KETONES AND ALDEHYDES. The ketones and aldehydes were removed from each fraction by shaking with a concentrated solution of acid sodium sulphite, keeping the mixture cool during the reaction. The crystalline precipitates were filtered by suction through muslin, and dried. A second precipitation with sulphite was always attempted. As in the hard oil, the precipitates from the lower fractions were distinctly crystalline and became more gelatinous with the higher fractions, but, curiously, when the higher fractions were reached, viz., from 100° upward, the precipitates became crystalline again. In filtering the lower fractions a strong odor as of acrolein was developed. The precipitates contained very small quantities of aldehydes. Assuming that half the weight of the dried precipitate is the volume of the ketone the following approximation is reached. It will be seen that while there is not nearly so large a percentage of ketones in the fir as in the hard oil yet there are marked accumulations at 55°-60° (this is probably acetone), at 70°-75°, at 85°-90°, and at 135°-140°. We attempted to separate the ketones from the sulphite fractions, but the quantities were too small to be of use in further investigation. However, in the fraction 125°130° a test was made for mesityl oxide which was not found by Mr. Fraps in the hard oil. The solution was distilled with strong caustic soda and a strong odor of peppermint was developed, showing the possible presence of mesityl oxide. ETHEREAL SALTS. The residual oil after removal of the ketones was dried and fractionated. The fractions were shaken with a caustic soda solution (14) for fifteen to twenty hours. To accomplish this the glass-stoppered bottles were fastened to the face of a wooden pulley about 8 inches in diameter which made nine revolutions per minute. The oils were measured before and after saponification and the loss in volume was considered to be due to the saponification of ethereal salts. This loss was for each fraction as follows: It will be observed that there are marked accumulations at certain temperatures and also that there is no marked decrease in the amount of oil saponified as the boiling-point of the fraction rises. In the higher boiling fractions a gummy solid of a yellow color was formed, which while insoluble in water dissolved easily to a purple solution in nitric, hydrochloric, or sulphuric acids. This color was not destroyed by boiling but disappeared on standing and on addition of water. No attempt to discover its nature was made. The caustic soda solutions of the ethereal salts were distilled to remove alcohols. No odor of ammonia was developed. The alcoholic distillates were all found to contain methyl alcohol by the test of Mulliken and Scudder.1 The alcoholic distillates were also treated with iodine and caustic potash and always gave a decided test for ethyl alcohol. The acids were now freed by addition of sulphuric acid and distilled. The silver salts precipitated from the fraction boiling at 40°-50° gave 68.74 per cent. silver. Calculated percentage of silver in silver formate is 70.59; in silver acetate 64.66. The acid was therefore probably a mixture of the two, since methyl formate boils at 30.4° and some of the oil passed over before that temperature was reached. The silver salt of the 50°-55° fraction gave: 1 Am. Chem. 1., 24, 444. Percentage of silver... .... Found. Formic acid. Acetic acid. 64.66 This result we take to indicate the presence of ethyl formate (54.9°) and methyl acetate (57.3°). The silver salt from fraction 55°-60° gave 64.99 per cent. of silver (calculated for acetic acid, 64.66). It hence consisted almost entirely of methyl acetate (57.3°). The presence of acetic acid was also indicated by qualitative tests in fraction 70°-75°. Satisfactory results from the silver salt were not obtained because of the small quantity at our disposal. The same statements apply to fractions 75°-80° in which the boiling-point and odor indicate the presence of methyl propionate (79.5°). From the fraction 102°-105°, by acidifying with sulphuric acid, an oil separated which was by odor butyric acid and indicates the presence of methyl butyrate (102.3°). The investigation was necessarily interrupted at this point but will probably be taken up at some future date. There seems to be enough of interest in the wide difference between this oil and that from other varieties of wood to warrant further investigation. SEATTLE, WASH., March 3, 1902. INVESTIGATION OF THE OIL OF THE RED ELDERBERRY, "SAMBUCUS RACEMOSA ARBORESCENS." BY H. G. BYERS AND PAUL HOPKINS. Received May 17, 1902. On the western slopes of the Cascade Mountains and on the lowlands about Puget Sound grow great quantities of a red elder-. berry which, by reason of its large size, is denominated a variety of the species racemosa. The berries are a bright crimson and serve as food for birds but because of an unpleasant odor and the presence in them of a considerable quantity of a yellow oil are not used by the people as food nor are they converted into wine. An investigation of this oil was made with the following results. From about 10 gallons of the berries it was possible to get about 500 cc. of the oil by pressing the juice from berries and ex tracting with ether the layer of crude oil which rose to the surface of the liquid. The oil as obtained from the ether solution by spontaneous evaporation is of a light yellow color but darkens markedly on standing or when the ether is evaporated by means of a water-bath. The oil has a specific gravity of 0.9072 at a temperature of 15° C. It solidifies at 8° and melts at about o°. It has no definite boiling-point but decomposes when distilled even at a pressure of 20 mm. It proved to be a mixture of the glycerides of the fatty acids and contains 6.65 per cent. free acid calculated as oleic acid. Because of a marked resemblance to olive oil a very careful determination of its constants and composition was made. Unsaponifiable Matter.-The unsaponifiable matter of the oil, which contained the characteristic odor of the oil, formed 0.66 per cent. of the whole. It crystallizes in light yellow hexagonal plates. Glycerol. The fats were saponified and the glycerol determined, the amount being 11.4 per cent. Fatty Acids. The lead salts of the acids were made and thoroughly extracted with ether in a Soxhlet apparatus. The insoluble residue was converted into its barium salt and crystallized from alcohol in three fractions. These fractions gave the following results when their barium content was determined as barium sulphate. The crystals from the first two fractions were white plates. The third fraction was discolored by the impurities of the motherliquor. The oil evidently contains no saturated fatty acid save palmitic acid. The solution of the lead salts in ether was fractionally crystallized and converted into the barium salt. The barium salt was refractionated and the barium determined in the first fraction. The iodine absorption of the fatty acid from this fraction was also 90.6 and 89.5, the calculated value for oleic acid being 90.07. A number of fractional precipitations of the potassium salt of the mixed acids were made from a weakly ammoniacal solution by means of barium chloride. The iodine numbers of the free acids from these fractions were: The fatty acid from VII and VIII was highly colored and somewhat impure from oxidation, yet the results indicate the presence of an acid, probably linoleic, having an iodine absorption greater than that of oleic acid. If linoleic acid, it is present to an extent of not less than 7-8 per cent. The presence of soluble acids was determined by the method of Muter.1 The Reichert-Meissl number being but 1.54, thus showing the practical absence of butyric or other volatile acid, the results of the titrations were calculated to an acid having a molecular weight of 136, which is the mean of the molecular weights of capric, caprylic, and caproic acids. The results showed the presence of 2.95 per cent. of these acids. The quantity of palmitic and oleic acids was determined by Lang's "Modification of Muter's Method". The results show oleic acid and linoleic acid 72 per cent.; palmitic acid 21.66 per cent. The saponification equivalent was found to be 209.3. The Hehner number is 91.75. From the results indicated in the foregoing discussion the properties and composition of the oil are as given below. For convenience of comparison the corresponding values for olive oil are given in parallel. 1 Allen's "Commercial Organic Analysis," Vol. II, Part I, p. 189. 2 Pharm. J., 59, 61. .... .... |