PURDUE UNIVERSITY THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION Alex Zletz _____________________________ by A STUDY OF THE EXISTENCE OF ROTATION ISOMERISM IN en titled TRI-/JuHiA-NAPHTHYLBORON AND ITS ADDITION COMPOUNDS COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF Ehe De Professor in Charg-e or Thesis Head of School or Department TO THE LIBRARIAN:----- THIS THESIS IS NOT TO BE REGARDED AS CONFIDENTIAL. PROFESS OH m CHARGE GRAJD. SCHOOL FORM 9—3.4 9—IM A STUDY OF THE EXISTENCE OF ROTATION ISOMERISM IN TRI-ALPHA-KAPHTHH^ORON AND ITS ADDITION COMPOUNDS A Thesis Submitted to the Faculty of Purdue University by Alex Zletz In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy June, 1950 ProQuest Number: 27714159 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 complete 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 27714159 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 Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 Acknowl edgment I wish to acknowledge iqy indebtedness to Professor Herbert C. Brown under whose guidance th is research has been carried out. Many thanks are due to him for encouragement and advice. I would also like to express ny appreciation to the Research Corporation and to the Purdue Research Foundation for financial assistance which made this study possible. TABLE OF CONTENTS Page ABSTRACT..................................................................................................................... i CHAPTER I. INTRODUCTION Statement of Problem ...................... 1 A Literature Survey of the Triarylborons and Their Addition Compounds 2 Comparison of the Observations of Brown and Sujishi with Those of Krause and Nobbe ............................................ 6 CHAPTER II. THE PREPARATION OF VARIOUS FORMS OF TRI-ALPHA- NAPHTHXLBORON AND ITS ADDITION COMPOUNDS 1 D iscussion....................................... 11 The Preparation of TNB by the Method of Brown and Sujishi . . . . . . . . .................................................. 11 The Preparation of TNB by the Method of Krause and N obbe...................... • 12 Purification of TNB Obtained from the Ether S olution.............................................................. 13 The Preparation of TNB-benzene from Heat-treated TNB. lh Experimental D e ta ils...........................................................................lU The Preparation of TNB by the Method of Brown and Sujishi • • • • • • . . . . . . . . . . . . . . 15 The Preparation of TNB by the Modified Method of Brown and Sujishi ............................... 16 The Preparation of TNB by the Procedure of Krause and Nobbe ..................................................... 19 The Preparation of TNB by a Modified Procedure of Krause and Nobbe Using a Larger Proportion of E th e r.......................... 20 The Purification of TNB Using the Three-bulb Apparatus of Krause and Polack .................. . . . . . . 22 The Preparation of TNB-benzene.......................................25 Page CHAPTER III. THE BEHAVIOR OF TRI-ALPHA-NAPHTHYIBORON AND ITS ADDITION COMPOUNDS ÜTTHE SOLID STATE Observations and D iscu ssio n ....................................................................26 Dissociation Pressure Measurements of TNB-ammonia. The Observation of a Minimum in the Pressure- composition Curve.................................................................. . 26 The Behavior of Heat-treated TNB upon Addition of 50 Mole Per Cent Ammonia .......................... 39 The Behavior of TNB Obtained from the Krause and Nobbe Procedure upon Addition of Ammonia . . . . . 1+0 An Attempt to Prepare Symmetrical TNB in the Solid S ta te ................................................. U3 Dissociation Pressure Measurements on TNB-benzene . • U5 The Behavior of TNB-benzene with Ammonia............................51 The Behavior of TNB, Obtained upon Liberation of Benzene at 80°, with Ammonia .....................................52 Experimental D etails ................................ . . . . . . . . . . . 5U Preparation and Purification of G ases............................... 5U Dissociation Pressure Measurements on TNB-ammonia . . 5U An Attempt to Prepare Symmetrical TNB.......................... . 57 Dissociation Pressure Measurements on TNB-benzene • . 57 The Behavior of TNB-benzene with Ammonia...................... 59 The Behavior of TNB, Obtained upon liberation of Benzene at 80°, with Ammonia...................... 65 CHAPTER IV. THE NATURE OF THE PRODUCT OBTAINED BY RE CRYSTAL­ LIZING HEAT-TREATED TRI-ALPHA-NAPHTHYLBORON FROM VARIOUS SOLVENTS AND THE' SOLUBILITY OF TRI-ALPHA- NAPHTHYLBORON Recrystallization of Heat-treated TNB from Various S olvents...................... 69 Page In tro d u ctio n ..........................................................................................69 The Q ualitative Results of Procedure No* 1 . . . . . 70 The Results of Procedure No * 2 ........................................ • 72 Discussion ........................................ 83 The Behavior of the Residual TNB towards 50 Mole Per Cent Ammonia ...................... 85 The Solubilities of TNB . * * * * . . . * * * . . * 87 The Solubility of TNB in Various Solvents from the Data of Procedure No* 2 87 The Solubility of D ifferent Preparations of TNB in E th e r................................................................................* * * 92 Experimental D e ta ils........................................................................... 92 M aterials...................................................................................................92 R ecrystallization of Heat-treated TNB from Various Solvents . . . . . . . . • • • • • 93 Procedure No. 1 . . . . . . . . . . . 93 Procedure No. 2 ...................... 93 The Solubility of the Krause and Nobbe TNB in Ether • 96 CHAPTER V. THE BEHAVIOR OF TRI-ALPHA-NAPHTHYLBORON AND ITS BENZENE SOLVATE IN SOLUTION Introduction........................................................................................................99 The Reaction with Ammonia............................................................100 The Reaction with Trimethylamine........... 101 Experimental Deatils ............................... 107 The Reaction with Ammonia....................... 107 The Reaction with Trimethyl a m in e .............................................I ll Preliminary Experiments ..............................I ll Precipitation Experiments in the Vacuum Line . • 116 Page CHAPTER VI. THE EXISTENCE OF ROTATION ISOMERISM IN TRI- ALPHA-NAPHTHYLBORON AND ITS ADDITION COMPOUNDS Summary of Results .......................... • • • • 121* Preparations . .............................. • • • • 121* Behavior of TNB and Its Addition Compounds in the Solid State ..............................12l* The Nature of the Product Obtained by Re crystal­ lizing Heat-treated TNB from Various Solvents and the Solubilities of TNB . . . . . . . . . . . 128 The Behavior of TNB and Its Benzene Solvate in Solution . . . . . . . • • • • • 129 Discussion . . . . . . . . . . . . . . . . . . . . . . . 131 C onclusions..................................................... 135 BIBLIOGRAPHY..........................................................................................................136 VITA LIST OF TABLES Table Page 1» A List of Triarylborons and Their Addition Compounds •with References to the L ite ra tu re ................................................ 3 2, Ratio of Benzene to TUB in TNB-benzene.................................. . 25 3* Dissociation Pressures of TNB-ammonia . ....................... 27 U. Summary of Dissociation Pressures for Five Samples of TNB-ammonia..................................................... . . . 28 5. Variation of Dissociation Pressure of TNB-ammonia m th Change in Mole Per Cent of Ammonia at II4O0 . . . . . . . . 30 6. Variation of Dissociation Pressure of TNB-anmonia with Change in Mole Per Cent of Anmonia at lU0° . . . . . . . . 35 7. Variation of Dissociation Pressure of TNB-ammonia with Change in Mole Per Cent of Anmonia at IÎ4O0 . . . . . . . . 36 8. Change of Pressure with Time of Freshly Prepared TNB- ammonia Using Heat-treated TNB at 80.0 Î 0 . 3 ° ............................hi 9# Change of Pressure with Time of Freshly Prepared TNB- ammonia Using TNB from the Krause and Nobbe Preparation . hh 10. Dissociation Pressure of TNB-benzene, Preparation No. 1, at 2 5 .0 °.................................................................................................................h6 11. Dissociation Pressure of TNB-benzene, Preparation No. 1, at 3 9 .1 °.................................................................................................................h6 12* Dissociation Pressure of TNB-benzene, Preparation No. 1, with 97 Mole Per Cent Benzene at 25*0° ......................* h7 13* Dissociation Pressure of TNB-benzene, Preparation No. 2, with 106 Mole Per Cent Benzene................................................• • • h7 lh* Dissociation Pressures of TNB-benzene, Preparation No. 1, with 97 Mole Per Cent Benzene from the Reverse Reaction at 2 5 .0 °.............................. h9 15* Dissociation Pressure of TNB-benzene, Preparation No. 2, with 96 Mole Per Cent Benzene at 2 5 .0 °................................... . h9