_Balsamum Styracis_; _Liquid Storax_; F. _Styrax liquide_; G.
_Flüssiger Storax_.
=Botanical Origin=—_Liquidambar orientalis_ Miller (_L. imberbe
Aiton_), a handsome, umbrageous tree resembling a plane, growing to
the height of 30 to 40 feet or more,[1036] and forming forests in the
extreme south-western part of Asia Minor. In this region the tree
occurs in the district of Sighala near Melasso, about Budrum (the
ancient Halicarnassus) and Moughla, also near Giova and Ullà in the
Gulf of Giova, and lastly near Marmorizza and Isgengak opposite Rhodes.
It also grows in the valley of the El-Asi (the ancient Orontes), as
proved by a specimen in the Vienna herbarium, collected by Gödel,
Austrian Consul at Alexandretta. In this locality it was seen by
Kotschy in 1835, but mistaken for a plane. The same traveller informed
one of us that he believed it to occur at Narkislik, a village near
Alexandretta.
The tree is not known to grow in Cyprus, Candia, Rhodes, Kos, or indeed
in any of the islands of the Mediterranean.[1037]
=History=—Two substances of different origin have been known from a
remote period under the name of _Styrax_ or _Storax_, namely the resin
of _Styrax officinalis_ L. (see further on), and that of _Liquidambar
orientalis_ Miller, the latter commonly distinguished as _Liquid
Storax_.
According to Krinos of Athens, who has carefully investigated the
history of the drug,[1038] the earliest allusions to Liquid Storax
occur in the writings of Aëtius and of Paulus Ægineta,[1039] who
name both _Storax_ and _Liquid Storax_ (πύρα ζυγρὸς). Of these Greek
physicians, who lived respectively in the 6th and 7th centuries, the
second also mentions the resin of Ζυγία, which is regarded by Krinos as
synonymous with the latter substance.[1040]
[1035] The feminine gender of Styrax has been in use for a long time.
In Greek it denotes the tree, as also does sometimes the masculine
gender, the _neutral_ being reserved to the resin. In Latin the resin
is masculini generis (Dr. Rice).
[1036] For a good figure of _L. orientalis_, see Hooker’s _Icones
Plantarum_ (3rd series, 1867) pl. 1019, or Hanbury, _Science Papers_,
1876. 140; also Bentley and Trimen, _Medicinal Plants_, part 27 (1877).
[1037] The fine old trees existing at the convent of Antiphoniti on the
north coast of Cyprus, and at that of Neophiti near Papho, specimens
of which were distributed by Kotschy as _Liquidambar imberbis_ Ait.,
agree in all points with the American _L. stryaciflua_ L., and not with
the Asiatic plant. Kotschy has told me that they have _certainly been
planted_, and that no other examples exist in the island.—D. H. The
same opinion is adopted by Boissier, _Flora Orientalis_, ii. (1872)
8319.
[1038] Περί Στύακοτ δίατριβὴ ϕαρμακογραϕικὴ ἐν Ἀθῆναιπ, 1862.—This
pamphlet is also the subject of a paper of Prof. Planchon, _Journ. de
Pharm._ 24 (1876) 172. 243.
[1039] _Medicæ Artis Principes post Hippocratem et Galenum_, Par.
1567.—Aëtii tetr. 4. serm. 4. c. 122; P. Ægineta, _De re med._ vii. 20.
[1040] The foliage of the Liquidambar much resembles that of the common
maple (_Acer campestre_ L.); hence the two trees as well as the plane
(_Platanus orientalis_ L.) are confounded under one name,—Ζυγὸς or
Ζυγίᾳ. So _Styrax officinalis_ L., from the resemblance of its leaves
to those of _Pirus Cydonia_ L., is known in Greece as Ζυγὸς κυδωνήα
kydônêa, i.e. _wild quince_.
We find in fact the term _Sigia_ frequently mentioned by Rhazes (10th
century) as signifying Liquid Storax. This and other Arabian physicians
were also familiar with the same substance under the name of _Miha_
(_may’a_), and also knew how and whence it was obtained.[1041]
A curious account of the collecting of Liquid Storax from the tree
_Zygia_, and from another tree called _Stourika_, is given in the
travels through Asia Minor to Palestine of the Russian abbot of Tver in
A.D. 1113-1115.[1042]
The wide exportation and ancient use of Liquid Storax are very
remarkable: even in the first century, as appears by the author of the
Periplus of the Erythrean Sea, Storax, by which term there can be but
little doubt _Liquid Storax_ was intended, was exported by the Red
Sea to India. Whether the _Storax_ and _Storax Isaurica_ offered to
the Church of Rome under St. Silvester, A.D. 314-335, by the emperor
Constantine,[1043] was Liquid Storax or the more precious resin of
_Styrax officinalis_ L., is a point we cannot determine. That the
Chinese used the drug was a fact known to Garcia de Orta (1535-63):
Bretschneider[1044] has shown from Chinese sources that, together with
olibanum and myrrh, it was imported by the Arabs into China during
the Ming dynasty, A.D. 1368-1628. This trade is still carried on: the
drug is conveyed by way of the Red Sea to Bombay, and thence shipped
to China. Official returns show that the quantity thus exported from
Bombay in the year 1856-57 was 13,328 lb. In the time of Kämpfer
(1690-92), Liquid Storax was one of the most profitable articles of
shipment to Japan.[1045]
Liquid Storax is known in the East, at least in the price-currents and
trade statistics of Europeans, by the strange-sounding name of _Rose
Malloes_ (_Rosa Mallas_, _Rosum Alloes_, _Rosmal_), a designation for
it in use in the time of Garcia de Orta. Clusius[1046] considered it to
be Arabic, which, however, the scholars whom we have consulted do not
allow. Others identify it with _Rasamala_, the Malay name for _Altingia
excelsa_. (See further on.)
The botanical origin of Liquid Storax was long a perplexing question
to pharmacologists. It was correctly determined by Krinos, but his
information on the subject published in a Greek newspaper in 1841, and
repeated by Kosté in 1855,[1047] attracted no attention in Western
Europe. The question was also investigated by one of the authors
of the present work, whose observations, together with a figure of
_Liquidambar orientalis_ Miller, were published in 1857.[1048]
[1041] _Ibn Baytar_, Sontheimer’s transl. ii. 539.
[1042] Noroff, _Pèlerinage en Terre Sainte de l’Igoumène russe Daniel_,
St. Pétersb. 164.4°.—The passage has been kindly abstracted for us by
Prof. Heyd of Stuttgart.
[1043] Vignolius, _Liber Pontificalis_, Romæ, i. (1724) 94.—The ancient
Isauria was in Cilicia, the country of _Styrax officinalis_ L.
[1044] _On the knowledge possessed by the Chinese of the Arabs_, etc.,
Lond. 1871. 19.
[1045] _Hist. of Japan_, ed. Scheuchzer, i. 353.
[1046] _Exoticorum Libri_, 245.
[1047] Ἐγχειρίδιον Φαρμακολογίας, ύπὸ Ν. Κωστῆ, 1855. 356.
[1048] Hanbury, _Pharm. Journ._ xvi. (1857) 417. 461, and iv. (1863)
436; _Science Papers_, 127-150.
=Method of Extraction=—The extraction of Liquid Storax is carried on
in the forests of the south-west of Asia Minor, chiefly by a tribe of
wandering Turcomans called _Yuruks_. The process has been described
on the authority of Maltass and McCraith of Smyrna, and of Campbell,
British Consul at Rhodes.[1049] The outer bark is said to be first
removed from the trunk of the tree and rejected; the inner is then
scraped off with a peculiar iron knife or scraper, and thrown into pits
until a sufficient quantity has been collected. It is then boiled with
water in a large copper, by which process the resin is separated, so
that it can be skimmed off. This seems to be performed with sea water;
some chloride of sodium can therefore be extracted from the drug. The
boiled bark is put into hair bags and squeezed under a rude lever, hot
water being added to assist in the separation of the resin, or as it
is termed _yagh_, i.e. _oil_. Maltass states that the bark is pressed
in the first instance _per se_, and afterwards treated with hot water.
In either case the products obtained are the opaque, grey, semi-fluid
resin known as _Liquid Storax_, and the fragrant cakes of foliaceous,
brown bark, once common[1050] but now rare in European pharmacy, called
_Cortex Thymiamatis_.
We are indebted to M. Felix Sahut of Montpellier for a specimen of
the bark of _Liquidambar orientalis_, cut from the trunk of a fine
tree on his property at the neighbouring village of Lattes. The bark
which is covered with a very thick corky layer and soaked in its own
fragrant resin, shows no tendency to exfoliate. The investigations
of Unger[1051] in Cyprus are consequently to us inexplicable; he
asserts that the bark scales off, like that of the plane, by continued
exfoliation, which is not the case with that of M. Sahut’s tree.
[1049] Hanbury, _l.c._
[1050] It is no doubt the “_Cortex Olibani_” met with in the tariff of
1571, in Flückiger, _Documente zur Geschichte der Pharmacie_, 26.
[1051] Unger u. Kotschy, _Die Insel Cypern_. Wien, 1865. 410.
=Description=—Liquid Storax is a soft viscid resin, usually of the
consistence of honey, heavier than water, opaque and greyish brown. It
always contains water, which by long standing rises to the surface.
In one sample that had been kept more than 20 years, the resin at the
bottom of the bottle formed a transparent layer of a pale golden brown.
When liquid storax is heated, it becomes by the loss of water dark
brown and transparent, the solid impurities settling to the bottom.
Spread out in a very thin layer, it partially dries, but does not
wholly lose its stickiness. When free from water (which reddens litmus)
it dissolves in alcohol, spirit of wine, chloroform, ether, glacial
acetic acid, bisulphide of carbon, and most of the essential oils, but
not in the most volatile part of petroleum (“petroleum ether”). It has
a pleasant balsamic smell, especially after it has been long kept; when
recent, it is contaminated with an odour of bitumen or naphthalene
that is far from agreeable. Its taste is sharply pungent, burning and
aromatic.
When the opaque resin is subjected to microscopic examination, small
brownish granules are observed in a viscid, colourless, transparent
liquid, besides which large drops of a mobile watery liquid may
be distinguished. In polarized light, numerous minute crystalline
fragments with a few larger tabular crystals are obvious. But when
thin layers of the resin are left on the object glass in a warm
place, feathery or spicular crystals (styracin) shoot out on the
edge of the clear liquid, while in the large, sharply-defined drops
above mentioned, rectangular tables and short prisms (cinnamic acid)
make their appearance. On applying more warmth after the water is
evaporated, all the substances unite into a transparent, dark brown,
thick liquid, which exhibits no crystalline structure on cooling, or
only after a very long time. Among the fragments of the bark occurring
in the crude resin, liber-fibres are frequently observable.
=Chemical Composition=—The most abundant constituent of Styrax is
probably the _Storesin_, C₃₆H₅₅(OH)₃, discovered in 1877 by W. von
Miller, or rather cinnamic ethers of it and of an isomeric substance.
Storesin is an amorphous substance melting at 168° C., readily soluble
in petroleum ether. Several other compound ethers have also been
observed in the drug, as for instance _cinnamic ether of phenylpropyl_,
_cinnamic ether of ethyl_, cinnamic ether of benzyl, and especially
cinnamate of cinnamyl, C₉H₇O₂·C₉H₉, the so-called _Styracin_. This
substance, discovered by Bonastre in 1827, can be removed by ether,
benzol or alcohol, after the separation from the resin of the cinnamic
acid; it is insoluble in water, and volatile only in super-heated
steam. It crystallizes in tufts of long rectangular prisms, which
melt at 38° C., but it frequently does not solidify in a crystalline
form, or only after a long time, or remains as an oily liquid. In its
pure state it is inodorous and tasteless. By concentrated solution
of potash, it is resolved into a cinnamate, and cinnamic alcohol
(_Styrone_) C₉H₁₀O, which latter is not present in Liquid Storax. The
_cinnamic acid_ may be extracted to a small extent by boiling water,
more completely by means of a boiling solution of carbonate of sodium,
as it is present in the drug partly in the free state. Its compound
ethers may be decomposed by caustic lye. The yield of cinnamic acid
accordingly varies from 6 to 12 per cent.—or even, according to Löwe,
as much as 23 per cent. of crystallized cinnamic acid can be obtained.
The acid dissolves abundantly in ether, alcohol, or hot water, slightly
in cold water; it is inodorous, but has an acrid taste. It fuses at
133° C., and boils at 290° C.; at a dull red heat it is resolved into
carbonic acid and styrol, which latter is therefore related to it in
the same manner as benzol (benzene) to benzoic acid. Liquid styrax is
in fact the best source of cinnamic acid.
Another constituent of styrax is a fragrant substance, perhaps
_ethylvanillin_, occurring in but small quantity.
Laubenheimer (1872) has shown that probably _Benzylic Alcohol_, C₇H₈O,
boiling at 206° C., likewise occurs in Liquid Storax; it has not been
found by Miller. The latter chemist also showed that water removes from
the drug a little _benzoïc acid_; he observed moreover a substance
similar to _caoutchouc_ among the constituents of liquid styrax.
There is further to be mentioned as having been met with in Liquid
Storax a hydrocarbon, C₈H₈, first prepared by Simon in 1839, which
exists in the resin as a liquid, and also in a polymeric form as a
solid. The former called _Styrol_, _Cinnamene_, or _Cinnamol_, has a
sp. gr. of 0·924, and a boiling point of 146° C. It is a colourless,
mobile liquid which may be obtained by distilling with water liquid
storax, the odour and burning taste of which it possesses. When heated
for a considerable time to 100°, or for a shorter period to 200° C.,
it is converted without change of composition into the colourless,
transparent solid _Metastyrol_, which, unlike styrol, is not soluble
in alcohol or ether. It has a sp. gr. of 1·054, and may be cut with
a knife. By prolonged heating, it can be converted into its original
liquid form.
Styrol is to be regarded as phenylated ethylene; it can be
artificially obtained by shaking powdered cinnamic acid with saturated
hydrobromic acid, when crystalline hydrobromated cinnamic acid,
C₆H₅·CH₂·CHBr·COOH, is formed. One part of the latter, 10 parts of
water, and a little more carbonate of sodium than the quantity required
for saturation are mixed. The bromhydrocinnamate of sodium partly
splits up immediately, even at 0°, according to the following equation
C₆H₅·CH₂·CHBr·COONa = CO₂ + NaBr + C₆H₅·CH·CH₂.
Bromhydrocinnamate Styrol.
of sodium.
24 parts of bromhydrocinnamic acid, recrystallized from boiling
bisulphide of carbon, yield about 7 parts of styrol; no other method
affords as much as this.
Styrol has been discovered in Styrax, but is not regularly, and at all
events to a minute amount only, found in the drug of the present day.
We have no explanation for the strange fact that it was apparently more
abundantly met with in former times.
Lastly there has been found in Liquid Storax, by J. H. van t’Hoff
(1876), about 0·4 per cent. of an _essential oil_, probably C₁₀H₁₆O;
Miller also pointed out a compound ether of probably the same
(alcoholic) substance as occurring in styrax.
By the action of oxidizing agents, as nitric or chromic acids, or
peroxide of lead, the cinnamyl compounds are easily reduced, carbonic
acid and water being evolved; and at the same time benzoic acid, bitter
almond oil, and hydrocyanic acid are produced. These compounds are in
fact abundantly evolved when 6 parts of Liquid Storax are gently warmed
with 1 p. of caustic soda, and then mixed with 3 p. of permanganate of
potassium dissolved in 20 p. of water.
We have examined several samples of Liquid Storax of average quality,
and found by exposure of small quantities to the heat of the steam
bath, that it lost from 10 to 20 per cent. of water. The remainder
treated with alcohol yielded a residue amounting to 13 to 18 per cent.,
consisting chiefly of fragments of bark and inorganic impurities.
The percentage of the drug soluble in alcohol, to which is due its
therapeutic value, thus amounts to 56 to 72. This part, as may be
inferred from the foregoing statements, consists chiefly of storesin,
the various compound ethers above mentioned, of cinnamic acid and of
styracin, no doubt in greatly varying proportions.
=Commerce=—The annual production of Liquid Storax was estimated by
Campbell in 1855 as about 490 cwt. for the districts of Giova and Ullá,
and 300 cwt. for those of Marmorizza and Isgengak. The drug is exported
in barrels to Constantinople, Smyrna, Syra and Alexandria. Some is also
packed with a certain proportion of water in goatskins, and sent either
by boats or overland to Smyrna, where it is transferred to barrels and
shipped mostly to Trieste.
The chief consumption of Liquid Storax would appear to be in India and
China. In the fiscal year 1866-67, Bombay imported 319 cwt. from the
Red Sea. Liquid Storax is seldom seen in the London drug-sales.
=Uses=—Liquid Storax, which the _British Pharmacopœia_ directs to be
purified by solution in spirit of wine, is an ingredient in a few
old-fashioned preparations but is hardly ever prescribed on its own
account. It is stated to be expectorant and stimulant, and useful in
chronic bronchial affections. It has been recommended by Pastau, Berlin
(1865), as an external application for the cure of scabies, for which
purpose it is mixed with linseed oil and now largely used.
=Adulteration=—The drug is occasionally mixed with sand, ashes, and
other substances; these would be detected by solution in spirit of
wine, as well as by the microscope.
Allied Substances.
_Styrax Calamita_ (_Storax en pain_ Guibourt)—The substance that now
bears this name is by no means the _Styrax Calamita_ of ancient times,
but is an artificial compound made by mixing the residual Liquidambar
bark called _Cortex Thymiamatis_ (p. 273), coarsely powdered, with
Liquid Storax in the proportions of 3 to 2. It is at first a clammy
mass, acquiring after a few weeks an appearance of mouldiness, due to
minute silky crystals of styracin. It is usually imported in wooden
drums, and has a very sweet smell. When the bark is scarce, common
sawdust is substituted for it, while qualities still inferior are made
up with the help of olibanum, honey, and earthy substances. This drug
is manufactured at Trieste, Venice and Marseilles.
Several other odoriferous compounds, of which Liquid Storax appears to
be the chief ingredient, are made in the East and may still be found in
old drug warehouses.[1052]
_Resin of Styrax officinalis_ L.; =_True Storax_=—This was a solid
resin somewhat resembling benzoin, of fragrant, balsamic odour,
held in great estimation from the time of Dioscorides and Pliny
down to the close of the last century. It was perhaps the “storace
odorifero” exported in the 12th century from Pantellaria[1053] and
Sicily. The drug was obtained from the stem of _Styrax officinalis_ L.
(_Styraceæ_), a native of Greece, Asia Minor and Syria, now found also
in Italy and Southern France. This plant when permitted to grow freely
for several years, forms a small tree, in which state alone it appears
to be capable of affording a fragrant resin. But in most localities it
has been reduced by ruthless lopping to a mere bush, the young stems
of which yield not a trace of exudation. True storax has thus utterly
disappeared.
Professor Krinos of Athens has informed us (1871) that about Adalia
on the southern coast of Asia Minor, a sort of solid storax obtained
from _S. officinalis_ is still used as incense in the churches and
mosques. The specimen of it which he has been good enough to send us,
is not however resin, but _sawdust_; it is of a pale cinnamon-brown,
and pleasant balsamic odour. By keeping, it emits an abundance of
minute acicular crystals (styracin?). The substance is interesting
in connection with the statement of Dioscorides, that the resin of
_Styrax_ is adulterated with the _sawdust of the tree itself_, and the
fact that the region where this sawdust is still in use is one of the
localities for the drug (Pisidia) which he mentions.
[1052] The _Storax noir_ of Guibourt is one of these.
[1053] Quoted before, p. 163, note 3; in the same book “_cotone storace
e corallo_“ occur as articles of export from Sicily.
_Resin of Liquidambar styraciflua_ L.—a large and beautiful tree,
native of North America from Connecticut and Illinois southward to
Mexico and Guatemala. In the United States, where it is called _Sweet
Gum_, the tree yields from natural fissures or by incision, small
quantities of a balsamic resin, which is occasionally used for chewing.
We have before us an excellent sample of it collected for Messrs.
Wallace Brothers of Statesville, N. Carolina.[1054]
In Central America this exudation is far more freely produced;
an authentic specimen from Guatemala in our possession is a pale
yellow, opaque resin of honey-like consistence, becoming transparent,
amber-coloured and brittle by exposure to the air. It has a rather
terebinthinous, balsamic odour. In the mouth it softens like benzoin
or mastich, and has but little taste. Another specimen also from
Guatemala, a thick, fluid oleo-resin, of a golden brown hue, was
contributed to the Paris Exhibition in 1878.
The resin of _L. styraciflua_ L. has been ascertained by Procter[1055]
to contain cinnamic, but not benzoic acid. Harrison[1056] found it to
contain styracin and essential oil (styrol?).
_Resin of Liquidambar formosana_ Hance—This tree, which we suppose
may be the _Styrax liquida folio minore_, which Ray names[1057] as
occurring in a collection of plants from Amoy, is a native of Formosa
and Southern China, where it affords a dry terebinthinous resin,
of agreeable fragrance when heated. Of this resin, which is used
by the Chinese, a specimen collected in Formosa by Mr. Swinhoe has
been presented to us by Dr. Hooker. A tree figured under the name of
_Fung-heang_ in the _Pun-tsao_[1058] is, we presume, this species.
_Resin of Altingia excelsa_ Noronha (_Liquidambar Altingiana_ Bl.)
=_Rasamala_= of the Javanese and Malays—The _Rasamala_ is a magnificent
tree of the Indian Archipelago, Burma and Assam. In Java it yields by
incisions in the trunk an odorous resin, yet only very slowly and in
very small quantity; this resin is not, or at least not regularly,
collected. In Burma, on the other hand, the tree affords a fragrant
balsam, of which according to Waring[1059] there are two varieties,
the one pellucid and of a light yellowish colour, obtained by simple
incision; the other thick, dark, opaque, and of terebinthinous odour,
procured by boring the stem and applying fire around the trunk.