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STUDIES in CHEMOTHERAPY PREPARATION of CERTAIN ACRIDINE DERIVATIVES a Thesis Presented in Fulfillment of the Requirements for Th

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STUDIES in CHEMOTHERAPY PREPARATION of CERTAIN ACRIDINE DERIVATIVES a Thesis Presented in Fulfillment of the Requirements for Th '• V ... • -■.6'; * i'„ S' (<. ".. *• STUDIES IN CHEMOTHERAPY PREPARATION OF CERTAIN ACRIDINE DERIVATIVES \ U A thesis presented in fulfillment of the requirements for / the degree of Doctor of Philosophy at the University of Glasgow v <. ** ... ■. i •" r • - ■■ . ~ - «■ t I* ... - >.*v, >r:.v;•/••' r • \ >. • .> - • .v ~ . v. - ■?«■-*223®$^:-• r fey Margaret Joan Hunter I \ \ k /1I _ y . • •• A v % , _ um • . *• V * ' •tw* . •« J u * . .* • :-* -.i• * -. V. — .-• •" -* . « — . i ’ ’ v»-sr » •. ProQuest Number: 13855720 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 com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 13855720 Published by ProQuest LLC(2019). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 The author wishes to acknowledge the assistance and encouragement given by the late Professor F.J. Wilson, Dr. M.Jff. J. Sutherland and, Professor W.M. Cumming. CONTENTS Introduction....... 2 Nomenclature .... 2 Preparation of Acridine Derivatives....... 3- Properties of Acridine Derivatives................. 11 Preparation of Nitriles ....... 13 Therapeutic Activity................................... 15 Introductory. ................. 15 Structure and Activity........... 17 Mode of Action.................... 19 Effects on Host...........’....... 22 Uses.............. 23 Activity of Amidine Grouping.... ^ * * .. 24 Reasons for Research... ................. 25 Part I Theoretical . 28 Experimental........................... ........ :...... 40 Preparation of 2-cyaho-8-aminoacridine.............. 40 Preparation of 2,8-dicyanoacridine.................. 43 Preparation of 5-cyanoacridine . ....... 46 Preparation of 5-amidinoacridine ..... 55 Part II Theoretical. J. 62 Experimental, ................... 80 Syntheses of 1-cyanoacridines * Preparation of 2-aminobenzonitrile................ 84 Preparation of 2 -cyanodiphenylamine-2- carhoxylic acid. ............... 87 Preparation of 1-cyanoacridone * .88,106 Preparation of l-cyano-5-ehloroacridine..... 89,106 Preparation of l-amidino-5-aminoacridine........... 91 A Preparation of 1-cyanoacridine................ 92 Preparation of l-cyano-5-ethoxyacridine............. 95 Preparation of 3-cyano-2-bromobenzoic acid.......... 97 Preparation of 6-cyanodiphenylamine-2- carboxylic acid................................ 304,108,X9 Preparation of sodium 2-bromo-3-cyanobenzoate...... 108 Syntheses of 2- and 4-cyanoacridines Preparation of 3-aminobenzonitrile............... 110 Preparation of 3 -cyanodiphenylamine-2- carboxylic acid...................... 112 Preparation of 2- and 4-cyanoacridones............ 113 Preparation of 2- and 4-cyano-5-chloroacridines 114 Separation of 2- and 4-cyanoacridones.............. 115 Preparation of 2-cyano-5-chloroacridine........... 118,134 Preparation of 4-cyano-5-chloroacridine........... 119 Preparation of 4-amidino-5-aminoacridine.......... 120 Separation of 2- and 4-cyano-5-chloroacridines..... 120 VPreparation of 2-bromo-4-cyanobenzoic acid......... 122 Preparation of 5-cyanodiphenylamine-2- carboxylic acid................................. 130 Preparation of 2-cyanoacridone............... 133 Preparation of 2-amidino-5-aminoacridine.......... 135 Preparation of 2-cyanoacridine............... 136 Preparation of 2-chloro-6-nitrotoluene........... 138 Preparation of 3-nitrophthalic anhydride.......... 139 Preparation of 3-chlorophthalic acid * . 140 Preparation of diphenylamine-2,3-dicarboxylic acid... 141 Preparation of 4-carboxyacridone.-................. 142 Syntheses of 3-cyanoacrldines Preparation of 4-aminobenzonitrile 144 I Preparation of 4 -cyanodiphenylamine-2-carboxylic . j acid................. r.... .............. 149 Preparation of 3-cyanoacridone .......... .150,165 Preparation of 3-cyano-5-chloroacridine........... 15(^166 Preparation of 3-amidino-5-aminoacridine.......... 153 Preparation of 3-eyanoacridine.............. 158 Preparation of 3-cyano-5-ethoxyacridine........... 159 Preparation of 2-chloro-5-cyanobenzoic acid. ...... 161 Preparation of 4-cyanodiphenylamino-2-carboxylic acid........................................... 163 Syntheses of 2,6- and 2,8-dicyanoacridines Preparation of 2 -5-dicyanodiphenylamine-2- carboxylic acid............................ 167 Preparation of 2,6- and 2,8-dicyanoacridones. 168 Preparation of 2,6- and 2,8-dicyano-5-chloro- acridines.............................. 169 Separation of 2,6- and 2,8-dicyanoacridones.... 169 Preparation of 2,8-dicyano-5-chloroacridine...... 171 Preparation of 2,8-diamidino-5-aminoacridine 171 * Preparation of 2,6-dicyano-5-chloroacridine...... 173 Preparation of 2-amidino-5-amino-6-cyanoacridine.. 174 Appendix , Preparation of catalysts.................. ..... 175 Drying of solvents........ 1*77 % Summary.......... 179 Bibliography. ......... '......................U 7. * t SOHWV;, INTRODUCTION Representation of the Acridine Molecule The structural formula of acridine was formerly thought to he due to the compound's formation-from diphenylamine and formic acid in the presence of zinc chloride (29). + Zr»Cl x MCOOH >* -n .o -HvO It was shown, however, hy Ramart-Lucas, Grume z and Martynoff (139) that the absorption spectra of acridine in Visible and U.V. light are almost the same as those for anthracene, indicating that the nitrogen atom is spectrographic ally similar to -C=. This, in conjunction with the chemical properties of the molecule has led to the adoption of an anthracene-like structure for the acridine molecule. i In this thesis, however, the following contracted form will represent the acridine molecule:- Nomenc la ture There are two methods of nomenclature of the acridine series in common use at the present time. There is the A 3 system employed in The Ring Index (143) which number^ according to a given set of rules irrespective of the source or components of the system and is used in British publications. This is the system adopted throughout this thesis* 9 10 I In American and German publications the numbering of the acridine system follows that for anthracene which was numbered before the introduction of The Ring Index (143) to emphasize that the reactivity of the 9,10 positions was distinctly different from those at other positions. 5 io 4 Recently, a new system of notation has been proposed by Dyson (51) for all organic compounds. On this system acridine itself is denoted by T.10ZH. Acridone7CQ3 becomes u f•10ZN.9,10H.9EQ., while 5-chloroacridine (British numbering) becomes T.10ZH.9G1 and 3-cyanoacridine becomes T.10ZN.2C.11E3N. Preparation of Acridine Derivatives As the acridine molecule is a chromophore, much attention has been devoted to methods of preparation of acridine derivatives by dyestuffs chemists since the end of last century and in this century by pharmaceutical chemists. Despite this, only a few types of syntheses have been evolved since, in all cases, ring-elosure of the meso-ring (i.e. the central pyridine ring) has had to be effected. / The methods of synthesis can be grouped under three headings:- 1) Prom diphenyl-methane derivatives, 2) From diphenylamine derivatives, 3) Prom benzyl- and benzal- anilines. 1) FROM DIPHENYL-METHANE DERIVATIVES (a) From diamines and aldehydes When an aldehyde is condensed with an amine of the benzene series, there is little tendency for the methylene group to take up the ortho position, the product being almost entirely the para derivative. /X XX R.cho 2.PH.NHZ r — 5 * i- little X/ n h c k m n ' c ' X / R p-cLcrwa.l'lve. p— The simplest method of ensuring that the product shall contain amino -groups ortho to the aldehyde residue is to use a meta diamine (118) . R NH, -/X. C.'V, PK.CHQ t Z H N H , H,N NHj_ H.N X/ NH, 5 By the use of 2-4-diaminotoluene, 3-aminodimethylaniline and many other substituted m-diamines a series of 2-8-substit- uted acridines can readily be obtained (155). Me Me Me HCHO NH. (4W HN NH HH, NH SN (b) From p-substltuted amines and aldehydes If the para position is occupied, the entrant group is forced into the ortho-position and the product can be converted into an acridine (156). Thus Ullman prepared 3-7-dimethyl-5-phenylac ridine Me.^ > ^H x Me Ph.cho^- NH jl HxN / Zi/a sf ieU This method is general and can be used with any para- substituted aromatic amine. The methane base which is formed as an intermediate may be acridinated without the use of zinc chloride by simply heating to 200° with p-toluidine hydrochloride. (e) From o-nitrobenzyl chloride TJllman and Baezner (157) obtained acridines by condensing o-aminobenzyl alcohol with /*-naphthol, resorcinol or diethyl- -m-j CHj^OH + • - vuinerc, X a OM Of N H , ' H O X- ■ X / ’• (d) By oxidation of o-amino-diphenylme thanes or reduction of o -ni t rophenylme thane s. Fischer and Schutte (62) synthesised acridine by oxidation of o-aminodiphenylmethane with lead oxide. NH- The hydroxylated nitrogen compound which may be regarded as an intermediate in the above synthesis is also obtainable by reduction of o-dinit rophenylme thane derivatives. Thus Fischer (63) prepared dihydroacridine. H*. -C. - WO, ■HHOH By using substituted diphenylamines as starting materials many substituted acridines
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