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2 - I98o Pharmaceutisch Weekblad Scientific Edition
NARANG,K. K., and J. K. GUPTA(I976) J. Inorg. Nucl.
Chem. 3 8, 589; Ibidem (I977) Transition Met. Chem. 2,
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SAWlCKI,C. a., and F. P. SCARINGELLI(I97t) Microchem. J.
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TURCZAN, J., and T. MEDWXCK(I972) J. Pharm. Sci. 6z, 434.
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ABSTRACTS OF DUTCH PH.D. THESES
Under this heading abstracts will be published of doctoral dissertations that are of interest for the pharmaceutical sciences
and are submitted to Dutch universities, or to foreign universities by Dutch pharmacists. Abstracts should be submitted by
invitation only.
Comparative study of isolation procedures for essential oils
Hydrodistillation versus solvent extraction
A. KOEDAM 1, University of Leiden, June 26, I980
Promoter: Prof. Dr. A. BAERHEIMSVENDSEN(Leiden)
Referees: Prof. Dr. K.-H. gUB~-CZKA(Wtirzburg) and Prof. Dr. TH. M. MALn~GR~(Groningen)
The influence of hydrodistillation on the com-
position of some essential oils has been de-
scribed.
Part I (chapters I and 2) is c o n c e r n e d with
volatile seed oils of some species of the U m b e l -
liferae. The effect of the time of distillation on
the composition of the oils from seed of ajowan,
caraway, coriander and cumin (chapter I) and
of dill (chapter 2) is examined. It is d e m o n -
strated that the o r d e r of recovery of the oil
constituents is d e t e r m i n e d by their rate of dif-
fusion through the plant tissues. As this dif-
fusion is governed by the degree of solubility in
the distillation water, the oxygenated com-
pounds, although with higher boiling points,
distil before the hydrocarbons. In chapter i
evidence is presented to suggest that p - c y m e n e
in the oils of ajowan and cumin is (partly) an
artefact of distillation. The ratio o f c / s - d i h y d r o -
carvone to t r a n s - d i h y d r o c a r v o n e in dill oil
(chapter 2) was found to change with varying
~Department of Pharmacognosy, Gorlaeus Laboratories, University of Leiden, P. O. Box 9502, 2300 RA Leiden, The
Netherlands.
Pharmaceutisch Weekblad II5-I98o
I95
amine tetraacetic acid. D. van Nostrand Company Inc.,
New York, r49.
VAMASmTA,S., Y. SEVAMAand N. ISnlrAWA(I978) Expe-
rientia 34,472.
Received July i98o
Accepted for publication July I980.
pH of the distillation water. Isomerization of
cis-dihydrocarvone into t r a n s - d i h y d r o c a r v o n e
was catalysed by trace metals present in the
seed.
In Part n (chapters 3, 4 and 5) the compo-
sitions of some coniferous leaf oils isolated by
the techniques of hydrodistillation and solvent
extraction are compared. C h a p t e r 3 reports on
the hitherto uninvestigated A r n o l d fir ( A b i e s x
arnoldiana Nitz.). The identity of 35 com-
ponents in the oil could be established. It is
shown that also with this fir species diffusion of
the oil c o m p o n e n t s out of the oil canals pre-
dominates over the boiling points of the com-
pounds during distillation. The a m o u n t of san-
tene diminishes gradually as the p H of the dis-
tillation water is lowered. Hydrolysis of esters
during distillation is discussed; attention is fo-
cused on the problem of crystallization of com-
pounds (e.g. borneol, camphor) in the con-
denser of the distillation apparatus. In the
I703
196
chapters 4 (Leyland cypress) and 5 (Savin juni-
per) special reference is given to the acidity of
the distillation water during isolation of the
compounds. Acid catalysis generated appreci-
able amounts of terpinen-4-ol, ct- and y-terpi-
nene and terpinolene at the expense of sabinene
and its hydrates. The solvent extract of
Leyland cypress (chapter 4) contained some
genuine sesquiterpene hydrocarbons which
could not be recovered by distillation.
Part lal (chapter 6) is concerned with the vol-
atile leaf oils of two species of the Labiatae, viz.
rosemary and sage. The experiments revealed
that the oils distill almost quantitatively within i
hour. The acidity of the distillation water is of
minor importance. Only at extreme pH values
(2-3) small effects on some constituents could
be noticed. These results are explained by the
fact that the epidermal glands burst upon con-
tact with the (acidic) boiling water and give off
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Vol. 2 - t98o Pharmaceutisch Weekblad Scientific Edition
their oil quickly, thus preventing the formation
of artefacts.
CONCLUSION
The superficial oils of the Labiatae are well-re-
covered by distillation because time-consuming
diffusion is ruled out. However, if diffusion is
the rate determining factor during distillation
(as is the case with umbelliferous seeds and
coniferous leaves), then solvent extraction has
to be preferred. This procedure eliminates dif-
ferences in-distillation rate of compounds (as a
result of diffusion) as well as rearrangements
due to the acidity of the distillation water. It also
avoids crystallization of high-melting com-
pounds in the condenser. In general it may be
stated that solvent extraction is superior to the
distillation method as it gives a more reliable
picture of the composition of essential oils as
present in plant material.
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