Oleum Sassafras. - Sassafrasbl. - Essence de Sassafras.

Origin and History. The sassafras tree, Sassafras officinale, Nees., family Lauraceae, is widely distributed over the American continent from Canada to Florida and Alabama, and westward as far as Kansas6) and northern Mexico. In the southern states it often attains a height of 15 m. and the trunk a thickness of 1/3 m.

Contrary to earlier statements, the older bark and the wood are odorless. When crushed, the green parts of the tree are slightly aromatic, but do not smell of safrol. The wood of younger stems contains oil cells which disappear later. The wood of the roots is richer in oil cells, more particularly the root bark.

1) Zeitschr. d. allg. osterr. Apoth. Ver. 29 (1891), 2.

2) Forsch.-Ber. ub. Lebensmittel u. i. Bezieh. z. Hyg. 1 (1894), 13.

3) Schimmel's Bericht October 1888, 42.

*) Arch, der Pharm. 228 (1890), 22 and 687.

■) Liebig's Annalen 258 (1890), 340. - Arch, der Pharm. 229 (1891), 116. 6) R. J. Brown, Medicinal Flora of Kansas. - Proceed. Americ. Pharm. Ass. 29 (1881), 446.

Fig. 43. One of the smaller sassafras stills in Virginia.

Fig. 43. One of the smaller sassafras stills in Virginia.

The distillation of sassafras Oil began early in the past century. Like that of wintergreen oil and sweet birch oil, it has been carried out in the most rudimentary fashion up to the present time1). The still consisted of a barrel of heavy oak staves, the bottom of which was many times perforated. The barrel was tightly fitted into a conical iron vessel. The lid of the barrel was so arranged that it could be removed for filling the barrel with sassafras bark and put back steam-tight. An iron pipe, twice bent at right angles, was placed in a hole bored in the lid. The long arm turned downward passed through a barrel which served as condenser and which was supplied with cold water. The iron vessel was filled with water almost up to the perforated bottom of the barrel. The water was kept boiling, and was replaced as evaporation required until the bark was completely exhausted.

This method of distillation was very slow but was carried out by the farmers themselves. Moreover, the cost of production consisted merely of the price of the cheap utensils and the labor.

In recent years the distillation has been conducted more rationally. The unpeeled roots are delivered in logs about a meter in length. With the aid of a saw mill, mostly driven by water power, they are cut into thin slices. Through a hopper they are transferred directly to the still constructed of 3 inch pine planks. This still, 4 to 5 ft. high and 12 ft. square, is held together by iron bands. One of the side walls is provided with two tight fitting doors: one above for filling, the other below for discharging. The steam generated in a boiler is conducted by means of a pipe into the bottom of the still and then passes through the root wood resting on a false bottom. The vapors saturated with oil are condensed by means of a worm cooler and the distillate is collected in a large copper flask with a capacity up to 20 gal. About two inches from the bottom the receiver is provided with a stop cock through which the oil is drawn off from time to time. After the wood has been exhausted the still is emptied, the wood is dried by exposure to the sun and utilized as fuel under the boiler.

1) W.Procter jr., Proceed. Americ. pharm. Ass. 14 (1866), 211 to 222. - Americ. Druggist 1887, 45. - New Remedies (New York) 1883, 224. - Oil, Paint and Drug Reporter, Sept. 14.1891. - Pharmaceutical Journ. III. 22 (1891), 491.

Fig. 44. Sassafras saw mill and still in Lexington (Virginia).

Fig. 44. Sassafras saw mill and still in Lexington (Virginia).

A still of this description has a capacity of about 20000 lbs. and the distillation of this quantity lasts about 48 to 50 hrs.

The root bark yields 6 to 9 p.c, the root wood somewhat less than 1 p.c. of oil.

Up to the middle of the past century the distillation of sassafras oil was conducted principally in the states of Pennsylvania, Maryland and Virginia, Baltimore and Richmond being the principal commercial centres for this oil. At the beginning of the civil war, in 1860, as much as 50000 lbs. of sassafras oil are said to have entered the market from Baltimore alone1). After the sixties much oil was also distilled in New jersey, New York, Ohio, Indiana, Tennessee and Kentucky2), as well as in the New England states, until the lack of trees in many parts of these states rendered the enterprise unprofitable.

Properties. Sassafras oil is a yellowish or reddish-yellow liquid with an odor of safrol and an aromatic taste. d15o1,070 to 1,080; aD + 2 to +4°; nD20o about 1,530; A. V. 0; E. V. 1 to 2; soluble in all proportions of 95 p.c. alcohol and in 1 to 2 vol. of 90 p.c. alcohol. An oil distilled by Schimmel & Co.3) (yield 3,25 p.c.) had the following properties: d16o1,075; aD + 2°14'; nD20o1,52885; A. V. 0; E. V. 1,9; soluble in 1,8 vol. or more of 90 p.c. alcohol. 100 cc. of oil were distilled from an ordinary fractionating flask and the distillate collected in fractions of composition. The odor and the most important properties of the sassafras oil are due to its principal constituent, safrol, C10H10O2. This substance was observed by Binder1) in 1821, it having separated out in a crystalline condition from the oil. Later investigators2) restricted their experiments to the action of chlorine, bromine, etc. on the oil and the safrol contained therein. Thus, while Faltin8) neutralized with lime and distilled with steam an oil that had been saturated with chlorine, he discovered a second constituent, viz., the ordinary camphor4).

d15o

aD

1,0066

+ 5°40'

1,0546

+ 4°36'

1,0764

+ 3°55'

1,0830

+ 2°57'

1,0877

+ 2°5'

1,0916

+ 1°30'

1,0930

+ 0°45'

1,0942

+ 0°12'

1,0905

- 0°19'

1,0770

1) Alpheus P.Sharp, Americ. Journ. Pharm. 35 (1863), 13. - W. Procter, ibidem 33 (1861), 1 and 38 (1866), 484.

2) F. Rabak, Americ. Perfumer 5 (1910), 220. 3) Report of Schimmel & Co. April 1906, 61.

10 cc. each: - .

1.

208 to 216°

2.

216 „ 221°

3.

221 „ 225°

4.

225 „ 225°

5.

225 „ 226°

6.

226 „ 227°

7.

227 „ 228°

8.

228 „ 229°

9.

229 „ 234°

10.

Residue

Fig. 45. Grubbing of sassafras roots.

Fig. 45. Grubbing of sassafras roots.

The name safrol was introduced by E. Grimaux and ). Ruotte5) who also ascertained the composition of the substance as C10H10O2. In addition, they isolated a fraction C10H16 boiling between 155 and 157° and named the hydrocarbon safrene. They also observed a phenol which had the odor of cloves and which yielded a green color with ferric chloride. Its identity with eugenol was later established by Pomeranz").

A better insight into the composition of the oil, however, was first obtained by Power and Kleber7) who examined an oil distilled by themselves.

The air-dried root bark yielded 7,4 p.c. of oil; d15o1,075 and aD+3°16'. After most of the safrol had been removed by freezing, the eugenol (m. p. of benzoyl eugenol 69°) was shaken out with lye. The oil, freed from both safrol and eugenol, wasthen fractionated. Fraction 155 to 160° revealed itself as u-pinene (m. p. of nitrol benzylamine base 123°). Fraction 160 to 175° contained phellan-drene as was shown by its nitrite. Hence the so-called safrene of Grimaux and Ruotte is nothing more nor less than pinene.

From the next higher fraction camphor (m.p. of camphor-oxime 115°) separated which proved to be the common dextro1) Buchner's Repertorium f. d. Pharm. 11 (1821), 346.

2) Bonastre, Journ. de Pharm. et Chim. II. 14 (1828), 645; Trommsdorff's Neues Journal der Pharm. 19, I. (1829), 210. - Saint-Evre, Annal. de Chim. et Phys. III. 12 (1844), 107. - Compt. rend. 18 (1844), 705; Liebig's Annalen 52 (1844), 396.

3) Liebig's Annalen S7 (1853), 376.

*) The statement made by G. R. Pancoast and W. A. Pearson (Americ. Journ. Pharm. 80 (1908), 219), viz., that sassafras oil contains no camphor is evidently based on an insufficient knowledge of the literature upon this subject.

5) Compt. rend. 68 (1869), 928.

6) Monatsh. f. Chem. 11 (1890), 101; Chem. Zentralbl. 1890, II. 62. 7) Pharm. Review 14 (1896), 101.

gyrate modification. Its quantitative determination - reduction to borneol and acetylation of this alcohol - showed that the oil contains 6,8 p.c. of camphor. Fraction 260 to 270° presumably contains a sesquiterpene.

According to this investigation, oil of sassafras consists of 80 p.c. safrol, 10 p.c. pinene and phellandrene, 6,8 p.c. d-camphor, 0,5 p.c. eugenol, high boiling portions, sesquiterpene and residue about 3 p.c. = 100,3 p.c.

Adulteration. In America sassafras oil is very often adulterated with camphor oil. Indeed it may be said that a strictly pure oil is rarely met with in commerce. Inasmuch as camphor oil contains all the constituents of sassafras oil, its detection is exceedingly difficult. It can be proved only when the physical constants, more particularly the boiling temperature, deviate greatly. Fractions of camphor oil, the specific gravity of which correspond to that of sassafras oil, are sold as "artificial sassafras oil".