Chapter XIII: Part 13

The cotyledons yield to boiling ether ½ to ⅓ per cent. of fatty oil, and after exhaustion by ether and alcohol, afford to cold water 12 per cent. of albuminous and mucilaginous constituents. The proportion of starch according to Teich[765] amounts to 48 per cent., the albuminous matter to 23 per cent. The entire seed furnishes 3 per cent. of ash, chiefly phosphate of potash. These constituents do not widely differ in proportion from those found in the common bean, which yields 23 to 25 per cent. of albuminous matters, and 32 to 38 per cent. of starch, besides 1 to 3 per cent. of oil.

[765] _Chemische Untersuchung der Calabarbohne_.—Inauguralschrift, St. Petersburg, 1867. We calculate the albuminous matters with reference to _Teich’s_ analysis, which proved the kernels to contain 3·65 per cent. of nitrogen.

The shells of Calabar bean are stated by Fraser to be by no means devoid of active principle.

Vée asserts that if to a solution of eserine, a little potash, lime, or carbonate of sodium be added, there is developed a red colour which rapidly increases in intensity. This colour is transient, passing into yellow, green and blue. If chloroform is shaken with such coloured solution, it takes up the colour; ether on the other hand remains uncoloured.

=Uses=—Calabar has been hitherto chiefly employed as an ophthalmic medicine, for the purpose of contracting the pupil. It has however been occasionally administered in tetanus and in neuralgic, rheumatic, and other diseases.

=Adulteration=—Other seeds are sometimes fraudulently mixed with Calabar beans. We have noticed in particular those of a _Mucuna_ and of the Oil Palm, _Elæis guineensis_ Jacq. The slightest examination suffices for their detection.

KINO.

_Kino_, _Gum Kino_, _East Indian Kino_; F. and G. _Kino_.

=Botanical Origin=—_Pterocarpus Marsupium_ Roxb., a handsome tree 40 to 80 feet high, frequent in the central and southern parts of the Indian Peninsula and also in Ceylon, and affording a valuable timber. In the Government forests of the Madras Presidency, it is one of the _reserved trees_, the felling of which is placed under restrictions.

_Pt. indicus_ Willd., a tree of Southern India, the Malayan Peninsula and the Indian and Philippine Islands, is capable of yielding kino, and is the source of the small supplies of that drug that were formerly shipped from Moulmein.

Several other plants afford substances bearing the name of _Kino_, which will be noticed at the conclusion of the present article.

=History=—The introduction of kino into European medicine is due to Fothergill, an eminent physician and patron of economic botany of the last century. The drug which Fothergill examined was brought from the river Gambia in West Africa as a rare sort of Dragon’s Blood, and was described by him in 1757[766] under the name of _Gummi rubrum astringens Gambiense_. It had been noticed at least twenty years before as a production of the Gambia, by Moore, factor to the Royal African Company, who says that the tree yielding it is called in the Mandingo language _Kano_.[767] Specimens of this tree were sent to England in 1805 by the celebrated traveller Mungo Park, and recognized some years later as identical with the _Pterocarpus erinaceus_ of Poiret.

It seems probable that African kino continued to reach England for some years, for we find “_Gummi rubrum astringens_” regularly valued in the stock of a London druggist[768] from 1776 to 1792.

Duncan in the _Edinburgh Dispensatory_ of 1803, while asserting that “_kino is brought to us from Africa_,” admits that some, not distinguishable from it, is imported from Jamaica. In a later edition of the same work (1811), he says that the African drug is no longer to be met with, and alludes to its place being supplied by other kinds, as that of Jamaica, that imported by the East India Company, and that of New South Wales derived from _Eucalyptus resinifera_ Sm. It will thus be seen that at the commencement of the present century several substances, produced in widely distant regions, bore the name of _Kino_. That however which was principally used in the place of the old African drug, was _East Indian_ Kino, the botanical origin of which was shown by Wight and by Royle[769] (1844-46) to be _Pterocarpus Marsupium_ Roxb.,—a tree which, curiously enough, is closely allied to the kino tree of Tropical Africa.

This is the drug which is recognized as legitimate kino in all the principal pharmacopœias of Europe. It appears to have been first prepared for the European market in the early part of the present century, on a plantation of the East India Company called Anjarakandy, a few miles from Tellicherry on the Malabar Coast; but as we learn from our friend Dr. Cleghorn, it was not grown there but on the ghats a short distance inland.

=Extraction=—Kino is the juice of the tree, dried without artificial heat.[770] As it exudes, it has the appearance of red currant jelly, but hardens in a few hours after exposure to the air. In the Government forests of the Malabar Coast whence the supplies are obtained, permission to collect the drug is granted on payment of a small fee, and on the understanding that the tapping is performed skilfully and without damage to the timber. The method pursued is this:—A perpendicular incision with lateral ones leading into it, is made in the trunk, at the foot of which is placed a vessel to receive the outflowing juice. This juice soon thickens, and when sufficiently dried by exposure to the sun and air, is packed into wooden boxes for exportation.

=Description=—Malabar kino[771] consists of dark, blackish-red, angular fragments rarely larger than a pea, easily splitting into still smaller pieces, which are seen to be perfectly transparent, of a bright garnet hue, and amorphous under the microscope. In cold water they sink, but partially dissolve by agitation, forming a solution of very astringent taste, and a pale flocky residue. The latter is taken up when the liquid is made to boil, and deposited on cooling in a more voluminous form. Kino dissolves almost entirely in spirit of wine (·838), affording a dark reddish solution, acid to litmus paper, which by long keeping sometimes assumes a gelatinous condition. It is readily soluble in solution of caustic alkali, and to a large extent in a saturated solution of sugar.

[766] _Medical Observations and Inquiries_, i. (1757) 358.

[767] _Travels into the Inland Parts of Africa_, by Francis Moore, Lond. 1737. pp. 160. 209. 267.

[768] J. Gurney Bevan, Plough Court, Lombard Street.—The drug was priced in 1787 as having cost 16_s._, and in 1790-92, 21_s._ per lb.

[769] _Pharm. Journ._ v. (1846) 495.

[770] Cleghorn, _Forests and Gardens of South India_, 1861. 13.—Also from information communicated by him orally.

[771] Our sample obtained from _Pt. Marsupium_ Roxb. on the Sigúr Ghat, Feb. 1868, was kindly submitted to us by Mr. McIvor of Ootacamund.—We find it to agree with commercial East Indian Kino.

=Chemical Composition=—Cold water forms with kino a reddish solution, which is at first not altered if a fragment of ferrous sulphate is added. But a violet colour is produced as soon as the liquid is cautiously neutralized. This can be done by diluting it with common water (containing bicarbonate of calcium) or by adding a drop of solution of acetate of potassium. Yet the fact of kino developing an intense violet colour in presence of a proto-salt of iron, may most evidently be shown by shaking it with water, and iron reduced by hydrogen. The filtered liquid is of a brilliant violet, and may be evaporated at 100° without turning green; the dried residue even again forms a violet solution with water. By long keeping the violet liquid gelatinizes. It is decolorized by acids, and turns red on addition of an alkali, whether caustic or bicarbonated. Catechu, as well as crystallized catechin, show the same behaviour, but these solutions quickly turn green on exposure to air.

Solutions of acids, of metallic salts, or of chromates produce copious precipitates in an aqueous solution of kino. Ferric chloride forms a dirty green precipitate, and is at the same time reduced to a ferrous salt. Dilute mineral acids or alkalis do not occasion any decided change of colour, but the former give rise to light brownish-red precipitates of _Kino-tannic Acid_. By boiling for some time an aqueous solution of kino-tannic acid, a red precipitate, _Kino-red_, is separated.

Kino in its general behaviour is closely allied to Pegu catechu, and yields by similar treatment the same products, that is to say, it affords _Pyrocatechin_ when submitted to dry distillation, and _Protocatechuic Acid_ together with _Phloroglucin_ when melted with caustic soda or potash.

Yet in catechu the tannic acid is accompanied by a considerable amount of catechin, which may be removed directly by exhaustion with ether. Kino, on the other hand, yields to ether only a minute percentage of a substance, whose scaly crystals display under the microscope the character of _Pyrocatechin_, rather than that of catechin, which crystallizes in prisms. The crystals extracted from kino dissolve freely in cold water, which is not the case with catechin, and this solution assumes a fine green if a very dilute solution of ferric chloride is added, and turns red on addition of an alkali. This is the behaviour of catechin as well as of pyrocatechin; but the difference in solubility speaks in favour of the crystals afforded by kino being pyrocatechin rather than catechin.

We thought pyrocatechin must also occur in the mother plant of kino, but this does not prove to be the case, no indication of its presence being perceptible either in the fresh bark or wood.[772]

Etti (1878) extracted from kino colourless prisms of _Kinoïn_ by boiling the drug with twice its weight of hydrochloric acid, about 1·03 sp. gr. On cooling, kino-red separates, very little of it remaining in solution together with kinoïn. The latter is extracted by exhausting the liquid with ether, which by evaporation affords crystals of kinoïn. They should be recrystallized from boiling water; they agree with the formula C₁₄H₁₂O₆, which is to be regarded as that of a methylated gallic ether of pyrocatechin, viz., C₆H₄ (OCH₃) C₇H₅O₅.

Kinoïn by heating it to 130° C. gives off water and turns red:

2 C₁₄H₁₂O₆ = OH₂ · C₂₈H₂₂O₁₁.

The latter product is an amorphous mass agreeing with kino-red; by heating it at 160-170° it again loses water, thus affording another anhydride.

Etti succeeded in preparing methylic chloride, pyrocatechin CH₄(OH)₂ as well as gallic acid C₇H₆O₅, by decomposing kinoïn.

We have prepared kinoïn from _Australian kino_ (see page 198), but failed in obtaining it from Malabar kino, which however Etti states to have used. Kino affords about 1½ per cent. of kinoïn.

The solutions of kinoïn turn red on addition of ferric salts.

Commercial kino yielded us 1·3 per cent. of ash.

=Commerce=—The quantity of true kino collected in the Madras forests is comparatively small, probably not exceeding a ton or two annually. The drug is often shipped from Cochin.

=Uses=—Kino is administered as an astringent. It is said to be used in the manufacture of wines, and it might be employed if cheap enough in tanning and dyeing.

Other sorts of Kino.

1. _Butea Kino_, _Butea Gum_, _Bengal Kino_, _Palas or Pulas Kino_, _Gum of the Palas or Dhak Tree_.

This is an exudation from _Butea frondosa_ Roxb. (_Leguminosæ_), a tree of India and Burma, well known under the name of _Palas_ or _Dhak_, and conspicuous for its splendid, large, orange, papilionaceous flowers.[773] According to Roxburgh it flows during the hot season from natural fissures or from wounds made in the bark, as a red juice which soon hardens into a ruby-coloured, brittle, astringent gum.

[772] We have to thank Mr. Broughton, late of the Cinchona Plantations, Ootacamund, for determining this point. In the bark almost saturated with fresh liquid kino, he utterly failed to obtain any indication of pyrocatechin by the tests which he found to render it easily evident in dry kino.

[773] See Nees von Esenbeck, _Plantæ medicinales_, Düsseldorf, iii. (1833) tab. 79.

Authentic specimens of this kino have been placed at our disposal by Mr. Moodeen Sheriff of Madras and by Dr. J. Newton of Bellary. That received from the first-named gentleman consists of flattish, angular fragments (the largest about ½ an inch across) and small drops or tears of a very dark, ruby-coloured gum, which when held to the light is seen to be perfectly transparent. The flat pieces have been mostly dried on leaves, an impression of the veins of which they retain on one side, while the other is smooth and shining. The substance has a pure astringent taste, but no odour. It yielded us 1·8 per cent. of ash and contained 13·5 per cent. of water. Ether removes from it a small quantity of _pyrocatechin_. Boiling alcohol dissolves this kino to the extent of 46 per cent.; the solution which is but little coloured, produces an abundant greyish-green precipitate with perchloride of iron, and a white one with acetate of lead. It may be hence inferred that a tannic acid, probably kino-tannic acid, constitutes about half the weight of the drug, the remainder of which is formed of a soluble mucilaginous substance which we have not isolated in a state of purity. By submitting the Butea kino of Mr. Moodeen Sheriff to dry distillation we obtained pyrocatechin.

The sample from Dr. Newton is wholly in transparent drops and stalactitic pieces, considerably paler than that just described, but of the same beautiful ruby tint. The fragments dissolve freely and almost completely in cold water, the solution being neutral and exhibiting the same reactions as the former sample.

Butea kino, which in India is used in the place of Malabar kino, was long confounded with the latter by European pharmacologists, though the Indian names of the two substances are quite different. It is not obtained exclusively from _B. frondosa_, the allied _B. superba_ Roxb. and _B. parviflora_ Roxb. affording a similar exudation.

2. _African or Gambia Kino._—Of this substance we have a specimen collected by Daniell[774] in the very locality whence it was obtained by Moore in 1733 (see p. 195), and by Park at the commencement of the present century. The tree yielding it, which still bears the Mandingo name _Kano_, and grows to a height of 40 to 50 feet, is _Pterocarpus erinaceus_ Poiret, a native of Tropical Western Africa from Senegambia to Angola. The juices exude naturally from crevices in the bark, but much more plentifully by incisions; it soon coagulates, becoming deep blood-red and remarkably brittle. That in our possession is in very small, shining, angular fragments, which in a proper light appear transparent and of a deep ruby colour. In solubility and chemical characters, we can trace no difference between it and the kino of the allied _Pt. Marsupium_ Roxb. This kino does not now find its way to England as a regular article of trade. From the statement of Welwitsch, it appears that the Portuguese of Angola employ it under the name of _Sangue de Drago_.[775]

3. _Australian, Botany Bay, or Eucalyptus Kino._—For some years past, the London drug market has been supplied with considerable quantities of kino from Australia; in fact at one period this kino was the only sort to be purchased.

[774] See his paper _On the Kino Tree of West Africa, Pharm. Journ._ xiv. (1855) 55.

[775] _Madeiras e Drogas medicinaes de Angola_, Lisboa, 1862, 37.

As it is the produce of numerous species of _Eucalyptus_, it is not surprising that it presents considerable diversity of appearance. The better qualities closely agree with Pterocarpus kino. They are in dark reddish-brown masses or grains, which when in thin fragments are seen to be transparent, of a garnet red hue and quite amorphous. The substance is mostly collected by the sawyers and wood-splitters. It is found within the trunks of trees of all sizes, in flattened cavities of the otherwise solid wood which are often parallel to the annual rings. In such place the kino, which is at first a viscid liquid, becomes inspissated and subsequently hard and brittle. It may also be obtained in a liquid state by incisions in the stems of growing trees: such liquid kino has occasionally been brought into the London market; it is a viscid treacle-like fluid, yielding by evaporation about 35 per cent. of solid kino.[776]

Authentic specimens of the kino of 16 species of _Eucalyptus_ sent from Australia by F. von Müller, have been examined by Wiesner of Vienna.[777] He found the drug to be in most cases readily soluble in water or in spirit of wine, the solution being of a very astringent taste. The solution gave with sulphuric acid a pale red, flocculent precipitate of _Kino-tannic Acid_; with perchloride of iron (as in common kino) a dusky greenish precipitate,—except in the case of the kino of _E. obliqua_ L’Hér. (Stringy-bark Tree), the solution of which was coloured dark violet.

Wiesner further states, that Eucalyptus kino affords a little _Catechin_[778] and _Pyrocatechin_. It contains no pectinous matter, but in some varieties a gum-like that of _Acacia_. In one sort, the kino of _E. gigantea_ Hook,[779] gum is so abundant that the drug is nearly insoluble in spirit of wine.

By Etti’s process, as given at page 197, we obtained kinoïn from an Australian Kino, which contained numerous fragments of the wood. We noticed that both Australian and Malabar kino emitted a somewhat balsamic odour, when they were treated with hydrochloric acid.

From this examination, it is evident that the better varieties of Eucalyptus kino, such for instance as those derived from _E. rostrata_ Schlecht. (_Red_ or _White Gum_, or _Flooded Gum_ of the colonists), _E. corymbosa_ Sm. (_Blood-wood_) and _E. citriodora_ Hook., possess the properties of Pterocarpus kino and might with no disadvantage be substituted for it.

[776] Victoria Exhibition, 1861.—Jurors’ Report on Class 3. p. 59.

[777] _Zeitschrift des österreich. Apotheker-Vereines_ ix. (1871) 497; _Pharm. Journ._ Aug. 5, 1871. 102.

[778] In our opinion this is doubtful.

[779] Bentham unites this species to _E. obliqua_ L’Hér (_Flor. Austr._ iii. 204).

LIGNUM PTEROCARPI.

_Lignum Santalinum rubrum_, _Santalum rubrum_; _Red Sanders Wood_, _Ruby Wood_; F. _Bois de Santal rouge_; G. _Rothes Sandelholz_, _Caliaturholz_.

=Botanical Origin=—_Pterocarpus santalinus_ Linn. fil.—A small tree not often exceeding 3½ to 4 feet in girth, and 20 to 25 feet in height; it is closely related to _Pt. Marsupium_ Roxb., from which it differs chiefly in having broader leaflets always in threes. It is a native of the southern part of the Indian Peninsula, as Canara, Mysore, Travancore and the Coromandel Coast, but also occurs in Mindanao, in the southern Philippines. In India the districts in which the wood is at present chiefly obtained are the forests of the southern portion of the Kurnool Hills, Cuddapah and North Arcot (W. and N.W. of Madras). The tree is now being raised in regular plantations.[780]

The wood is a staple article of produce, and the felling of the trees is strictly controlled by the forest inspectors. The fine trunk-wood is highly valued by the natives for pillars in their temples and other buildings, as well as for turnery. The stumps and roots are exported to Europe as a dye-stuff, mostly from Madras.

=History=—It is difficult to tell whether the appellation _Red_ Sandal-wood used in connexion with _Yellow_ and _White_ Sandal-wood by some of the earlier writers on drugs, was intended to indicate the inodorous dyewood under notice or the aromatic wood of a species of _Santalum_. Yet when Marco Polo[781] alludes to the sandal-wood imported into China, and to the _red_ sandal (“_Cendal vermeil_”) which grows in the island of Necuveran (Nicobar), it is impossible to doubt that he intended by this latter name some such substance as that under notice.

Garcia de Orta, who wrote at Goa in the middle of the 16th century, clearly distinguished the fragrant sandal of Timor from the red inodorous wood of Tenasserim and the Coromandel Coast. It is remarkable that the wood of _Pt. santalinus_ is distinguished to the present day in all the languages of India by names signifying _red-coloured sandal-wood_, though it has none whatever of the peculiarities of the odorous wood of _Santalum_. Red Sanders Wood was formerly supposed to possess medicinal powers: these are now disregarded, and it is retained in use only as a colouring agent.

During the middle ages, it was used as well as alkanet for culinary purposes, such as the colouring of sauces and other articles of food. The price in England between 1326 and 1399 was very variable, but on an average exceeded 3_s._ per lb.[782] Many entries for the purchase of Red Sanders along with spices and groceries, occur in the accounts of the Monastery of Durham, A.D. 1530-34.[783]

=Description=—The wood found in English commerce is mostly that of the lower parts of the stem and that of the thickest roots. It appears in the market in ponderous, irregular logs, rarely exceeding the thickness of a man’s thigh and commonly much smaller, 3, 4 or 5 feet in length; they are without bark or sapwood, and are externally of a dark colour. The internal wood is of a deep, rich, blood-red, exhibiting in transverse section zones of a lighter tint, and taking a fine polish.

At the present day, druggists generally buy the wood rasped into small chips, which are of a deep reddish-brown hue, tasteless and nearly without odour.

[780] (Beddome), _Report of the Conservator of Forests_, for 1869-70, Madras, 1870, pp. 3. 39. 123; for figure of the tree, see _Flora Sylvatica of Southern India_ of the same author, tab. xxii.

[781] Pauthier, _Livre de Marco Polo_, 580—_Pt. indicus_ Willd. grows in the adjacent Andaman Islands.

[782] Rogers, _Agriculture and Prices in England_, 1866, i. 631, ii. 545, &c.—The average price of a sheep during the same period was about 1_s._ 6_d._

[783] _Durham Household Book_, Surtees Soc. 1844. 215; also Pegge, _Form of Cury_, Lond. 1780. p. xv.

=Microscopic Structure=—The wood is built up for the greater part of long pointed cells, having thick walls (libriform). Through this ligneous tissue, there are scattered small groups of very large vessels. In a direction parallel to the circumference of the stem, there are less coloured small parenchymatous layers, running from one vascular bundle to another. The whole tissue is finally traversed by very narrow medullary rays, which are scarcely perceptible to the unaided eye. The parenchymatous cells are each loaded with one crystal of oxalate of calcium, which are so large that, in a piece of the wood broken longitudinally, they may be distinguished without a lens. The colouring matter is contained especially in the walls of the vessels and the ligneous cells.

=Chemical Composition=—Cold water or fatty oil (almond or olive) abstracts scarcely anything from the wood, and hot water but very little. On the other hand, ether, spirit of wine, alkaline solutions, or concentrated acetic acid, readily dissolves out the colouring matter. Essential oils of bitter almond or clove take up a good deal of the red substance; that of turpentine none at all. This resinoid substance, termed _Santalic Acid_ or _Santalin_,[784] is said to form microscopic prismatic crystals of a fine ruby colour, devoid of odour and taste, fusing at 104° C., insoluble in water but neutralizing alkalis and forming with them uncrystallizable salts.

Weidel (1870) exhausted the wood with boiling water, containing a little potash, and obtained by means of hydrochloric acid a red precipitate, which was redissolved in boiling alcohol and then furnished _colourless_ crystals of _Santal_, C₈H₆O₃. They are devoid of odour or taste, not soluble in water, benzol, chloroform, bisulphide of carbon, and but sparingly in ether. Santal yields with potash a faintly yellow solution which soon turns red and green. The wood afforded Weidel not more than 3 per mille of santal.

Cazeneuve (1874)[785] mixed 4 parts of the wood with 1 part of slaked lime, and exhausted the dried powder with ether containing a little alcohol. After the evaporation of the ether, a small amount of colourless crystals of _Pterocarpin_ was obtained, which were purified by recrystallization from boiling alcohol. They melt at 83° C., and are abundantly soluble in chloroform, in bisulphide of carbon, very little in cold alcohol, not at all in water. Pterocarpin agrees with the formula C₁₇H₁₆O₅. It yields a red solution with concentrated sulphuric acid, and a green with nitric acid 1·4 sp. gr. By submitting it to destructive distillation pyrocatechin appears to be formed.

Franchimont (1879) assigns the formula C₁₇H₁₆O₆ to another principle of Red Sanders Wood, which he isolated by means of alcohol. It is an amorphous substance, melting at 105°. By extracting the wood with a solution of carbonate of sodium, Hagenbach (1872) obtained a fluorescent solution. Red Sanders Wood yielded us of ash only 0·8 per cent.

=Commerce=—In the official year 1869-70, Red Sanders Wood produced to the Madras Government a revenue of 26,015 rupees (£2,601). The quantity taken from the forests was reported as 1,161,799 lb.

[784] Gmelin, _Chemistry_, xvi. (1864) 259; the formula assigned to santalic acid (C₁₅H₁₄O₅) appears to be doubtful. Weidel in proposing the formula C₁₄H₁₂O₄ points out that it may be allied to alizarin, C₁₄H₈O₄.

[785] See _Dictionnaire de Chimie_, art. _Santaline_, p. 1434, and for particulars: Cazeneuve, _Recherche et extraction des alcaloïdes_, etc. Paris, 1875. 66. It would appear that the author obtained about 4 per _mille_ of pterocarpin from the wood.

=Uses=—Red Sanders Wood is scarcely employed in pharmacy except for colouring the Compound Tincture of Lavender; but it has numerous uses in the arts. The latter applies also to the wood of _Pterocarpus angolensis_ DC., which is largely exported from the French colony of Gaboon; it is the “Santal rouge d’Afrique of the French,” or Barwood of the English commerce.

BALSAMUM TOLUTANUM.

_Balsam of Tolu_; F. _Baume de Tolu_; G. _Tolubalsam_.

=Botanical Origin=—_Myroxylon Toluifera_ H B K. (_Toluifera Balsamum_ Miller, _Myrospermum toluiferum_ A. Rich.),[786] an elegant and lofty evergreen tree with a straight stem, often as much as 40 to 60 feet from the ground to the first branch. It is a native of Venezuela, and New Granada,—probably also of Ecuador and Brazil.

=History=—The first published account of Balsam of Tolu, is that of the Spanish physician Monardes, who in his treatise on the productions of the West Indies, which in its complete form first appeared at Seville in 1574,[787] relates how the early explorers of South America observed that the Indians collected this drug by making incisions in the trunk of the tree. Below the incisions they affixed shells of a peculiar black wax to receive the balsam, which being collected in a district near Cartagena called _Tolu_, took its name from that place. He adds that it is much esteemed both by Indians and Spaniards, that the latter buy it at a high price, and that they have lately brought it to Spain, where it is considered to be as good as the famous Balsam of Mecca.

Francisco Hernandez, who lived in 1561-1577 in Mexico, stated[788] that the balsam of the province of Tolu was thought to be quite as useful as, if not superior to, “balsamum indicum,” _i.e._ peruvianum.

A specimen agreeing with this description was given to Clusius[789] in 1581 by Morgan, apothecary to Queen Elizabeth, but the drug was certainly not common till a much later period. In the price-list of drugs of the city of Frankfort of 1669, _Balsamus tolutanum_ (sic) is expressly mentioned,[790] but there can be but little doubt that _Balsamum Americanum resinosum_[791] or _siccum_ or _durum_ as occurring in many other tariffs of the 17th century, printed in Germany, was also the balsam under notice;[792] in a similar list emanating from the city of Basle in 1646,[793] we noticed _B. indicum album_, _B. peruvianum_ and _B. siccum_,—the last with the explanatory words, “_trockner Balsam in der Kürbsen_” (_i.e._ in gourds), meaning probably balsam of Tolu.

[786] Fig. in Bentley and Trimen, _Med. Plants_, part 23 (1877) under the name of _Toluifera Balsamum_. Though the change of names may be justified by the strict rules of priority, we are of opinion that at present it would be fraught with more of inconvenience than advantage.—_Myroxylon punctatum_ Klotzsch, a tree stated to grow nearly all over the northern part of South America, is referred to the same species by Bentley and Trimen.

[787] _Historia de las cosas que se traen de nuestras Indias occidentales_, cap. del Balsamo de Tolu.

[788] _Nova Plantarum, animal. et mineral. mexicanorum. Historia_, Reccho’s edition, Romæ, 1651. fol. 53.

[789] _Exoticor._ etc. 1605. lib. x. fol. 305.

[790] _Pharm. Journ._ vi. (1876) 102.

[791] Pharmaceutical tariff (“Taxa”) of the city of Wittenberg 1632 (in the Hamburg library).

[792] Flückiger, _Documente zur Geschichte der Pharmacie_, Halle, 1876. 49. 50. 53.—Balsamum _Peruvianum_ first occurs in the tariff of the city of Worms of 1609.—_Documente_, p. 39; _Pharm. Journ. l. c._

[793] Contained in the _Medicine Tariffs_, in the library of the British Museum, bound together in one volume ({777. c.}/5). They include Schweinfurt 1614, Bremen 1644, Basle 1647, Rostock 1659, Quedlinburg 1665, Frankfort on Main 1669 (quoted above).

As to the tree, of which Monardes figured a broken pod, leaflets of it, marked 1758, exist in Sloane’s herbarium. Humboldt and Bonpland saw it in several places in New Granada during their travels (1799-1804), but succeeded only in gathering a few leaves. Among recent collectors, Warszewicz, Triana, Sutton Hayes, and Seemann were successful only in obtaining leaves. Weir in 1863 was more happy, for by causing a large tree of nearly 2 feet diameter to be felled, he procured good herbarium specimens including pods, but no flowers. Owing to this tree having been much wounded for balsam, its foliage and fruits were singularly small and stunted, and its branches overgrown with lichens.

That which botanists had failed to do, has been accomplished by an ornithologist, Mr. Anton Goering, who, travelling in Venezuela to collect birds and insects, made it a special object, at the urgent request of one of us (H.), to procure complete specimens of the Balsam of Tolu tree. By dint of much perseverance and by watching for the proper season, Mr. Goering obtained in December 1868 excellent flowering specimens and young fruits, and subsequently mature seeds from which plants have been raised in England, Ceylon and Java.

=Extraction=—The most authentic information we possess on this subject is derived from Mr. John Weir, plant collector to the Royal Horticultural Society of London, who when about to undertake a journey to New Granada in 1863, received instructions to visit the locality producing Balsam of Tolu. After encountering considerable difficulties, Mr. Weir succeeded in observing the manner of collecting the balsam in the forest near Plato, on the right bank of the Magdalena. Mr. Weir’s information[794] may be thus summarized:—

The balsam tree has an average height of 70 feet with a straight trunk, generally rising to a height of 40 feet before it branches. The balsam is collected by cutting in the bark two deep sloping notches, meeting at their lower ends in a sharp angle. Below this =V=-shaped cut, the bark and wood is a little hollowed out, and a calabash of the size and shape of a deep tea-cup is fixed. This arrangement is repeated, so that as many as twenty calabashes may be seen on various parts of the same trunk. When the lower part has been too much wounded to give space for any fresh incisions, a rude scaffold is sometimes erected, and a new series of notches made higher up. The balsam-gatherer goes from time to time round the trees with a pair of bags of hide, slung over the back of a donkey, and empties into them the contents of the calabashes. In these bags the balsam is sent down to the ports where it is transferred to the cylindrical tins in which it reaches Europe. The bleeding of the trees goes on for at least eight months of the year, causing them ultimately to become much exhausted, and thin in foliage.

In some districts, as we learn from another traveller, it is customary to let the balsam flow down the trunk into a receptacle at its base, formed of the large leaf of a species of _Calathea_.

[794] _Journ. of the R. Hort. Soc._, May 1864; _Pharm. Journ._ vi. (1865) 60.

From the observations of Mr. Weir, it appears that the balsam tree is plentifully scattered throughout the Montaña around Plato and other small ports on the right bank of the Magdalena. He states that he saw at least 1,500 lb. of the drug on its way for exportation. From another source, we know that it is largely collected in the valley of the Sinu, and in the forests lying between that river and Cauca. None is collected in Venezuela.

=Description=—Balsam of Tolu freshly imported is a light brown, slow-flowing resin, soft enough to be impressible with the finger, but viscid on the surface.[795] By keeping, it gradually hardens so as to be brittle in cold weather, but it is easily softened by the warmth of the hand. Thin layers show it to be quite transparent and of a yellowish brown hue. It has a very agreeable and delicate odour, suggestive of benzoin or vanilla, especially perceptible when the resin is warmed, or when its solution in spirit is allowed to evaporate on paper. Its taste is slightly aromatic with a barely perceptible acidity, though its alcoholic solution decidedly reddens litmus.

In very old specimens, such as those which during the last century reached Europe in little calabashes[796] of the size and shape of an orange, the balsam is brittle and pulverulent, and exhibits when broken a sparkling, crystalline surface. This old balsam is of a fine deep amber tint and superior fragrance.

When Balsam of Tolu is pressed between two warmed plates of glass so as to obtain it in a thin even layer, and then examined with a lens, it exhibits an abundance of crystals of cinnamic acid. Balsam of Tolu dissolves easily and completely in glacial acetic acid, acetone, alcohol, chloroform or solution of caustic potash; it is less soluble in ether, scarcely at all in volatile oils, and not in benzol or bisulphide of carbon. The solution in acetone is devoid of rotatory power in polarized light.

=Chemical Composition=—The balsam consists partly of an _amorphous resin_, not soluble in bisulphide of carbon, which is supposed to be the same as the dark resin precipitated by the bisulphide from balsam of Peru. Scharling (1856) assigned the formula C₁₈H₂₀O₅ to that part of the balsam which is soluble in potash.

If Tolu balsam is boiled with water, it yields to it cinnamic and benzoic acid, which we have (1877) perfectly succeeded in separating by repeated recrystallization from water; we have before us good specimens of either, showing not only different melting points (133° C. and 121° C.), but as to our crystals of benzoïc acid, isolated from the balsam as stated above, we find that they also do _not_ evolve bitter almond oil when mixed with sulphuric acid and chromate of potassium. The acids may also be removed by boiling bisulphide of carbon.

Busse[797] showed that _benzylic_ ethers of both benzoic and cinnamic acid are also constituents of the balsam, the cinnamate of benzyl being present in larger quantity.

Upon distilling the balsam with water, it affords 1 per cent. of _Tolene_, C₁₀H₁₆, boiling at about 170° C. This liquid rapidly absorbs oxygen from the air. By destructive distillation, the balsam affords the same substances as those obtainable from balsam of Peru, among which _Phenol_ and _Styrol_ have been observed.

[795] I have seen it imported very fluid into London by way of New York.—Sept. 1878.—F. A. F.

[796] The gourds, “Kürbsen,” of the list of Basle of 1647.

[797] _Berichte der Deutschen Chemischen Gesellschaft_, 1876. 833.

=Commerce=—The balsam is exported from New Granada, packed in cylindrical tins holding about 10 lb. each. The quantity shipped from Santa Marta in 1870 was 2,002 lb.; in 1871, 2,183 lb.; in 1872, 1,206 lb. In 1876 from the port of Savanilla 27,180 kilogrammes are stated to have been exported.

=Uses=—Balsam of Tolu has no important medicinal properties. It is chiefly used as an ingredient in a pleasant-tasting syrup and in lozenges.

=Adulteration=—We have twice met with spurious Balsam of Tolu, but in neither instance did the fraudulent drug bear any great resemblance to the genuine.

Colophony, which might be mixed with the balsam, can be detected by warm bisulphide of carbon which dissolves it, but removes from the pure drug almost exclusively cinnamic and benzoic acid.

BALSAMUM PERUVIANUM.

_Balsam umindicum nigrum_; _Balsam of Peru_; F. _Baume de Pérou, Baume de San Salvador_; G. _Perubalsam_.

=Botanical Origin=—_Myroxylon Pereiræ_ Klotzsch (_Myrospermum Pereiræ_ Royle), a tree attaining a height of about 50 feet, and throwing out spreading, ascending branches at 6 to 10 feet from the ground.[798]

It is found in a small district of the State of Salvador in Central America (formerly part of Guatemala), lying between 13°·35 and 14°·10 N. lat., and 89° and 89°·40 W. long., and known as the _Costa del Balsamo_ or Balsam Coast. The trees grow naturally in the dense forests; those from which the balsam is obtained are, if in groups, sometimes enclosed, in other cases only marked, but all have their distinct owners. They are occasionally rented for a term of years, or a contract is made for the produce of a certain number.

The principal towns and villages around which balsam is produced, are the following:—Juisnagua, Tepecoyo or Coyo, Tamanique, Chiltiuapan, Talnique, Jicalapa, Teotepeque, Comasagua and Jayaque. All the lands on the Balsam Coast are _Indian Reservation Lands_.

The Balsam of Peru tree was introduced in 1861 into Ceylon, where it flourishes with extraordinary vigour.

[798] We are not yet prepared to accept the opinion of Baillon, that _M. Pereiræ_ is specifically identical with _M. Toluifera_, though we admit they are very closely related. According to our observations, the two trees exhibit the following differences:—

_M. Toluifera._ | _M. Pereiræ._
|
Trunk tall and bare, | Trunk throwing off
branching at 40 to 60 feet | ascending branches
from the ground, and forming | at 6 to 10 feet from
a roundish crown of foliage. | the ground.
|
Calyx rather tubular. | Calyx widely cup-shaped, shallow.
|
Racemes dense, | Racemes loose,
3 to 4½ inches long. | 6 to 7 inches long.
|
Legume scarcely narrowed | Legume much narrowed
towards the stalk-end. | towards the stalk-end.

See also Bentley and Trimen, _Medicinal Plants_, part 10 (1876), _Toluifera Pereiræ_.

=History=—As in the case of Balsam of Tolu, it is to Monardes of Seville that we are indebted for the earliest description of the drug under notice. In a chapter headed _Del Balsamo_,[799] he states that at the time he wrote (1565) the drug was not new, for that it had been received into medicine immediately after the discovery of New Spain. As the conquest of Guatemala took place about 1524, we may conclude that the balsam was introduced into Europe soon afterwards.

Monardes further adds, that the balsam was in such high estimation that it sold for 10 to 20 ducats (£4 10_s._ to £9) the ounce; and that when taken to Rome, it fetched even 100 ducats for the same quantity. The inducement of such enormous prices brought plenty of the drug to Europe, and its value, as well as its reputation, was speedily reduced.

The description given by Monardes of extracting the balsam by boiling the chopped wood of the trunk and branches, raises a doubt as to whether the drug he had in view was exactly that now known; but he never was in America, and may have been misinformed. Evidence that our drug was in use, is afforded by Diego Garcia de Palacio, who, in his capacity of Auditor of the Royal Audiencia of Guatemala, wrote an account to Philip II., king of Spain, describing the geography and productions of this portion of his majesty’s dominions. In this interesting document, which bears date 1576 and has only recently been published,[800] Palacio tells the king of the great balsam trees of Guaymoco and of the coasts of Tonala,[801] and of the Indian method of promoting the exudation of the balsam by scorching the trunk of the tree. Prior to the conquest of the country by the Spaniards and for a short time after, balsam formed part of the tribute paid to the Indian chiefs of Cuscatlan, to whom it was presented in curiously ornamented earthen jars.

The idea of great virtues attaching to the balsam is shown by the fact that, in consequence of representations made by missionary priests in Central America, Pope Pius V. granted a faculty to the Bishops of the Indies, permitting the substitution of the balsam of Guatemala for that of Egypt, in the preparation of the chrism used in the Roman Catholic Church. This document, bearing date August 2, 1571, is still preserved in the archives of Guatemala.[802]

In the 16th century, the balsam tree grew in the warm regions of Panuco and Chiapan in Mexico, whence it was introduced into the famous gardens of Hoaxtepec near the city of Mexico, described by Cortes in his letter to Charles V. in 1552.[803]

A rude figure of the tree, certainly a _Myroxylon_ and probably the species under notice, was published in the _Thesaurus Rerum Medicarum Novæ Hispaniæ_ of Hernandez,[804] who also says that it had been transferred to the “Hoaxtepecences hortos” of the Mexican kings “delitiarum et magnificentiæ gratia.”

[799] Occurring in the first book of the work quoted in the Appendix, which was published separately at Seville in 1565.

[800] Squier, _Documents and Relations concerning the Discovery and Conquest of America_, New York, 1859.—Frantzius, _San Salvador und Honduras im Jahre_ 1576. Berlin, 1873.

[801] The ancient name of the Balsam Coast; Guaymoco is a village between Sonsonate and San Salvador. The pillars of wood of _Myroxylon_ in the church are, perhaps, says Squier, the very same as those mentioned with admiration by Palacio.

[802] It may be found _in extenso_ in the original Latin in _Pharm. Journ._ ii. (1861) 447 as well as in Hanbury’s _Science Papers_, 1876. 294.

[803] Clavigero, _Hist. of Mexico_, English trans. i. (1787) pp. 32. 379.

[804] Rome, 1628; 2nd ed. 1651. fol. 51; the book written in the town of Mexico, bears at the same time also the title given in the Appendix.

Balsam of Peru was well known in German pharmacy in the beginning of the 17th century (see article _Balsamum Tolutanum_).

The exports of Guatemala being shipped chiefly at Acajutla, were formerly carried to Callao, the port of Lima, whence they were transmitted to Spain. This circumstance led to the balsam acquiring the misleading name of _Peru_, and in part to the notion that it was a production of South America.

The history of Balsam of Peru was much amplified by a communication of the late Dr. Charles Dorat, of Sonsonate, Salvador, in 1860 to the _American Journal of Pharmacy_, and by still further information accompanied by drawings and specimens, transmitted to one of us in 1863.[805] These statements have lastly been confirmed again on the spot by Mr. Theophilus Wyss, a Swiss apothecary, established in San Miguel la Union, San Salvador.[806]

=Extraction of the Balsam=—Early in November or December, or after the last rains, the stems of the balsam trees are beaten with the back of an axe, a hammer or other blunt instrument, on four sides, a similar extent of bark being left unbruised between the parts that are beaten. The bark thus injured soon cracks in long strips, and may be easily pulled off. It is sticky as well as the surface below it, and there is a slight exudation of fragrant resin, but not in sufficient quantity to be worth collecting. To promote an abundant flow, it is customary, five or six days after the beating, to apply lighted torches or bundles of burning wood to the injured bark, whereby the latter becomes charred. About a week later, the bark either drops or is taken off, and the stem commences to exude the balsam. This is collected by placing rags (of any kind or colour), so as entirely to cover the bare wood. As these rags in the course of some days become saturated with the exudation, they are collected, thrown into an earthen vessel of water, and gently boiled and stirred until they appear nearly clean, the balsam separating and sinking to the bottom. This process goes on for some hours, the exhausted rags being from time to time taken out, and fresh ones thrown in. As the rags are removed they are wrung out in a sort of rope bag, and the balsam so saved is added to the stock. When the boiler has cooled, the water is decanted, and the balsam is poured into _tecomates_ or gourds, ready for the market.

The balsam prepared by means of rags is termed “balsamo de trapo;” a little balsam of inferior quality is also produced, according to Wyss, by boiling the bark with water. This method affords “Tacuasonte” or “balsamo de cascara,” which is sometimes mixed with the balsamo de trapo. Tacuasonte means prepared without fire.

[805] Hanbury in _Pharm. Journ._ v. (1864) 241. 315; also _Science Papers_, 294-309.

[806] See my paper, with map, in _Schweizerische Wochenschrift für Pharmacie_, 1878. 219 (Library of the Pharm. Soc., London).—In the Catalogue of the contributions of San Salvador to the Paris exhibition, p. 33, Dr. D. J. Guzman gives: “Détails sur le moyen, d’extraire et travailler le _Balsamo negro_ du Salvador,” which are far from satisfactory.—F. A. F.

The Indians work a tree a second year, by bruising the bark that was left untouched the previous year. As the bark is said to be renewed in the short space of two years, it is possible to obtain from the same tree an annual yield of about 2 lb. of balsam for many years, provided a few years of rest be occasionally allowed. Clay or earth is sometimes smeared over the bare wood.

The trees sometimes exude spontaneously a greenish gum-resin of slightly bitter taste, but totally devoid of balsamic odour. It has been analyzed by Attfield (see opposite page).

=Secretion of the Balsam=—No observations have yet been made as to the secretion of the balsam in the wood, or the part that is played by the operation of scorching the bark. Neither the unscorched bark nor the wood, as we have received them, possess any aromatic odour.

The old accounts speak of a very fragrant resin, far more valuable than the ordinary balsam, obtained by incisions. We have made many inquiries for it, but without the least success. Such a resin is easily obtainable from the trunk of _M. Toluifera_.

=Description=—Balsam of Peru is a liquid having the appearance of molasses, but rather less viscid. In bulk it appears black, but when examined in a thin layer, it is seen to be of a deep orange-brown and perfectly transparent. It has a balsamic, rather smoky odour, which is fragrant and agreeable when the liquid is smeared on paper and warmed. It does not much affect the palate, but leaves a disagreeable burning sensation in the fauces.

The balsam has a sp. gr. of 1·15 to 1·16. It may be exposed to the air for years without undergoing alteration or depositing crystals. It is not soluble in water, but yields to it a little cinnamic and traces of benzoic acid; from 6 to 8 parts of crystallized carbonate of sodium are required to neutralize 100 parts of the balsam. It is but partially and to a small extent dissolved by dilute alcohol, benzol, ether or essential or fatty oils, not at all by petroleum ether. The balsam mixes readily with glacial acetic acid, anhydrous acetone, absolute alcohol or chloroform. Its rotatory power is very insignificant.

=Chemical Composition=—The peculiar process by which balsam of Peru is obtained, causes it to contain a variety of substances not found in the more natural resin of _Myroxylon Toluifera_; hence the two drugs, though derived from plants most closely allied, possess very different properties.

Three parts of the balsam mix readily with one part of bisulphide of carbon, yet a further addition of the latter will cause the separation of a brown flocculent resin. If the balsam be mixed with thrice its weight of bisulphide, a coherent mass of dark resin, sometimes amounting to about 38 per cent. of the balsam, is precipitated. The bisulphide of carbon forms then a perfectly transparent brown liquid. If this solution is shaken with water, the latter removes _Cinnamic_ and _Benzoic_ acids. To separate them, ammonia is cautiously added, yet not in excess.[807] The solution of cinnamate and benzoate thus obtained and duly concentrated, yields both these acids in white crystals on addition of acetic or hydrochloric acid.

[807] By saturating the acid aqueous liquid with ammonia, it assumes a transient bright yellow hue; an excess of ammonia transforms the whole mixture into an emulsion, from which the cinnameïn again separates but imperfectly.

The resin separated by means of bisulphide of carbon as above stated, is a black brittle amorphous mass, having no longer the specific odour of the balsam. It is soluble in caustic alkalis, also in alcohol; the solution in the latter which may be considerably purified by charcoal, reddens litmus, and is abundantly precipitated by an alcoholic solution of neutral acetate of lead. Kachler (1869) by melting this resin with potash obtained about ⅔ of its weight of protocatechuic acid.[808] By destructive distillation, it furnishes benzoic acid, styrol, C₈H₈, and toluol, C₇H₈.

As to the solution obtained with bisulphide of carbon, it forms, after the bisulphide has evaporated, a brownish aromatic liquid of about 1·1 sp. gr., termed _Cinnameïn_. This substance may also be obtained by distillation, yet less easily, on account of its very high boiling point, about 300° C.

Cinnameïn, C₁₆H₁₄O₂, is resolved by concentrated caustic lye into benzylic alcohol, C₇H₁₄O₂, and cinnamic acid, C₉H₈O₂, whence it follows that cinnameïn is _Benzylic Cinnamate_. This is, according to Kraut (1858, 1869, 1870) and to Kachler (1869, 1870), the chief constituent of the balsam. The former chemist obtained from it nearly 60 per cent. cinnameïn. Kachler assigns to the balsam the following composition: 46 per cent. of cinnamic acid, 32 of resin, 20 of benzylic alcohol. These latter figures however are not quite consistent: 46 parts of cinnamic acid (molecular weight = 148) would answer to 73 parts of benzylic cinnamate; and 20 parts of benzylic alcohol require on the other hand only (mol. weight = 108) 27·4 parts of cinnamic acid in order to form benzylic cinnamate (mol. = 238).

Benzylic cinnamate, prepared as above stated, is a thick liquid, miscible both with ether or alcohol, not concreting at -12° C., boiling at 305° C., yet under ordinary circumstances not without decomposition. By exposure to air, it slowly acquires an acid reaction; by prolonged action of potash, especially in an alcoholic solution, toluol is also formed. In this process, cinnamate of potassium finally forms a crystalline mass, while an oily mixture of benzylic alcohol and toluol, the so-called “_Peruvin_” constitutes the liquid part of the whole.

Grimaux (1868) has artificially prepared benzylic cinnamate by heating an alkaline cinnamate with benzylic chloride. Thus obtained, that substance forms crystals, which melt at 39° C., and boil at 225 to 235° C. They consequently differ much from cinnameïn.

Delafontaine (1868) is of the opinion, that cinnameïn contains besides benzylic cinnamate, cinnamylic cinnamate, C₃₆H₃₂O₄, the same substance as described under the name of styracin in the article _Styrax liquida_. He states that he obtained benzylic and cinnamylic alcohol when he decomposed cinnameïn by an alkali. The two alcohols however were separated only by fractional distillation.

From the preceding investigations it must be concluded, that the bark of the tree contains resin and probably benzylic cinnamate. The latter is no doubt altered by the process of collecting the balsam, which is followed on the Balsam Coast. To this are probably due the free acids in the balsam and its dark colour.

Another point of considerable interest is the fact, that the tree exudes a gum-resin, containing according to Attfield 77·4 per cent. of resin,[809] which is non-aromatic and devoid of cinnamic acid, and therefore entirely distinct from balsam of Peru. The leaves of the tree contain a fragrant oil.

[808] Numerous resins as benzoin, guaiacum, dragon’s blood, myrrh, etc., and many other substances are capable of affording the same acid.

[809] _Pharm. Journ._ v. (1864) 248.

=Commerce=—The balsam is shipped chiefly at Acajutla. It used formerly to be packed in large earthenware jars, said to be Spanish wine-jars, which, wrapped in straw, were sewed up in raw hide. These packages have of late been superseded by metallic drums, which have the advantage of being much less liable to breakage. We have no exact statistics as to the quantity exported from Central America. In the catalogue of San Salvador (quoted above, page 207, note 2) p. 39, the value of the balsam exported in 1876 from that country is stated to have been 78,189 dollars. The value of tobacco amounted to 69,717 dollars, that of coffee to 1⅓ millions of dollars, indigo to 2¼ millions.

=Uses=—Occasionally prescribed in the form of ointment as a stimulating application to old sores, sometimes internally for the relief of asthma and chronic cough. It is said to be also employed for scenting soap.

=Adulteration=—We have before us a sample of an adulterated balsam, which, we are told, is largely prepared at Bremen. It is less aromatic, less rich in acids, and contains usually much less than 38 per cent. of resin separable, as above stated, by means of bisulphide of carbon. At first sight however the adulterated drug is not so easily recognized.