Haenke, W. J

Jones, T. G. H. (Thomas Gilbert Henry)

University of Queensland eSpace

University of Qyeensland 
PAPERS 
DEPARTMENT OF CHEMISTRY 
Volume I 1937 Number 
Essential Oils from the Queensland Flora 
Part lX.-Melaleuca lJiridi/lora, Pari I. 
BY 
T. G. H. JONES, D.Sc., A.A.C.I., and W. L. HAENKE, B.Sc., B.Sc. (App.) 
REPRINTED 
from 
THE PROCEEDINGS OF THE ROYAL SOCIETY OF QUEENSLAND 
VOL. XLVIII, No.6, pp. 41.44 
MAY, 1937 
ESSENTIAL OILS FROM THE QUEENSLAND 
FLORA 
PART IX.-MELALEUCA VIRIDIFLORA, PART I. 
By 
T. G. H. JONES, D.Sc., A.A.C.I. 
and 
W. J. HAENKE, B.Sc., B.Sc. (App.) 
Chemistry Department, University of Queen-sland 
[Reprinted from the Proceedings of the Royal Society of Queensland, 
Vol. XLVIII., No. 6, pp. 41-44.]
DAVID WHYTE, Goverpment Printer, lJrisbaue, 
VoL. XLVIII., No.6. 
Essential Oils jtrom the Queensland Flora. 
Part IX.-Melaleuw v·iridifiora, Pa1·t I. 
By 'I'. G. H. JONES, D .Sc., A.A.C.l.
and 
W. J. HAENKE, B.Sc., B.Sc. (APP.)
Chemistry Department, University of Queensland. 
[Tabled before the Royal Society of Queensland, 31st August, 1936.] 
41 
JNVESTIGATIONS of the essential oil from the broad leafed tea tree,
which is a very common tree in Eastern Australia, have been carried 
out by several workers, and the main constituents of the oils examined 
by them placed on record.1 Botanical investigation has likewise pro­
ceeded and the tree is referred to in this paper as Melaleuca viridifiora, 
although other names, such as Melaleuca Leucadendron (var. lancifolia) 
and Melaleuca Maideni have from time to time figured in the literature. 
Owing to the reported high cineol content of the oil, it has never been 
of economic value, but in view of several inconsistencies which appeared 
in the results of various workers, it appeared desirable to make a new 
and systematic investigation of the whole problem of the essential oils. 
In this work the authors have had the co-operation of the Forestry 
Department, which supplied many of the consignments of leaves and 
assisted the investigation as far as possible. It soon became apparent 
that at least two varieties of Melaleuca viridiflora existed, one in which
cineol was the principal constituent, but the other contained no cineol, 
and trees of this type were readily differentiated from the cineol variety 
by the marked difference of odour of the crushed leaves. This particular 
variety was first located from a consignment of leaves from the neigh­
bourhood of Maryborough, and fortunately the leaves were collected 
from two trees only which were kept separate until their identity was 
established. Trees of this same type were subsequently discovered in 
dose proximity to Brisbane and, while a complete survey of the Brisbane 
area has not yet b€en carried out, it would appear that its distribution 
is considerably less than that of the cineol variety, although the two
varieties grow together. 
'fhe investigation of the oil from this variety has been completed 
and forms the subject of this paper. It is intended to submit the results 
obtained from the examination of the cineol and possibly other varieties 
at a later date. 
The oil described in this paper has been found to consist almost 
exclusively of the two alcohols linalol and nerolidol with a little ses­
quiterpene, citral and traces of a phenol. As the alcohols can be
readily separated from one another and appear uncontaminated with 
other substances, the oil may be regarded as a convenient source of 
these alcohols, and in view of the linalol content (at least 50 per cent.) 
is of undoubted economic value. 
It appears likely that the oils examined by previous workers were
mixtures of the two varieties mentioned above, as indiscriminate picking 
of leaves was no doubt indulged in by collectors. 
EXPERIMENTAL. 
One and a-quarter cwt. of leaves collected at Antigua (near Mary­
borough) on 18th June, 1935, gave 700 ccs. of oil, while 200 lb. collected 
near Brisbane gave 1,000 ccs. of oil, the yield being in each case 
42 PROCEEDINGS OF THE ROYAL SOCIETY OF QUEENSLAND. 
approximately 1 per cent. In the case of the Maryborough consignment 
the leaves were from two trees only and kept separate till their identity 
was established, while with the Brisbane leaves, careful selection of 
trees was resorted to in order to obtain samples from the same variety. 
The following constants were recorded :-
dl5'5 
N£ 
[a]n 
Ester Value 
Acetyl Value . .
[a ]n after acetylation 
Mary borough Sample. 
·8764 
1·4700 
+15·5 
Nil 
146·2 
-2 
Brisbane Sample. 
·880 
1·4719 
+ 14·26 
Nil 
150 
-2 
Both oils possessed a pleasant rose-like odour due to the presence 
of linalol. 
The oils were �ashed with dilute Na2003, and then dilute NaOH 
solutions. The NaOH washing gave in each case about i ccs. of dark­
coloured oil smelling of eugenol. The colour reaction with ferric chloride 
solution was reddish-brown (eugenol gives a green). Tests for f3 
diketones were negative. A small quantity of crude benzoyl derivative
. was obtained, but it could not be sufficiently purified for i
dentification. 
The oil 790 ccs. (Brisbane sample only described as the Mary­
borough oil gave similar results) was next submitted to fractional dis­
tillation under diminished pressure 4 mm. and the following fractions 
collected :-
Temp. Vol . 
I. 0-59°0. 18 cos. 
II. 59-62°0. 355 cos. 
III. 68-118°0. 20 ccs. 
IV. 118-121°0. 370 cos. 
Resinous Residue 25 ccs. 
dl5'5 N� ao 
·884 1·4654 + 9·39 
·868 1·4607 + 16·70 
·900 1·4780 + 5·29 
·884 1·4785 + 11·54 
Repeated refractionation ultimately resolved the various fractions 
into two main fractions (b) and (d) with a small head fraction (a) and 
a sesquiterpene fraction (c ) . 
The small head fraction (a) 10 ccs. possessed the following con­
stants:-
dl5'5 
N� 
a= 
b.p. app. 
·8858 
1·4660 
+ 6·65 
186°0. 
Examination revealed the presence of linalol (as would be expected 
in view of fraction (b), which required, therefore, that some consti­
tuent of density higher than ·8858 should be present. Cineol was 
naturally suspected under these circumstances, but only negative tests 
were obtained and similarly tests for pinene and other terpenes were 
negative. 
It appears certain however by analogy with other oils containing 
linalol that some linalol monoxide ( dl5'5 ·9520) would be present.2 
Aerial oxidation of linalol while still in the tree is stated to give rise to 
small amounts of linalol monoxide. In all probability fraction (a) 
ESSENTIAL OILS FROM THE QUEENSLAND FLORA-PART I., ETC. 43 
consisted of linalol with some contamination with monoxide sufficient to 
raise the density to that indicated. 
Fraction (b) consisted essentially of linalol. The following 
constants were determined:-
d15'5 
D 
N2o 
[a]n 
b.p. 
·868 
1-4607 
+ 18·5 
60°0. 4 mms. 
The fraction was submitted to critical examination in the following 
experiments:-
Primary alcohols.-Extraction with phthalic anhydride in benzene
solution gave no indication of primary alcohols. 
Terpenes.-Purification of the linalol was accomplished by the
formation of sodium linalol; the non-alcoholic portion being then removed 
by vacuum distillation. Dihydromyrcene (a by-product of the action of 
sodium on linalol) was identified by means of its tetra bromide M.P. 
88°0. The constants for this dihydromyrcene were as follows :-
d15.5 ·783
N� 1·4523
indicating that it was almost pure and that there could not be any 
appreciable quantities of non-alcoholic bodies in fraction (b). Linalol 
purified from its sodium compound possessed the following constants :-
d15.5 ·869 
Nfo 1·4618 
[a]n + 18·5 
which do not differ markedly from those of the original fraction. 
Identification of Linalol.-'l'he phenyl and napthyl urethanes 
(M.P's 66°, 54°0.) were prepared and oxidation with dichromate gave 
good yields of citral. M.P. of semicarbazone 164°0. Acetylation. The 
acetylation of the fraction gave geramyl acetate as main product while 
the rotation became slightly negative in accordance with the well-known 
behaviour of linalol in this reaction. 
4cetic Acid. Benzidine Test.-The main linalol fraction gave a
pronounced test with acetic acid benzidine solution, indicating the 
presence of an ·aldehyde. This test was also readily given by a sample 
of commercial linalol, but not with linalol prepared from sodium 
linalol. Extraction with semicarbazide acetate solution gave on isolation 
about i- per cent. of aldehyde material which gave a pronounced benzi­
dene test similar to that of citral (which substance is a normal oxidation 
product of linalol). It appears therefore that the linalol is contaminated 
with small amounts of citral insufficient for isolation. 
Fraction (c) .-20 ccs. of this fraction were available . . The following
constants were determined:-:-
d15'5 ·900 
N� 1·4780 
[a]n + 5·29 
b.p. 68-118°0. 4 mms. 
The bromine-acetic acid test for sesquiterpene was strongly positive. 
'rhe usual method of removing alcohols from sesquiterpene fractions, 
44 PROCEEDINGS OF THE ROYAL SOCIETY OF QUEENSLAND. 
that is distillation over sodium, could not be used in this instance owing 
to the production of hydrocarbons from linalol and nerolidol (fraction 
d) by the action of sodium.
No solid derivatives could be obtained, and the fraction apparently . 
consisted of some sesquiterpene in admixture with linalol and nerolidol. 
Fraction (d) .-360 ccs. possessed the following constants:-
d15.5 ·8836
N� 1·4782 
[a]o 1- 1·5 
Identification of this fraction with nerolidol (melaleucol) has 
already been described in this Journal.8 
Purification of nerolidol by the sodium method (as described above 
for linalol) gave as by-product a hydrocarbon with the following con­
stants :-
dl5'5 ·8335
N� 1·4700 
[a]o 0 
[Found C = 87-4 H = 12·6 C15H26 requires C = 87·3 H = 12·6.] 
This hydrocarbon gave a characteristic solid bromide M.P. 131°0. 
by addition of bromide. 
The percentage of bromide was 69·5 per cent. and evidently corres­
ponded with a hexa bromide [Br. = 69.9]. 
Although this hydrocarbon does not appear to have been previously 
described, its constitution by analogy with dihydromyrcene and linalol 
is that of dihydrofarnesene. 
CH3-C=CH-CH2-CH2-C=CH-CH2-CH2-C=CH-CH3 
6na 6na �H3
This hydrocarbon was subsequently prepared by reduction of £arne­
sene (from nerolidol via farnesol) with sodium and alcohol, and the same 
hexabromide prepared, M.P. 131°0., alone or in admixture with the
abovementioned sample. 
Our thanks are due to Mr. C. T. White, Government Botanist, for
critical examination of the leaves submitted as samples. 
1 The Essential Oils (Finnemore) 556, 557. 
2 Schimmel & Co. Reports 1912. October, 80. 
• Jones and Harvey. R.S.Q. 1936 2-3.


Essential oils from the Queensland flora. Part IX, Melaleuca viridiflora. Part 1

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Essential oils from the Queensland flora. Part IX, Melaleuca viridiflora. Part 1

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