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SYNTHESES and REACTIONS of POLYVINYLTHIAZOLES By Syntheses and reactions of polyvinylthiazoles Item Type text; Dissertation-Reproduction (electronic) Authors Schilling, Curtis Louis, 1940- Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 28/09/2021 14:03:41 Link to Item http://hdl.handle.net/10150/565147 SYNTHESES AND REACTIONS OF POLYVINYLTHIAZOLES by Curtis Louis Schilling, Jr. A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 1 9 6 7 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by CliPfrls Louis Scflilling Jl*»____________________ entitled Syntheses and Reactions of Folyvlnylthlazrtlaa be accepted as fulfilling the dissertation requirement of the degree of Dbotor of Philosophy _______________________________ - A a , Dr / Date (J 1 After inspection of the dissertation, the following members of the Final Examination Committee concur in its approval and recommend its acceptance:* Q ^ - ^ . ~i-l ( L m l ... I t ' ? *This approval and acceptance is contingent on the candidate's adequate performance and defense of this dissertation at the final oral examination. The inclusion of this sheet bound into the library copy of the dissertation is evidence of satisfactory performance at the final examination. STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to bor­ rowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or re­ production of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the proposed use of the material is in the in­ terests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: ACKNOWLEDGMENT The author would like to acknowledge the guidance, direction, and assistance of his preceptor, Dr, James E, Mulvaney, both in the preparation of this dissertation and in other matters of importance, and would like to thank Donald R, Stevenson for supporting work and Dr. M. Barfield for helpful suggestions. The Continental Oil Company is acknowledged for awarding the author a fellowship for the academic year 1966-1967. The author is grateful for the sacrifices made by his family during the course of this study and dedicates this dissertation to them. iii TABLE OF CONTENTS Page LIST OF TABLES ooooooooooooeooeeooooeoooVH LIST OF FIGURES ooeeoooooeoeoooooooooooovlll ABSTRACT O O. oooooooodooooooeeeoooooooo12C INTRODUCTION ooooooooooosooeosooooooooo 1 RESULTS AND DISCUSSION . , « , „ „ © „ * , . „ „ * o . © © © « 9 Syntheses and Reactivity of Vinyl and Isopropenylthiazoles © 9 Syntheses and Reactivity of Thiazolium Monomers and P oLyme rs oo©©©©©©©©©©©©©©©©©©©©©©©© 31 EXPERIMENTAL ©©©©©©©©©©©©©©©o©©©©©©©©©© A2 2~Benzoxypropionitrile ©©©©©©©©©©©o©©©©©©© 42 2-B enzoxy th i op r op i onamid e ©©©©©©©©©©©©©©©o© 43 2-(1-Benzoxyethy1)thiazole o©©©©©©©©©©©©©©©© 43 2«Vinylthiazole ©©©©©©o©©©©©©©©©©©©©©© 44 2-^Br omo th iazole ©©©©©© o©©©©©©©©©©©©©©© 43 2-(2~Hydroxy-2~propyl)thiazole ©©©©.©©©©©©©©©o 45 2-( 2*-Acetoxy-2~propyl) thiazole ©©©©©©©©©©©©©©© 47 2-Isopropenylthiazole ©©©©©©©©©©©©©© ©©©©© 47 * • 2-(1-Hydroxyethy1)thiazole ©©©©©©©©©©©©©©©©© 48 2-Acetoxy-2-methylpropionitrile ©©©©©©©©©o©©©© 49 3-B enz oxy-2-bu tanone ©©©©o©©©©©©©©©©©©©©© 50 l-Bromo-3-benzoxy-2-butanone ©©©©©©©©©©©©©©©© 51 Thioforuiami.de ©o©©©©©©©©©©©©©©©©©©©©© 52 4«(1-Benzoxyethy1)thiazole ©©©©©©©©©©©©©©©©o 54 iv V TABLE OF CONTENTS--Continued Page 4-Vinyl thiazole •oo«oooo«e»»«»-«oo««e0«e.54 3-B enz oxy-3-me thy1-2-bu tanone 00ooooooo6oooooo 55 l”Bromo-3-benzoxy-3-methyl-2-butanone ooooooeooaoo 55 4-Isopropenylthiazole oooooooooooooooogooo 56 4-(2-Benzoxy-2-propyl)thiazole oooooooooooooooo58 4-Methyl-5-(2~hydroxyethyl)thiazole ooooooooooooo 59 4-Methy1-5"(2-acetoxyethyl)thiazole ooooooooooooo 59 4-Me thyl-5-vinyl thiazole eo»oooooeeoo»oeoo.oo 60 Polymerizations of Vinyl and Isopropenylthiazoles o o o e 0 o 61 Copolymerizations of 2-Vinyl- and 4-Vinylthiazole with Styrene oooooooooeooooooooooooooooo62 2-Methyl-4-(l-benzoxyethyl)thiazole ooooooooooooo 62 2-Methyl-4-benzoxy-4'-(l-hydroxyethyl)-2-thiazoline o o o o o o 63 2-Amino-4-(l-benzoxyethyl) thiazole 0 ooooooooooooo 65 2-Amino-4-is opropenyl thiazole ooo o oeoeoooooo. oo 65 2-Methyl-4-benzoxy-4-( 2-hydroxy-2-propyl )-2-thiazoline and 2-Methy1-4-(2-hydroxy-2-propyl)thiazole ooooooooo 66 Furom Test ooooooooooooooooooooooooo69 . Copolymer of 4-Vinylthiazole and 3-Methyl-4-vinylthiazolium Iodide Ooooooooooooooooooooooooo oeo70 Copolymer of 4-Methyl-5-vinylthiazole and 394-Dimethy1-5~ vinylthiazolium Iodide Oooooooooooooooooeoo70 3-Methyl-4=>isopropenylthiazolium Iodide ooooooooooo 71 3-Methyl-4-(2-benzoxy-2-propyl)thiazolium Iodide 0 o o 0 o o o 72 Thiazole oooooooooooeooooooooooooooo72 vi TABLE OF CONTENTS--Continued Page 2-Amino-4-raethylthiazole oooeea*,,* @*@<,00* 0*0 73 4"Methy1thlazoleo * * o o @ * * * * » * * » * @ & « * * e @ o 74 3-Benzyl""4-*inethylthiazolium Bromide o************ 75 3-AllyIthiazolium Bromide @*@*@*@*@@@@@@@0** 75 3 g4-Dime thylthiazolium Iodide o«00oeo««o««»«oo 76 Copolymer of 4-Isopropenylthiazole and 3-Methy1-4-iso- propenylthiazolium Iodide 00* 00*** 00000**000 76 Qua terni za t i on of 4-Vinylthiazole @ 00000*** 00**0 77 Quaternization of 2-Vinylthiazole @ 00000* 0*00000 77 jREN CES oooooooooeooeoooooeoodoeoboo 79 LIST OF TABLES Page Table I POLYMERIZATIONS OF VINYL AND ISOPROPENYLTHIAZOLES 15 II COPOLYMERIZATION OF 2-VINYL AND 4-VINYLTHIAZOLE WITH STYRENE oo«ooooooooo«oeooooo«o20 III REACTIVITY RATIOS . ........... 27 IV FUROIN TESTS o^eoeeoeoeeeeeeedeeeeo 35 V ACETOIN TESTS oeoooooooooooooooooeoo37 vli LIST OF FIGURES Page Figure 1„ Mayo-Lewis Plot for Styrene and 2-Vinylthiazole . « „ e 0 22 20 Fineman-Ross Plot of Styrene and 2-Vinylthiazole . 0 o 23 3,, Mayo-Lewis Plot for Styrene and 4-Vinylthiazole 0 0 o » 24 40 Fineman-Ross Plot of Styrene and 4-Vinylthiazole 0 o 0 o 25 viii ABSTRACT Synthetic approaches to vinyl and isopropenylthiazoles were in­ vestigated with the object of preparing polymeric analogs of thiamine0 Several new thiazole monomers and precursors were prepared, including 2-(2-hydroxy-2-propyl)thiazole, 2-(2-acetoxy-2-propyl)thiazole, 2-iso- propenylthiazole, 4-(l-benzoxyethyl)thiazole, 4-vinylthiazole, 4-isopro- penylthiazole, 4-(2-hydroxy-2-propyl)thiazole, 4-(2-benzoxy-2-propyl)- thiazole, 2-methy1-4-(1-benzoxyethyl)thiazole, 2-methyl-4-(2-hydroxy-2- propyl)thiazole, 2-amino-4-(1-benzoxyethyl)thiazole, and 2-amino-4- isopropeny1thiazoleo Two known thiazole monomers, 2-vinylthiazole and 4-methy1-5-vinylthiazole, were also prepared0 Reactivity ratios and Price-Alfrey Q,e values were determined for 2-vinylthiazole and 4-vinylthiazole from copolymerization experiments with styrene* For styrene (comonomer^) and 2-vinylthiazole (comonomerg)', r^ = 0*14 + 0 o07 and - 3,32 + 0,48 by the Mayo-Lewis method, and = 0,18 and X 2 = 3,45 by the Fineman-Ro'ss method. The Q,e values for 2- vinylthiazole are Q = 3,56 and e = 0,08, For styrene (comonomer^) and 4-vinylthiazole (comonomerg), r^ = 0,66 + 0,11 and r^ = 0,82 + 0,13 by the Mayo-Lewis method and r^ = 0,60 and r^ = 0,80 by the Fineman-Ross method. The Q,e values for 4-vinylthiazole are Q = 2,82 and e = -1,58, The condensation reaction of thioacetamide with l-bromo-3- benzoxy-2-butanone and l-bromo-3-benzoxy-3-methyl-2-butanone, respec­ tively, produced two unusual compounds, C^hj^NO^S and C^^H^^NO^S, . tentatively assigned the structures of 2-methyl-4~benzoxy-4-(1“hydroxy~ ethyl)-2-thiazoline and 2-methyl-4-benzoxy-4-(2-hydroxy-2-propyl)-2« thiazolineo These compounds may have arisen from intramolecular transesterifications of'intermediates which would normally lead to 2-methyl-4-(1-benzoxyethyl)thiazole and 2-methy1-4-(2-benzoxy-2-propyl)- thiazole, respectively0 A copolymer of 4-vinylthiazole and 3-methyl-4-vinylthiazoliura iodide and a copolymer of 4-methy 1-5-vinylthiazole and 394-dimethyl*5.»f • vinylthiazolium iodide were prepared by treatment of poly(4-vinylthia­ zole) and poly(4-methyl-5-vinylthiazole), respectively, with methyl ibdideo The catalytic activity of these copolymers was compared with that of several monomeric thiazolium salts in the formation of furoin from furfuralo The yields of furoin using monomeric and polymeric catalysts indicate ttiat the copolymers possess catalytic activity per thiazolium unit equivalent to or higher than that of the monomeric thiazolium salts* INTRODUCTION Thiamine pyrophosphate (I) is involved as a coenzyme in a number 0 OH +1 I CH-CH-0 POPOH 2 2 I 1 + HO 0 of biochemical reactions including oxidative and nonoxidative decarbox­ ylations of <K-keto acids and acyloin reactions.* The respective equa­ tions for these reactions are: rcoco2h + to2 rco2h + co2, r c o c o 2h RCHO + C02, and RCHO + r 'c HO ---^ RCHOHCOR Early workers demonstrated the catalytic activity of thiamine and even of simple thiazolium salts in the nonenzymatic formation of benzoin and acetoin from the respective aldehydes. Breslow was the first to prove that the 2-carbon atom in the thiazolium ring is respon­ sible for the catalytic activity. In brief, Breslow's proof of the mechanism of catalysis is based^'^ on the discovery that the proton at­ tached to the 2-carbon of compound II exchanges with solvent deuterium at a rate too fast to measure at pH 7. Obviously, the ylid III is readily formed. It is electronically similar to cyanide ion and acts as a specific catalyst for the reaction as shown below.
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