FLAVOUR AND FRAGRANCE JOURNAL, VOL.
2, 21-27 (1987)
Essential Oil Isolates from the Australian Flora. Part 2”
Ian A. Southwell
North Coast Agricultural Institute, Wollongbar, NS W 2480, Australia
The sources of several additional isolates of interest from the Australian flora are listed along with details of yield,
isolation procedure and use.
KEY WORDS Essential oil isolates Australian flora
for synthesis
INTRODUCTION
In the ten years following the publication of a first
list of essential oil isolates from the Australian
flora,’ many more native species have been inves-
tigated and several isolates of interest examined.
Numerous requests for natural sources of isolates
and for compositional data on local oils also
prompted the compilation of a second list. The
increasing demand for natural perfumes, flavours
and medicines also makes such a list of value.
RESULTS AND DISCUSSION
Table 1 lists such additional isolates along with
omissions and corrections of the earlier list. As
before, entries are restricted to isolates which (i)
are in use commercially (perfumery, flavouring,
medicinal, starting materials for synthesis) or pos-
sess commercial potential, (ii) constitute a high
percentage of the oil or (iii) can be readily separ-
ated from associated oil components. Where
many species contain the same constituent (e.g.
cineole), only varieties containing more than 50%
(on average) of that constituent in the oil are
recorded. As the natural abundance of most
species is restricted, their commercial exploitation
may involve plantation establishment. Table 1
contains examples of isolates from morpho-
logically identical plant sources where essential
oil variation exists. Consequently, the selection of
propagation material from varieties yielding
optimum quantities of the appropriate isolate is
imperative for trial plot establishment.
‘For Part 1 , see Reference 1.
0882-5734/87/01002 1 -07S05.00
0 1987 by John Wiley & Sons, Ltd.
Perfumery Flavouring Medicinal Starting material
Although synthetic isolates are often available,
natural flavour and fragrance isolates for specific
use are also in high demand. Consequently, the
isolation of substantial quantities of benzaldehyde
( l ) , citronella1 (10) and methyl cinnamate (18)
from Zieria and Eucalyptus species provides
excellent natural sources of these sought-after
flavour and fragrance materials. Boronia latipinna
provides a superior source of the fragrant (+)-
bornyl acetate (2) for perfumery preparations.
Potential also exists for the commercial use of its
insect-deterrent proper tie^.^ The abundance of
the monoterpenoid car-3-en-2-one (3), chrysan-
thenone (4), chrysanthenyl acetates (5) and (6),
and (+)-perilly1 acetate (21) in certain Zieria and
Kippista species provides ready sources of mat-
erials with perfumery potential. On the other hand,
the Melaleuca and Prostanthera sources of cineole
(7) are all inferior to the already commercial
Eucalyptus sources.’ Melaleuca acacioides (Derby
form) gives a low-yielding terpinen-4-01 (29) oil
containing the lemon fragrance, citral (8 + 9 ) .
With an enhanced yield, this oil could be a more
pleasant substitute to the commercially available
M . alternifolia oil, provided the bactericidal and
fungicidal activity was retained. The terpinen-4-01
levels of M. dissitiflora and M . linariifolia indicate
that these chemical variants could have commer-
cial potential equal to M. alternifolia. Indeed, the
Australian Standard for this commercial product
has recently been revised from ‘Oil of Melaleuca
f
alterni olia’” to ‘Oil of Melaleuca, Terpinen-4-01
Type’ with these levels in mind. The natural
Zieria styrenes ( l l ) , (30) and (31), although of
interest phytochemically and chemotaxonomi-
cally, seem to possess little commercial potential.
The new sources of limonene (16) and a-pinene
Received 9 March 1987
Revised I I May I987
22 1. A. SOUTHWELL

CHO

G
I

1 2
O6 3
0

CH3CO0 43 5
CH3CO0

6
7
0 Q
9 10 11 12

OCH3
I

16
 AUSTRALIAN ESSENTIAL OILS 23

COOCH,

y
ocn,

// OCH,

18

cn,ooccn , I I

A 24
22 23
21

cnZon

26

qn4”
OH
,1111..

H‘
‘

29
CH30 Q
.O
:CH’
ocn,

\\
30
ow,

28
ocn,

CH30

31
OCHS

$32
 Table 1 N
P

Plant Oil y i e l d Isolate Isolation

lsolate Species Part" Family (%) in oilc procedure Use Reference
(N)
.. -.

Benzaldehyde (1) Zieria cytisoides LT Rutaceae 0.4 59 Regeneration from Flavouring, 2.3
sens. strict.d.e bisulphite adduct perfumery,
2. laevigata var. 1.1 84 synthesis
fiaserid*c
(+)-Bornyl Boronia latipinna LT Rutaceae 0.9, 1.4 61 Chromatography Flavouring 4
acetate ( 2 ) perfumery,
insect deterrent
~ar-3-en-z-one(3y Zieria granulata LT Rutaceae 0.7 67 Chromatography May have 2, 3
var. adenodontac perfumery
2. laevigata sens. potential
LT 0.3 49
2. sp.nov.lle LT 1.0, 4.3 51
Chrysanthenone Zieria aspalathoides LT Rutaceae 0.5 75 Chromatography Perfumery5 2, 3
(4)f 't+ forme.3
2. cytisoides LT 0.4 55
'b' formd.c,3
2. obcordata LT 1.s 77
2. robustar LT 2.4 73
cis-Chrysanthenyl Zieria cytisoides LT Rutaceae 0.3 54 Chromatography May have 2. 3
acetate (5)f sens. medicinal use
trans- Chrysanthenyl Zieria cytisoides LT Rutaceae 0.4 60 Chromatography None at 2. 3
acetate (6)f sens. strict.'.e present
1.8-Cineole (7) Callistemon LT Myrtaceae 1.0-1.8 64 Fractionation Medicinal, 6
viminalis flavouring
Eucalyptus L 1.58 75 7
intertexta
var. fruticosa
E . lucens L 0.58 75 7
E. mannensis L 1.58 80 7
E. normantonensis L 1.28 75 7
E. orbifolia L 1.78 74 7
E. pachyphylla L 0.68 68 7
E. pulverulenta LT 4.88 83 8
E sparsa L 2.58 90 7
Melaleuca adnaia LT 1.4 66 9
M . armillaris LT 0.9-2.2 69 10
iM.dissitiflora LT 2.08 66 10
,M.linariifolia LT 1.5 62 11
M . nodosa LT 1.7 55 9
.
i ~quinquenerviad.e LT 1.3 65 12-14
M. stenostachya LT 1.5 56 12
IM.symphyocarpa LT 1.6-4.3 68 12
M. viridiflorad.c LT 1.9 59 12-14
 Prostarchera LT Lamiaceae 1.5-2.9 63 15
aspalathoides
P. decussata LT 0.7 73 15
P. denticulata LT 0.3-0.8 79 15
P. granitica LT 1.2 83 15
P. sp. aff. granitica LT tr 50 15
P. hirtula LT 0.1 65 15
Citral [geranial (8) M elaleuca LT Myrtaceae 0.03-0.22 27 Reeeneration from Perfumerv.,. 30
+ nerd (9)] acacioides Gsulphite adduct flavour,
syntheses
Citronella1 (10)f Zieria aspalathoides LT Rutaceae 0.9 90 Regeneration from Perfumery, 2. 3
var.nov. 1 bisulphite adduct synthesis
2.6-Dimethoxy- Zieria arborescens LT Rutaceae 0.3-1.6 21 Chromatography None at 1, 3, 16
3,4-methylenedioxy- ‘c’ form3 present
styrene (11) 2.smithii ‘d‘form3 LT 0.7-2.1 42 17
2,4-Dimethylphlor- Acradenia fran klinii LT Rutaceae 1.2 90 Recrystallization of None at 17
acetophenone (12) filtered crystals present
Elemicin (13) Cymbopogon LT Poaceae 1.38 70 Fractionation None at 17, 18
exaltatus present
Farnesol (14) Zieria minuti ora LT Rutaceae 0.3 31 Chromatography Perfumery, 2, 3
‘b’form 3 . f
Santaium spicatumh W Santalaceae 2.0 50 Fractionation fixative 18-20
Globulol (15)f Prostanthero LT Lamiaceae 1.9 59 Chromatography None at 17
ovalifoIiad present
Limonene (16)f Melaleuca LT Myrtaceae 0.3-1.3 26-35 Fractionation Perfumery, 12
lassiandra
Zieria aspalathoides LT Rutaceae 0.6 62 flavouring, 2, 3
sens.strictP*c
2.sp. afinspala- LT 0.4, 0.9 63 synthesis 2, 3
thoides 3.r
Z. minutiflora sens. LT 0.7 54 2, 3
strict.c
Z . pilosa LT 0.3-1.1 71 2, 3
Maaliol (17)’ Prostanthera LT Lamiaceae 0.5 60 Recrystallization of None at 15
cuneata filtered crystals present
(E)-Methyl cinnamate (18) Eucalyptus sp. nov. LT Myrtaceae 1.6-6.1 95 Recrystallization of Perfumery, 17
aff. campanulatar filtered crystals flavouring
Methyl eugenol (19) Zieria c tisoides ‘b’ LT Rutaceae 0.5 53 Chromatography Perfumery, 2, 3
formzc.3 flavouring
Myristicin (20) Zieria sp.aff. LT Rutaceae 0.4 23 Chromatography Flavouring 2, 3
arbores~ens~*~*~
(+)-Perilly1 acetate ( 2 1 ) Kippistia suaedi- WP Asteraceae 1.2 65 Chromatography Perfumery 21
folia
/3-PheUandrene (22)f Zieria cytisoides LT Rutaceae 0.2-0.6 20 Fractionation Synthesis’‘ 2, 3
sens. strict.d*eJ
Z . minutiflora LT 0.1 25
‘b’formd,e.3
a-Pinene ( ~ ) f Boronia algida LT Rutaceae 0.3 74 Fractionation Synthesis 17
iUelaleuca arcana LT 0.8 50 12 N
v,
 N
QI
Table 1

Plant Oil yieldb Isolate Isolation

Isolate Species Part' Family (%I in oilc procedure Use Reference
(96)

M. cajuputi",c LT 0.6 73 12
M . thymifolia LT Myrtaceae 0.7 84 9
M . trichosrachya LT 1.38 50 10
Rosifoliol (24)' Rubus rosifolius LT Rosaceae 0.9 70 Recrystallization of None at 23-25
filtered crystals present
Safrole (25) Zieria arborescens LT Rutaceae 0.6 94 Fractionation Perfumery, 2, 3
(cv formd.c,3 flavouring,
Z . smithii 'e' f ~ r m ~ .LT ~ 0.9-2.0 59 synthesis
Z . smirhii 'f' f ~ r m ~ .LT ~ 0.5 41
2. sp. aff. s r n i ~ h i i ~ . ~ LT 0.6-4.6 96
Santalol (26) Sanra1um spicarum W Santalaceae 2.4 45 Fractionation Perfumery 18-20
Selinene (27) Melaleuca LT Myrtaceae 0.3-0.8 80 Fractionation Natural celery 30
acaciodesd seed oil
component 22
Spathulenol (28)f Melaleuca dealbata LT Myrtaceae 0.1 20 Chromatography None at 12
present
M . nervosa LT 0.2 41 12
Terpinen-4-01 (29) Melaleuca LT Myrtaceae 0.2 27 Fractionation Perfumery, 30
acacioidesd flavouring
M. dissirijlora ' LT 1.4-4.3 51 medicinal 10
M . linariifoliad LT 1.6 37 26.27
2.3.4.6-Tetrame thoxy- Zieria arborescens LT Rutaceae 0.7-1.3 59 Chromatography None at 2, 3, 16
ac) formd.c.3
styrene (30) . ~.~
.. present
Z . smithii 'b' f ~ r m ~ . ' LT
,~ 0.8-1.4 42
2.4,6-Trimethoxy- Zieria chevalieri] LT Rutaceae 0.4 28 Chromatography None at 2, 3, 16
present
Zierone
styrene(32) Zieria arborescens LT Rutaceae 0.2-3.1 68 Fractionation None at 1-3
sens. strict.d*C present
Z . sp. aff. LT 1.o-2.0 45
arbore~cens'*~~~

'LT = leaf and terminal branchlets; L = leaf; W = wood; WP = whole plant.

'Calculated as volume (ml)/fresh weight (g) unless indicated otherwise.
Maximum given where more than one sample has been examined.
'Chemical variation with this species has been observed-this entry relates only to one chemovar.
'This species has either experienced a name change since the commencement of chemical investigation or is at present undergoing taxonomic revision.
fAbsolute stereochemistry not established.
gYield based on the weight of air-dried material.
h A n omission from Part 1 .
',Structural revision since Part 1.
/Endemic to neighbouring New Caledonia but listed here as it is only non-Australian Zieria.
 AUSTRALIAN ESSENTIAL OILS 27

(23) are unlikely to compete with the abundance 3. T. M. Flynn and 1. A. Southwell, Phyrochemistry. 26,
of citrus peel and turpentine oils respectively. The 1673 (1987).
4. J. J. Brophy. I. A. Southwell and I. A. Stiff, 1. Nat. Prod..
structure of rosifoliol (24) has been r e ~ i s e d ~ ~ . ' ~49, 183 (1 986).
since the first listing' and confirmed by X-ray 5. S. K. Bhatt, J. K. Sthapak and K. U. Singh. Fitoterapia,
~rystallography.~~ Chemical varieties of Zieriu 55, 183 (1984).
species are good sources of safrole (25) with one 6. J. J. Brophy, E. V. Lassak and R. F. Toia, J. Proc. Roy.
undescribed variety giving a high yield of a 92% SOC.NSW, 118, 101 (1985).
7. J. J. Brophy and E. V. Lassak, J. Proc. Roy. SOC.NSW (in
safrole oil. It is unlikely that Santulum spicutum press).
oil will regain its place on the world market as a 8. J. J. Brophy, E. V. Lassak and R. F. Toia. Planta Medica,
competitor for East Indian sandalwood oil. The 170 (1985).
abundance of 2,4-dimethylphloracetophenone 9. E. V. Lassak. J. Proc. Roy. SOC.NSW. 112, 143 (1979).
J. J. Brophy and E. V. Lassak, J . Proc. Roy. SOC.NSW,
(12) in Acradenia fiunklinii is of interest chemo- 10. 116, 7 (1983).
taxonomically in relation to the placement of 11. T. G. H. Jones, Proc. Roy. SOC.Qld., 48, 48 (1936).
Acradenia in the family Rutaceae. The com- 12. J. J. Brophy, Department of Chemistry, University of
mercial value of the remaining species as sources New South Wales unpublished results.
of terpenoids, farnesol(14), globulol(lS), maaliol 13. R. 0. Hellyer and E. V. Lassak, Ausr. J. Chem.. 21. 2585
(1 968).
(17). P-phellandrene (22), selinene (27), spathul- 14. T. G. H. Jones and W. L. Haenke, Proc. Roy. SOC.Qld.,
enol (28) and zierone (32), and aromatic ethers, 49, 95 (1937).
elemicin (13), methyl eugenol(19), and myristicin 15. E. V. Lassak. 8th Int. Congr. Ess. Oils, Oct. 1980. p. 409,
(20), is likely to remain low owing to poor yields, Fedarom, Grasse, 1982.
1. A. Southwell, Phytochemistry, 20, 1448 (1981).
poor demand and the availability of better 16. 17. I. A. Southwell, North Coast Agricultural Institute, New
sources. South Wales, 1986, unpublished results.
18. E. Guenther, The Essential Oils, Van Nostrand, New
York (1948).
19. T. G. H. Jones and F. B. Smith, Proc. Roy. SOC.Qld.. 41.
17 (1929).
Ackrzowledgemenrs-The author would like to thank Dr J. J. 20. A. 3. Birch, K. M. C. Mostyn and A. R. Penfold, A m . J.
Brophy, Department of Chemistry, University of New South Chem., 6, 391 (1953).
Wales for permission to list some of his unpublished data. The 21. J. J. Brophy, T. M. Flynn, E. V. Lassak and J. Pickard.
following are also acknowledged for critical comments and Phytochemistry, 21, 812 (1982).
checking of the manuscript: Dr E. V. Lassak, Kalgoorlie Col- 22. K. Bauer and D. Garbe, Common Fragrance and Flavor
lege; Dr L. A. S. Johnson, New South Wales Botanic Gardens Maferials, Verlagsgesellschaft, Weinheim (1985).
and Herbarium; Dr J. A. Armstrong, Australian National 23. I. A. Southwell, Tetrahedron Lett., 873 (1977).
Botanic Gardens and Herbarium and Dr J. J. Brophy, Univer- 24. 1. A. Southwell, Awf. J. Chem., 31, 2527 ( 1 978).
sity of New South Wales. 25. B. Beagley. R. G. Pritchard, R. Ramage and I. A. South-
well, Acra Crysr.. B38, 1391 (1982).
26. A. R. Penfold, .I. Proc. Roy. SOC.NSW, 59, 306 (1925).
27. J. B. Davenport, T. G. H. Jones and M. D. Sutherland,
Univ. Qld. Dept. Chern. Papers, l(36). 1 (1949).
REFERENCES 28. Standards Association of Australia, AS K175-1967. Oil
of Melaleuca alrernifolia, SAA, Sydney, 1967.
29. Standards Association of Australia, AS 2782-1985.
1. E. V. Ldssak and I. A. Southwell, Int. Flav. Food Add., Essential Oils-Oil of iMelaleuca, Terpinen-4-01 Type,
126 (1977) SAA. North Svdnev. 1985.
2. 1. A. Southwell and J. A. Armstrong, 8th Int. Congr. Ess. 30. J. J. Brophy, E. V. iassak and D. J. Boland, J. Proc. Roy.
Oils. Oct. 1980. p. 323, Fedarom, Grasse, 1982. SOC.NSW (1987) in press.