Part I: Some methyl ethers of mannitol Part II: The structure of rubremetine

156 Pages·028.065 MB·English

by  Wood, Hamish Christopher Swan

Port I
SQLiE METHYL ETHERS OP
Port II
TÜ1I':: OP RUBm.ûi:TIIŒ
A Thesis
presented by
m m
\wüD. B.so^
to the
^GITY OF 3AIKT
in application for the
Degree of
DOCTOR OP PIIIL030P1IY.
April, 1950.
ProQuest Number: 10166107
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DSCL.ÆxTION.
I hereby declare that the following Thesis is a
record of experiments curried out by me, that the Thesis
is my own composition and has not previously been presented
for a Higher Degree.
The investigation was carried out in the Chemical
Research Laboratory of the United College, under the direction
of John Dewar, B.Sc., Ph.D., and II.T. Openshaw, M.A., D.Phil.
PifCrX, 1^50.
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(11)
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I hereby certify that Lir. Hamish C.S. Wood, B.Sc.,
has spent nine terras at Research Work in the Cheroical
Research Laboratory of United College, that he has
fulfilled the conditions of Ordinance No. 16 (St. ^mdrews),
and that he is qualified to submit the accompanying Ihesis
for the Degree of Ph.D.
I
% 't
(ill)
I entered the University of St. Andrews in Ootober, 1943,
pursuing the oourse of study leading to the Degree of B.So.,
t,
which I obtained in June, 1946. In June, 1947, I was awarded
First Class Honours in Chemistry.
I was admitted as a Research Student of the University of
St. .indrews in October, 1947, and for a period of one year
carried out Research Work on the Methyl Ethers of liannitol
f under the supervision of Dr. John Dewar. From October, 1948,
{
f urtil the present date, I have been engaged on research into
the structure of Rubremetine under the direction of Dr. H.T.
Openshaw.
In Ootober, 1947, I obtained a D.S.I.R. Grant, which I
still hold, and in Ootober, 1949, was awarded an Honorary
Pcst-Graduate Scholarship by the University of St. Andrews.
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Part I
ÊÊÊÊÊ_WmiYL j':TUP.R3 OF ILilHilTOL
Page.
Introduction.......................... 1
Acetone derivatives of mannitol , . / / t i t . . . . 6
Di- and tribenzoates of ciannitol....................... 10
"Hie preparation of methyl ethers of mannitol . . . . . 13
Synthesis of 3:4-dimethyl-mannitol . . . . . . . 13
Synthesis of 1:2-dimethyl-mannitol............... 15
Attempted synthesis of l:£:3:4-tetramethyl-
mannitol . . . . 16
Synthesis of 2:5-dimethyl-mannitol............... 18
Attempted synthesis of 2:3:4:5-tetramethyl-
mannitol . • • • 20
Discussion of results .................. . . . . . . 21
Summary................................................ 29
Experimental Section .................................... 32 -
Bibliography ............................................ 46
Part II
Ü5IE STRUCTURE OF RLTBR: L,ETHD£
Introduction . . . . . .................................. 48
Page.
Historical Section . . . ............................. 49
Investigations on the structure of emetine
and related alkaloids ................. 49
Researches into the structure of rubremetine . . 57
Theoretical Section . . . . . ....................... 66
Study of the dehydrogenation of emetine........ 66
Examination of rubremetine.................... 82
Degradation of K-aoetylemetine............... 91
S ummary.............................................. 95
Experimental Section.......... 98
Extraction of Ipecacuanha r o o t ................. 98
Study of the dehydrogenation of emetine........ 102
Examination of rubremetine................ .. . 120
' Degradation of K-acetyleaetine ................ 136
Bibliography......................................... 140
Acknowledgements.
P.\RT I
A Contribution
.jgjjlÊIÊLÆMly of the methyl :thers of iJanniitfi
.;gg0,^^gpD6oial Ueferenoe to Optioal Uotatpry
Power
1.
INTRODUCTION
The investigation of the relationship between the
ohemioal constitution of a compound and the optioal activity
which it exhibits has been the subject of numerous researches
during the past sixty years. Despite the large amount of
experimental data which has been aocuraulated the problem has
not yet been solved.
‘fhe first workers to attempt to infer the degree, and
the sign, of the optioal activity of a compound by a quantitative
evaluation of the asymmetry of the molecule were Crum Brown (1)
and Ph. A. Guye (2). This theory had to be abandoned, however,
as it failed to take into account many factors which influence
optical activity. Further molecular theories of optical
rotatory power were developed in subsequent years by Gray (3),
de Malleman (4), and Boys (5) and it Is possible to calculate
the approximate specific rotation of simple molecules by such
methods.
Kuhn (6) and Born (7), on the other hand, attempted to
explain the origin of optical rotatory power on the basis of
the elementary physical processes occurring in the molecule
and have developed an eaplanation of optical activity which
forms the keystone of most modern theories. The problem is
essentially one of quantum optics and the position today is best
summarised/