A Study of the Existence of Rotation Isomerism in Tri-Alpha-Naphthylboron and Its Addition Compounds

177 Pages·06.946 MB·English

by  Zletz, Alex

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