CHAPTER 1

REVIEW OF LITERATURE
 REVIEW OF LITERATURE

History of ancient civilisations is replete with

references to spices. Ancient Indian medicine refers to
most of the important spices known today. But recorded
history of spices is available only since the last few
centuries. A few publications written exclusively on spices
are available tOday41-45.

CLOVE
Clove which is the dried unopened flower buds of the
evergreen tree, §.Y.?.YKiUIIl aromati~ (syn. Eugenia
caryophYJllJdR) is an important spice noted for its flavour as
well as medicinal values. The clove tree is indigenous in
the J.\'Ioluccas p , which was later introduced to adjoining
countries. The major producer of the spice today are
Zanzibar, Indonesia ffi1d Madagascar. The important clove
growing regions in India are southern districts of Tamil
Nadu and Kerala and South Canara. The clove bud has been
reported to contain a steam volatile oil, a fixed oil,
resins, tannins, proteins, cellulose, pentosans and mineral
elements 46 • The chemical composition of the spice may vary
according to its geographical origin, grade and the
condition and duration of storage.

Clove oil which is the main quality determining

factor of the spice will be present in the range of 16-21%,
 7
but usually around 17%. The nature of the clove oil may
vary according to the type of distillation employed.
Gildemeister and Hoffmann 47 have recorded that whole cloves
on distillation yield oils with a high eugenol (I) content
ffi1d a specific gravity above 1.06 while crushed cloves give
oil with low percentage of eugenol (specific gravity (1.06).
Smith4B observed that water distillation yields an oil with
finer aroma and having eugenol content of 85-89% compared
to strong oils obtained by steam distillation where the
eugenol content is 91-95%. Guenther 49 analysed Zanzibar
and Madagascar clove bud oils and found that both had very
similar properties and odour characteristics (Table 1).

Freshly distilled clove oil is a colourless oil which

darkens on aging. Studies on chemical composition of clove
bud oil were initiated from late nineteenth century. Clove
oil distilled from dried clove buds was reported to contain
free eugenol (I, 70-90%), eugenol acetate (II, upto 17%)50-52
and caryophyllene (III, 5_12%)53,54. Gildemeister and
Hoffmann55 recorded that caryophyllene in clove oil
occurred chiefly as lower boiling (-) ~-caryophyllene (blue
nitrosochloride, ~w. 164-165 0 ) and in small amounts, as
higher boiling optically inactive o(-caryophyllene
(nitrosochloride, MP.177 0 ). According to Naves 56 , steam
distilled clove oil contains (z-and p -caryophyllenes (5-12%)
OH

I II . III

O-CH 2
I
"
@
0

'-CH -CH = CH
2 2

IV V VI

O-CH 2
I
o

VII VIII IX

CH = CH.CHO
 8

whereas oil extracted from clove with volatile solvents

contains practically none. Vielitz 57 and Treibs 58 have
advffi!ced evidence for the presence of caryophyllene epoxide
also in clove oil. Naves 59 observed that a benzene extract
of clove buds contains no caryophyllene,'but epoxydihydro-
caryophyllene (C 15H240) (the caryophyllene oxide of Treibs).
The extracted clove on further steam distillation yields
chiefly caryophyllene. It was then concluded that caryo-
phyllene is not a natural biological component of clove oil.
This view has been supported by Arctander52 • Smith
suggested that eugenol, eugenol acetate and caryophyllene
together constituting 99% of the oil are not responsible for
the characteristic fresh and somewhat fruity note of a pure
clove bud oil. Methyl amyl ketone identified at the
laboratories of Schimmel and Co~O was supposed to be an
important one of the trace components of clove oil which
contributed to its characteristic odour. Other trace
constituents identified in clove oil were methyl salicylate
61
by Marson and Methyl alcohol, furfural, B-pinene
(tentative), methyl benzoate and valeraldehyde (tentative)
by Schimmel Chemists 62 ,63. Marson 64 also noted the
presence of minor constituents like 2-heptanol, furfuryl
alcohol, dC-methyl furfural, 2-nonanol, benzyl alcohol,
methyl furfuryl alcohol (tentative) and dimethyl furfural
 9
. 6
(tentative) in clove oil. Gildemeister and Hoffmann 5
reported the presence of vanillin in clove oil which has
been confirmed later by Jorissen and Hairs 66 and Van Urk67 •
Physical methods of analysis were used by a number of
workers 68 - 70 for characterisation of clove oil at a later
time. Thin layer chromatography was applied for detection
of the major constituents by Paris and Godon71 • Gas liquid
partition chromatography was applied for the analysis of
clove oil by EI-Deeb et al72 and Cerma and StanGhe~73.
Presence of coniferyl aldehyde reported by colourimetric
detection by Wabha and Sinsheimer74 has not be~n c~nfirmed
in later analyses. Attempts for quantitative determination
of eugenol in clove by iodometric semimicro technique by
Kartha and Kidwai 75 , u~ spectrophotometric method by Kaul
and Nigam76~bY nonaqueous potentiometric method by Mario
Covello et al 77 and colourimetric method by Karawya and
Wahba 78 were made during the period. Various physiological
properties of clove oil namely reaction of human dental
puI p 79 an d an t'lspasmo d lC
. ac tlVl
· · t y80 ,were a 1 so repor t e d •
Several reports on the preservative properties and cosmetic
quality of clove oil suggested by several workers has been
confirmed by Tukatoshi ffild Kimie 81 in 1969.

Gas chromatographic characterisation of clove oil by

Genin et al82 only confirmed the presence of compounds
reported earlier. In a recent investigation using GC-MS,
 10

Deyama and Horiguchi83 reported the presence of benzaldehyde,

benzyl acetate, m-methoxyber-zaldehyde,~-ylangeneand

chavicol in addition to compounds reported earlier. A new

compound, 2-hydroxy, 4,6-dimethoxy-5-methyl acetophenone to
the extent of 35% in mother clove oil was reported by
Huneck84 • The controversy over the presence of 13 -
caryophyllene as a natural constituent in clove oil surfaced
again in 1972 when Walter85 reported the identification by
gas chromatography of 8-caryophyllene in clove oleoresin
extracted by benzene. Naves86 has, however, questioned it
saying that the ethanol solvent used by Walter during the
extraction process might have helped the formation of 13 -
caryophyllene. Recent work of Eiserle and Rogers 87 in
clove oleoresin and Ono and Tanaka 88 on clove essential oil
have not added any new compound to the list. The influence
of storage conditions and type of containers on the rate of
volatile oil loss from clove has been stUdied by Gerhard~9.
A sensitive colourimetric method for estimation of eugenol
in clove oil has been suggested by Korany et a190 • In a
recent investigation on ground cloves Koller~ identified
acetone, methyl acetate, ethyl acetate,?(- andp -pinenes (IV,V)
myrcene, terpinene and limonene in the volatile oil in
addition to previously reported compounds.
 11

Chemical investigation of the non-volatile principles

of clove was overlooked for long time. Oleanolic acid
(caryophyllin),.a pentacyclic triterpenoid was isolated for
the first time in clove by Lodibert in 1825, but its
chemical nature was understood only after 1927 following
the work of Bonastre, Dumas, Mylius, Herzog and Dogge 92 •
Gasic et a1 93 have reported the oleanolic acid content of
clove in the range of 0.68-1.0%. Carbohydrates of three
different species of clove were analysed by Laura94 and
were reported as glucose, rhamnose, xylose, galactose and
fructose. Narayanan and Natu95 identified maslinic acid
(~~.15%) and sitosterol (ca.0.1%) in addition to oleanolic
acid (ca.1.0%) in Indian cloves. They also reported the
presence of glucose, xylose and traces of arabinose in clove
residues obtained after steam distillation and naphthalene
(0.1%) in the essential oil. Brieskorn et a1 96 reported
the presence of methyl ester of 2c(-hydroxy oleanolic acid
and the glucosides of sitosterol, stigmasterol and
campesterol. Clove also contains a fixed oil to the extent
of 5-10% and it is composed of a fatty oil and resins.
According to Salzer97 saturated acids account for about 94%
of the total component acids of the fatty oil with stearic
acid predominating (v~89% of the total). Clove has been
reported to contain tannins to the extent of 10-18%.
 12

Vosgen and Hermann98 have reported considerable concentra-

tion of aglycones of quercetin and kaempferol, minor con-
centration of rhamnetin and kaempferide and smaller
quantities of quercetin ffi1d kaempferol glycosides in clove.
HPLC technique was used by Gracza 99 to identify phenyl
propanoids like trans-anethole, trans-isomethyl eugenol,
iso-asarone and cis-isoasarone in addition to eugenol,
methyl eugenol and acetyl eugenol. Takechi and Tanaha 100
have isolated and characterised an antiviral compound,
eugeniin from clove.

Clove oleoresin is prepared by solvent extraction and

contains the volatile oil, fatty oil and a number of other
constituents soluble in the particular solvent used.
Naves86 obtained 18-22% oleoresin from clove by extraction
with benzene which contained 90-92% volatile oil fraction.
With alcohol, a yield of 23-32% oleoresin was obtainedJbut
the product contained high amount of resins which is
unsuitable for perfwnery purposes. The fact that oleoresin
has a superior odour and flavour compared to volatile oil
is a matter of interest for study.

Clove stem ~~d clove leaf oils are two important

by-products of the clove industry. Clove stem gives 6% of
a colourless oil with coarser and more woody odour than
 13

bud oil. Early workers101-103 reported a higher percentage

of eugenol (83-95%)'in clove stem oil. Guenther104 has
recorded the physico-chemical properties of clove stem oil
from Madagascar distilled in a modern still (Table 1).

A relatively lower percentage of eugenol acetate has

been reported in stem oil as compared to bud oil in early
literature. Presence of ~=-caryophyllene,p-caryophyllene,

furfural and methyJ. alcohol also have been reported by

earlier workers104 • The trace constituents which give the
characteristic fruity odour like methyl-n-amyl ketone are
present in stem oil also, but at a lower concentration.
Van Soden and ROjahn105 identified naphthalene in clove
stem oil. Se~nler and Mayer106 recogniSed a bicyclic
sesquiterpene alcohol (C 15 H26 0) which is yet to be
characterised. Deussen107 has reported the presence of an
amorphous alcohol-insoluble substill~ce (MP.146 o ) with
empirical formula (C 21 rI30 0)5 (tentative) in clove stem oil
which has not been identified so far.

Clove leaves give 2-3% of a colourless volatile oil

with somewhat harsh, woody and dry phenolic odour. A
typical leaf oil from Madagascar examined by Guenther104
is reported to have the properties given in Table 1.
Eugenol content (80-88%) is lower tllan that of bud oil
and eugenol Qcetate is present only in small amounts. The
caryophyllene content was usually high108 •
 Table 1 : Physj.co-q.hEillli2§..~_characteristics oJ cl.9 v e oill

~- ~ = =,---~----~
Zanzibar Nadagascar Madagascar Madagascar
clove bud clove bud clove stem clove leaf
o~'1 49 oi1 49 oil 104 oi1
104

Yield oi' oil 17.46% 17.40%

Specific gravity (25°) 1.051 1.054 1.051 1.040

Optical rotation - 0° 32' _ 0° 25' _ 0° 50' _ 1° 40' -J.

+:--

Refractive index (20°) 1.5318 1.5321 1.5353 1.5321

Total phenol content 91% 93% 91.5% 84%

Solubility in 70% alcohol Soluble in Soluble in Soluble in Soluble in

1 vol. or 1 vol. or 1 vol. or 1 vol. or
more more more more
-'C": ~~-. ...... =4)_
 15

Traceconstituents like methyl- n..-amyl ketone which

give the characteristic pleasant odour to the bud oil are
supposed to be negligible in leaf oil. Presence of
naphthalene has been reported by Schimmel Chemists 109 in
leaf oil. However, no detailed analysis of the leaf oil
has been made.

There are also reports110 ,111 about wild cloves

existing in some parts of the world. The presence of two
unusual compounds eugenone (2,4,6-trimethoxy benzyl
acetone) and eugenin (2-methyl-5-hydroxy-7-methoxy chromone)
in an oil distilled from wild cloves obtained from Moluccas
(3.0-7.7%) has been identified. In addition, isoeugenitin
(2,6-dimethyl, 5-hydroxy-7-methoxy chromene) and
isoeugenitol (2,8-dimethyl, 5,7-dihydroxy chromene) were
obtained by solvent extraction of the wild clove buds112-114.

NUTl\'IEG Al\TD 11ACE

The nutmeg tree, !1Ysj"pt.:Lqa fraKr.§.1l§. Houtt., is unique

among the spice plants by giving two separate and distinct
spices, the nutmeg which is the kernel of the seed, and
the mace which is the aril that surrounds the seed within
the fruit. There is mention about these spices in
ancient Indian medicine. However, modern history records
that this evergreen tree discovered in 1512 A.D. is native
 16

to the Moluccas in the East Indian Archipelago and belongs

to a small farl1ily, lVIyristicaceae. Later it was introduced
to adjoining tropical regions. Today the major produce~s

of nutmeg are Grenada and Indonesia. It is also grown in

cOLmtries like Sri Laru(a and India. The family
IVlyristicaceae includes 18 genera and 300 species of which
~yri~_tica ~ra&r2112. is the commercially important species.
The Papua nutmeg (M. g,rl~§tPtg Vlarb~ and Bombay nutmeg (M.
~alab9r~~ Lam) are inferior varieties used for adultera-
tion of M. J.r~~ns. The ratio of output of nutmeg to
mace is usually 7~1 to 8~1. The trade recognises mainly
two important types of nutmeg and mace namely (1) East
Indian nutmeg and mace and (2) West Indian nutmeg and mace.
There are definite differences between the physical and
chemical characteristics of nutmeg and mace of these two
types. The flavour of East Indian nutmeg products is
preferred by certain users and for particular applications
while the West Indian nutmeg and mace are favoured else-
where. Even under a particular type~ wide variations in
quality is being observed. Nutmeg and mace are marketed
as whole spice, powdered form, spice oils or oleoresins.
The oil, butter and oleoresin content of nutmeg and mace
are given in Table 2.
 17

Table 2 ~ G~~el:al cOll]lqsit19n of nutmeg and mace

Volatile Nutmeg Oleoresin

oil butter
% v/w % v/w %

Nutmeg 7-16 25-40 31-37 (Benzene)·

4-17 20-35 27-32 (Petroleum
ether)

The essential oils of nutmeg and mace have been

subjected to a lot of investigations in the past. They are
the primary contributors to the characteristic odour and
flavour of these spices. The fixed oils of these spices
have an important modifying effect on ~heir flavour, but
other non-volatile principles do not have any beneficial
effect on flavour. The polyphenols of nutmeg imparts an
astringent taste to the spice. Nutmeg and mace have almost
identical chemical composition, but the mace oil has a
finer aroma and flavour.

Nutmeg and mace contain essential oil, fixed oil,

proteins, cellulose, pentosans, starch, resins and mineral
elements115-116. The physico-chemical characteristics of
typical samples of East Indian and West Indian nutmeg oils
have been detennined by Gildemeister and Hoffmann 11'7 and
Clevenger 118 respectively. The geographical origin very
 18

much affects the physico-chemical properties and quality

of the essential oi1119 (Table 3). In addition, the grade
of the nutmeg and the method of distillation also are found
to influence the characteristics.

Nutmeg oil is a colourless mobile liquid having warm

spicy and aromatic odour with a rich sweet and spicy body
note. Fresh oil has rubber like top note which subsides
on storage. Analysis of nutmeg oils was started from
early 19th century and much of the information on the oil
has been collected by Schacht120 , Wallach121 , Semmler122 ,
Thoms123, Power and Salway124 and Schimmel and Co .125 •
The compounds reported by these investigators were:~­
pinene (IV)120,121 camphene124 , [-)-pinene (V)125
I

dipentene1~1, 124, 125, p-cymene125 , d-linalooi124 , 1-

terpenen _4_01125 , borneol124 , dl c( -terpineo1124 ,
, . 1124 ,safrole ( VI )124pn aldehyde124 ,myristicin .
geranlo
iVII)124 -124. 124
\ ,eugenol., lsoeugenol • l'lyristicin vvi th its
toxic and narcotic properties was found to be an important
constituent of the oil. Power and Salway124 also noticed
in the saponification lyes of the oil the presence of
formic, acetic, butyric, caprylic and myristic acids along
with an unidentified monocarboxylic acid, C12H 0COOH.
17
According to them, the nutmeg oil contained mainly mono-
terpene hydrocarbons (-"'-"88%), their oxygenated compounds
 Table 3 : £1lysico-chemical= pr0J2..~rti~§_.2J21~tmegn.oils 1:'::
East Indian West Indian
nutmeg oil nutmeg oil
-=__ o=o_ _ ~ ~ ~ o===o _
~=",-=~-~-=----=---~.=-=,-~..-._-~=-=",=~~"

Yield of oil, % (v/w) 8.5-10.0

Specific gravity 0.865-0.925 (15°) 0.895-0.868

...,.
I..Q
Optical rotation + 8° 0' to + 30° 0' + 40° 48' to 49° 4B'
Refractive index 1.479 to 1.488 (20°) 1.469 to 1.472 (20°)
Solubility Soluble in 0.5 to 3 vol.
of 90?6 alcohol'
L~~~~a-=-.~. ~ :::a:_ =-==
 20

(\..""6%) and myristicin ('-A4%) along with traces of phenols,

esters, free acids, etc. Compositions of nutmeg oils of
unspecified origin have been reported by Lee et a1126 ,
Ikeda et al127 and Jaureguiberry and Wolff128 • The
presence of (+) sabinene (VIII) in nutmeg oil was first
reported by Jaureguiberry and Wolff. The presence of
elemicin ~IX) in the oil was suggested by Shulgin129 •
Studies on Raman spectra130 , colourimetry131 and thin layer
chromatog~aphy132 ~f the oil were also reported during the
period. A comparative study of East Indian and West Indian
nutmeg oils were made by Bejnarowicz and Kirch133 in 1963.
Shulgin and Kerlinge~34 reported the presence of methoxy
eugenol and trans-isoelemicin in nutmeg oil. Itty and
Nigam135 reported a GC profile of Indian nutmeg oil wherein
they have detected linalyl acetate (1.5%), bornyl acetate
~0.9%) and an aromatic ether, C15H2502 as components of
the oil. The chemistry and psychopharmacology of nutmeg
has been described by Shulgin group136. Accordingly nutmeg
has (1) a fixed oil fraction (25-40%), (2) a volatile oil
fraction (8-15%), (3) ffil aromatic fraction and (4) residue
(45-60%). The prGsence of stilbine,Y-terpinene, p-cymene
and toluene in the oil has been reported by the same group.
The aromatic fraction containing myristicin, elemicin and
safrole was suggested to be the source of the psychotropic
 21

activity of nutmeg. Elemicin was supposed to be the more

active psychotropic agent than myristicin while safrole
has no such activity. The pharmacology of myristicin and
nutmeg as such has been studied by Truitt, Jr. 137 • GC
analysis of the oil by S~~my and Nawar138 indicated the
presence of ,"<-phellandrene, myrcene, ,:>(-terpinene,
terpinolene, citronellol, P-terpineol and caryophyllene
in addition to earlier reported compounds. Vfuile studying
the effect of storage on the volatile oil composition of
nutmeg Sanford and Heinz139 newly reported~-thujene,
L\3-carene, 1(7),2~p-menthadiene and trans- and cis-
sabinene hydrate in nutmeg oil. The changes in volatile
constituents of the oil due to the influence of various
factors have been examined by Gerhardt140 • According to
Klein et a1141 and Mathews et a1 142 who have studied the
composition of nutmeg oils in detail, p-cymene, p-methyl
isopropenyl benzene, cyclamen aldehyde and cumene detected
in the oils are probably artefacts. Monoterpene content
in distilled oils as compared to oleoresin or natural spice
is usually high as per the reports of various workers143-144.
This may be due to the incomplete distillation of high
boiling fractions of the oil. Braun and Kalben145 advanced
evidence for the bioconversion of myristicin-like components
of nutmeg into amphetamine derivatives which are known
 22

hallucinogens. In a comparative study of East Indian and

146
West Indian nutmeg oils Baldry et a1 identified trans-
sabinene hydrate, copaene, cis-sabinene hydrate, cis-p-
menth-2-en-1-ol, terpine-4-acetate and cis-piperitol for
the first time in nutmeg oil. A more comprehensive study
of nutmeg oil was made by Schenk and Lamparsky147 recently
using GC-I1S method. The 8.l1.alysis showed 70% monoterpenes,
1% sesquiterpene hydrocarbons, 17-18% aromatic ethers,
8-9% monoterpene alcohols and traces of esters.' A new
method of direct mass spectral analysis (lf~-MS) of nutmeg
kernel has been tried recently148.

The qualitative difference between East Indian and

West Indian nutmeg oils has been described by various
workers. The West Indian oil has a weak spicy odour
compared to East Indian oil as the latter has a higher
amount of aromatic ethers141 • Bejnarowics and Kirch133
suggested the method of distinguishing the oil by the study
of some minor components. According to Lee et al~49
inferior quality oils contain very less limonene and
linalool. The difference between East Indian and West
Indian nutmeg oils may be summarised as below:
 23

Higher myristicin content Low myristicin content

( \',-" 13.5%) ( <1%)
Higher ~ -pinene content Low~-pinene/safrole content
Low sabinene content Higher sabinene content
Strong nutmeg flavour Turpentine note

The flavour and hallucinogenic properties of nutmeg

are attributed to aromatic ethers (safrole, myristicin and
elemicin). The mono-t;erpenes of nutmeg oil have a strong
tendency to polymerize and produce undesirable 'off notes'
upon heating. Deterpenated nutmeg oils are therefore used
for flavouring food products and for perfumery.

Mace has an attractive scarlet colour at the time of

harvest and yields a colourless oil (4-17%) having physico-
chemical and organoleptic properties similar to that of
nutmeg oi1116-119. Since it was generally believed to be
identical with the nutmeg oil, not much individual attention
was paid to the study of mace oil till recently. Shulgin
et al 134 analysed a number of mace oils where the aromatic
ether fraction ranged from 8-18%. While myristicin was
the major aromatic ether, safrole and elemicin were also
detected in small amounts. Forrest and Heacock 150 reported
87.5% monoterpenes, 5.5% monoterpene alcohols and 6.596
 24

aromatic ethers. The composition was similar to that of a

typical East Indian nutmeg oil. Dehydro-diiso-eugenol was
1-1
also isolated from mace oil by the same authors ~. Gas
chromatography of volatile oil distilled from mace
oleoresin has been reported to have higher myristicin
content than that of nutmeg oil 152 • However, no mention of
the geographic origin of the raw material is made in the
paper. The results of a comparative study of West Indian
nutmeg and mace oils by Dann et a1 153 are summarised in
Table 4.

Table 4 :

West Indian West Indian

nutmeg oil mace oil
% %

IVIonoterpene 85-93 75-94

hydrocarbons
Oxygenated 4.7-17.6
monoterpenes
Aromatic ether 0"'3.5 0-5.9

WhilecC-pinene content was lower in mace oil the general

composition of monoterpene hydrocarbon and oxygenated
 25

mono-terpene fractions were comparable in the two oils.

The aromatic ether fraction was more in mace oil than in
nutmeg oil as mentioned by Salzer 152 earlier. The role of
aromatic ether in flavour formation of nutmeg and mace oils
is well recognised. Elemicin is found to be the major
psychotropic agent in West Indian oils. This is in contrast
with East Indian nutmeg and mace oils in which myristi~in

is reported to be the major active compound.

Fixed oil of nutmeg ranges from 25-40% and that of

mace from 20-35%. Worm-eaten nutmegs and mace may appear
to have a higher volatile oil content as most of the starch
and fixed oil of the spice are eaten by the insects.
Oleoresin of the spices extrac-ted with nonpolar solvents
~{ill have a higher fixed oil content, while oleoresin
extracted with polar solvents will have less of fixed oil
and more of resins and other extractives. Oleoresins of
nutmeg and mace are reported to have a more true to nature
odour and flavour probably because of the higher content
of oxygenated compounds in oleorcsins as compared to a
distilled oil. Loss of low boiling constituents and
formation of artefacts during distillation may be other
factors responsible.
 26

The fixed oil or 'nutmeg butter' obtained by hot

expression of the spice usually possesses nn aromatic odour
due to occlusion of some volatile oil inside. Extensive
studies on the fixed oil have been made by Power and
S a 1 way 154 , Collin and Hilditch 155 Heiduschka and Habe1 156
and Pathak and Ojha 15 I .
rJ

It is generally composed of
trymyristin (,70-8576), other fats '. "",3.5%, some fatty acids
and nonsaponifiable matter up-to 2076 comprising phytosterol,
resins, myristicin, etc. Pathak and Ojha 157 have given
the fatty acid composition of nutmeg fat as~ lauric 0.4%,
myristic 71.8%, tetradecenoic 0.8%, palmitic 14.3%,
hexadecenoic 4.8~6, stearic 1.2%, oleic 5.20% and linoleic
acid 1.5%. Narayanan and Kartha 158 observed that
saturated acids (myristic acid being the major one)
comprised 92 0 6% of the total fatty acids in nutmeg while
saturated acids in mace constituted only 37.6% (with
palmitic and oleic acids being the major component acids)
i.e. the ratio of saturated to unsaturated acids is 2;3.
The nature of the component glycerides was as given in
Table 5.
 27

Nutmeg Mace

Trisaturated 80.7 o
Disaturated 16.5 32.9
dono saturated 47.2
Triunsaturated 0.0 19.9

It is believed that the fixed oils have a role in modifying

the flavour of the two spices. The mace and its oleoresin
are considered to possess a finer fresh fruit character.

klother group of chemical compounds recently

identified by I,sogai et a1 159 include 13 phenyl propanoids
(7 newly reported) which are lipid soluble and have growth
inhibitory e ff ec t on Sl'IIK worm 1 arvae. ~
~orrest et a 1
160 ,161

identified similar compounds in nutmeg as well as in mace.

.
Harvey 162 h as l'd· en t'f'
l le d mos t 0 f th e p h eny1 propanol'ds b y

GC-lVlS analysis. These compounds are of interest for chemo-

taxonomic purposes, but have no flavour properties.

The genin from a triterpenic saponin isolated from

nutmeg was identified as oleanolic acid by Varshney and
Sharma 163 • No systematic work on the flavanoids of nuuneg
and mace has been made so far.
 28

Quality variation of nutmeg and mace during storage

has been discussed by Wurziger 164 , Parry165 al1d Garhardt 140 •
Sanford and Heinz 139 reported that during prolonged storage
of nutmeg the low volatile compounds are lost and the free
myristic acid content increases due to hydrolysis of tri-
myr.ls t .In.
o 0
.Th'lessen andr."0C hOd
e1. e 166 0 b serve dslgm
O ' f .lcan-c
. 0

changes in flavour quality of the spice and its oleoresins

when heated above 90°C.

l"leyer 167 0bt·

T"
a1.ne d an aroma t1.C
O O 01.
SPlCY . I ,\
. 1. 56 0L70 ) b" Y

steaLl distillation of dried nutmeg leaves from East Indies.

The oil contained:·(. -pinene (80%) and myristicin (10%).
Khan and Krislmaswamy168 have reported 0.41-0.62% oil in
Indian nutmeg leaves. GC profile of nutmeg leaf oil from
Grenada is said to be similar to that of West Indian nutmeg
oi1 169 • The flavour quality of leaf oil is, however,
inferior to that of nutmeg oil.

The bark of the nutmeg is reported to yield an oil

(0.14%)170,171. No aldehyde has been detected in this oil.

The fleshy pericarp from the ripe nutmeg fruit

contains an acidic astringent JUl.ce with an aromatic
flavour. Early reports 172~~'174 give the analysis of the
rind as: Hoisture 86.8%, protein 10%, ether extract 0.4%,
carbohydrates 11.290 and mineral matter 0.6% [Ca.O.. 04% ~
P 0001%, Fe 2 mg and carotene (Vitamin A) 8 I.U./100 gm]
 29

Cinnamon is one of the oldest spices known. to mankind

and historical references to its prominence in the ancient
trade are available in plenty. It is indigenous in Sri
Lanka which is the largest producer of good quality
cinnamon today followed by Seychelles. In India i t is grown.
in limited areas of Kerala State and Tamil Nadu. Cinnamon
is the dried bark of C:;i~al1l.q,rm-lill LeJZ=u.!!! (Syn. C. ~'y'~anicum),
an evergreen bushy tree of the tropics growing to a height
of 10-15 m. The major by-products are cinnamon bark oil and
cinn@TIon leaf oil obtained by steam distillation of the
respective parts of the tree. Ciru!amon bark has a delicate
flavour and is used in baking, pickling, medicine, and in
incense. The bark and leaf oils find uses in flavouring and
perfumery. The latter is a good source of eugenol.

The genus Cinnamomum Schaeffer belongs to the family

Lauraceae and includes some 32 genera and 2000-2500 species.
Nearly 250 species of cinnamomwTI are listed by Willis 175 ,
but a correct, botanical characterisation of the species is
yet to be made 176 • All the species are aromatic having
either cinnamaldehyde, eugenol, safrole or camphor as the
major constituents in the oil. ~~~9.~Yill y~~ Presl (Syn.

,g,. ~~§xJ.~[~rL-i9..1.J.m blume~ LEilltJd§"(ltL~IlLsmL1..!ffi L.) is the true

cinn@TIon of commerce and has cinnamaldehyde(X) as the chief

constituent in the volatile oil.
 30

Cassia which is usually considered somewhat inferior

to true cinnamon is a group of spices obtained from
different species of cinnamomum. Prominent among them are~

Bote-D:h.cal name

Chinese cassia South Eastern

China
Indonesian cassia Cinnamomum burmannii Indonesia and
rc7 G. and Th. Nees7 some other
Blume parts of
Sou-t;h East
Asia
Saigon cassia .QiJ}fLamQ!ll.1illl 1-..0l.d£~~irii Nees Vietnam
Indian cassia Cinnamomum tamala India
"[EuCh-Ham) 1'ri:= Nees and
Eberm
Oliveri s bark Australia

The four cinnamomum species of importance in international

trade are C. yer~ (True cinnamon) and the Cassias from

under different vernacular names and have been listed

according to species by Lawrence 177 • The present investi-
gation is limited mostly to characterisation of £.
#~laI).i..9JJill grown in India.

The grading of cinnamon is an elaborate process of

the trade. Usually cinnamon quills measuring over 1 mare
 31

sorted into different grades according to the thickness of

the bark. The lower grades obtained as by-products in the
preparation of quills are known as quillings, featherings
and chips.

The volatile oil is the principal contributor to the

characteristic flavour of cinnrunon and is produced either
by steam or by hydrodistillation with cohobation. According
to Arctander 178 the distillate has to be extracted with
solvent to get the cOQplete flavour of the oil.

The yield of oil from the barks varies from 0.5 to 2.0%
Gildemeister and Hoffmann 179 and Guenther 180 have reported
the physico-chemical properties of bark oils from different
grades 0 f .::>ri Lanl;:an cinnamon and its loaf oil (Table 6).

Guenther observed that bark oil obtained from certain

regions of Sri Lanka had abnormally high eugenol content
(,.--. 34%) and hence different physico-chemical properties.
The presence of higher eugenol content in oil from chips
modifies the true cinnamon flavour to a certain extent.
Wide variatio:ll in aldehyde content of the oils depending
upon the condition of raw material, its age and processing
has also been reported 180 •

The true cinnamon contains a volatile oil, a fixed

oil, tannin, resin, proteins, cellulose, pentosans,
 32

nucilage, starch, calcium oxalate and mineral elements.

The composition may vary according to source, grade and age
of the raw materia1181-186
•

The Sri Lankan cinnamon yields 10-1296 oleoresin with

ethanol and 2.5-4.3% with benzene 187 • The cinnamon
oleoresin contains a stemn volatile oil, a fixed oil and
other extractives of the spice soluble in the particular
solvent employed. The volatile oil content of the
oleoresin is around 16%. Since the volatile oil renders
the·~ue flavour of the spice, complete extraction of the
constituents while preparing the essential oil or oleoresin
is important. Coumarin present in small illflOunt in the
spice may not be co~pletely extracted during distillation.
Organoleptically, oleoresin is more close to the natural
spice as compared to volatile oil.

Cinnamon bark oil is a pale yellow liquid, possessing

characteristic aroma of the spice and a sweet pungent taste.
The first chemical investigation of the oil was started by
Blanche t 188 as early as in 1833. Dumas and Peligot 189 ' 190
identified cirulamaldehyde (X) as the major constituent of
f. zey~~~g~ as well as f. ~a oils. Detailed investi-
gation of the oil was carried out later191-193. According
toWalbaumand Huthig, the bark oil contains eugenol in the
range of 4-10% whereas it is much higher, upto 95% in the
 33

leaf oil. These early investigations also revealed the

presence of several chemical constituents namely methyl-n-
amyl ketbne 192 , furfural 192 , 1~_pinene192, I-phellandrene 191 ,
p_cYffiene 192 , benzaldehyde 192 , cuminaldehyde 192 , hydroxy-
cirulamaldehyde 192 , l_linalool191-193, linanyl isobutyrate
(tentative)191-193, eugenol 191 and caryophyllene191:193 in
the oil.

Recently Wijesekera et al 194 carried out detailed gas

chromatographic analysis of the oils of leaves,. bark and
root bark of Sri Lankan cinnamon. Twentysix compounds were
identified in the bark oil in this study. Besides cinnam-
aldehyti.e (0".;.. . 74%), other relatively important components
detected were eugenol, cinnamyl acetate (XI), linalool,
1:8-cineole, p-caryophyllene and benzyl benzoate. The new
compollilds reported in the study included~3-carene, sabinene,~~
and Y-terpinenes, 1 :8-cineole, geraniol, piperi tone, (";12-
terpineol, cinnamyl alcohol, cirulamyl acetate, eugenol
acetate, safrole, benzyl benzoate, humulene and~=-ylangene.

The composition is likely to vary according to the type of

distillation employed. The aldehyde content in Sri Lankan
oils varies from 51 to 76% and eugenol from 5 to 18%. A
critical review195 on the chemistry and technology of cinnamon
has come ou-c, of late. Analysis of g. ~eJLl~~cum leaf, stem
bark and root barl\: oils by Senanayake et al 196 helped in
 34

identifying 72 compounds of which 32 were newly reported

compounds in the oil. All the three oils had a similiar
array of compounds but in varying proportions.

Seychelles cinnamon has been rated inferior in colour,

odour and flavour to Sri Lankan. products by early
WOrlcers197-200. The cinnamaldehyde content was reported to
be below 36%. With improved teChniques i t has been possible
to get an yield of O.S% oil with cinnamaldehyde content at
acceptable levels (64%)201. Later studies202-205 have
indicated that the cimiamaldehyde content was comparable to
that 0 f Sri Lankan bark oil but eugenol content varied
from 2w8%, usually in the rffi1ge of 3-5%. Contrary to earlier
reports camphor has not been detected in seychelles oil. In
general, the seychelles bark oil is slightly inferior in
quality to Sri Lffiikan oil. The poor solubility of the oil
in alcohol is attributed. to higher proportion of terpenes
and low content of eugenol. The quality variation of the
seychelles bark oil is believed to be due to environmental
factors or due to evolved varietal differences.

Nalagasy cinnamon bark oil with an aldehyde content of

62-65% is also reported to be inferior in quality to Sri
Lanl{an oi1 206 , 179. However, some doubts exd.st as to their
botanical classification207 ,20S. Various reports on
 35

composl"t"lon 0 f _C0 ~~J:~ Ol"I S 209-213 pOln

" t t o.th e f ac t tha t

environmental fact~ors, varietal changes, nature of raw

material and type of distillation are influencing the com-
position of the oil. Investigations by Angmor et a1 214 ,215
of an oil from Ghana showed differences in composition of
the minor components compared to Sri Lankan oil. The
unusually high percentage of cinnamyl acetate (\/'18%) was
found to be dependent on the age of the bark harvested.
Younger green shoots are found to have a higher concentration
of cinnamyl acetate than older branches. It was also noted
that fermentation reduced the content of cinnamyl acetate
and enhanced that of cinnamaldehyde probably due to the
action of hydrolytic and oxidative enzymes.

Cinnamon leaves yield on distillation about 1% of oil.

The oil is an yellowish liquid possessing warm spicy, but
harsher odour compared to bark oil. The major constituent
is eugenol while ciru1amaldehyde is always less than 5%.
Even in Sri Laru{an cinnamon leaf oils the eugenol is reported
to vary from 60-80% according to the sources 180 • Stenhouse 216
identified the major component of cinnamon leaf oil as
eugenol in 1855. This was followed by analytical reports by
"
varlOUS work ers 217-221 • W'"
lJese k era 194"In a recen t s tudy
reported 24 compounds in leaf oil. The major component was
eugenol l.. . ·" 8776) and other important compounds were
cinnamaldehyde, benzyl benzoate, linalool and ~­
caryophyllene. The monoterpene composition was qualita-
tively similar to that of bark oil.

Seychelles leaf oil is reported to contain 78-94% of

eugenol and 5% of cinnronaldehyde, whereas Malagasy leaf oil
is found to have 70-90% eugeno1 180 • Glichitch 222 observed
that when eugenol content is low in leaf oil it normally
contained relatively large amounts of benzyl benzoate and
cinnrunyl esters. Angmor et a1 215 detected 92% eugenol, 2%
eugenol acetate and 1% cill..namaldehyde ,but only traces of
benzyl benzoate in leaf oil from Ghffi~a.

No exhaustive studies have been made on Indian Q. y~~

leaf oils. Krishna e-G a1 223 reported the physico-chemical
properties of some Indian leaf oils (eugenol, 70-80%).
~Ienon224 ffi~d Bhramaramba and Mahboob 225 have made comparative
studies on leaf oils from cultivated and wild trees.
Cultivated trees gave higher yield of oil and eugenol content
compared to \vild trees. Bhramaramba and Mahboob 225 detected
methyl eugenol in leaf oils of both the cultivated Kerala
cinnamon and wild ely growing cinnamon from Mysore forest.
An unusual oil 'v'li th 15% eugenol and 62% sesquiterpenes have
been reported in an oil from Mysore region by Shintre and
226
Rao
 Table 6 ~ fJ:1'y"si~Q.::£hemicall?£~.E~ties of.....§ri LanlLan c~BP-EIf!.0n"..Q.t.1~

Quills 179 Quillings 180 Featherings 180 Chips180 Leaf 180

~ .,. -....,.~~=-....... "_-.:::=:oa::: ............ rc-r--- =ao: .......,.,._~ ===- . .. em

Specific gravity 1.023-1.040 1.039 1.039 1.042 1.050

(15°)
Optical rotation _ 1° _ 0° 20' _ 0° 24' - 0° 16' + 0° 20'

Refractive index 1.581-1.591 1.585 1.583 1.568 1.534

~
(20°)
Aldehyde content 65-76% 64.7% 62.7% 44.2% 2.8%

Eugenol content 4-10% 16% 18% 38% 82.5%

Solubility in 70% Soluble in Soluble in Soluble in Soluble in Soluble in

alcohol (20°) 2 to 3 vol. 2 vol. or 2 vol. or 2 vol. or 1.5 vol.
more more more
t:=.~~~~_.,.-=-.-=:::d'= -====:_::a=_.... ::::a= .. _~~ =:a=:= ~=-==--= ...
 38

The cinnamon root bark oil (yield 1.0-2.8%) is a colour-

less or light yellowish brown liquid with characteristic but
I
weak odour of bark oil. The oil has a cmnphoraceous note.
Early investigations on cinnamon root bark oil were carried
out by Tomsdorff227 ,Dumas ill1d Pellgot
. 189 ,Holmes 228 and

Chemists of Schimrnel and Co. 191 • Pilgrim 229 reported the

presence of camphor in 'the root oil. Studies were also
carried out later on Seychelles samples 230 • Recently
k 194
ulJese~era
1"T"
e t a1 an d'Angmor e t a~-,214 h ave~one
-.:J GC ana l '
YSlS
of the root oil. Monoterpene compounds accoill1ted for 80% of
the root oils. The oil from Ghana contained 8% of
cinnamaldehyde and traces of eugenol also. Among the 22
compoilllds identified in Sri Lankan root oil, camphor accounted
for 60%. 1~8-cineol (15%), eugenol (5%) and cinnamaldehyde
(4%) were the important minor components. The monoterpene
composition of Sri Lankan root oil was qualitatively similar
to that of the stem bark ffild leaf oils.