A Special Study of the Alpha-Chlorinated Toluenes and Their Onom Deuterium Derivatives

Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1952 A Special Study of the Alpha-Chlorinated Toluenes and Their onoM Deuterium Derivatives. Stuart Baker Eglin Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Part of the Chemistry Commons Recommended Citation Eglin, Stuart Baker, "A Special Study of the Alpha-Chlorinated Toluenes and Their onoM Deuterium Derivatives." (1952). LSU Historical Dissertations and Theses. 8003. https://digitalcommons.lsu.edu/gradschool_disstheses/8003 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. A SPECTRAL STUDT OF THE ALPHA-CHLORINATED TOLUENES AND THEIR MONO DEUTERIUM DERIVATIVES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Stuart Baker Eglin B. s*, Louisiana State University, 1947 M. S*, Louisiana State University, 1949 August, 1951 UMI Number: DP69381 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI Dissertation Publishing UMI DP69381 Published by ProQuest LLC (2015). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 MANUSCRIPT THESES Unpublished theses submitted for the master!s and doctor*s degrees and deposited in the Louisiana State University Library are available for inspection* Use of any thesis is limited by the rights of the author* Bibliographical references may be noted, but passages may not be copied unless the author has given permission# Credit must be given in subsequent written or published work# A library which borrows this thesis for use by its clientele is expected to make sure that the borrower is aware of the above restrictions# LOUISIANA. STATE UNIVERSITY LIBRARY 119-a 214 S60e8 AGKN0WL£IXJEKjc3JT The author wishes to express his sincere appreciation for the advice and assistance of Dr. 0. A. Nance and Dr. A. R. Choppin who directed this research. He Is also indebted to Dr. George L. Cunningham for helpful advice and suggestions, te Dr. 0. A. Nance, who determined the infrared absorption spectra of the meaodeuierated derivatives of toluene, and to Nr. John W. NoQuaid, who determined the infrared absorption spectra of the monedeuterated derivatives of bsnzal / chloride, for permission to include these spectra in this study. 51 1 7L> Lldod I i s I it c 448893 TABLE OF CONTENTS Acknowledgjaant ....... 11 List of Tables.. •.......... ...... iv List of Figures.• ......................... v A b s t r a c t * . ...... vl Introduction....... 1 Review of the Literature.«......... 3 Experimental Methods. ................... 14 Discussion of Results....................... 42 Conclusions.............. *....... 69 A Selected Bibliography...,....................... 71 Vita.................................................. 79 ill LIST OF TABLES Page I Estimated Resolution and Accuracy of Typical Measurements• •....... ♦...... .. 25 II The Infrared Absorption Spectra of Toluene and the Mq r d douterated Toluenes ....«............ 26 III The Infrared Absorption Spectra of Bensyl Chloride and the tfsnodouterated Benzyl C h l o r i d e s . ,.................. 29 IV The Infrared Absorption Spectra of Benzal Chloride and the Menodeuterated Benzal Chlorides ..... 31 V The Infrared Absorption Spectra of Benzotrichloride and the Monodeufcerated Benzotrlchlorldes ..... 33 VI Assignment of Fundamentals Derived from the Species A^ Vibrations of Toluene ......... 40 VII Assignment of Fundamentals Derived from the Species Vibrations of Toluene. ...... 41 iv LIST OF FIGURES Page 1* The Infrared Absorption Spectra of Bensotriehloride and the Monodeuterated Derivatives} Relative Intensity versus Wave Number* ................ 35 2* The Infrared Absorption Spectra of Bensotriehloride and the Msnodeuterated Derivatives} Per Cent Transmission versus Wave Number; 700 * 2000 enT^*.*«•».»»»*»• .......36 3* The Infrared Absorption Spectra of Bensotriehloride and the Monodeuterated Derivatives; Per Cent Transmission versus Wave Number; 2000 * 3200 earl* .......... 37 4* The Normal Forms of the A^ Carbon Vibrations of Toluene ........ 3# 5* The Normal Forms of the Carbon Vibrations of Toluene*•••••«••.... 39 ABSTRACT The infrared absorption spectra of bensotriehloride and its aonodeuterated derivatives have been determined In the region from 700 - 3200 enT^, These spectra, together with those of the remain* ing alpha-ehl©rinated toluenes and their monodeuter&ted derivatives have been interpreted and frequency assignments made* The results of this Investigation show that the effect of the methyl group of toluene on the vibrational forms of the hydrogen valence-stretching vibrations is to considerably increase the relative motion of the ortho hydrogen atoms. In the lew frequency region, certain of the observed bands appeared to be doublets. This was particularly noted in the spectra of bensal chloride and benzotrichloride. In these molecules, the relatively large chlorine atoms restrict the rotation of the chloromethyl group. If the hindrance to rotation is sufficiently great then the possibility exists that the molecule has two possible con figurations. The hydrogen vibrations of the methyl group of toluene and of the chloromethyl group of benzyl chloride have been studied. In particular, the synmetrical hydrogen has been observed to have a lower frequency than that to which it was previously assigned. vi INTRODUCTION la recent years, increasing efforts have been made to determine the structures and the internal force systems of benzenold compounds through the study of spectral data. The plane regular hexagon structure fer the bensene molecule has been established by means of the interpre* tation of the infrared and Raman spectra ef bensene and certain of its derivatives. in extension ef this work is the effort to interpret orientation phenomena in terns of spectral activity* Changes brought about in the foree constants for the carbon-hydro gen bonds of the benzene ring by the Influence of substituent groups should be of great significance in view of the relation ef the force constants to the formal charges at the various positions of the ring* In order to detect changes in the force constants, the fundamental frequencies which correspond to vibrational modes consisting essentially of ration of the hydrogen atoms must be identified in the spectrum of the molecule. Then the analogous frequencies in the spectra of substituted molecules must be identified so that comparisons can be made. It is ap parent therefore, that a detailed interpretation of the spectra of benzene derivatives having increasing degrees of substitution is of funda mental importance in any study of orientation phenomena. The work to be described consists of the preparation of the monodeuterated derivatives of the alpha-chlorinated tolueneB and the determination (i) (2) ef their infrared spectra* An analysis of these spectra and the tentative assignment of some of the observed frequencies comprise the major portion of this work. REVIEW OF THE LITERATURE Within recent years, many advances have been made in the fields having relation to molecular spectra and their dependence on molecular structure* This review is not intended as a comprehensive survey of all such advances* Instead, it is intended to present in context a group ef representative papers and ether publications covering the work done on problems directly related to the present one* For the formal treatment ef the theory and methods ef spectral analysis, reference is given to certain books and review papers which are considered to be authoritative in their respective fields* Outstanding among these is Hersberg's Infrared and Raman Spectra ef Polyatomic Mole cules (3 7) which is generally recognised aj definitive work in the field* It includes a thorough development of the fundamental theory and the methods used in the interpretation of molecular spectra and applies them to specific molecules of many symmetry types* Theoretical Chemistry by Gladstone (32) contains an excellent treatment ef the methods and theory ef the interpretation ef vibrational spectra* The book by Kohlrausch, (4 7 ) is a useful reference work dealing with the analysis ef spectra, with considerable emphasis on aromatic compounds* Actual data for many compounds are cataloged, and literature references are given for many more compounds not included in the cataloged data* Structure of Molecules and the Chemical Bond by Syrkin and Dyatkina (#4) is a major contribution which describes the methods of determining molecular structure (3) (4) from various physical characteristics including vibrational frequencies* Vibrational

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