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Part I Amine-Boranes: Hydrolytic Stability and Stereochemistry of Formation Part Ii Aminoboranes: Barrier to Rotation About the Boron-Nitrogen Bond

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Part I Amine-Boranes: Hydrolytic Stability and Stereochemistry of Formation Part Ii Aminoboranes: Barrier to Rotation About the Boron-Nitrogen Bond University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Summer 1973 PART I AMINE-BORANES: HYDROLYTIC STABILITY AND STEREOCHEMISTRY OF FORMATION PART II AMINOBORANES: BARRIER TO ROTATION ABOUT THE BORON-NITROGEN BOND EVERETT WEST SOUTHWICK Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation SOUTHWICK, EVERETT WEST, "PART I AMINE-BORANES: HYDROLYTIC STABILITY AND STEREOCHEMISTRY OF FORMATION PART II AMINOBORANES: BARRIER TO ROTATION ABOUT THE BORON-NITROGEN BOND" (1973). Doctoral Dissertations. 1026. https://scholars.unh.edu/dissertation/1026 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. INFORMATION TO USERS This material was produced from a microfilm copy of the original document. 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 original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1.The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated witli a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image. You will find a good image of the page in the adjacent frame. 3. Whai a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It is customary to begin photoing at the upper left hand corner of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row and continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. 5. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. Xerox University Microfilms 300 North Zeeb Road Ann Arbor, Michigan 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. I 74-7021 t t SOUTHWICK, Everett West, 1941- I PART I. AMINE-BORANES: HYDROLYTIC STABILITY I: AND STEREOCHEMISTRY OF FORMATION. PART II. i AMINOBORANES: BARRIER TO ROTATION ABOUT THE BORON-NITROGEN BOND. University of New Hampshire, Ph.D., 1973 Chemistry, inorganic I University Microfilms, A XERQ\ Company, Ann Arbor, Michigan 0 1974 EVERETT WEST SOUTHWICK ALL RIGHTS RESERVED TH IS DISSERTATION HAS BEEN MICROFUM ED. EXACTLY AS RECEIVED. R eproduced w ith perm ission o f the copyright ow ner. F urther reproduction prohibited w ithout perm ission. PART I AMINE-BORANES: HYDROLYTIC STABILITY AND STEREOCHEMISTRY OF FORMATION PART II AMINOBORANES: BARRIER TO ROTATION ABOUT THE BORON-NITROGEN BOND by EVERETT WEST SOUTHWICK B.A., University of Rhode Island, 1963 A THESIS Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of Doctor of Philosophy The Graduate School Department of Chemistry August, 1973 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This thesis has been examined and approved. itobert E . Lyle, of. of Chemistry Thesis Director Colin D. Hubbard, Assoc. Professor of Chemistry Glqiria G. Lyle, Ass6 c. Professor of Chemistry Miyoshi %awa. Prof. of Biochemistry Jam^s D. Morrison, Prof. of Chemistry August 22, 1973 Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS The author wishes to express his appreciation to Dr. Robert E. Lyle for providing the research area and for his patience and understanding during its development. He would also like to express his appreciation to Dr. Colin D. Hubbard for his help in the preparation of the thesis. Special thanks are due to Dr. James Kaminski who, as a collaborator in the work on amine-boranes, was the recipient of numerous harangues concerning the interpreta­ tion of the data. Appreciation is also expressed to the personnel at the UNH Computation Center who guided the author success­ fully through a maze of computer jargon. The author expresses his gratitude to Dr. Alexander R. Amell and the faculty of the Department of Chemistry not only for their assistance during the development of this problem, but also for the opportunities to teach chemistry that they provided. The experience of teaching was a very important adjunct to the author's graduate education. The assistance of Miss Anne Kohl in the preparation of this manuscript is gratefully acknowledge. There is no adequate expression of appreciation that can be extended to the author's wife, Sandi, for her per­ sistent encouragement throughout the development of this thesis. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS LIST OF FIGURES............................................ vii LIST OF TABLES.............................................. ix ABSTRACT................................................................................................................................................................................................. X PART I. AMINE-BORANES........................................1 INTRODUCTION.........................................1 DISCUSSION........................................... 6 Quantitative Determination of Amines.......... 6 Stereochemistry of Borane Coordination.......16 PART II. AMINOBORANES...................................... 56 INTRODUCTION...................................... 56 Preparation of Piperidinoboranes.................59 The Existence of Monomeric Species...............62 Planarity of B-N Bond.............................6 6 Geometry of the Piperidine Moiety................67 Dynamic Nuclear Magnetic Resonance Study........75 Analysis of Mass Spectra of Aminoboranes........ 84 EXPERIMENTAL................................................ 99 General................................................. 99 Methods............................................ 99 Melting Points...............................99 Infrared Absorption Spectra (IR)........... 99 Proton Magnetic Resonance (PMR) Spectra....99 Fluorine Magnetic Resonance Spectra (I^F-NMR)...............................99 Carbon Magnetic Resonance Spectra (CMR)...100 Elemental Analyses......................... 100 Low Resolution Mass Spectra................100 Preparation of Amines................................. 100 General...........................................100 IV Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Preparation of 1,3-Dimethylpiperidine (£)........... 101 Preparation of 1,4-Dimethylpiperidine (. 3 ) ........... 101 Preparation of cis-1,2,6 -Trimethylpiperidine (11)...101 Preparation of l-Methyl-2-n-propylpiperidine (^)....101 General................................................ 101 Preparation of Amine-Boranes............................... 102 Preparation of 1,3-DimethyIpiperidine Borane (4A and .......................................102 Preparation of 1-MethyIpiperidine Borane (3^)......... 103 Preparation of 1,4-Dimethylpiperidine Borane (3A and 3E)...................................... 103 Preparation of 1-Methyl-2-n-propyIpiperidine Borane (2A and 2E)...................................... 103 Preparation of cis-1,2,6 -TrimethyIpiperidine Borane (1^).............................................. 103 Preparation of 1,2,6 -TrimethyIpiperidine Trifluoro- borane (]J)...................................... 104 Preparation of Diethyl Phenylboronate ( ^ ) .......... 104 Preparation of Pyridine Phenylborane (^)............ 105 Reaction of Pyridine Phenylborane (M with Tertiary Amines............................................ 106 Preparation of Aminoboranes................................ 106 General................................................ 106 Preparation of Phenyldichloroborane (30)......... .106 Preparation of PhenyIchloro-(2-methyIpiperidino)- borane (33)...................................... 107 Preparation of PhenyImethyl-(2-methylpiperidino)- borane (l^)...................................... 107 Preparation of p-ChlorophenyImethyl-(2-methylpiper­ idino) borane (2 0 )................................ 108 V Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Preparation of Dichloro-(2-methylpiperidino)- borane (3j6)....................................... 108 Preparation of Chloromethyl-(2-methylpiperidino)-
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