Western Michigan University ScholarWorks at WMU Dissertations Graduate College 8-1984 Naphthalene-2,3-Dialdehyde: A Synthon to 7,9-Polymethylene-8H- Cyclohepta[B]Naphthalene-8-One and a Study of Their Aromaticity Edward O. Crapps Western Michigan University Follow this and additional works at: https://scholarworks.wmich.edu/dissertations Part of the Organic Chemistry Commons Recommended Citation Crapps, Edward O., "Naphthalene-2,3-Dialdehyde: A Synthon to 7,9-Polymethylene-8H- Cyclohepta[B]Naphthalene-8-One and a Study of Their Aromaticity" (1984). Dissertations. 2380. https://scholarworks.wmich.edu/dissertations/2380 This Dissertation-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Dissertations by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. NAPHTHALENE-2,3-DIALDEHYDE: A SYNTHON TO 7,9-POLYMETHYLENE- 8H-CYCLOHEPTA0b}NAPHTHALENE-8-ONE AND A STUDY OF THEIR AROMATICITY by Edward 0. Crapps A Thesis Submitted to the Faculty of The Graduate College in partial fulfillment of the requirements for the Degree of Doctor of Philosophy Department of Chemistry Western Michigan University Kalamazoo, Michigan August 1984 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. NAPHTHALENE-2,3-DIALDEHYDE; A SYNTHON TO 7,9-POLYMETHYLENE- 8H-CYCL0HEPTA|b|NAPHTHALENE-8-0NE AND A STUDY OF THEIR AROMATICITY Edward C. Crapps, Ph.D. Western Michigan University, 1984 This report describes the synthesis of naphthalene-2,3-dialdehyde, and an analytical method for determining its purity by thin layer chromatography. Subsequently, the dialdehyde was condensed with various cyclic ketones to generate a series of polymethylene bridged naphthotropones. It was found that planarity and aromaticity increase with the size of the methylene bridge, although, the bridge must con­ tain six or more methylene groups for the latter to be true. The claim for aromaticity is supported by NMR and IR data, which indicates the positive charge for a perchlorate cation salt is delocalized over the naphthalene and tropone ring system. Furthermore, from the available data, the order of aromaticity for the following tropone derivatives is: tropone > naphthotropone > benzotropone > pyrazolotropone > furo- tropone. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 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. 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Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. 8425233 Crapps, Edward C. NAPHTHALENE-2,3-DIALDEHYDE: A SYNTHON TO 7,9-POLYMETHYLENE 8H-CYCL0HEPTA(B) NAPHTHALENE-8-ONE AND A STUDY OF THEIR AROMATICITY Western Michigan University Ph.D. 1984 University Microfilms Internstionel300 N. zeeb Road, Ann Arbor, Ml 48106 Copyright 1984 by Crapps, Edward C. All Rights Reserved Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Copyright by Edward C. Crapps 1984 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. DEDICATION My mother has waited a long time for this deserving dedication for partial fulfillment of her dream. We have gone through a lot of good and bad times together, and i t has been very seldom in my life that I have been able to say, "mama everything is okay." It's always been trials and tribulations from place to place in my career, mainly because I am too honest and too fair, to let my mother tell it. But, that's the way I was raised. And I feel that i t is only fa ir and honest to dedicate all my efforts that i t took to acquire this degree to you Mama, L illie Crapps, the sweetest lady I know. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS I t has been an honor to work for Professor Robert E. Harmon, a fine chemist, humanitarian, and friend. Any value and significance of this research is due to his outstanding chemical insight. His comprehensive knowledge of chemistry combined with patience and friendship made this endeavor possible. The author would like to express his gratitude to Western Michigan University faculty and staff and to his colleagues in the Department of Chemistry for their help and suggestions. He is especially grateful to his mother and family for their patience, understanding, encouragement, and support during this endeavor. Edward C. Crapps 11 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS ACKNOWLEDGEMENTS i i LIST OF TABLES........................................................................................................ v Chapter I. INTRODUCTION ......................................................................................... 1 I I. STATEMENT OF THE PROBLEM............................................................... 4 I I I . REVIEW OF LITERATURE ........................................................................ 5 Aromaticity ............................................................................... 5 Tropones and Benzotropones .................................................. 8 IV. RESULTS AND DISCUSSIONS............................................................... 13 Preparation of Naphthalene-2,3-dialdehyde................. 13 Spectral Data for the Dialdehyde vs. the Tetrabromide 18 Analytical Method for Determining Purity of Dialde­ hyde ........................................................................................ 21 Calculation .................... 22 Synthesis of 7,9-Polymethylene-8H-cyclohepta[b]naph- thalene-8-ones ................................................................... 24 Naphthotropyl ium I o n s.......................................................... 29 V. EXPERIMENTAL........................................................................................ 32 Instrumentation ....................................................................... 32 General ............................................................................... 32 M a te r ia ls................................................................................... 32 Preparations ............................................................................... 33 i i i Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Naphthalene-2,3-dialdehyde..................................... 33 2 ,2 ,3 ,3-Tetrabromodimethylnaphthalene ................. 33 7.9-Pentamethylene-8H-cyclohepta[b]naphthalene- 8 -o n e........................................................................... 34 7.9-Hexamethylene-8H-cyclohepta[bj naphthal ene-8- o n e ............................................................................... 35 7.9-Nonamethylene-8H-cycl ohepta j^bj naphtha lene- 8-o n e........................................................................... 36 7.9-Decamethylene-8H-cyclohepta ^bj naphthalene- 8-o n e........................................................................... 36 2.7-Diemthyl-4,5-Naphtho [b ]tro p o n e..................... 37 l-Ethoxy-l,3-dihydronaphtho [2,3-c]furan .... 38 7.9-Pentamethyl enecycl ohepta [^b j naphthal