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Comparison of the Ozonolysis Products of the Methylnaphthalenes and Dimethylnaphthalenes in Hexane, Methanol, and Water Michael Dale Gaul Iowa State University

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Comparison of the Ozonolysis Products of the Methylnaphthalenes and Dimethylnaphthalenes in Hexane, Methanol, and Water Michael Dale Gaul Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1984 Comparison of the ozonolysis products of the methylnaphthalenes and dimethylnaphthalenes in hexane, methanol, and water Michael Dale Gaul Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Analytical Chemistry Commons Recommended Citation Gaul, Michael Dale, "Comparison of the ozonolysis products of the methylnaphthalenes and dimethylnaphthalenes in hexane, methanol, and water " (1984). Retrospective Theses and Dissertations. 8988. https://lib.dr.iastate.edu/rtd/8988 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting through an image and duplicating adjacent pages to assure complete continuity. 2. When an image on the film is obliterated with a round black mark, it is an indication of either blurred copy because of movement during exposure, duplicate copy, or copyrighted materials that should not have been filmed. For blurred pages, a good image of the page can be found in the adjacent frame. If copyrighted materials were deleted, a target note will appear listing the pages in the adjacent frame. 3. When a map, drawing or chart, etc., is part of the material being photographed, a definite method of "sectioning" the material has been followed. It is customary to begin filming at the upper left hand comer of a large sheet and to continue from left to right in equal sections with small overlaps. If necessary, sectioning is continued again-beginning below the first row and continuing on until complete. 4. For illustrations that cannot be satisfactorily reproduced by xerographic means, photographic prints can be purchased at additional cost and inserted into your xerographic copy. These prints are available upon request from the Dissertations Customer Services Department. 5. Some pages in any document may have indistinct print. In all cases the best available copy has been filmed. Universi^ Micrallms International 300 N. Zeeb Road Ann Arbor, Ml 48106 8423633 Gaul, Michael Dale COMPARISON OF THE OZONOLYSIS PRODUCTS OF THE METHYLNAPHTHALENES AND DIMETHYLNAPHTHALENES IN HEXANE, METHANOL, AND WATER Iowa State University PH.D. 1984 University Microfilms Intornstionsl 300 N. Zeeb Road, Ann Arbor, Ml 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V . 1. Glossy photographs or pages 2. Colored illustrations, paper or print 3. Photographs with dark background 4. Illustrations are poor copy 5. Pages with black marks, not original copy 6. Print shows through as there is text on both sides of page 7. Indistinct, broken or small print on several pages 8. Print exceeds margin requirements 9. Tightly bound copy with print lost in spine 10. Computer printout pages with indistinct print 11. Page(s) lacking when material received, and not available from school or author. 12. Page{s) seem to be missing in numbering only as text follows. 13. Two pages numbered . Text follows. 14. Curling and wrinkled pages 15. Other University Microfilms International Comparison of the ozonolysis products of the methylnaphthalenes and dimethylnaphthaienes in hexane, methanol, and water by Michael Dale Gaul A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Chemistry Major; Analytical Chemistry Approved ; Signature was redacted for privacy. In Charge/^f Major Work Signature was redacted for privacy. Signature was redacted for privacy. Iowa State University Ames, Iowa 1984 ii TABLE OF CONTENTS Page LIST OF ACRONYMS AND ABBREVIATIONS iv INTRODUCTION 1 LITERATURE REVIEW 8 Ozonolysis of Naphthalene and Derivatives in Nonparticipating Solvents 8 Ozonolysis of Naphthalene and Derivatives in Participating Solvents 28 METHODS 61 Preliminary Work 61 Ozone generator 61 Reagents 63 Ozonolysis Reaction Conditions 65 Hexane 65 Methanol 67 Water 68 Instrumental Methods of Analysis 74 Gas chromatography 74 Gas chromatography-mass spectrometry 78 Gas chromatography-Fourier transform infrared spectrometry 80 Synthesis of Authentic Standards 81 RESULTS 83 Reactions in Organic Solvents 83 Preliminary work 83 iii Page The methylnaphthalanes 88 The dimethylnaphthalenes 94 Reactions in Water 109 Preliminary work 109 The methyInaph thaienes 113 The dimethylnaphthalenes 116 DISCUSSION 139 Preliminary Work 139 Reaction conditions 139 Post-reaction treatment 152 Analysis 158 Ozonolysis Products in n-Hexane and Methanol 168 Ozonolysis Products in Water 184 SUMMARY AND CONCLUSIONS 203 SUGGESTIONS FOR FUTURE WORK 206 BIBLIOGRAPHY 208 ACKNOWLEDGEMENTS 217 APPENDIX 218 Spectral Data 218 iv LIST OF ACRONYMS AND ABBREVIATIONS BHT - butylated hydroxytoluene CI - chemical ionization EC - electrochemical (detector) EI - electron ionization GC - gas chromatography GC-FTIR •- gas chromatography-Fourier transform infrared spectrometry GC-MS - gas chromatography-mass spectrometry G-S - Gram-Schmidt HPLC - high performance liquid chromatography IR - infrared Mt - molecular ion (odd electron) MH"^ - protonated molecular ion (even electron) NMR - nuclear magnetic resonance m/z - mass-to-charge ratio ppm • part per million psi • pounds per square inch UV • ultraviolet (detector) 1 INTRODUCTION "With crack on crack of thunder, Zeus let fly a bolt against the ship, a direct hit, so that she bucked, in reeking fumes of sulphur and all the men were flung into the sea." Homer (1) The Odyssey Ozone is a product of electrical discharges and photochemical reac­ tions in the earth's atmosphere. Ozone's characteristic odor attracted scientific attention as early as 1785 (2) when van Marum, a Dutch physicist, noted its presence. In 1801, Cruickshank (as cited in Rideal (2)) and also Schonbein (3) in 1840 observed ozone's characteris­ tic odor during electrolysis and sparking experiments. Schonbein recog­ nized that this was the same substance produced by lightning during storms and gave the name "ozone" to this new substance. The name ozone was derived from the Greek word "ozein" meaning "to smell". Schonbein, along with other scientists, went on to characterize this new chemical substance thoroughly during the following years. Scientific discovery and advancement involving ozone was closely paralleled by progress in industrial applications and technology. Advances in the industrial technology were made so quickly that they often preceded a physical and chemical understanding of the industrial process. Almost ten years before the determination of the molecular formula of ozone, von Siemens (4) developed an ozone generator which was the prototype of the modern electrical discharge generators. The power­ ful oxidizing properties of ozone, particularly with organic matter, 2 were noted by Schonbein and were put to industrial use as early as 1868. Before the turn of the century, ozone was being used for sugar refining, linen bleaching, food preservation, artificial aging of alcoholic bever­ ages, and the deodorization of noxious gases. A major reference on ozone technology was published in 1904 by La Coux des Roseaux (5) which has over 250 pages devoted to the industrial uses of ozone. What proved to be the single most important industrial use of ozone was discovered in 1886 by de Meritens in France as cited by La Coux des Roseaux (5). He found that ozonated air very effectively disinfected polluted water. This was the beginning of the use of ozone for potable water treatment- Commercial water disinfection using ozone was shown feasible by Tindal on a pilot plant scale in Paris in 1896 (6). Between 1902 and 1906, three full-scale water treatment plants using ozonation went into operation in both Germany and France. By this time, the value of ozone in water treatment was widely recognized and full-scale water treatment plants incorporating ozone appeared in several countries after 1906. It seems likely that the first continuous water treatment process used in the United States incorporated ozone for water disinfection (7). These treatment plants were installed in Philadelphia between 1900 and 1905 by Vosmaer (6), a native to the Netherlands, Ozonation, however, continued to be used predominantly in Europe where its use in water treat­ ment increased despite the economic advantages of chlorine. In 1940, there were 114 water treatment plants using ozonation (7). Of these 114 plants, 90 were located in France and only two in the United States,
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