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 Institute 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 under stood that any copying from, or publication of, this dis sertation which involves potential financial gain will not be allowed without written permission. 7/25/68 SYNTHESES AND REARRANGEMENTS OF ORGANOALKALI COMPOUNDS A THESIS Presented to the Faculty of the Graduate Division by Yao-Ming Cheng In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemistry Georgia Institute of Technology September, 1970 SYNTHESES AND REARRANGEMENTS OF ORGANOALKALI COMPOUNDS < o u >- ui Q Z >- CQ < Z o < z ui Approved: z I- >- co a z o ca Date applied by Chairman ACKNOWLEDGMENTS The author wishes to express his sincere appreciation to Dr. Erling Grovenstein. Jr. for his suggestion of this problem and for his advice and assistance during the course of this work. The author wishes to thank Dr. Drury S. Caine and Dr. Charles L. Liotta for serving as members of the reading committee. The Graduate Assistantships provided by the Department of Chemistry, which were supported by the National Science Foundation and the National Aeronautics and Space Administration and were held by the author during the course of this research, are greatly appreciated. Fellow students and friends (especially John McKelvey, Dr. Craig Smith, and Don Weser) are also to be thanked for their help and valuable discussions. Among the least known contributors are the librarians (especially Ann Evans), and chemistry staff (especially Don Lillie, G. O'Brien, M. Rucker, and G. Turner). The author also wishes to thank Dr. J. A. Knight for his friendship, encouragement, understanding, and assistance during the period of 1966 to 1967. Above all, the author is indebted, to his wife for her patience, understanding, encouragement, and the sacrifices she made throughout the entire period of graduate study. iii TABLE OF CONTENTS Page ACKNOWLEDGMENTS ii LIST OF ILLUSTRATIONS vi LIST OF TABLES vii SUMMARY ix Chapter I. INTRODUCTION 1 II. REAGENTS AND SOLVENTS 7 III. GENERAL PROCEDURE OF REACTIONS AND INSTRUMENTAL ANALYSES OF PRODUCTS lk IV. EXPERIMENTAL DETAILS l8 Synthesis of l-Chloro-2-p-biphenylylethane 18 p_-Biphenylylacetic Acid 2-p-Biphenylylethanol 1-Chloro-2-p-biphenylylethane Synthesis of l-Chloro-2-p_-biphenylylethane-l, l-d2 23 Methyl p_-biphenylylacetate 2-p-Biphenylylethanol-l,l-d^ l-Chloro-2-p-biphenylylethane-l,1-d^ Synthesis of 2,2-Dimethyl-3-phenylpropanoic Acid 25 2-Benzyl-2-propanol 2-Benzyl-2-chloropropane 2,2-Dimethyl-3-phenylpropanoic Acid Synthesis of Alkyl Anions 26 Reaction of 1-Chlorobutane with Cesium Alloys Reaction of Di-n-butylmercury with Cs-K-Na Alloy Reaction of 1-Chloroheptane with Cesium Alloy iv TABLE OF CONTENTS (Continued) Chapter Page Neophyllithium 35 Preparation and Photochemistry Stability and Rearrangement Effect of N,N,N',N'-Tetramethylethylene- diamine (TMEDA) Effect of Absence of Methyl Iodide Effect of Presence of One Percent of Sodium in Lithium Metal Effects of Iodine and Halides Cleavage with Cs-K-Na Alloy Reaction of Neophyl Chloride with Cesium Alloys 53 Reaction of Neophyl Chloride with Sodium in Dioxan-t-Armyl Alcohol 57 Reaction of Neophyl Chloride with Potassium 57 Synthesis of Phenethyllithium 58 Synthesis of 2-p-Biphenylylethyllithium 59 Reaction of l-Chloro-2 -p_-biphenylylethane - 1,1-d^ with Lithium 69 Reaction of l-Chloro-2-p-biphenylylethane with Cesium and Cs-K-Na Alloy 77 Reaction of l-Chloro-2-p-biphenylylethane- 1,1-d with Cs-K-Na Alloy 80 Reaction of l-Chloro-2-p-biphenylylethane with Potassium 85 Reaction of l-Chloro-2-p-biphenylylethane- 1,1-d^ with Potassium 87 V. DISCUSSION 92 Syntheses 92 1 - Chlor o - 2 -p_-b iphe nylyle thane l-Chloro-2-p-biphenylylethane-l,1-d^ V TABLE OF CONTENTS (Concluded) Chapter Page Syntheses of Simple Primary Carbanions $K Rearrangement During Synthesis of Neophyllithium 98 Reaction of Neophyl Chloride with Potassium and Potassium-Cesium Alloys 106 Analysis of p-Biphenylylethyl and p-Biphenylyl- ethyl-d^ Compounds by NMR Spectroscopy 109 Syntheses and Stability of 2-Arylethyllithium 110 Reactions of l-Chloro-2-p-biphenylylethane and l-Chloro-2-p-biphenylylethane-1,1-d with Cesium, Potassium and Cs-K-Na Alloy 120 VI. RECOMMENDATIONS 133 Appendices A. INFRARED SPECTRA OF p-BIPHENYLYLETHYL AND p-BIPHENYLYLETHYL-d2 COMPOUNDS 13b B. ANALYSIS OF LiAlD^ 135 C. CALCULATION FOR THE PRODUCTS FROM POTASSIUM-t-BuOD REACTION 136 LITERATURE CITED Ib2 VITA 1^+5 vi LIST OF ILLUSTRATIONS Figure Page 1. Synthetic Route to 1-Chloro-2-p-biphenylylethane 93 2. Synthetic Route to l-Chloro-2-p-biphenylylethane-1,1-d 9^ vii LIST OF TABLES Table Page 1. Columns for VPC Analyses of Reaction Products 15 2. Typical Operating Conditions for VPC Analyses 17 3. Reaction of 1-Chlorobutane with Cesium Alloys 28 k. Absolute Yields of Acid and Neutral Material from the Reaction of 1-Chloroheptane with Cesium Alloy 3U 5. Neophyllithium, Effects of Iodine k6 6. Neophyllithium, Effects of Ethyl Iodide and Neophyl Chloride kS 7. Neophyllithium, Effects of Neophyl Chloride ^9 8. Vapor-Phase Chromatographic Analyses of the Acidic Products from Cesium Alloy Reactions of Neophyl Chloride 5^ 9« Vapor-Phase Chromatographic Analyses of Neutral Products in the Synthesis of 2-p-Biphenylylethyl- lithium (Run 3) 6h 10. VPC Analyses of Neutral Products in the Syntheses of 2-£-Biphenylylethyllithium (Runs 5 and 6) 67 11. Vapor-Phase Chromatographic Analysis of the Neutral Material in Run 2 90 12. The nmr Spectra of p-Biphenylylethyl Compounds Ill 13- Reaction of l-Chloro-2-p-biphenylylethane with Lithium 113 lk. Reaction of 1-Chloro-2-p-biphenylylethane-1,1-d with Lithium , 116 15. Reaction of l-Chloro-2-p-biphenylylethane with Cesium and Cs-K-Na Alloy 121 viii LIST OF TABLES (Concluded) Table Page 16. Reaction of l-Chloro-2-p_-biphenylylethane with Potassium 122 17. Reaction of l-Chloro-2-p-biphenylylethane-l, l-d? with Cesium and Cs-K-Na Alloy 123 18. Reaction of l-Chloro-2-p-biphenylylethane-l,l-d^ . with Potassium 12^ 19. The Mass, Abundance (after correction for C-13), Possible Compounds, and Designation of the Satu rated Hydrocarbon Products 130 20. Infrared Spectral Data 13^ ix SUMMARY The purpose of this research was to study the syntheses and possible rearrangements of some organoalkali compounds using lithium metal or cesium alloys as the source of the alkali metal cation. In the first part of this research, the syntheses of simple alkyl anions were investigated under various conditions via the reaction of a simple alkyl halide or a dialkylmercury compound with a binary cesium- potassium alloy (m.p. -kl° ) consisting of 22 percent of cesium and 78 per cent potassium (by weight) or a ternary alloy (m.p. -79.2°) consisting of 73 percent cesium, 2k percent potassium, and 3 percent sodium. The products from these reactions were reacted with solid carbon dioxide to convert the organoalkali compounds to carboxylic acids. These acids were then converted to the corresponding methyl esters by reacting with diazomethane and the esters analyzed by quantitative vapor-phase chromatography. Some of the hydrocarbons which accompanied the acids were analyzed by the same technique. The reaction of 1-chlorobutane with the binary cesium alloy for a short time (from three to 20 minutes) in tetrahydrofuran or diethyl ether at -36 to -^3° gave 0.6 to 5'5 percent of butyl anion as demonstrated by the isolation of valeric acid. In order to test the effect of temperature, the ternary cesium alloy was reacted with 1-chlorobutane in tetrahydrofuran or diethyl ether at temperatures from -73 to -95° for time intervals from two to 15 minutes. The yields of butyl anion ranged from 0.4 to 19.0 per cent with the maximum yield of 19 percent in diethyl ether. The same reac tion in dimethyl ether, over the temperature range ca. -60 to -107° gave X from 0.2 to 13-3 percent yield of "butyl anion. The yield of butyl anion was found to decrease with increasing reaction time. The reaction of 1-chloroheptane with the ternary cesium alloy in tetrahydrofuran at -65° in 17 minutes followed by carbonation gave 1.5 percent of octanoic acid, 2b percent heptane, lb percent of 1-heptene, and 29 percent unreacted chloride. A similar reaction in trimethylamine gave 7*5 percent of octanoic acid, 1.8 percent heptane, 0.5 percent 1- heptene, 5*0 percent octane, and 0.6 percent unreacted chloride. The low yields of products were presumably due to solvent distillation of the hydrocarbon products. In view of the fact that under basic conditions a primary alkyl halide undergoes dehydrohalogenation to give an olefin which, in turn, may react with the excess alkali metal or with carbanion to give unde- sired side products, a better starting material was desirable. The choice for this purpose was di-n-butylmercury. The cleavage of di-n-butylmercury with the ternary cesium alloy for one hour in tetrahydrofuran at -67° gave up to 3^- percent yield of butyl anion. When this cleavage reaction was carried out in diethyl ether at -70°, a 37 percent yield of butyl anion was obtained in 15 minutes and the yield decreased to 11.0 percent after an additional 30 minutes of reaction; in the meantime the yield of the un reacted di-n-butylmercury recovered was found to decrease from bb percent to 2.2 percent.

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