 20 2 15.9 ± 0.2 -10.8 ± 0.8 FCH2I BrCHBr 1 .0798 ± .0004 10.0 ± .2 20.0 ± 0.2 ± o.5 C1CH2Br .228 ± .002 25.1 ± .3 19.4 t 0.1 -8.6 ± o .3 FCH2Br 1.88 ± .03 152 ± 5 18.1 ± 0.2 -9.2±0.8 1 C1CH2C1 .0214 ± .0010 3 .222 ± .007 21.1 ± 0.7 -12.5 ± 2.6 -Rate constants contain a statistical factor of one-half. 2 At 30 °C. 3At 20,35 °C. Consistent with the data obtained from the reactions with iodide and methoxide, the alpha substituent halogens are seen to deactivate hal- ide displacement by thiophenolate in the order Br>I>C1>F The deactivation effects in the reactions with thiophenolate are found to exhibit greater quantitative similarity to those with iodide than with methoxide ion.
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