Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1952 Some derivatives of dibenzofuran and dibenzothiophene Robert Kelly Ingham Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Ingham, Robert Kelly, "Some derivatives of dibenzofuran and dibenzothiophene " (1952). Retrospective Theses and Dissertations. 13987. https://lib.dr.iastate.edu/rtd/13987 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]. SOME DERIVATIVES OP DIBENZOPURAN AND DIBENZOTHIOPHENE by Robert Kelly Ingham A Dissertation Submitted to the Graduate Faculty in Partial Pulfillment of The Requirements for the Degree of DOCTOR OP PHILOSOPHY Major Subject: Organic Chemistry Approved: Signature was redacted for privacy. In Charge of Major Work Signature was redacted for privacy. Head of Major Departil^nt Signature was redacted for privacy. Dean of Graduate College Iowa State College 1952 UMI Number: DP12780 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. UMI UMI Microform DP12780 Copyright 2005 by ProQuest Information and Learning Company. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest Information and Learning Company 300 North Zeeb Road P.O. Box 1346 Ann Arbor, Ml 48106-1346 ACKNOWIEDOMENT The author wishes to express his sincere appreciation to Dr. Henry Gilman for helpful advice, criticism and encouragement given throughout the course of this investigation. TI04'H) -lli- TABLE OP CONTENTS Page INTRODUCTION . 1 HISTORICAL ..... 5 Chemotherapy of Tuberculosis 5 Dialkylaminoalkylamines of Fused Heterocyclic Systems . 3k- Derivatives of Dibenzofuran and Dibenzothiophene. 43 EXPERIMENTAL 122 Dibenzofuran Derivatives 122 Preparation of 3-nitrodibenaofuran .... 122 Preparation of 3-®u»inodibenzofuran .... 123 Bromination of 2-bromo-3-acetaraino- dibenzofuran ............... 12$ Preparation of 2«-br(»nodibenzof\u:>an .... 126 Reductive debromination of 2-brcHttO- dibenzofuran ....... 127 Reductive debromination of 2,8-dibromodibenzofuran. ........ 128 Rim X 126 Run II 128 Run III 128 Run IV 128 Nitration of 2,8-dibromodibenzofuran . 129 Preparation of 2-bromo-7-nitro- dibenzofuran I30 Preparation of 2-bromo-7-amino~ dibenzofuran I3I Preparation of 2-brorao-7-acetamino- dibenzofuran I32 Bromination of 2-brorao-7-acetamino- dibenzofuran ...... 4, . 132 Preparation of 2,8-dibrorao-3-anilno- dibenzofuran 133 Deamination of 2,8-dibr<»no-3-amino- dibenzofuran 133 -Iv- Page Preparation of 2-nitrodibenzoftiran .... 13ii. Preparation of 2-bromo-8-nitro- dibensofiiran 135 Preparation of 3-cyanodibenzofuran .... 136 Preparation of 3-dil5«nzofuran- carboxylic acid 137 Metalation of 3-aminodibenzofuran. .... 138 Preparation of l^-aminodibenzofuran .... 139 Preparation of 3-nitrodibenzof\aran from 3-<uninodibenzofuran II4.0 Preparation of i|.-nitrodibenzof\xran frcan l4.-aminodlbenzofuran li|2 Preparation of 2-chloromethyl- dibenzofuran ll|J2 Run I IkZ Run II Ili3 Rtin III liiif Run IV liil^. Dibenzothiophene Derivatives IkS Preparation of 2-bromodibenzo- thiophene li\$ Preparation of 2-broraodibenzo- thiophene oxide. li).6 Preparation of 2-bromo-7-nitro- dibenzothiophene-5-dioxide lij.? Preparation of 2-brcaBO-7-aiaino- dibenzothiophene-S-dioxide ....... Riui I.... 1)4.3 Run II lJi9 Preparation of 2-nitrodibenzo- thiophene. 11|.9 Preparation of 2-acetaininodibenzo> thiophene I51 Nitration of 2-acetaminodibenzo- thiophene 152 Attempted hydrolysis of nitro-2- acetaminodibenzothiophene 153 Run I........ 153 Run II 153 R\in III 153 -V- Preparation of 2-bromo-8-nitro- dibenzothiophene . 15^4- Preparation of 2-bromo-8-araino- dibenzothiophene ..... .. 155 Preparation of dibenzothiophene-5-oxlde. 156 Reaction of dibenzothiopheno-5"0*l<i® with bromine 157 Reaction of dibenzothiophene-5-oxide with hydrogen bromide. 158 Reaction of dibenzothiophene-5-oxide with N-bromosuccinimide . 159 Preparation of 3'-Aminodibenzothlophene . 160 Preparation of 3-hromodibenzothlophene . 161 From 3--^inodibenzothiophene 161 Prom 3-bromodibenzothiophene-5- dioxide 163 Preparation of I|.-aminodibenzothlophene . • I6i|. Preparation of 4-(P-dimethylamino- ethylamino)-dibenzothiophene 1614. Preparation of I4.-(p-dimethylamino- isopropylaralno)-dibenzothiophene .... 165 Nitrogen Heterocyclic Derivatives 166 Reaction of phenothiazine with lithiixm . 166 Run I 166 Run II 168 Run III . 168 Reaction of 10-ethylphenothiazine with lithium 169 Run I 169 Run II. ....... 170 Reaction of carbazole with lithium .... 160 Preparation of some heterocyclic sulfides ...... 170 Preparation of 2-(benzyl- meroapto)-<luinoline I7I Preparation of 2-(n-dodecyl- mercapto)-quinolTne 172 Preparation of 2-(n-hexadecyl- mercapto)-quinolTne 172 -vl- Page Preparation of 2-(n-octadecyl- mercapto)oquinolTne 172 Preparation of 2-benzothiazolyl 2-quinolyl sulfide 173 Preparation of 2-{l|.-phenyl- thiazolyl) 2-quinolyl sulfide . • 173 Preparation of 2-benzlinidazolyl 2-quinolyl sulfide 173 Preparation of i|.-(7-chloro- quinolyl) 2-benzothiazolyl sulfide 1714- DISCUSSION 175 Dibenzofuran Derivatives. 175 Dibenzothiophene Derivatives. ... 186 Nitrogen Heterocyclic Derivatives ....... 195 Suggestions for Further Research 199 SUMMARY 202 INTRODUCTION The llteratvire of dibenzofxiran (I) and dlbenzothlo- phene (la) is somewhat confusing because of the different systems of niarabering employed. The system used In this work and In all recent publications in this coxmtry is that adopted in 1937 by Chemical Abstracts. I la The numbering system employed by Chemical Abstracts prior to 1937 and that still employed in most coimtries other than the United States is II Ila Usually, when the former system (I,la) is involved the com­ pound is listed as a derivative of dibenzofuran or dibenzo- thiophene, while with the latter system (II,Ila) it is described as a derivative of diphenylene oxide or diphenylene sulfide; this generalization is not infallible, however, especially with the older literature. A third system of numbering recommended by Professor A. M. Patterson in this country and by Professor M, Richter abroad^ was prevalent in the literatxire of the early 1930»s (III,Ilia). This system was discarded before it had become common. Ill Ilia Due to these divergent systems considerable care must be taken when consulting the literature to ascertain the method of numbering* A brief review of the chemistry of dibenzofuran may be found among Elderfield's heterocyclic volumes.2 Perhaps for a more complete accoxmt of the chemistry of dibenzofuran, and especially for accounts of the problems of orientation and structure proof of derivatives of dibenzofuran and the solutions to these problems one should consult, preferably * ^ H. Oatfield, Unpublished Master's Thesis, Iowa State College, 1933• 2 R. C. Elderfleld, "Heterocyclic Compounds", John Wiley and Sons, Inc., New York, N. Y., 1951 * Vol. 2. -3- consecutively, dissertations from this laboratory concerning this toplc.l'3A.5.6.7,8,9,10 A brief review of the chemistry of dibenzothiophene likewise may be found in Elderfield'a Volume II.2 An addi­ tional review can be obtained by consulting works of Jacoby,^^ Avakian,^^ Nobis and Esmay.^^ A bibliography ^ D. M. Hayes, Unpublished Master's Thesis, Iowa State College, 19311-. ^ M. W. Van Ess, Doctoral Dissertation, Iowa State College, 1936. ^ P. R. Van Ess, Doctoral Dissertation, Iowa State College, 1936. ^ L. C. Cheney, Doctoral Dissertation, Iowa State College, 1938. 7 j« Swislowsky, Doctoral Dissertation, Iowa State College, 1939* ® H. B. Willis, Doctoral Dissertation, Iowa State College, 1943• ^ J. R. Thirtle, Doctoral Dissertation, Iowa State College, 19i4-3 • J. A. Hogg, Doctoral Dissertation, Iowa State College, 191^1.. A. L. Jacoby, Doctoral Dissertation, Iowa State College, 1938• S. Avakian, Doctoral Dissertation, Iowa State College, 19iji|.« J, P. Nobis, Doctoral Dissertation, Iowa State College, 19i|.8 • D. L. Esiaay, Doctoral Dissertation, Iowa State College, 1951• of dibenzothiophene and its derivatives through 1950 may be found in the dissertation of Esmay.^ The increased interest in dibenzofuran and dibenzothio­ phene is evidenced by the increased volume of literature concerning these compounds and their derivatives. It is also noteworthy that a considerable number of patents con­ cerning derivatives of dibenzofwan and dibenzothiophene have been granted in recent years, the chief interests being toward possible pharmaceuticals or dyes. HISTORICAL The purpose of the literature survey to be discussed In the following pages Is to furnish a general backgrotmd of information pertinent to the experimental work carried out during the course of this study. The