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

Wright, S.E.

University of Queensland eSpace

.· 
University · ol ·Qyeensland 
PAPERS 
() DEPARTM ENT OF CH EMISTRY 
Volume I 1946 Number• 27 and 28 
• 
. . 27. Essential Oils from the Queensland Flora 
Part XXI.-E110tlia Elleryana 
BY 
T. G. H. jONES, D.Sc .• F.A.C.I., and S. E. WRIGHT, M.Sc., Dip. Pharm. 
28. Alkaloids of Queensland Flora·
Part 1.-Daphnandra· repandula. 
BY 
I 
I. R. <:;. BlCK, B.A., M.Sc., A.A. C:l., and T . . G. WHALLEY, B.Sc. 
Prie• : 011e Shilll"f 
PUBLISHED AS ORIGINAL PAPERS BY THE UNIVE�SITY OF QUEENSLAND 
• 
DATE OF PUBLICATION: · 
18th OCTOBER. 1946 . 
I 
VoLUME 1 
DEP_<\RT.ME:NT OF CHE:UIR'T'RY 
1946 NuMBER 27 
ESSENTIAL OILS FRO�l THE QUEENSLAND 
FLORA-PART XXI. 
PART XXI.-EvoDIA ELLERYANA. 
By 
T. G. H . . Jmms, D.Sc., F.�l.C.l., 
and 
S. E. WRIGHT, :\I.Sc., Dip. Pharm. 
Department of Ghem,istry. University of Queensland, 
DATE OF PUBLICATION: 
18TH OCTOBER, 1946. 
A. H. TUCKER, Government Printer, Brisbane. 
ESSENTIAL OILS FROM THE QUEENSLAND 
FLORA-PART XXI. 
The Essential Oil of Evodia Elleryana. 
By T. G. H. JONES, D.Sc. , F.A.C.I., and S. E. WRIGHT, M.Sc. , Dip. Pharm. 
Evodia Elleryana is a tree growing abundantly in the Mackay area of Queens­
land, whilst scattered groups occur along the coastal fringe of Southern Queensland, 
including the Moreton Bay shore of Stradbroke Island. A small amount of oil obtained 
from the lastnamed locality was examined in this Department by Dr. F. N. Lahey 
and Mr. D. T. Robertson and the presence of a solid ketone established. Later, 
larger quantities of leaves became available from. both Mackay and Stradbroke 
Island, and this paper deals with the chemical constituents of the volatile oils 
obtained from. them. 
The tree grows up to 20 feet high in places and the foliage is by no means 
dense. In both cases the yield of oil was poor. The Mackay leaves (air dried) 
gave 0·2 per cent. and the Stradbroke Island leaves (fresh) gave 0·23 per cent. An 
interesting local variation was discovered in the constituents of these oils. The 
Stradbroke Island sample consists of sesquiterpenes, a liquid sesquiterpene ketone, 
a crystalline methoxylated ketone M.P. 57° C., a small amount of a mixture of phenols 
and a small amount of a crystalline methoxylated neutral solid M.P. 81 o C. The 
Mackay oil contains the same liquid sesquiterpene k etone and small amounts of 
sesquiterpenes, phenols and a neutral m.ethoxylated solid, M.P. 107° C. 
The solid k etone M.P. 57° C. , which does not appear to have been isolated 
previously, has been named Evodione. Analysis indicate its molecular formula to be 
C16H2005 and the presence of three rnethoxyl groups and one carbonyl group was 
detected. This solid gives a red colour with concentrated sulphuric acid and may be 
recrystallised from alcohol or petrol. It may be characterised by a number of 
derivatives-a crystalline orange red 2: 4 dinitrophenylhydrazone M. P. 153°C., an 
oxime M.P. ll9° C. , a semicarbazone, M. P. 184°- 185° C., and a pale yellow benzylidene 
derivative M. P. 133° C. The liquid sesquiterpene ketone isolated from both oils by 
its semicarbazone (M. P 177-179° C. ) and subsequent regeneration aiso appears to 
be new and has been named Elleryone. Analysis indirate a moiecular formula C15H220. 
It gives a purple colour with bromine and glacial acetic acid, characteristic of many 
azulene- yielding sesquiterpenes. 
Little information is available about the minor constituents of the oils because 
of the poor yields obtained. Analyses indicate a molecular formula C16H2005 for the 
neutral solid M. P. 8 1  o C., isolated from the Stradbroke oil. This solid contains three 
methoxyl groups, gives a red colour with concentrated sulphuric acid but no carbonyl 
derivatives could be isolated. The crystalline solid, M. P. 107° C. ,  isolated from the 
Mackay oil, appears to have the formula C16H2004, contains two methoxyl groups, 
gives a red colour with concentrated sulphuric acid, but no derivatives could 
be obtained. 
B 
2 ESSENTIAL OILS FROM THE QUEEJ.�SLA.VD FLORA. 
EXPERIMENT�-\L. 
All melting points uncorrected. 
A. From Stradbroke Island. 
68 kg. of leaves, collected in May were steam. distilled for 2 days. The volatile 
oil was viscous and heavy and required collecting in light petroleum.. After removing 
the petrol under reduced pressure, 150 ml. of oil were obtained having the following 
.constants :-
15·5 nn 
Dl5·5 
15·5 
[a]D 
Ester value 
Ester value of acetylated oil 
1·523 
1·0189 
too dark 
13·5 
38·1 
The oil was diluted with ether and shaken with sodium. carbonate solution 
and sodium. hydroxide. No acids were present, and 3 ml. of a dark yellow liquid 
phenol were extracted. The phenolic fraction gave a deep green colour with ferric 
chloride, and on distillation, a white solid phenol crystallised, which on recrystallisa­
tion from. petrol, melted at 76° (20 mgm.. obtained) . It was not found possible to purify 
the liquid phenol any further. After removal of the ether, the oil (120 ml.) was distilled 
at 2 mm. . .  pressure 
Fraction (1 ) B.P. Vol. 
76-85° c. 14 m.l. 
Dl5·5 15·5 
0·9178 
n� D 1·5020 
[a]D -21 
Fraction (2 ) B.P. Vol. 
85�90° c. 10 m.l. 
D15·5 15·5 0·9383 
n� D 1·5080 
[a]D -26 
Fraction (3) B.P. Vol. 
90-100° c. 40 m.l. 
Dl5·5 15·5 0·9784 
n�D 1·5140 
[a]D -106 
ESSENTIAL OILS FROM THE QUEENSLAND FLORA. 3 
The remainder of the oil was then diluted with light petrol and refrigerated. 
A cry,;talline mass of evodione formed overnight. The crystals were filtered and 
recrystallised from petrol, to give M. P. 57° C. Yield 17 gms. The petrol was removed 
from, the oil and distillation continued. 
Fraction (4 ) B.P. Vol. 
II0-115° C. 8 m,l. 
D15·s 15·5 1·00 
n�D 1·5190 
[a]D -15 
The residue was again diluted with petrol and after refrigeration a second 
crop of evodwne (3 gms.) was obtained. The distillation was continued to give a 
fraction, the constants of wJtich were not determined, but when diluted with petrol 
and refrigerated, deposited crystals which were recrystallised from petrol to give 
M.P. 82° C. Yield 0·6 gms. 
Evodione. -This solid crystallised in large prisms frorr. petrol. It gave a red 
colour with concentrated sulphuric acid and was optically inactive. 
Found C 65·5 
H 6·9 
65·7 
6·8 
65·6 
6·9 
H = 6·9 per cent. 
Molecular weight by depression of freezing point of benzene 285. 298. 
C16H20 5 requires 292. 
Methoxyl determinations 31·8 31·1 32·5 per cent. 
C16H20 5 (3CH30-) requires 31·85 per cent. 
Derivatives of Evodione :-O:time. -Prepared by the method of Cousins and 
Lions 1 0·3 gms. was refluxed for eight hours with 3 gms of hydroxylamine hydro­
chloride dissolved in 20ml. of alcohol together with excess barium carbonate. The 
barium carbonate was then filtered off, the filtrate diluted with water, and extracted 
with ether. The ether was removed leaving a dark oil which crystallised slowly. 
After several recryi'ltallisations from petrol, a white oxime, M. P. 114° C. , was obtained. 
Yield 0·1 gm. 
Found C 
H 
N 
62·5 
6·4fi 
4·8 
62·8 
7·1 
H = 6·84 N = 4·56 per cent. 
4 ESSENTIAL OILS FROM THE QUEENSLAND FLORA. 
Benzylidene derivati'Ve.-0·5 gm. of evodione, 0·5 benzaldehyde, and 10 ml. of 
4 per cent. NaOH solution were dissolved in I5 m.l. of alcohol, shaken for 4 hours and 
then stood overnight. Pale yellow needles separated which were recrystallised 
from. alcohol. M.P. I33° C. Yield 0·4 gm.. 
Found C = 72·9 72·6 72·5 
H = 6·22 6·6 6·4 
H = 6· 36 per cent. 
2 : 4 dinitrophenylhydrazone-Brady' s method-orange red needles recrystal­
lised from. alcohol, M. P. I53° C. 
Found C = 56·4 H = 5·3 N = I2·0 
H= 5·I N = ll·9 per cent. 
Semicarbazone.-Using sem,icarbazide hydrochloride and sodium. acetate, 
obtained colourless needles, recrystallised from. aqueous alcohol M. P. I84-l85° C. 
Found N = I2· 2 
C17H2305N3 requires N = I2·04 per cent. 
Second Solid. -Crystallised in rhomboids from, petrol, M. P. 82° C. , gave a red 
colour with concentrated sulphuric acid. 
Found C = 65·4 
H = 6·9 
65·8 
7·06 
66·3 
6·9 
C16H2005 requires C = 65·75 H = 6·9 per cent. 
Molecular weight by depression of freezing point of benzene = 285. 
C16H200 5 requires 292 
Methoxyl determination 32·6 per cent. 
C16H2005 (3CH30-) requires 3I·85 per cent. 
Liquid constituents.-The constants of fractions (I) and (2) indicated sesquiter­
penes and after several refractionations and final distillation over sodium, the following 
constants were recorded :-
Fraction (I) 
15·5 nD I·5003 3 m,l. 
D15·5 15·5 ·9IOI 
[a]D -24 
Fraction (2) 
15·5 I·5030 n-D 5 m,l. 
D15-5 15·5 ·9129 
[a]D -I0·5 
ESSENTIAL OILS FROM THE QUEENSLAND FLORA. 5 
The high density and high rotation of fraction (3) indicated a sesquiterpene 
alcohol or ketone or both. This fraction (36 gms.) was diluted with alcohol and 
mixed with an aqueous solution of 20 gms. of sem,icarbazide hydrochloride and 26 gm.s. 
of sodium acetate. The solution was warmed on a water bath until turbid and set 
aside for several days. Crystals separated which were filtered and recrystallised 
from absolute alcohol to constant melting point 177-179° C. Yield 11.0 gm.s. The 
filtrate WitS shaken with petrol, and on standing a second crop of sem.icarbazone 
formed (2·2 gms.) . After filtering and removing the petrol the residue was steam 
distilled to yield only a small amount of oil. The residue in the distillation flask 
Wits then refl.uxed with aqueous oxalic acid and again steam, distilled. An oil was 
recovered (3·5 m.l.) which was again treated with semicarbazide hydrochloride and 
sodium. acetate to yield 3 gm.s. of sem.icarbazone identical with above. 
Semicarbazone 
[a]D = -143 (C = 2·1 in alcohol) 
Found C = 69·2 70·3 
H = 9·1 8·9 
N = 15·6 15·5 
C16H25N3 requires C = 69·8 H = 9·0 N = 15·3 per cent. 
Regeneration of Elleryone .from the semicarbazone.-5 gm.s. of the sem.icarbazone 
were refl.uxed with 4 gm,s. of oxalic acid dissolved in 60 m.l. of water for 1 hour and 
then steam, distilled. 2·2 G. of a pale yellow ketone were recovered. The ketone was 
distilled under reduced pressure and the following constants recorded 
B. Pt. (m.m.. 0·5 ) 70-72° c. 
15·5 nil 1·5163 
Dl5·5 
15·5 0·9750 
[a]j¥ -118 
[RL]n 67·63 
Found c = 82·3 
H= 9·96 
H = 10·16 per cent. 
B. From Mackay. 
70 kg. of air dried leaves (received in June) were steam distilled for 2 days and 
the oil collected in light petroleum.. Yield of oil 130 m,l., having the following 
constants. 
[a]D 
Ester value 21·3. 
Ester value of acetylated oil 51·3. 
1·5147 
0·980 
too dark 
fi ESSENTIAL OILS FROM THE QUEENSLAND FLORA. 
The oil was diluted with ether and extracted with sodium, carbonate solution 
to give a small amount of a solid recrystallised with difficulty from. petrol, M.P. 
59-60° C. (15 m.gs. of product obtained.) 
The diluted oil was then extracted with sodium, hydroxide solution to give a 
small am.ount of a solid white phenol recrystallised from. petrol, M.P. 80° C.-(recovered 
0·1 gm..) . This phenol gave a purple colour with ferric chloride. 
The ether was removed from. the oil and the residue 120 m.l. distilled at 2 m.m.. 
pressure to give the following fractions :-
Fraction (1) 
B.P. Vol. 
72-76° c. 12 m,l. 
22 nn 1·5027 
Dl5·5 15·5 ·9515 
[a]D -2 1 
Fraction {2 ) 
B.P. Vol. 
110-1 12° c. 20 m.l. 
22 nn 1·5092 
Dl5.515·5 ·9724 
[a]D -82 
Fraction (3 ) 
B.P. Vol. 
112�115° c. 15 m.l. 
n� D 1·5 107 
Dl5·5 15·5 ·9802 
[a]D -70 
Fraction (4) 
B.P. Vol. 
116-118° c 20ml. 
n� D 1·5120 
D15·515·5 ·9852 
[a]D -70
The residue in the flask was then diluted with petrol and refrigerated. A 
colourless crystalline solid separated, which when filtered and recrystallised from 
petrol (sparingly soluble) melted at 107° C. Only 0·6 gm.. of solid was obtained. 
Found C = 69·7 69·3 . 
H = 7·02 7·28 
C16H20 4 requires C = 69·5 H = 7·24 per cent. 
Methoxyl determination 23·1 22·0 per cent. 
C16H20 4 (2CH30) requires 22·8 per cent. 
ESSENTIAL OILS PROM THE QDRENSLAND FLORA. 7 
All the above fractions gave a positive test for ketone with semicarbazide 
hydrochloride. Accordingly each fraction was treated with semicarbazide hydro­
chloride and sodium. acetate, as outlined above for the Stradbroke Island oil. Each 
fraction gave a sem,icarbazone M.P. 177-179° C. which by m,ixed melting point was 
shown to be identical with the sem,icarbazone isolated from. the Stradbroke Island 
oil. Total yield of sem.icarbazone from, this oil = 20 gm.s. 
[a]D = --144 (C = 2·0 in alcohol) 
Regeneration of Elleryone from the semicarba'Zone.-5 gm.s. of sem,icarbazone 
were treated with oxalic acid as above and the ketone Elleryone isolated. Yield 
2·3 G. Its constants were determined after distillation and found to be 
B. Pt. t m.m.. 70-72° C. 
15·5 nu 
D15·5 15·5 
[aJi¥ 
1·5168 
0·9749 
-ll6 
The fractions also contained sm,all am,ounts of sesquiterpene ·and possibly 
sesquiterpene alcohol. These remained in the residues after extracting the ketone 
but little success was m.et with in fractionation because of the com.plex m,ixture and 
sm.all am,ounts recovered. 
REFERENCES. 
(1) Cousins and Lions. Proc. Roy. Soc. N.S.W. Vol. LXX., 413. 
ACKNOWLEDGMENTS. 
This work was m,ade possible by a Com,m,onwealth Government Research 
Grant to the University of Q.ueensland for which due acknowledgment is m,ade. 
The authors wish to acknowledge the assistance of Mr. J. H. Buzacott and Mr. 
D. McBryde in obtaining specimens from, Mackay, and the Government Botanist, 
Mr. C. T. White, and staff in botanical determinations. · 


Essential oils from the Queensland flora. Part XXI, Evodia elleryana

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Essential oils from the Queensland flora. Part XXI, Evodia elleryana

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