Addition compounds of trimethylphosphine oxide

78 Pages·02.623 MB·English

by  McKee, William Edgar

ADDITION COMPOUNDS OF
TRIMETHYLPHOSPHINE OXIDE
A Thesis
Presented to
the Faculty of the Department of Chemistry
University of Southern California
In Partial Fulfillment
of the Requirements for the Degree
Master of Science in Chemistry
by
William Edgar McKee
September 1950
UMI Number: EP41587
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This thesis, written by
William...Edgar .McKee.....;..
under the guidance of h£S...Faculty Committee,
and approved by all its members, has been
presented to and accepted by the Council on
Graduate Study and Research in partial fulfill­
ment of the requirements for the degree of
Master of Science
Date... October JL550>^
Faculty Committee
Wat
hairman
jr .....
..
ACKNOWLEDGMENT
The author is indebted to Dr. A. B. Burg
for his valuable assistance and encouragement
during this investigation.
TABLE OP CONTENTS
CHAPTER PAGE
I. THE PROBLEM................................ 1
Theoretical introduction to the problem . . 1
Historical background ................ . . 6
II. PREPARATION AND PURIFICATION OP REAGENTS . . . 15
Trimethylphosphine oxide ................ 15
Purification of phosphoryl chloride. . . . 19
Purification of chloroform .............. 19
Purification of ethylene dichloride . . . 20
Purification of methylene chloride . . . . 20
Purification of benzene ....... 20
Purification of toluene . ........... 20
Purification of Skellysolve A .......... 20
Purification of ether ................. 20
Purification of ethyl alcohol ......... 20
Purification of boron trifluoride . . . . 21
Preparation of sulfur dioxide .......... 21
Preparation of sulfur trioxide .......... 22
III. THE REACTION OF TRIMETHYLPHOSPHINE OXIDE WITH
BORON TRIFLUORIDE . . . . . . . .......... 23
IV. THE REACTION OF TRIMETHYLPHOSPHINE OXIDE AND
SULFUR TRIOXIDE ......................... 31
Preparation Method 1 .................... 32
lv
CHAPTER PAGE
Studies toward purification of the
product............................. 35
Preparation Method 2 .................... 38
Preparation Method 3 .......... 38
Preparation Method 4 . . ................ 39
V. THE REACTION OF TRIMETHYLPHOSPHINE OXIDE
AND SULFUR DIOXIDE....................... 45
VI. DISCUSSION AND CONCLUSIONS ........... 57
The reaction of boron trifluoride with
trimethylphosphine oxide ................ 57
The reaction of sulfur trioxide with
trimethylphosphine oxide ................ 57
The reaction of sulfur dioxide with
trimethylphosphine oxide ................ 59
VII. SUGGESTIONS FOR FUTURE INVESTIGATIONS . . . . 63
VIII. SUMMARY............... . . . . .'........ 65
BIBLIOGRAPHY........... 68
LIST OF TABLES
TABLE
I. Addition Compounds of Trimethylphosphine
O x i d e ......................... .........
II. Addition Compounds of Trimethylamine Oxide
of Interest in the Present Study ..........
III. Combining Ratio of (CH3)3PO and BF3 . . . . .
IV. Combining Ratio of (CH3)3PO and SO3 ........
V. Analysis of the Product formed by the
Sulfur Trioxide-Trimethylphosphine Oxide
Addition Compound and G2H^0H ..............
VI. Analysis of the Sulfur Trioxide-
Trimethylphosphine Oxide Addition
Compound (Method 4) .....................
VII. Pressure-Composition Isotherms of System
(CH3)3P0-S02
1.192 X 10“3 moles (CH3)3PO in System . . .
VIII. Pressure-Composition Isotherms of System
(CH3)3P0-S02 at 0°C.
1.192 X 10“3 moles (CH3)3PO in System . . .
IX. Pressure-Composition Isotherms of System
(CH3)3P0-S02 at -23°C.
1.192 X 10“3 moles (CH3)3PO in System . . .
vi
TABLE PAGE
X. Vapor Pressures of SC^-CCHgJ^PO Mixtures
in Constant Pressure Range
Moles SC^/CCH^J^PO Approximately 0.2-1.1 . . 55
XI. Equilibrium Pressures of SC^-CCH^J^PO
Systems.............................. .. 60
LIST OF FIGURES
FIGURE PAGE“
1. Sublimation Apparatus for (CH3)3PO ........ 18
2. Apparatus for Preparing SO3 and Adding it
to (CH3)3P O ............................... 18
3. Apparatus for the Reaction of (CH3)3PO with
bf3 ............................... 27
4. Titration of (CH3)3P0-S03 with 0.01948 N
NaOH ........... 42
5. Apparatus for Treating (CH3)3PO with SOg . . . 46
6. Vapor Pressure-Composition Isotherms of
S02-(0H3)3P0 Mixtures ..................... 53
CHAPTER I
THE PROBLEM
Trimethylphosphine oxide is formally similar to
trimethylamine oxide which has been shown to have great
external bonding power as a Lewis type base.1,2* 3 > 5 it
would be of interest to. know whether the two compounds have
similar basic properties and to attempt a comparison of
their electron donor strengths. This should be possible by
making various addition compounds of trimethylphosphine
oxide and comparing their properties to similar addition
compounds of trimethylamine oxide.
I. THEORETICAL INTRODUCTION TO THE PROBLEM
g
Lewis postulated a dative nitrogen-oxygen bond and
1 A. B. Burg, J. Am. Chem. Soc., 65/ 1692 (19^3).
2 A. B. Burg and J. H. Bickerton, J. Am Chem. Soc.,
67. 2261 (19^5).
3 J. H. Bickerton, Master's thesis in Chemistry, The
University of Southern California, Los Angeles, 194-3*
^ W. K. Godfrey, Master's thesis in Chemistry, The
University of Southern California, Los Angeles, 19^0 .
5 H. Z. Lecher and W. B. Hardy, J. Am. Chem. Soc.,
I0> 3789 (1948).
^ G. N. Lewis, "Valence and the Structure of Atoms
and Molecules," Chemical Catalogue Co., New York, N. Y.,
1923, P. 13^.