_Benzoïnum_; _Benzoin_, _Gum Benjamin_; F. _Benjoin_; G.
_Benzoëharz_.[1474]
=Botanical Origin=—_Styrax Benzoin_ Dryander, a tree of moderate
height, with stem as thick as a man’s body and beautiful crown of
foliage, indigenous to Sumatra and Java, in the first of which islands
benzoin is produced.
[1474] _Benzoin_ in Malay and Javanese is termed _Kamâñan_, _Kamiñan_,
and _Kamayan_, abbreviated to _mâñan_ and _miñan_ (Crawfurd); it is
called in Siamese _kom-yan_ or _kan-yan_; in Chinese _ngán-si-hiáng_.
The name _Benzoin_ is also applied to the beautiful prisms C₁₄H₁₂O₂
obtained by treating Bitter Almond Oil with an alcoholic solution of
potash.
The tree yielding the superior benzoin of Siam, though commonly
referred to this species, has never been examined botanically, and is
actually unknown. The French expedition for the exploration of the
Mekong and Cochin China (1866-68), reported the drug to be produced
in the cassia-yielding forests on the eastern bank of the river in
question in about N. lat. 19°. Whether any benzoin is obtained from _S.
Finlaysoniana_ Wall, as conjectured by Royle, we know not.
=History=—There is no evidence that the Greeks and Romans,[1475] or
even the earlier Arabian physicians, had any acquaintance with benzoin;
nor is the drug to be recognized among the commodities which were
conveyed to China by the Arab and Persian traders between the 10th and
13th centuries, though the camphor of Sumatra is expressly named.
The first mention of benzoin known to us (disregarding the word
kalanusari, which in the St. Petersburg Dictionary is given as the old
Sanskrit name of benzoin) occurs in the travels of Ibn Batuta,[1476]
who having visited Sumatra during his journey through the East, A.D.
1325-49, notes that the island produces _Java Frankincense_ and
camphor. The word _Java_ was at that period a designation of Sumatra,
or was even used by the Arabs to signify the islands and productions
of the Archipelago generally.[1477] Hence came the Arabic name _Lubán
Jáwí_, i.e. _Java Frankincense_, corrupted into _Banjawi_, _Benjui_,
_Benzui_, _Benzoë_ and _Benzoïn_, and into the still more vulgar
English _Benjamin_.
We have no further information about the drug until the latter half of
the following century, when we find a record that in 1461 the sultan
of Egypt, Melech Elmaydi, sent to Pasquale Malipiero, doge of Venice,
a present of 30 _rotoli_ of _Benzoi_, 20 _rotoli_ of Aloes Wood, two
pairs of Carpets, a small flask of balsam (of Mecca), 15 little boxes
of Theriaka, 42 loaves of Sugar, 5 boxes of Sugar Candy, a horn of
Civet, and 20 pieces of Porcelain.[1478] Agostino Barberigo, another
doge of Venice, was presented in a similar manner in 1490 by the sultan
of Egypt with 35 _rotoli_ of Aloes Wood, the same quantity of _Benzui_
and 100 loaves of Sugar.[1479]
Among the precious spices sent from Egypt in 1476 to Caterina
Cornaro, queen of Cyprus, were 10 lb. of Aloes Wood and 15 lb. of
_Benzui_.[1480] These notices indicate the high value set upon the drug
when first brought to Europe.
The occurrence of benzoin in Siam is noticed in the journal of the
voyage of Vasco da Gama,[1481] where, in enumerating the kingdoms of
India, it is stated that Xarnaux (Siam[1482]) yields much benzoin worth
3 _cruzados_, and aloes worth 25 _cruzados_ per _farazola_. According
to the same record, the price of benzoin (_beijoim_) in Alexandria was
1 _cruzado_ per _arratel_, half the value of aloes wood.
[1475] Crawfurd suggests that the _Malabathrum_ of the ancients is
possibly _benzoin_.—_Dict. of Indian Islands_, 1856. 50.
[1476] _Voyages d’Ibn Batoutah_, traduit par Defrémery et Sanguinetti,
Paris, 1853-59. iv. 228. 240.
[1477] Yule, _Book of Ser Marco Polo_, ii. (1871) 228.
[1478] Muratori, _Rerum Italicarum Scriptores_, xxii. (1733) 1170.—100
_rotoli_ = 175 lb. avoirdupois.
[1479] L. de Mas Latrie, _Hist. de l’île de Chypre_, etc. iii. (1861)
483.
[1480] _Ibid._ iii. 406.
[1481] _Roteiro da Viagem de Vasco da Gama em 1497_, par Herculano e o
Barão Castello de Paiva, segunda edição, Lisboa, 1861. 109.
The Roteiro is also found in Flückiger, _Documente zur Geschichte der
Pharmacie_, Halle, 1876. 13.
[1482] Yule, _op. cit._ ii. 222.
The Portuguese traveller Barbosa[1483] visited in 1511 Calicut on the
Malabar Coast, and found _Benzui_ to be one of the more valuable items
of export, one _farazola_ (22 lb. 6 oz.) costing 65 to 70 _fanoes_;
camphor fetched nearly the same price, and mace only 25 to 30 _fanoes_.
From other sources we gather that benzoin was an article of Venetian
trade in the beginning of the 16th century.
Garcia de Orta, writing at Goa (1563), was the first to give a lucid
and intelligent account of benzoin, detailing the method of collection,
and distinguishing the drug of Siam and Martaban from that produced in
Java and Sumatra.
It began then to be regularly imported into Europe,[1484] being
frequently called _Asa dulcis_. The chemists of that time submitted
it, like many other substances, to dry distillation. Benzoic acid
occasionally separating from the oily products (“_oleum Benzoës_”) was
noticed already by Nostredame,[1485] Rosello,[1486] Liebaut,[1487]
Blaise de Vigenère,[1488] and others. It was a common pharmaceutical
preparation, under the name of _Flores Benzoës_, since the 17th
century.[1489]
In the early part of the 17th century, there was direct commercial
intercourse between England and both Siam and Sumatra, an English
factory existing at Ayuthia (Siam) until 1623; and benzoin was
doubtless one of the commodities imported. The import duties levied
upon it in England in 1635 amounted to 10_s._ per lb.[1490]
=Production=—Benzoin is collected in Northern and Eastern Sumatra,
especially in the Batta country, lying southward of the state of
Achin.[1491] The tree grows in plenty also in the highlands of
Palembang in the south and its resin is collected. It is chiefly on
the coast regions that considerable plantations are found. Teysmann
saw the cultivation in the tracts of the river Batang Leko, the trees
being planted about 15 feet apart. The benzoin from the interior is
mostly from wild trees, which occur at the foot of the mountains at an
elevation of 300 to 1000 feet.
The trees, which are of quick growth, are raised from seeds grown on
the [edges of?] rice-fields; they require no particular attention
beyond being kept clear of other plants, until about 6 or 7 years old,
when they have trunks 6 to 8 inches in diameter, and are capable of
yielding the resin. Incisions are then made in their stems, from which
there exudes a thick, whitish, resinous juice, which soon hardens by
exposure to the air, and is carefully scraped off with a knife.
[1483] Flückiger, _l.c._, page 14.
[1484] Cardanus, _Les livres de la subtilité_, Paris, 1556 (first
edition, 1550), page 160 _b._ states: “belzoi est de vil prix pour
l’abondance.”
[1485] _Excellent et moult utile opuscule à touts necessaire qui
desirent avoir cognoissance de plusieurs exquises receptes_, 1556.
[1486] Alexii Pedemontani (or Hieron. Rosello), _De secretis libri
vi._, Basil, 1560, page 107.
[1487] _Quatre livres de secrets de medecine et de la philosophie
chimique_, Paris, 1579, page 146.
[1488] _Traicté du feu et du sel_, Paris, 1622, page 99.—Vigenère
speaks distinctly of “filamens ou aiguilles,” i.e. crystals.—He died in
1596.
[1489] Flückiger, _Pharm. Journ._ vi. (1876) 1022.
[1490] _The Rates of Marchandizes_, London, 1635.
[1491] Miquel, _Prodromus Floræ Sumatranæ_, 1860. 72; Marsden, _Hist.
of Sumatra_, London, 1783. 123.—The latter author resided at Bencoolen,
as an official of the English Government.
The statement of Crawfurd, _l.c._, that benzoin is collected in
Borneo “_on the northern coast in the territory of Brunai_” is to us
inexplicable. Mr. St. John, British Consul in Borneo, in an official
report on the trade of Brunai, dated from that place 29 January 1858,
enumerates the various productions of the district, but does not name
benzoin.
The trees continue to yield at the rate of about three pounds per
annum for 10 or 12 years, after which period they are cut down. The
resin which exudes during the first three years is said to be fuller
of white tears, and therefore of finer quality, than that which issues
subsequently, and is termed by the Malays _Head Benzoin_. That which
flows during the next 7 or 8 years, is browner in colour and less
valuable, and is known as _Belly Benzoin_; while a third sort, called
_Foot_, is obtained by splitting the tree and scraping the wood; this
last is mixed with much bark and refuse.[1492]
Benzoin is brought for sale to the ports of Sumatra in large cakes
called _Tampangs_, wrapped in matting. These have to be broken, and
softened either by the heat of the sun or by that of boiling water, and
then packed into square cases which the resin is made to fill.
The only account of the collection of _Siam Benzoin_ is that given by
Sir R. H. Schomburgk, for some years British Consul at Bangkok.[1493]
He represents that the bark is gashed all over, and that the resin
which exudes, collects and hardens between it and the wood, the former
of which is then stripped off. This account is confirmed by the aspect
of some of the Siam benzoin of commerce as well as by that of pieces
of bark in our possession; but it is also evident that _all_ the Siam
drug is not thus obtained. Schomburgk adds, that the resin is much
injured and broken during its conveyance in small baskets on bullocks’
backs to the navigable parts of the Menam, whence it is brought down to
Bangkok.[1494]
Whether benzoin owes its original fluidity to a volatile oil holding
the resin in solution, and its solidification to the volatilization
of this oil, or whether the resin itself hardens by oxidation,—what
occasions the remarkable diversity of aspect between the opaque and
milk-like, and the completely transparent resin, are questions to be
investigated by some future observer.
=Description=—Benzoin (always termed in English commerce _Gum
Benjamin_) is distinguished as of two kinds, _Siam_ and _Sumatra_.
Each sort occurs in various degrees of purity, and under considerable
differences of appearance.
1. _Siam Benzoin_—The most esteemed sort is that which consists
entirely of flattened tears or drops, an inch or two long, of an
opaque, milk-like, white resin, loosely agglutinated into a mass.
More frequently the mass is quite compact, consisting of a certain
proportion of white tears of the size of an almond downwards, imbedded
in a deep, rich amber-brown, translucent resin. Occasionally the
translucent resin preponderates, and the white tears are almost
wanting. In some packages, the tears of white resin are very small,
and the whole mass has the aspect of a reddish-brown granite. There is
always a certain admixture of bits of wood, bark, and other accidental
impurities.
[1492] The terms _Head_, _Belly_ and _Foot_, equivalent to our
words _superior_, _medium_ and _inferior_, are used in the East to
distinguish the qualities of many other commodities, as Borneo Camphor,
Esculent Birds’-nests, Cardamoms, Galbanum, &c.
[1493] This account must have been derived from others, for Sir R. H.
Schomburgk never visited the region producing benzoin.
[1494] _Pharm. Journ._ iii. (1862) 126.
The white tears when broken, display a stratified structure with layers
of greater or less translucency. By keeping, the white milky resin
becomes brown and transparent on the surface.
Siam benzoin is very brittle, the opaque tears showing a slightly waxy,
the transparent a glassy fracture. It easily softens in the mouth and
may be kneaded with the teeth like mastich. It has a delicate balsamic,
vanilla-like, fragrance, but very little taste. When heated it evolves
a more powerful fragrance, together with the irritating fumes of
benzoic acid; its fusing point is 75° C. The presence of benzoic acid
may be shown by the microscopical examination of splinters of the resin
under oil of turpentine.
Siam benzoin is imported in cubic blocks, which takes their form from
the wooden cases in which they are packed while the resin is still soft.
2. _Sumatra Benzoin_—Prior to the renewal of direct commercial
intercourse with Siam in 1853, this was the sort of benzoin most
commonly found in commerce.
It is imported in cubic blocks exactly like the preceding, from which
it differs in its generally greyer tint. The mass however, when the
drug is of good quality, contains numerous opaque tears, set in a
translucent, greyish-brown resin, mixed with bits of wood and bark.
When less good, the white tears are wanting, and the proportion of
impurities is greater. We have even seen samples consisting almost
wholly of bark. In odour, Sumatra benzoin is both weaker and less
agreeable than the Siam drug, and generally falls short of it in
purity[1495] and handsome appearance, and hence commands a much lower
price. The greyish-brown portion melts at 95°, the tears at 85° C.
A variety of Sumatra benzoin is distinguished by the London
drug-brokers as _Penang Benjamin_ or _Storax-smelling Benjamin_. We
have seen it of very fine quality, full of white tears (some of them
two inches long), the intervening resin being greyish.[1496] The odour
is very agreeable, and perceptibly different from that of Siam benzoin,
or the usual Sumatra sort. Whether this drug is produced in Sumatra
and by _Styrax Benzoin_ we know not; but it is worthy of note that _S.
subdenticulata_ Miq., occurring in Western Sumatra, has the same native
name (_Kajoe Kĕminjan_) as _S. Benzoin_, and that Miquel remarks of
it—“_An etiam benzoiferum?_”[1497]
=Chemical Composition=—Benzoin consists mainly of amorphous resins
perfectly soluble in alcohol and in potash, having slightly acid
properties, and differing in their behaviour to solvents. If two parts
of the drug are boiled with one part of caustic lime and 20 parts of
water, benzoin acid is removed. From the residue the excess of lime is
dissolved by hydrochloric acid, and the remaining resins washed and
dried. About one-third of them will be found readily soluble in ether,
the prevailing portion dissolves in alcohol, and a small amount remains
undissolved.
[1495] In the _Public Ledger_, May 2, 1874, the prices are quoted
thus:—Siam Gum Benjamin, 1st and 2nd qualities, £10 to £28 per cwt.;
Sumatra, 1st and 2nd, £7 10_s._ to £12.
[1496] There were 8 cases of this drug offered at Public Sale, 13 April
1871.
[1497] _Prod. Floræ Sumatranæ_, 1860. 474.
By distilling the resin of benzoin with ten times its weight of zinc
dust, Ciamician (1878) chiefly obtained toluol, C₆H₅(CH₃).
Subjected to dry distillation, benzoin affords as chief product
_Benzoic Acid_, C₇H₆O₂, together with empyreumatic products, among
which Berthelot has proved the presence (in Siam benzoin) of _Styrol_
(p. 274). The latter has been obtained in 1874 by Theegarten from
Sumatra benzoë by distilling it with water. When the resin is fused
with potash, it is partly decomposed and then, according to Hlasiwetz
and Barth (1866), yields among other products, protocatechuic acid
(more than 5 per cent.), C₆H₃(OH)₂COOH, para-oxybenzoic acid,
C₆H₄(OH)COOH, and pyrocatechin, C₆H₄(OH)₂.
_Benzoic acid_ exists ready-formed in the drug to the extent of 14 to
18 per cent.[1498] Although the acid dissolves in 12 parts of boiling
water, the resin in which it is imbedded precludes its complete
extraction by this means. It is however easily accomplished by the
aid of an alkali, most advantageously by milk of lime, which does not
combine with the amorphous resins.
Benzoin is not manifestly acted on by bisulphide of carbon, but if kept
in contact with it for a month or two, very large colourless crystals
of benzoic acid make their appearance. Brought into a warm room, the
crystals quickly dissolve, but are easily reproduced by exposure to
cold.
Most pharmacopœias require not the inodorous acid obtained by a wet
process, but that afforded by sublimation, which contains a small
amount of fragrant empyreumatic products. The resin, when repeatedly
subjected to sublimation, affords as much as 14 per cent. of benzoic
acid. It has long been known that the opaque white tears of benzoin are
less rich in benzoic acid than the transparent brown resin in which
they lie. From the latter, S. W. Brown (1833) extracted 13 per cent.
of impure acid, but from the former scarcely 8½ per cent. We are by no
means sure that such difference is constant.
Bitter almond oil, which by oxidation yields benzoic acid, is wanting
in benzoin. Very little volatile oil is in fact to be got; half a pound
of the best Penang benzoin yielded us by distillation with water only a
few drops of an extremely fragrant oil (_styrol?_).
Ferric chloride imparts to an alcoholic solution of benzoin a dark
brownish green, which is not acquired under the same circumstances by
the aqueous decoction of the powdered resin. Benzoin dissolves in cold
oil of vitriol, forming a solution of splendid carmine hue, from which
water separates crystals of benzoic acid.
Kolbe and Lautemann in 1860 discovered in Siam and Penang benzoin
together with benzoic acid, an acid of different constitution, which in
1861 they recognized as _Cinnamic Acid_, C₉H₉O₂. Aschoff (1861) found
in a sample of Sumatra benzoin, cinnamic acid only, of which he got
11 per cent.; and in amygdaloid Siam and Penang benzoin only benzoic
acid. In some samples of the latter, one of us (F.) has likewise met
with cinnamic acid. On triturating this sort with peroxide of lead and
boiling the mixture with water, the odour of bitter almond oil, due to
the oxidation of cinnamic acid, is evolved.
[1498] Löwe (1870) and Rump (1878) attempted to prove that the acid is
partly present in the form of a compound, but they have not shown with
which substance it is combined in the drug.
The simultaneous occurrence of benzoic and cinnamic acids, or the
absence of one or other of them in benzoin, is due to circumstances at
present unexplained. Rump is of the opinion that the last named acid
exclusively is present in the Penang (or Sumatra) benzoin and that no
variety of the drug contains both those acids.
Rump (1878) treated Siam benzoic with caustic lime (see p. 407),
precipitated the benzoic acid with hydrochloric acid, and agitated the
liquid with ether. The latter on evaporating afforded a mixture of
benzoic acid and _Vanillin_ (see article Vanilla).
=Commerce=—The statistics of Singapore,[1499] the great emporium of the
commerce of the Indian Archipelago, show the imports of Gum Benjamin
in 1871 as 7442 cwt., of which quantity 6185 cwt. had been shipped
from Sumatra and 405 cwt. from Siam. In 1877 only 1871 peculs (2227
cwts.) were exported from Singapore. Penang, which is also a mart
for this drug was stated in 1871 to have received from Sumatra for
trans-shipment, 4959 cwt. of Gum Benjamin.
Padang in Sumatra exported in 1870, 4303 peculs (5122 cwt.); and in
1871, 4064 peculs (4838 cwt.) of benzoin.[1500]
The imports of Gum Benjamin into Bombay in the year 1871-72 were no
less than 5975 cwt., and the exports 1043 cwt.[1501]
=Uses=—Benzoin appears to be nearly devoid of medicinal properties, and
is but little employed. It is chiefly imported for use as incense in
the service of the Greek Church.