Part 4

BOTANICAL DESCRIPTION AND DISTRIBUTION.

Ramona stachyoides (Benth.) Briquet (synonyms--Audibertia stachyoides Benth., Salvia mellifera Greene), commonly known as black sage (figs. 1 and 2), is a shrubby aromatic perennial, occurring from middle to southern California on low hills from April to June. The shrub attains a height of 3 to 6 feet and possesses herbaceous leafy branches with oblong leaves, green and wrinkled above and ash colored and hairy below. The flowers are white or lilac and in whorls or heads. The leaves have a strongly aromatic and decidedly camphoraceous odor, the woody branches being very brittle and also strongly aromatic.

DISTILLATION OF THE OIL.

A quantity of the fresh herb partly in bloom, including the flowering tops, branches, and leaves, was distilled by steam in the vicinity of Los Angeles, Cal., in April, 1908, and yielded 0.75 per cent of oil. The oil was nearly colorless and possessed a penetrating, camphoraceous, yet agreeable odor, with a bitter, camphorlike taste. At 24° C. the specific gravity was found to be 0.9144; specific rotation A_{D} = +30.2°; re-fraction at 24° C., 1.4682. The oil was soluble with clear solution in 1½ volumes of 70 per cent alcohol, becoming turbid with 3½ volumes or over.

SEPARATION OF STEAROPTENE.

Owing to the very strong camphoraceous odor of the oil, a separation of the stearoptene suggested itself. In order to separate a solid body which is held in solution by a volatile oil, the “freezing-out” method is usually employed. Accordingly 100 grams of the oil were subjected to a freezing mixture of ice and salt. A temperature of -15° C. was attained, and flaky crystals formed throughout the oil. The crystals were separated by being thrown on a force filter and the remaining oil again subjected to the cold, when a second lot was obtained, which was likewise separated. A total of 11.3 grams of crystals was separated, corresponding to a yield of 11.3 per cent. These crystals were soft and flaky in nature and possessed the characteristic odor of camphor.

IDENTIFICATION OF CAMPHOR.

In order to identify the crystalline substance obtained from the oil, a small quantity was sublimed, and the usual tests of melting point, boiling point, and rotation were applied. For further recognition of the compound, an attempt was made to prepare an oxime. Accordingly the method of Auwers was applied, which, briefly, is as follows: To a solution of 10 parts of camphor in 10 to 20 times the amount of 90 per cent alcohol is added a solution of 7 to 10 parts of hydroxylamine hydrochlorid and 12 to 17 parts of a soda solution. If turbidity results, more alcohol is added and the mixture is heated on a water bath until a small portion of the solution remains clear upon the addition of water or until the resulting turbidity disappears, when a few drops of soda solution are added and no free camphor remains. The mixture is then diluted with water, filtered if necessary, and neutralized with dilute hydrochloric acid. The camphor oxime which separates is recrystallized from alcohol or ligroin. It melts at 118° to 119° C.

The above method applied to the sublimed crystals resulted in the formation of an oxime which melted at 120° to 124° C. Since an oxime was obtained (indicating possible ketonic characters), application was made of another reaction for ketones, namely, the formation of semicarbazone. Tiemann’s method for the preparation of camphor semicarbazone was applied. The method is as follows: 1.5 grams of camphor dissolved in 2 cubic centimeters glacial acetic acid are treated with a solution of 1.2 grams of semicarbazid hydrochlorid and 1.5 grams of sodium acetate in 2 cubic centimeters of water. Water is added and the crystalline compound recrystallized from alcohol. The melting point of camphor semicarbazone is 236° to 238° C.

The sublimed crystals when treated in the above manner yielded a semicarbazone which melted at 232° C.

For a comparison of this substance with pure camphor, a tabulation was made of the more common physical properties and chemical tests.

+Table I.+--Comparison of properties of crystals from oil of black sage and of pure camphor.

---------------+-------------------------+------------------------ Test. | Crystals from | Crystals of pure | oil of black sage. | camphor. ---------------+-------------------------+------------------------ Melting point. | 174° to 175° C. | 175° C. Boiling point. | 205° C. | 204° C. Rotation in | +3.33° (20 per cent | +3.51° (20 per cent 50 mm. tube. | solution in alcohol). | solution in alcohol). Oxime. | M. p. 120° to 124° C. | 118° to 119° C. Semicarbazone. | M. p. 232° to 233° C. | 236° to 238° C. ---------------+-------------------------+------------------------

The table shows very close similarities in the melting point, boiling point, and rotation of the crystals from the oil of black sage and of pure camphor. The melting points of the oximes and semicarbazones, though not corresponding so well, seemed to indicate that the crystals were in all probability camphor. To further confirm the assumption that the compound from the oil was camphor, an elementary analysis of the compound was made after being twice sublimed.

0.1273 gram of crystals gave 0.1199 gram H_{2}O, corresponding to 10.5 per cent hydrogen.

0.1273 gram of crystals gave 0.3228 gram CO_{2}, corresponding to 79.7 per cent carbon.

C{10}H{16}O/camphor requires { 79 per cent carbon. { 10.5 per cent hydrogen.

0.1279 gram of crystals gave 0.1244 gram H_{2}O, corresponding to 10.8 per cent hydrogen.

0.1279 gram of crystals gave 0.3761 gram CO_{2}, corresponding to 79.9 per cent carbon dioxid.

The combustion results seemed to indicate that the compound is identical with that of camphor, as the above tabulation also clearly shows.

CHEMICAL EXAMINATION OF THE OIL.

CHEMICAL CONSTANTS.

Preliminary to the detailed chemical examination of the oil the usual chemical constants were determined.

By neutralization of a weighed quantity of the oil with standard potassium hydroxid V. S., the acid number (the number of milligrams of potassium hydrate required to neutralize 1 gram of oil) was found to be 2.

The ester number (the number of milligrams of potassium hydroxid required to saponify the esters in the oil) was found to be 2.5, which, calculated as bornyl acetate, corresponds to 0.88 per cent.

The ester number after acetylization of the saponified oil with acetic anhydrid (and which represents the total amount of alcohols present) was 27.1, which, calculated as borneol, represents a total of 7.58 per cent of borneol in the oil, both free and in combination.

FREE ACIDS.

The original oil was slightly acid, as indicated by the acid number previously mentioned. The free acid was shaken out from a quantity of the oil with a 10 per cent solution of sodium carbonate. The shaking was repeated several times and the alkaline liquids united. The united alkaline liquids were shaken out with ether in order to remove any oil held in suspension. The sodium-carbonate solution was then evaporated to a small bulk on a water bath, acidified with sulphuric acid, and distilled with steam. No oily globules separated, showing absence of higher insoluble acids. The distillate, which was decidedly acid, was neutralized with sodium-carbonate solution and evaporated to a small volume. The liquid which now represented the sodium salts of the free acids present in the oil was precipitated fractionally with a dilute silver-nitrate solution. Four fractions resulted. Each fraction was dried to constant weight and burned.