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NAME AND ADDRESS DATE
ACKNOWLEDCMEMT
The author wishes to express his most
sincere gratitude to Professor L. Carroll King
for his inspiration and guidance throughout the
course of these investigations.
To the other faculty members of the
Department of Chemistry, particularly professor
Ralph G. Pearson, the author is indebted for
their many valuable suggestions.
NORTHWESTERN UNIVERSITY
INVESTIGATIONS INTO THE MECHANISMS OF FORMATION
OF CERTAIN ORGANIC NITROGEN SALTS
ti
A DISSERTATION
SUBMITTED TO THE GRADUATE SCHOOL
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
for the degree
DOCTOR OF PHILOSOPHY
DEPARTMENT OF CHEMISTRY
By
LEE A* SUELUSKEY
EVANSTON, ILLINOIS
JUNE 1950
ProQuest Number: 10102022
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TABLE OF CONTENTS
Page
INTRODUCTION........................................ 1
i-STEROIDAL AND RELATED SYSTEMS.................... 3
Historical . . . . . ............. .............. 3
Cholesterylisothiuronium and Cholesterylpyridinium
Salts.............................................. 20
Experimental............... 23
Cholesteryl p-Toluenesulfonate.............. 23
i-Cholesteryl Methyl Ether . . . . . . . . . 23
Cholesterylisothiuronium p-Toluenesulfonate
From i-Cholesteryl Methyl Ether ......... 23
From Cholesteryl p-Toluenesulfonate . . . 24
Cholesteryl Mercaptan . . . . 24
Cholesteryl Disulfide ...................... 25
Cholesterylpyridiniimi p-foluenesulfonate
From i-Cholesteryl Methyl E t h e r ........... 25
From Cholesteryl p-Toluenesulfonate . . . 26
Mechanism of Formation of Cholesteryl isothiuronium
Salts from i-Cholesteryl Methyl Ether . ............28
Experimental............. 31
Materials.................................... 31
Methods...................................... 31
Kinetic R u n s ................................ 32
Calculations and Results ...................... 35
Discussion...................................... 40
Page
Mechanism of Formation of 6-Ketocholestanyliso-
thiuronium baits from i-Cholestene-6-one ........ 46
Experimental.................................... 49
Materials.................................... 49
i-Cholestene-6-one......... 49
Methods . . . . . .............................50
Kinetic Data.................................. 50
3 (y0)-Methoxy-6-ketocholestane................ 54
Calculations and Results ...................... 55
Discussion . . ................... 59
The Preparation of Some Quaternary Nitrogen baits
from Several Systems Related to i-0holestene-6-one. 61
Experimental.................................... 65
Source of Ketones............................ 65
3-Mesitoylpropylisothiuronium p-Toluene
sulfonate ............................ . . . 65
3-Benzoylpropylisothiuronium p-Toluene
sulfonate ......... ..........................65
3-Acetylpropylisothiuronium p-Toluene
sulfonate ...................... . . . . . . 65
Source of Quinones..........................66
2.5-Dihydroxyphenylpyridinium Iodide . . . . 66
2.5-DIhydroxyphenylquinaldinium Iodide . . . 66
3.4-Dihydroxy-l-naphthylpyridinium Iodide . . 66
1.4-Dihydroxy-2-naphthylpyridinium Iodide . . 66
Page
TRICYCLENIC SYSTEMS ................................ 68
Historical......................, ................68
Isobornylisothiuronium. baits .................... 95
The Racemization Question......................... 102
Experimental........................... Ill
Preparation of btarting Materials .......... Ill
Camphene . . . . . . . . . . . .......... Ill
Camphene Methyl Ether . . . . . ........ Ill
Tricyclene............................... 112
Bornyl p-Toluenesulfonate .............. 113
Isobornylisothiuronium p-Toluenesulfonate
From Camphene......... 114
From Camphene Methyl Ether .............. 115
From Tricyclene......................... 115
From Bornyl p-Toluenesulfonate .......... 115
Camphane by the Hydrogenolysis of Isobornyl
isothiuronium p-Toluenesulfonate .......... 115
Isobornyl Mercaptan ........................ 117
Isobornyl Disulfide ........................ 118
Mercuri Isobornyl Mercaptide .............. 118
Evidence for Racemic Compound Formation
between d-Kcvi and L-XCVI................... 118
The Diastereoisomeric Salts ................ 119
lylsobornylisothiuronium d-Camphor-
sulfonate............................... 119
d-Isobornylisothiuronium d-Camphor-
sulfonate............................... 120
Page
d,_l-Isobornylisothiuronium Iodide from
Tsobornylisothiuronium p-Toluenesulfo
nate ......... 120
1-Isobornylisothiuronium Iodide from
T-Isobornylisothiuronium d-Camphor-
sulfonate........... 121
d-Isobornylisothiuronium Iodide from
^-Isobornylisothiuronium jd-Camphor-
sulfonate............................... 121
Nature of Product from Camphene, Thiourea
and p-Toluenesulfonic Acid Versus Reaction
T i m e ....................................... 121
Discussion..................................... 122
SUMMARY............................................. 129
BIBLIOGRAPHY......................................... 131
VITA................................................. 136
INTRODUCTION
The beginning of modern organic chemistry can be
well marked by the advent of the structural thoughts of
Kelcule and the tetrahedral carbon atom concepts of LeBel
and van’t Hoff in the early sixties and seventies of the
last century. Because of the herculean tasks of establishing
the structural relationships of the many compounds that were
known then, and of the many that were to be isolated or
prepared in the ensuing years, it is easy to understand
why little or no concern was given to the study of reactions
from other than a purely preparative standpoint. As the
structural knowledge of the compounds grew, however, it
became more and more apparent that many reactions are
accompanied by the intriguing phenomena of inversions of
carbon atom configuration and molecular rearrangements.
It was only natural then that the interests of organic
chemists were expanded to include reactions studies from
a more theoretical standpoint in an effort to comprehend
these phenomena. The first evidences of this expansion
appears in the chemical literature of the early 1920’s.
Since that time an increasing amount of research has been
devoted towards this end. Today with the contributions
and techniques of physical chemistry, the study of organic
.
2
reactions, particularly in regard to the mechanisms by
which they proceed, enjoys wide popularity amongst both
organic and physical chemists.
The investigations which are the subject of this
dissertation were directed primarily along these lines.
More specifically, a general reaction for the preparation
of quaternary nitrogen and S-substituted isothiuronium
salts has been developed for the purpose of studying the
manner in which certain systems undergo reactions with
acids and strongly nucleophilic reagents. The systems that
have been considered are ones possessing i-steroidal or
potential i-steroidal structures and ones related to the
bicyclic terpene, camphane. The conclusions reached re
garding the mechanisms of these reactions are largely based
upon experimental data obtained concerning the molar
dependency of the reactants and the relative amounts and
nature of the products formed.
