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The Synthesis and Characterization of 1,3-Bis

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The Synthesis and Characterization of 1,3-Bis THE SYNTHESIS AND CHARACTERIZATION OF 1,3-BIS(ARYLIMINO)ISOINDOLINES USING PHTHALONITRILE OR DIIMINOISOINDOLINE AS STARTING MATERIAL A Thesis Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Master of Science Joshua L. Chavez December 2011 THE SYNTHESIS AND CHARACTERIZATION OF 1,3-BIS(ARYLIMINO)ISOINDOLINES USING PHTHALONITRILE OR DIIMINOISOINDOLINE AS STARTING MATERIAL Joshua L. Chavez Thesis Approved: Accepted: ______________________________ ______________________________ Advisor Dean of the College Chris J. Ziegler Chand K. Midha _____________________________ ______________________________ Faculty Reader Dean of the Graduate School Michael J. Taschner George R. Newkome ______________________________ ______________________________ Department Chair Date Kim C. Calvo ii ABSTRACT Both diiminoisoindoline and phthalonitrile can be used as synthetic precursors for the synthesis of bis-substituted isoindolines.1 Early investigation by Linstead et al. used diiminoisoindoline as a starting material.1,8,23 Siegle later modified the synthesis by using phthalonitrile as a synthetic precursor.24 This direct synthetic route did not include the isolation of diiminoisoindolione in the production of the bis-substituted isoindoline. A variety of adducts have been used to investigate the reactivity of phthalonitrile and diiminoisoindoline with primary aromatic amines. These adducts include aminophenol where the amine group can be ortho, meta or para to the alcohol substituent. A unique feature of the 2-aminophenol is that an intramolecular cyclization occurs which forms two benzoxazoles ortho to each other on a benzene which originated as the phthalonitrile. The other adducts such as the 3 and 4-aminophenols simply underwent a nucleophilic addition followed by intramolecular cyclization to produce the diiminoisoindoline-like compound with two adducts attached. In addition to a direct synthetic route of bis- substituted isoindolines, the formation of a three membered ring, 2-amino-phenoxazin-3- one, was produced due to the oxidation and condensation of the 2-aminophenol upon reflux. iii DEDICATION To my parents and sister iv ACKNOWLEDGEMENTS I would like to thank my advisor Dr. Chris Ziegler for all of his support, guidance and patience he has shown me throughout my time here in Akron. In particular, I would like to acknowledge all of his helpful feedback in regards to writing this thesis. None of this would have been possible if it wasn’t for you. I would also like to extend gratitude to Dr. Mike Taschner and Dr. Kim Calvo for taking the time to review this thesis. v TABLE OF CONTENTS Page LIST OF TABLES ........................................................................................................vii LIST OF FIGURES ..................................................................................................... viii LIST OF SCHEMES ...................................................................................................... xi CHAPTER I. INTRODUCTION……………………………………………………………………...1 Phthalocyanine and porphyrin macrocycles .......................................................... 1 Subphthalocyanine ............................................................................................... 9 Hemiporphyrazine.............................................................................................. 10 Triazolehemiporphyrazine .................................................................................. 14 Cyclization of amino alcohols ............................................................................ 19 Bis-substituted isoindoline ................................................................................. 20 II. THE SYNTHESIS AND BIS-SUBSTITUTEDISOINDOLINE USING DIIMINOISOINDOLINE AS ASTARTING MATERIAL…………………...………...27 Chapter II Experimental ..................................................................................... 28 Chapter II Results and Discussion ...................................................................... 33 III. A DIRECT SYNTHETIC ROUTE FOR THE SYNTHESIS OF BIS-SUBSTITUTED ISOINDOLINES USING PHTHALONITRILE AS A STARTING MATERIAL………………….………………47 Chapter III Experimental .................................................................................... 47 Chapter III Results and Discussion ..................................................................... 54 REFERENCES…………………………………………………………………….…….63 vi LIST OF TABLES Table Page 2.1 Crystal data and structure refinement for compound 1……………………….35 2.2 Crystal data and structure refinement for compound 2……………….…...….39 2.3 Crystal data and structure refinement for compound 3……………….………42 2.4 Crystal data and structure refinement for compound 4…………..…………...45 3.1 Crystal data and structure refinement for compound 6……………………..…62 vii LIST OF FIGURES Figure Page 1.1 Structures of porphyrin and phthalocyanine.......................................................... 1 1.2 Synthesis of regular porphyrin via condensation of pyrroles and aldehydes ......................................................................................... 2 1.3 Possible isomeric mixtures of porphyrin synthesis ................................................ 3 1.4 Structure of phthalocyanine .................................................................................. 4 1.5 Structures of a benzoporphyrin(A) and an azaporphyrin(B) .................................. 5 1.6 Possible precursors of phthalocyanine synthesis ................................................... 6 1.7 Synthetic pathway for phthalocyanine or diiminoisoindoline synthesis ................. 8 1.8 Synthetic pathway for isoindoline derivatives from ethylcyanoacetate.................. 9 1.9 Synthesis of supphthalocyanine .......................................................................... 10 1.10 Structure of hemiporphyrazine ........................................................................... 11 1.11 Synthesis of hemiporphyrazine........................................................................... 12 1.12 Reaction of 3-imino-1-ketoisoindoline with a primary amine ............................. 13 1.13 Structure of triazohemiporphyrazine .................................................................. 14 1.14 Triazohemiporphyrazine derivatives shown to increase solubility....................... 15 1.15 Regioselective synthetic pathway using stepwise methodology of the synthesis of triazolehemiporphyrazine .................. 16 1.16 Open three unit compound ................................................................................. 17 1.17 Possible reaction products of three unit compound reacted with benzene-1,3-diamine ...................................................................... 17 1.18 Various diamines used for macrocyclic formation with diiminoisoindoline...................................................................................... 18 viii 1.19 Synthesis of 2-substituted 2-oxazolines and 4H-5,6-dihydrooxazine ...................................................................................... 19 1.20 Synthesis of 1,3-bis(2’-pyridylimino)isoindoline ................................................ 20 1.21 An example of a palladium complex .................................................................. 21 1.22 Coordination of cadmium with pyridine and imine nitrogens .............................. 24 1.23 Reactions of Zn(II) with isoindoline ligand ........................................................ 24 2.1 13C NMR spectra of compound 1 ....................................................................... 34 2.2 ESI mass spectrum of compound 1 ..................................................................... 34 2.3 The structure of compound 1 with 35% thermal ellipsoids. Hydrogen atoms have been omitted for clarity................................................... 36 2.4 13C NMR spectra of compound 2 ....................................................................... 37 2.5 ESI mass spectrum of compound 2 ..................................................................... 38 2.6 The structure of compound 2 with 35% thermal ellipsoids. Hydrogen atoms have been omitted for clarity ................................................... 40 2.7 ESI mass spectrum of compound 3 .................................................................... 41 2.8 Compound 3 with 35% thermal ellipsoids. Hydrogen atoms have been omitted for clarity with the exception of the OH group on the phenol adduct .......................................................................... 43 2.9 ESI mass spectrum of compound 4 .................................................................... 44 2.10 Compound 4 with 35% thermal ellipsoids. Hydrogen atoms have been omitted for clarity .............................................................................. 46 3.1 1H NMR spectra of compound 5......................................................................... 55 3.2 ESI mass spectrum of compound 5 ..................................................................... 55 3.3 ESI mass spectrum of compound 7 ..................................................................... 56 3.4 ESI mass spectrum of compound 2 ..................................................................... 57 3.5 1H NMR spectra of compounds 2 and 6 .............................................................. 58 ix 3.6 1H NMR spectra of compound 6........................................................................
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