NEW CHEMISTRY OF SMALL RING NITRILES Item Type text; Dissertation-Reproduction (electronic) Authors Snider, Scott Christian 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 29/09/2021 06:07:17 Link to Item http://hdl.handle.net/10150/298446 INFORMATION TO USERS This was produced from a copy of a document sent to us for microfilming. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help you understand markings or notations which may appear on this reproduction. 1. 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THE UNIVERSITY OF ARIZONA, PH.D., 1978 University Microfilms International 300 N. 2EE8 ROAD, AWN ARBOR, Ml 48106 NEW CHEMISTRY OF SMALL RING NITRILES by Scott Christian Snider A Dissertation Sxabmitted 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 19 7 8 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by Scott Christian Snider entitled New Chemistry of Small Ring Nitriles be accepted as fulfilling the dissertation requirement for the degree of Doctor of Philosophy H-KJ-iJJ1, %• •!<< /T7 Dissertation Director Date As members of the Final Examination Committee, we certify that we have read this dissertation and agree that it may be presented for final defense. ?////7/ / //// /d ?/'/ /7? —2\f v 11 Final approval and acceptance of this dissertation is contingent on the candidate's adequate performance and defense thereof at the final oral 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 borrowers 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 reproduction 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 interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: C. DEDICATION To my wife, Lynda iii ACKNOWLEDGMENTS The author wishes to thank Dr. H. K. Hall, Jr., for his guidance and helpful suggestions during the course of this investigation. I also thank Dr. A. Deutschman, Jr., of the University of Arizona High Pressure Laboratory for doing the thermal cycloaddition reactions, Dr. C. Linstid for carrying out the cmr measurements and Dr. R. B. Bates for helpful discussions. The financial support given to the author by the Amoco Foundation Fellowship in Polymer Chemistry and U.S. Army Research Office is also gratefully acknowledged. iv TABLE OF CONTENTS Page LIST OF TABLES vii LIST OF ILLUSTRATIONS viii ABSTRACT ix INTRODUCTION 1 RESULTS 14 Synthesis of 3-Methylene-2-methylcyclo- butene-l-carbonitrile 14 Structure of 3-Methylene-2-methylcyclo- butene-l-carbonitrile 18 Homopolymerization of 3-Methylene-2- methylcyclobutene-l-carbonitrile 22 Copolymerization of 3-Methylene-2- methylcyclobutene-l-carbonitrile 24 Homopolymerization of 3-Methylenecyclo- butene-l-carbonitrile 28 Free Radical Copolymerization of 3-Methylenecyclobutene-l-carbonitrile 30 Dehydrohalogenation of 2-Cyano-3,3- dimethyl-4-chlorooxetane 32 "Metathesis" Polymerization of Bicyclobutane-l-carbonitrile 32 Attempted Synthesis of a Stereospecific 1,3-Dialkyl Cyclobutane-l-carbonitrile 33 DISCUSSION 36 Synthesis of 3-Methylene-2-methylcyclo- butene-l-carbonitrile 36 Structure of 3-Methylene-2-methylcyclo- butene-l-carbonitrile 37 Synthesis of 3-Methylenecyclobutene- 1-carbonitrile 38 Homopolymerization of 3-Methylene-2- Methylcyclobutene-l-carbonitrile and 3-Methylene-cyclobutene-l-carbonitrile 39 Copolymerization of 3-Methylene-2- methylcyclobutene-l-carbonitrile and 3-Methylenecyclobutene-l-carbonitrile 41 v vi TABLE OF CONTENTS—Continued Page Dehydrohalogenation of 2-Cyano-3,3- dimethyl-4-chlorooxetane 43 "Metathesis" Polymerization of Bicyclobutane-l-carbonitrile 44 Attempted Formation of the Anion of 3-Methylenecyclobutane-l-carbonitrile 44 SUMMARY 47 EXPERIMENTAL 49 Instrumentation 49 Monomer Synthesis 49 3-Methylene-2-methylcyclobutene- 1-carbonitrile (25) 49 Sample Polymerizations ~ 59 3-Methylene-2-methylcyclobutene- 1-carbonitrile Polymers 59 3-Methylenecyclobutene-l- carbonitrile Polymers 60 Attempted Anionic Polymerization . 62 Dehydrohalogenation of 2-Cyano-3,3- Dimethyl-4-Chlorooxetane 63 "Metathesis" Polymerization of Bicyclobutane-l-carbonitrile 64 Attempted Synthesis of a Stereospecific 1,3-dimethylcyclobutanecarbonitrile 65 Synthesis of 3[S-(3-hydroxyethyl)- thiomethyl]cyclobutane-l-carbonitrile ... 65 REFERENCES 68 LIST OF TABLES Table Page 1. Comparison of Cycloaddition of Substituted Allenes and Acrylonitrile in Pyrex and Stainless Steel Vessels 16 2. CMR of 3-Methylene-2-methylcyclobutene- 1-carbonitrile in DCCl^ 21 3. CMR of Poly-3-methylene-2-methylcyclobutene- 1-carbonitrile in Acetone-d6 23 4. Copolymers of 3-Methylene-2-methylcyclobutene- 1-carbonitrile 25 5. CMR Spectra of 3-Methylenecyclobutene-l- carbonitrile in DCCl^ 27 6. CMR Spectra of Poly-3-methylenecyclobutene- 1-carbonitrile in DMS0-d6 29 7. Copolymerization of 3-Methylenecyclobutene- 1-carbonitrile 31 8. Selected Q-e Values 42 vii LIST OF ILLUSTRATIONS Figure Page 1. Nmr of 3-Methylene-2-methylcyclobutene- 1-carbonitrile 19 viii ABSTRACT The correct structure for the compound originally reported as 3-methylene[2.1.0]bicyclopentane-l-carbonitrile [H. K. Hall, Jr. and R. E. Yancy, J. Org. Chem., 39_, 3862 (1974)] is 3-methylene-2-methylcyclobutene-l-carbonitrile 1, as shown by uv, nmr, cmr spectra and the structure of the homopolymer. Compound 1 was synthesized from 2-butyne-l,4- diol. By treating 3-methylenecyclobutane-l-carbonitrile with phosphorus pentachloride, followed by 1,5-diazabicyclO' [4.3.0]non-5-ene(DBN), the new compound 3-methylenecyclo- butene-l-carbonitrile 2 was obtained. Monomers 1 and 2 were free radically homopolymerized by 1,5 addition to film forming polymers. Both 1 and 2 were free radically copoly- merized with representative comonomers. Dehydrohalogenation of 2-cyano-3,3-dimethyl-4- chlorooxetane with two equivalents of potassium t-butoxide in THF gave t-butyl 3,3-dimethylacrylate 3. Formation of 3 is consistent with an oxabicyclobutane intermediate. The treatment of bicyclobutane-l-carbonitrile with tungsten hexachloride/ethylaluminum sesquichloride and the attempted formation of an anion of 3-methylenecyclobutane-l-carboni- trile are described. ix INTRODUCTION The search for new monomers which polymerize to use­ ful materials has always been a primary goal of the organic polymer chemist. The presence of nitrile groups in polymers often results in many desirable properties. The most common vinyl nitrile monomer is acrylonitrile which polymerizes free radically to a fiber-forming polymer. CN CH2CHCN R« + H2C=CHCN RCH2CHC=N<- -> RCH2CH=C=N •ch ch-4- etc 2 Although polyacrylonitrile is an important polymer (Idol 1974, Houtz 1950), it has several shortcomings: a tendency to yellow on exposure to base; blackening when heated; and being too hydrophilic as a fiber. One cause of the problems with polyacrylonitrile is that the nitrile groups are too close together. For example,