Oleum Terebinthinae. U. S. Oil of Turpentine.

Ol. Tereb. [Turpentine Oil, "Spirits of Turpentine"]

Related entry: Riga balsam - Rosin - White Pine Bark - Rectified Oil of Turpentine

"The volatile oil distilled with water from the concrete oleoresin obtained from Pinus palustris Miller or from other species of Pinus (Fam. Pinaceae). Preserve it in well-closed containers." U. S.

Essence de Terebenthine, Fr. Cod.; Huile volatile de Terebenthine, Fr.; Oleum Terebinthinse, P. G.; Terpentinöl, G.;

Essenza di trementina, It.; Esencia de trementina, Aceite volatil de trementina, Sp.

This oil is commonly called spirits (or spirit) of turpentine. It is prepared by distillation from our common turpentine, though equally afforded by other varieties. It may be distilled either with or without water, but in the latter case a much higher temperature is required, and the product is liable to be empyreumatic. To obtain it quite pure it should be redistilled from a solution of potassium hydroxide. The turpentine of Pinus palustris is said to yield about 17 per cent. of oil, while that from Pinus Pinaster affords 25 per cent., and that from Pinus sylvestris 32 per cent. Large quantities are distilled in North Carolina. The exportations of turpentine oil from the United States in 1913 amounted to 21,039,597 gallons, valued at $8,794,656; and in 1914, 18,900,704 gallons, valued at $8,095,958.

Pure oil of turpentine is "a colorless liquid having a characteristic odor and taste, both of which become stronger and less pleasant on aging or exposure to the air. Soluble in 5 volumes of alcohol. Specific gravity: 0.860 to 0.870 at 25° C. (77° F.). Optical rotation variable. Distil 200 mils of the Oil, at the rate of two drops per second, from a 300 mil globe flask, having the side tube 8 cm. above the bulb. Ninety per cent. of the Oil distils between 154° and 170° C. (309.2° and 338° F.), the temperature being read with the mercury column of the thermometer immersed in the vapor. Five mils of the Oil, shaken with an equal volume of potassium hydroxide T.S., does not become darker than a light straw yellow after standing twenty-four hours. Five mils of the Oil, evaporated in a small dish on a water bath, leaves not more than 0.1 Grm. of residue. Three drops of the Oil, placed on unsized, white paper, and exposed to the air, evaporates entirely without leaving a permanent stain (fixed oils). Five mils of the Oil shaken vigorously with an equal volume of hydrochloric acid in a test tube, and allowed to stand for a few minutes, does not produce a brownish or greenish color. Into a flask of from 35 to 50 mils capacity, having a long graduated neck (cassia flask), and containing 25 mils of fuming sulphuric acid, introduce very slowly, drop by drop, with constant shaking 5 mils of Oil of Turpentine, keeping the temperature just below 65° C. (149° F.) by immersion in cold water during the addition of the oil, and for five minutes thereafter, in the meantime frequently agitating the mixture cautiously but vigorously. Then cool, and add sulphuric acid until the flask is filled to the upper graduation on the neck. The clear, reddish, viscous layer, which forms after the dark mass has settled for two hours, does not exceed 1 per cent. of the volume of Oil taken. A large layer of colorless liquid with a refractive index of less than 1.5 at 20° C. (68° F.) shows the presence of mineral oil.

"Caution.—The addition of the Oil of Turpentine to the fuming sulphuric acid, drop by drop, is necessary because of the violence of the reaction." U. S.

As found in commerce, it is always somewhat ozonized, but when perfectly pure it consists exclusively of carbon .and hydrogen, and is composed of one or more terpenes, among which are pinene, which constitutes the major portion of the oil, and small amounts of camphene and fenchene with derivatives of pinene. The English or American oil (prepared from Pinus australis. is composed of dextro-pinene, while the French oil (prepared from Pinus Pinaster) is composed of laevo-pinene. On the other hand, the Russian turpentine contains, in addition to pinene, dipentene (or cinene) and sylvestrene, and the Swedish turpentine contains pinene and sylvestrene. Both the American and the French oil of turpentine boil at about 156° C. (312.8° F.). On heating oil of turpentine to about 300° C. (572° F.) in a sealed tube for several hours it is converted into a polymer called iso-terebenthene, C20H32, which is so oxidizable that it is converted into a viscid mass on exposure to the air for a few hours. It has, moreover, a marked odor, resembling oil of lemon, and boils at 176° to 177° C. (348.8°-350.6° F.). On treatment with a small portion of sulphuric acid, oil of turpentine yields an optically inactive liquid, which boils at 160° C. (320° F.). This is a mixture resolvable by repeated fractional distillation into terebene, C10H16, boiling at 150° C. (302° F.); cymene, C10H14, boiling at 175° C. (347° F.); a small quantity of a camphor-like body, boiling at 200° C. (392° F.); colophene, C20H32, boiling at 318° C. (604.4° F.), and a mixture of semisolid products of higher boiling point. Oil of turpentine absorbs hydrochloric acid gas, forming with it two compounds, one a red dense liquid, the other a white crystalline substance resembling camphor, and hence called artificial camphor. Both are mono-hydrochlorides, C10H16.HCl, but the latter is much more stable, and can be purified by crystallization from alcohol or ether. When turpentine oil is left in contact with concentrated hydrochloric acid a dihydrochloride is formed, C10H16.2HCl. This forms rhombic plates, insoluble in water, and decomposed by boiling with alcoholic potash, with formation of terpinol (C10H16)2.H2O. (Allen, Corn. Org. Anal., vol. ii, p. 51.) Nitric acid converts oil of turpentine into resin, and by long boiling into terebic acid, C7H10O4. Mixed with water and chlorinated lime, and then distilled, the oil yields a liquid which Chautard found to be identical with chloroform (J. P. C., 3e ser., xxi, 88). Turpentine oil and other terpenes unite with water to form crystals of terpin hydrate, C10H18(OH)2.H2O, which sublimes often from turpentine oil which has long stood in contact with water and has then been heated to water bath temperature. These crystals are sometimes found in the natural oil also. The presence of alcohol with the water and turpentine oil facilitates their formation. Thus, a mixture of 1 part of nitric acid, 1 part of alcohol, and 4 parts of turpentine oil, spread out in flat dishes, will yield within a few days crystals amounting to 20 per cent. of the oil taken. If these crystals be fused at 116° C. (240.8° F.) they will lose water, and terpin, C10H18(OH)2, will remain in crystalline needles, fusing at 104° C. (219.2° F.), and boiling at 258° C. (496.4° F.). If either of the hydrates just mentioned be boiled with sulphuric, phosphoric, or glacial acetic acid, terpineol, C10H17OH, will be formed along with hydrocarbons of the formula C10H16, such as terpinene, terpinolene, and dipentene. Terpineol is a thick, colorless, optically inactive liquid, with a pleasant hyacinthine odor and a bitter, feebly pungent taste. It is used extensively in perfumery. Baeyer (Ber. d. Chem. Ges., xxvi, p. 826) has also prepared the methyl ether of terpineol. Oil of turpentine may be made to yield cymene identical with that existing in the oil of cumin and with that obtained by dehydrating camphor. (See Cumin Seed; also see under Olea Volatilia.) Exposed to the air the oil absorbs oxygen, becomes thicker and yellowish, and loses much of its activity, owing to the formation of resin. A small proportion of formic acid is said also to be generated. Hence the older pharmacopoeias directed the oil to be rectified by distilling it with about four measures of water. But the process is difficult, in consequence of the great inflammability of the vapor, and its rapid formation, which causes the liquid to boil over. In this country it is scarcely necessary, as the recent oil can be obtained at an expense less than that which would be incurred by redistillation on a small scale. Another mode of purifying the oil is to agitate it with one-eighth of alcohol, which dissolves the resinous portion. About one-fifth of the alcohol is retained by the oil, but is readily separated by agitation with water. (See Oleum Terebinthinae Rectificatum.) For tests, see Proc. A. Ph. A., 1893, 156.

C. T. Kingzett has shown that the atmospheric oxidation of turpentine is accompanied by the formation of a body having the formula C10H14O4, which he regards as camphoric peroxide. This substance, by the action of water, is converted into hydrogen peroxide and camphoric acid. The disinfectant known as "sanitas" is produced by passing air through Russian oil of turpentine in contact with warm water. Berthelot has shown that oil of turpentine has, under certain conditions, the power, while undergoing oxidation itself, of causing the oxidation of other bodies, to which it imparts a portion of the oxygen absorbed from the air. All that is necessary to give this power to the oil is that soon after distillation it should be exposed to the air, as in a bottle half filled. Sunlight assists, but is not essential to, the change, which goes on even in the dark. The oil retains indefinitely the property thus acquired, but may be deprived of it by exposure to a boiling heat, or by agitation with reducing substances. No other chemical or physical change can be detected in the oil. (J. P. C., May, 1860, 351.)

In this country the oil of turpentine is frequently adulterated with petroleum distillates. The adulteration is best detected by the treatment with sulphuric acid followed by steam distillation of the oil layer remaining above the sludge acid; this treatment with acid and after-distillation to be repeated if necessary. The sulphuric acid will thus completely polymerize the essential oil, leaving the paraffin hydrocarbons unaffected in the residual oily layer. A shorter and more readily executed test with sulphuric acid, though not so complete, is now given in the official test of the U. S. P. IX.

Considerable quantities of a turpentine obtained by steam distillation of the so-called "lightwood," or resin saturated stumps and pieces of pine wood, have been offered in recent years. For an experimental study of this process and an account of the product see an article by Walker, Wiggins and Smith. (Chemical Engineer, Dec., 1905, p. 78.)

The several species of pine indigenous to California and the slopes of the Sierra Nevada appear to yield quite different products. Wenzell (A. J. P., March, 1872) described, under the name of abietene, an oil distilled from the exudation of the Pinus sabiniana (Nut Pine or Digger Pine). He found it to have a sp. gr. of 0.694, and to boil at 101° C. (213.8° F.). Sadtler (A. J. P., April, 1879, p. 176) examined an oil of turpentine from California said to have been obtained from the Pinus ponderosa (Heavy Pine), and found it to agree substantially with Wenzell's abietene. It had a sp. gr. at 16.5° C. (62° F.) of 0.6974, boiled at 101° C. (213.8° F.), and was slightly laevogyrate. It gave negative results when treated with hydrochloric acid for the formation of a hydrochloride, did not form a hydrate, and was not acted upon by sulphuric acid or by nitrosyl chloride. These anomalous results were at once explained by the publication of a study of the abietene which had been made by Thorpe, who showed (A. J. P., 1879, p. 293) that this exudation of the California pine is almost pure heptane, C7H16, one of the chief constituents of American petroleum. His results were also confirmed by Schorlemmer, who established the identity of the pine heptane with that from petroleum naphtha.

Uses.—The oil of turpentine is locally irritant and feebly antiseptic. It is absorbed through the mucous membrane of the alimentary canal and apparently also of the respiratory tract, and is eliminated partly with the breath to which it imparts its own odor, and through the urine to which it gives an odor resembling that of violets. After the ingestion of large doses it produces a sense of warmth in the stomach, accelerates the circulation, and causes a feeling of exhilaration associated with more or less vertigo and a sense of fullness in the head. These symptoms are attended frequently with nausea and frequently, although not always, succeeded by brisk catharsis. When given in small doses frequently repeated it at first stimulates the kidneys, augmenting the secretion of urine, but if the administration is continued too long it produces painful irritation of the urinary vessels amounting at times to violent strangury and may cause inflammation of the kidney with scanty, albuminous, or even bloody urine. In some constitutions it produces, even when taken internally, an erythematous eruption of the skin. Apparently enough may be absorbed after the inhalation of its vapor to irritate the urinary organs and it is stated that seamer of vessels loaded with turpentine sometimes develop strangury and hematuria.

Most of the therapeutic uses of the oil of turpentine may be attributed to its local irritant influence; thus during its elimination through the mucous membrane of the lungs it acts as a stimulant expectorant and is a useful remedy in chronic bronchitis. In the same way it acts as a stimulant to the kidney and is occasionally used as a diuretic, although this employment has largely passed out of vogue. As a carminative in flatulent colic it is one of the most valuable remedies we possess. It is sometimes of service for its local stimulant action for chronic diarrheas or dysentery. In typhoid fever it is useful not merely in tympanitic states for its carminative effects, but appears to have a direct influence upon the disease itself. According to the observations of Omelchenko (B. G. T., 1891), while it is very feeble in its general antibacterial properties it has a special toxicity for the typhoid bacillus and this organism will not grow in an atmosphere saturated with turpentine vapor.

Oil of turpentine has been used for many years in the treatment of hemoptysis. Of its mode of action we have no knowledge, but there is considerable clinical evidence as to its power to check bleeding; Smith (B. M. J., 1908, i, p. 1218) has even recommended it in purpura hemorrhagica. Among other conditions in which it has been from time to time recommended with more or less reasonableness, are helminthiasis, leucorrhea, chronic rheumatism, amenorrhea, and puerperal fever.

For ordinary purposes the dose is from 5 to 10 minims (0.3-0.6 mil) repeated every two to six hours as may be necessary. As a remedy against the tapeworm, the dose is from one-half to one fluidounce (15-30 mils), followed in half an hour by castor oil; the safety of these large doses is dependent upon the catharsis sweeping out 'the bowel before the turpentine can be absorbed. It is best administered in the form of an emulsion, although it is frequently given by dropping into a teaspoonful of sugar. The use of gelatin-coated capsules is not to be recommended because as soon as the gelatin dissolves in the stomach the undiluted oil comes in contact with the gastric mucosa and is liable to produce an undue degree of irritation. Lacambre gives the following process for making a pill of the oil. Take of oil of turpentine 8 grammes, white wax 20 grammes, powdered sugar 9 grammes, oil of lemon, 2 drops. Melt the wax in the oil of turpentine, pour into a mortar, allow to cool, then add the sugar and oil of lemon, and form a mass to be divided into pills of 0.2 or 0.25 Gm. (3 or 4 gr.) each. Roll them in powdered starch, and keep in a well-stoppered bottle. (J. P. C., Sept., 1873, p. 223.)

In the form of an enema the oil of turpentine is highly useful in obstinate constipation, tympanitis, and seat-worms. From one-half to two fluidounces (15-60 mils) may be added to a pint of warm soapsuds.

Externally it is an excellent rubifacient and is widely employed in the form of liniments in various rheumatic affections as lumbago, arthritis, neuralgias, and the like. For this purpose it should be diluted with from one to three parts of cottonseed or other bland oil. In the form of turpentine stupe it is advantageously employed as a counter-irritant in various deep-seated inflammations, especially of the abdomen. The turpentine stupe is made as follows: a piece of flannel is wrung out in hot water and then dipped in previously warmed turpentine, quickly wrung out and applied to the part. It was also formerly employed as a local application to burns in which it was supposed to allay the pain and promote healing. For this purpose it was usually mixed with the rosin cerate so as to form a liniment capable of being spread upon linen (see Linimentum Terebinthinae).

The following is the formula adopted many years ago by the Philadelphia College of Pharmacy for the rubefacient liniment known as British Oil, which is still in use in some parts of the country as a popular remedy. Oil of Turpentine, Linseed Oil, of each, 8 fl. oz., Oil of Amber, Oil of Juniper, of each, 4 fl. oz., Barbados Petroleum 3 fl. oz.. Crude American Petroleum 1 fl. oz.

It has likewise been recommended as a local application in parasitic skin diseases, especially pediculus capitis. The inhalation of its vapors has been employed in chronic bronchitis and has been especially recommended by Skoda in gangrene of the lungs.

For internal use the rectified oil should be used. (See Oleum Terebinthinae Rectificatum.)

Dose, five to ten minims (0.3-0.6 mil).

Off. Prep.—Linimentum Terebinthinae, U. S.; Oleum Terebinthinae Rectificatum, U. S.; Linimentum Opii Compositum, N. F.; Linimentum Terebinthinae Aceticum, N. F.; Linimentum Tiglii Compositum, N. F.; Petroxolinum Sulphuratum Compositum, N. F.

The Dispensatory of the United States of America, 1918, was edited by Joseph P. Remington, Horatio C. Wood and others.