As the compound gave reactions for Cl., determinations of that halogen were made according to Pringsheim's method by oxidizing the alkaloid with sodium peroxide. This method was used as it was thought possible that a replacement of Cl for OH had taken place. The method was, however, proven at this time to fail almost completely in oxidizing another, probably closely related alkaloid, and as it gave results for approximately but one atom of Cl in this case, the method of Carius, using 2 Cc. of fuming nitric acid and heating to 300°, was employed. The results from the two methods were made for HCl combined with the base to form the hydrochlorate, by dissolving the latter in water and precipitating with silver nitrate in the usual way. The results again were identical with those previously obtained. The conclusion therefore is that the hydrochlorate of the alkaloid was formed during the reaction and that no Cl was tubstituted in the molecule. A number of combustions for C, H and N were made, but al though they agreed fairly well among themselves, would not harmonize with any formula that would answer for Cl. The same must be said of the platinum compounds obtained. It is quite possible that we have here a condition such as obtains in the production of cotarnine upon the decomposition of marcotine and of hydrastinine, that a basic as well as a second, possibly acid, product result from the action of PCs upon the alkaloid, and that the nucleus of ẞ-homochelidonine is isoquinoline. As the material at our disposal is now exhausted, this part of the investigation will have to rest until more material can be obtained. Several attempts were made to obtain an acetyl compound of B-homochelidonine with both acetyl chloride and acetic anhydride, to determine the presence of OH, but so far these attempts have not been successful. A small amount of B-homochelidonine was fused with potassium hydroxyde. The fusion gave reactions indicating protocatechuic acid. Lack of material prevents further work in this direction at this time. Acids of Bocconia Cordata. Murrill and Schlotterbeck extracted Bocconia which had been moistened with ammonia water and dried, with chloroform. The mark was percolated with water and the percolate run down to a small volume. In this way a small quantity of a dry, dirty, gritty powder and a thick liquid containing the ammonium salts of the acids of the drug were obtained and placed aside for the time. As much of the powder as possible was dissolved in boiling water, strained through cloth and filtered. The residue was dissolved in hot dilute hydrochloric acid, boiled with purified animal charcoal and filtered and thrown out with ammonia. This was found to consist mostly of calcium phosphate. The aqueous percolate contained a large amount of nearly black gummy matter which was thrown out by pouring the aqueous liquid into a large volume of alcohol and decanting. The alcohol was recovered by distillation and the solution evaporated to about 250 Cc. This was then mixed with about ten times its volume of alcohol and set aside to crystallize. After standing for several days at a temperature of about -18° (0° F.) the entire surface of the flask became covered with beautiful hexagonal, microscopic, transparent crystals. We have not had time yet to ascertain their identity. School of Pharmacy, University of Michigan, June, 1905. The Volatile Oils: 1904. By I. W. Brandel. 4. American Oil (Spirit) of Turpentine. G.-H.-K., p. 239. Properties. According to Vezes and Mouline 1 turpentine oil and absolute alcohol are miscible in every proportion and do not separate even when the temperature is lowered considerably. Solutions of turpentine oil and aqueous alcohol cannot be so cooled without separating. The separation-temperature at constant pressure depends upon the strength of the alcohol and the proportion of the quantities of alcohol and turpentine oil. The authors have determined the separation-curves of a large number of mixtures of oil of turpentine and aqueous alcohol of various degrees of concentration and by combining the separation-curves thus obtained, have ascertained the separation-plane of the ternary mixture oil-alcohol-water. 1 Bull. Soc. Chim. (3) 31, p. 1043. By heating equal parts of oil of turpentine and salicylic acid to 130° for 50 hours, and removing the excess of acid with NaOH, and the liquid fractionated under diminished pressure, Tardy 2 obtained a crystalline ester which upon saponification yielded borneol. The ester melted at 44-45°; p = -34° 20′. When 10 grams of phosphorus are allowed to stand with 100 grams of oil of turpentine for 2 hours at 50° C, there results, according to Minovici, a white wax-like precipitate, which upon analysis corresponds to the formula C10H13PO(OH)2. It does not ignite spontaneously in the air, but when heated burns with a luminous flame, giving rise to a garlic-like odor. Adulteration. The determination of the iodine absorption number, is recommended by Worstall as a reliable test to detect the adulteration of oil of turpentine with rosin oil, kerosene, wood turpentine etc. The method is as follows: About 0.1 gram of the sample is weighed out from a dropping bottle into a glass stoppered bottle, 40 cc. of Hübl's solution added and the tightly stoppered bottle set away over night. The excess of iodine is then titrated back. The iodine absorption number for rectified turpentine oil was found to be 377; for rosin oil, 97; for kerosene 0; for wood turpentine 212. Adulterations with rosin oil and kerosene can, therefore, be readily detected by this method even if added only in small quantities. The adulterations with wood turpentine in small quantities cannot be detected. However, the cost of rectified wood oil is so little below that of oil of turpentine, that if used as an adulterant for the latter, it is usually added in the proportion of 25-50 percent to be profitable and such adulteration is easily shown by the decreased iodine number. A turpentine oil with an iodine absorption number of less than 370, should be suspected. McCandless claims, however, that the iodine absorption test can not be relied on, and recommends a modification of Armstrong's method (polymerisation with conc. sulphuric acid and subsequent steam distillation), by which an adulteration of less than 5 p. c. can be detected. The method is as follows: 2 Journ. de Pharm., (6) 20, p. 57. 8 Pharm. Centralh. 45, p. 532, 4 Journ. Soc Chem. Ind. 23, p. 302. 5 Journ. Am. Chem. Soc. 26, p. 77. 100 c. c. of oil are gradually mixed, with thorough shaking and cooling, with 50 c. c. conc. sulphuric acid; 25 c. c. of water are then added and the mixture submitted to steam distillation. As soon as the total distillate amounts to 100 c. c. the distillation is interrupted, and the volume and index of refraction of the separated oil ascertained. The oil is then treated with an equal volume of fuming sulphuric acid, the mixture poured into cold water and the separated oil distilled with water vapor in the same manner as the first time. This same process is carried out a third time, but with double the volume of fuming sulphuric acid. After each distillation the volume and index of refraction of the oil are determined. In the case of pure oil of turpentine the refractometer number determined at 25° with Zeiss's butter-refractometer is never less than 30, while the presence of even 1 percent of petroleum lowers the refractometer number after the third polymerization to 25 and after further polymerization to 22. To detect pine tar oil in turpentine oil, McCandless 6 proceeds as follows: When the absence of petroleum oil has been proven, 100 c. c. of the oil of turpentine are distilled very slowly and the refractometer number of the first 0.5 c. c. of the distillate determined. In the case of pure turpentine oil, the refractometer number should not be less than 60. If this test does not show any adulteration, the distillation should be continued, and the refractometer number of the 97th and 98th c. c. fraction determined. In the case of pure turpentine oil, this should not be more than 77. Herzfeld also recommends the determination of the refractometer numbers as a reliable method to detect adulterations in oil of turpentine. The detection of pine tar oils, can readily be accomplished by shaking the suspected oil with a solution of sulphur dioxide. If pine tar oil is present to an extent of not less than 10 p. c. the oily layer will turn yellowish green. According to Utz8 great quantities of Russian oil of turpentine are sent to America, where it is purified and mixed with American turpentine and then sold in Germany for pure American oil of turpentine. 7a. Greek Turpentine Oil. Origin and Preparation. The oleo-resin from Pinus halepensis, a species growing in the eastern Mediterranean countries, 6 loc. cit. 7 Ztschr. für öffentl. Chem. 10, p. 382. 8 Apoth. Ztg. 19, p. 678. yields about 20-22 percent of oil. The bulk of the commercial oil is, however, not distilled from the oleo-resin direct. The oleo-resin is first of all added, by the wine manufacturer, to the grape juices. in order to improve the keeping qualities of the wine and also to impart to the wines the much desired resinous taste. From the dregs of the wine containing the resin, the oil is then distilled with steam, and the residue is worked up for colophony and calcium tartrate. Properties. Greek oil of turpentine has a pleasant wine-like odor, due to its method of production. A sample of oil examined by Utz1 was found to have a specific gravity of 0.86342 at 15° C.; ap (in 200 mm. tube) +77.34°; index of refraction = 1.4678. The bulk of the oil boils between 150-155°, leaving only a slight residue. It is soluble in 12 parts of 90 percent alcohol. = According to Dambergis 2 the oil has a specific gravity of 0.8672 at 15° C.; ap (in 200 mm. tube) = +73.4°; boiling point 155–157°. An examination of the oleo-resin by the same author gave the following results: colophony 78.57 p. c.; oil 17.04 p. c.; loss at 100° 14.04 p. c.; ash 0.14 p. c.; acid number 149; ester number 6; saponification number 155. 7b. Indian Oil of Turpentine. Origin and Preparation. Considerable attention is being given towards fostering the production of turpentine oil in India. The annual reports of the Forest Dept. in India3 show that the oil and resin have been manufactured to a greater or less extent for some years. The industry is confined to the pine forests of the Himalayas in the United Provinces and the Punjab. In the United Provinces, the first distillery was erected in the Imperial Forest School, Dehra Dun, in 1888. Two more distilling stations, more favorably situated on account of their proximity to the forests, were erected, one in 1895 at Naina Tal and the other in 1899 at Nurpur, in the Province of Punjab. The crude oleo-resin is collected from the Chir pine, Pinus longifolia. The trees are tapped soon after the rains are over in October. Cuts or 'blazes' are made in the trunk of the tree, at the base of which pots are placed to catch the exuding resin. In the lower forests of Kumaon, the oleoresin begins to flow in March and as the warm weather advances the flow increases, the 1 Apoth. Ztg., 19, 628. 2 Oesterr. Chem. Ztg., 1904, p. -. 3 Chem. & Durgg., 65, p. 831. |