Table Of ContentA T H E S I S
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THE UNIVERSITY OF GLASGOW
in fulfilment of the
requirements for the
DEGREE OP DOCTOR OF PHILOSOPHY
WILLIAM MANSON
March, 1950.
ProQuest Number: 13870196
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The author wishes to record his sincere
appreciation of the guidance given during the
course of these investigations by Professor
F. S. Spring. He would also thank Dr.J.McLean
for his continued interest and encouragement,
and Dr. G-.T. Newbold for his assistance with
spectroscopic data.
C O N T E N T S
Page.
SUMMARY (i)
Part I - The Structures of c<-Amyrenol
and tfrsolic Acid.
HISTORICAL
Introduction 1
Dehydrogenation 4
The Unsaturated Centre and its Environment 9
The Ethylenic Linkage and the Hydroxyl Group 14
The Functional Groups of Ursolic Acid 20
The Oxidative Degradation of <*-Amyrenol 23
THEORETICAL
Introduction 31
J- <x -Amyradiene and its Oxidation Products 32
The Nature of the Carboxyl Group of Ursolic Acid 47
Ketoacetylursolic Acid and Related Oxidation
Products of Ursolic Acid 50
Methyl Metodihydro-acetylursolate and its
Oxidation Products 65
Conclusion 77
EXPERIMENTAL 82
BIBLIOGRAPHY 136
Part II- The Resin from Canarium Schweinfurthii.
HISTORICAL 140
THEORETICAL
Introduction 141
The Steam-Volatile Fraction 142
The Non-Volatile Acid Fraction 146
The Non-VolatileN eutral Fraction 149
Conclusion 153
EXPERIMENTAL 154
BIBLIOGRAPHY 176
3
SUMMARY
Part I - The Structures of c(-Amyrenol and Ursolic Acid.
Investigations have been carried out on the naturally
occurring triterpene, oc-amyrenol, CaoH5o0, and the
related substance ursolic acid, C30H4803, with a view to
the elucidation of the structure of the oc-amyrin group
of triterpenes
Oxidation with chromic anhydride of the unsaturated
hydrocarbon -amyradiene C30H48, yielded /-«-amyra-
diene oxideC30H480, which on further oxidation with the
same reagent was converted to J- ot -amyrenone oxide
C30H4602. In addition a number of well-defined mixed
crystals of the hydrocarbon and each of its oxidation
products were obtained, and one of these was identified
with a product previously obtained by treatment of
/- <x-amyradiene with perbenzoic acid.
An examination of molecular rotational differences
between certain derivatives of (X-amyrenol and the corres
ponding derivatives of cx-amyrenol has been made, from
which, in conjunction with the oxidation experiments on
J - <* -amyradiene, a partial formulation for of-amyrenol
has been derived.
Treatment of acetylursolyl chloride, C32H4903C1, with
phenylmagnesium bromide yielded the diphenylcarbinol,
(ii)
C44HQo03, which could not be dehydrated to the corres
ponding diphenylethylene derivative, and hence confirmed
the tertiary nature of the carboxyl group of ursolic acid.
Ketoacetylursolic acid when refluxed with quinoline
in presence of oxygen has been shown to yield nor- oC-
amyradienonyl acetate, C3iH4603, while in the absence of
air nor-<X-amyrenonyl acetate was produced. Under
similar conditions, ursonic acid C30H4603, acetylursolic
acid C32H6004 , and 0(-amyrenonyl acetate C3SH5003 have
been shown to be stable, from which the relative locations
of the ketone group and the carboxyl group of ketoacetyl
ursolic acid have been tentatively fixed.
Oxidation of acetylursolic acid with hydrogen
peroxide produced an oxido-lactone C32H4805, identical to
that obtained by Jeger, Borth, and Ruzicka (Helv.Chim.
Acta,1946,29,1999). In addition, there was produced an
acid which on methylation yielded methyl oxido-acetyl-
ursolate C33H6805, previously designated methyl keto
dihydro-acetylursolate (Jeger, Borth, and Ruzicka,loc.cit.)♦
Methyl acetylursolate on treatment with hydrogen
peroxide yielded methyl oxido-acetylursolate, C33H5805,
which by the action of dilute mineral acid was converted
to the isomeric methyl ketodihydro-acetylursolate. The
compound described in the literature as methyl ketodihydro-
acetylursolate was identified as methyl oxido-acetylursolate
(iii;
described above. Treatment of methyl oxido-acetyl-
ursolate and methyl ketodihydro-acetylursolate with
bromine yielded the same bromo compound C33H6105Br,
which on dehydrohalogenation gave methyl iso-ketoacetyl-
ursolate, C33H5O05. Oxidation of this with selenium
dioxide gave methyl iso-ketodehydro-acetylursolate
C33H480e, and from a comparison of the behaviour of this
compound with that of similar derivatives of 0C- and
^-amyrenol, a structure incorporating the partial
structures already obtained, has been derived.
Part II - The resin from Canarium Schweinfurthii.
The resin from the tree Canarium Schweinfurthii
has been examined analytically. The steam volatile
portion was found to consist of the terpene d-limonene
containing a trace of a phellandrene. The non-volatile
portion contained the triterpenes o<-amyrenol, /^-amyrenol,
<X-elemolic acid, ^-elemonic acid and a diol, C3oH50Oe,
which like of-elemolic and fl-edemonic acids contained
two unconjugated double bonds but which could not be
identified with any of the known triterpene diols.
THE OCCURRENCE AND CHEMISTRY OR CERTAIN TRITERRENES
WITH PARTICULAR REFERENCE TO THE OC-AMYRIN GROUP.
Being a Thesis presented in Two Parts*. -
PART I.
The Structures of «-Amyrenol and Ursolic Acid.
PART II.
The Resin from Canarium Schweinfurthii.
PART I
THE STRUCTURES OP OC-AMYRENOL AND URSOLIC ACID.
