Part 8

The fractions yielded the following percentages of cineol: 1, 40 per cent; 2, 70 per cent; 3 and 4, 43.7 per cent. Calculating from the original oil as a basis, the above results correspond to 19.7 per cent of cineol in the original oil.

Fenchone.--Fraction 5, boiling from 190° to 195° C., was a heavy liquid with a strong camphorlike odor. Pure levo fenchone from thuja oil is an oily liquid with a strong camphoraceous odor; boiling at 192° to 194° C.; specific gravity at 19° C., 0.946; (A_{D}) -66.9°.

An oxime was prepared from the fraction by reaction with hydroxylamine hydrochlorid according to the method of Wallach, which is as follows: To 5 grams of fenchone dissolved in 80 cubic centimeters of absolute alcohol is added a solution of 11 grams of hydroxylamine hydrochlorid in 11 grams of hot water. Six grams of powdered potash are added. The oxime separates in the form of crystals, upon standing for some time. Recrystallized from alcohol it melts at 164° to 165° C.

The oxime formed from the fraction by the above method, after recrystallization from ethyl acetate, melted at 170° C.

Provided that fraction 190° to 195° C. consists chiefly of fenchone the oil should contain 8 to 10 per cent of this compound.

Borneol.--The total amount of borneol contained in the oil was determined by the saponification of a small quantity of the original oil and subsequently fractionating the saponified oil. Twenty-five grams of the saponified oil were carefully fractionated and then refrigerated, 7.5 grams of borneol separating out. This corresponds to a total of 30 per cent borneol. After the separation of the borneol the oil was again fractionated, and the portion above 195° C. yielded, when frozen, an additional 2 grams of borneol, making a total of 9.5 grams, or 38 per cent, of total borneol separated from the oil. The theoretical quantity of borneol in the oil, as shown by the acetylization value, is about 43 per cent, the lower percentage which was actually obtained being caused by incomplete separation due to the smallness of the amount saponified.

Esters of borneol.--A careful examination of Table IV shows that the esters of borneol, possibly chiefly bornyl heptoate and valerianate, are found in the fractions boiling above 190° C., principally in the highest boiling fractions; a perfect separation of these esters was not feasible because of the existence of the esters as mixtures of several acids. The ester numbers of the fractions, however, show the distribution of the esters at the different temperatures.

SUMMARY.

Briefly summarizing the results of the analyses, the oil of wild sage may be said to be composed: (1) Of total borneol camphor, 43 per cent, of which about 6.8 per cent exists as bornyl heptoate (calculating the esters of the oil as heptoic acid salts of borneol), leaving 35.8 per cent of free borneol camphor present in the oil; (2) of cineol (eucalyptol), 18 to 20 per cent; (3) of fenchone, 8 to 10 per cent; (4) of free acids, chiefly œnanthylic, or heptoic, acid, 0.58 per cent, with traces of formic and caprylic acids; (5) of combined acids in form of esters, chiefly, œnanthylic acid, with smaller quantities of valerianic, undecylic, and formic acids. It is very probable that a small amount of terpenes were also present in the portion distilled below 175° C., which, however, were not identified.

As will be noted from the above, the chief constituents of the oil of wild sage are borneol camphor and cineol, each of which possesses valuable antiseptic qualities. Since there is a high percentage of these constituents, the oil from this wild plant should prove of value for medicinal purposes. Another important use of the oil is suggested by the high content of borneol, a constituent which finds application in celluloid manufacture, and which is readily separated from this oil. Lastly, combining the agreeable aromatic quality with its antiseptic qualities, the oil should prove important as an ingredient of medicinal soaps or as a scenting substance.

Inasmuch as the wild sage plant grows chiefly on sandy and stony hills which are practically waste lands and which require but little moisture, it would seem that the plant could be cultivated in various sections of the Northwestern States.

SWAMP BAY.

BOTANICAL DESCRIPTION AND DISTRIBUTION.

Persea pubescens (Pursh.) Sarg., commonly known as swamp red bay or swamp bay (figs. 5 and 6), is an aromatic evergreen tree attaining a height of 30 feet or more, but usually occurring as a shrub. The leaves and twigs of the tree possess a pleasant camphoraceous odor. The swamp bay occurs abundantly in swamps and hammocks from North Carolina to Florida and Texas. The tree is a member of the family Lauraceæ, to which the camphor tree belongs.

DISTILLATION OF THE OIL.

Because of the strong camphoraceous odor and its close relationship to the camphor tree, the extraction and possible utilization of the oil from this wild aromatic plant suggested itself. Accordingly, during the summer of 1910, with the assistance of Mr. S. C. Hood, in charge of the station at Orange City, Fla., a small quantity of the leaves and twigs of this plant was distilled and a yield of about 0.2 per cent of oil was obtained. But with proper conditions and precautions the yield could no doubt be very materially increased, depending largely upon the time at which the distillation is made, and also upon the proportion of twigs and branches included. The above distillation was made late in the summer, long after the blossoming period, the stage at which a plant is usually most productive in volatile oils, and the material also contained many branches and much woody matter.

The oil obtained was pale yellowish brown in color, with a strongly aromatic and camphoraceous odor, and a persistent bitter, slightly pungent, and camphorlike taste. The specific gravity at 25° C. was 0.9272; specific rotation, A{D} = +22.4°; refraction, N{D} 25° = 1.4695. The oil was soluble in one-third its volume of 80 per cent alcohol, becoming faintly turbid upon the addition of five volumes or more of alcohol.

CHEMICAL EXAMINATION OF THE OIL.

CHEMICAL CONSTANTS.

A preliminary examination of the oil disclosed considerable free acidity, the acid number being 2.8, while the ester content was rather low, the ester number being 14.5. The low ester number would seem to indicate a low percentage of alcoholic compounds in combination with acids, and would correspond to 4.9 per cent of esters calculated as the acetate of borneol. After acetylization of the oil with acetic anhydrid the saponification number was found to be 64, which corresponds to 14.6 per cent of free alcohol, calculated as borneol.

In order to identify conclusively the constituents of the oil and the forms in which they occur, and to separate quantitatively the predominant constituents, the oil was subjected to a more careful and detailed analysis.

FREE ACIDS.

The free acidity of the oil as indicated by the preliminary tests was removed by shaking with 10 per cent aqueous sodium carbonate solution in several portions. The aqueous alkaline extracts, after being deprived of any adhering oil by extraction with ether, were concentrated, acidified, and distilled with a current of steam. The acids which were obtained separated principally as oily globules on the aqueous distillate, which was only faintly acid.

The free insoluble acids which were separated from the aqueous distillate by extraction with ether and evaporation of the solvent were neutralized with a solution of potassium hydroxid and then precipitated in fractions with a solution of silver nitrate.

Fraction 1. 0.0227 gram silver salt gave 0.0130 gram silver = 57.2 per cent silver.

Fraction 2. 0.0213 gram silver salt gave 0.0119 gram silver = 55.8 per cent silver.

It appears from the above results that the only acid existing in the free state in the oil is butyric acid, since silver butyrate gives theoretically 55.3 per cent of silver, fraction 1 being slightly contaminated, due possibly to a slight excess of potassium hydrate which was added when the acids were neutralized and which would appear in the first precipitate.

From the remaining faintly acid distillate, after neutralization with barium carbonate and concentrating, only a trace of precipitate, insufficient for silver determination, resulted upon the addition of silver nitrate solution. The butyric acid detected in the free insoluble acids was evidently extracted by the ether, in which it is very soluble.