The presence of linalool, which was suspected by Barbier and Bouveault2), was proven by Schimmel & Co.3)4) by means of its phenylurethane melting at 65 to 66°. The fraction used for the preparation of this derivative had the following properties: d15o0,872; aD - 1°40'; nD20o1,4619.
The rose-like odor of geranium oil is due partly to a small content of phenylethyl alcohol (m. p. of phenylurethane 80°)4). Terpineol is present in somewhat larger amounts, viz., the inactive a-terpineol4) melting at 34 to 35°5). It was identified by means of its nitrosochloride (m. p. 114 to 115°), its phenyl-urethane (m. p. 109 to 111°) and the ketolactone (m. p. 62 to 63°) prepared from the trihydroxy terpane. While purifying the ter-pineol, traces of menthol were found, also traces of an alcohol with a peculiar odor reminding somewhat of borneol4). Finally, an alcohol that produced an irritation causing coughing should be mentioned. Its phenylurethane melted at 41 to 43°6). All of these alcohols are present partly free, partly as esters.
The acids separated from the mother liquid after saponification boiled between 100 and 210° and congealed in part. The silver content of its silver salt, also its dibromide melting at 87°, reveal its identity with tiglic acid7). The liquid acid mixture apparently contains valeric, butyric7) and acetic acids8).
1) Americ. Perfumer 1 (1907), No. 12, p. 12.
2) Compt. rend. 119 (1894), 281.
3) Report of Schimmel & Co. April 1904, 55.
4) Ibidem October 1910, 69.
5) Ibidem October 1911, 52. •) Ibidem April 1904, 55.
7) Ibidem April 1894, 32. It would be of interest to reinvestigate the statement that the aqueous distillate of Pelargonium roseum contains pelar-gonic acid (Pless, Liebig's Annalen 59 , 54) and to ascertain whether the acid was not a mixture which accidentally happened to have the composition of pelargonic acid.
s) Barbier and Bouveault, loc. cit.
The non-alcoholic constituents belong to a variety of classes of chemical compounds. In the lowest boiling fractions of both the Reunion and African oils, Schimmel & Co.1) found a sulphur-compound, the dimethyl sulphide. Though present in minimal amounts only, it exerts a marked influence on the odor of the oil. It was identified by its boiling point, viz., 37°, and by its characteristic reactions with mercuric and platinic chlorides.
Of terpenes the presence of l-a-pinene2) (m. p. of nitrol-benzylamine 122 to 123°) and of traces of phellandrene2) (probably B-phellandrene, m. p. of nitrite 114 to 115°) was demonstrated.
In the lower fractions Flatau and Labbe3) discovered l-menthone (m. p. of semicarbazone 179,5°). From an oil obtained b cohobation of the aqueous distillate, Charabot and Laloue4) isolated citral with the aid of acid sodium sulphite.
From the last fractions of the oil a crystalline substance that melted at 63° and that had the properties of rose oil stearoptene was isolated, judging from the behavior of the geranium oils toward 70 p.c. alcohol, the paraffin occurs most abundantly in in the Spanish variety.
The green color of individual oils, more particularly of those from Reunion, is due to a liquid ([C10H17]2O?) that boils at 165 to 170° under 10 mm. pressure6).
Adulteration and Examination. Geranium oil is adulterated with turpentine oil, cedar-wood oil and gurjun balsam oil6). Additions of these oils are recognized by their insolubility in 70 p.c. alcohol and by the lowering of the ester value of the adulterated oils. In order to render the detection of such adulterations more difficult, the ester content has been increased by the addition of artificial esters of benzoic acid7), oxalic acid8) and phthalic acid9).
1) Report of Schimmel & Co. April 1909, 55.
2) Ibidem April 1904, 55.
3) Bull. Soc. chim. 19 (1898), 788. 4) Compt. rend. 136 (1903), 1467.
5) Barbier and Bouveault, loc. cit.
6) Report of Schimmel & Co. April 1908, 56; October 1911, 53.
7) Ibidem October 1905, 36.
8) Parry, Perfum. and Essent. Oil Record 2 (1911), 83.
9) Report of Schimmel & Co. April 1913, 66.
Fatty oil, the presence of which is indicated by its insolubility in 70 p.c. alcohol, remains behind when the oil is distilled with water vapor, hence its presence can be proven without difficulty.
An oil adulterated with gingergrass oil has also been observed1).
Production and Commerce. The African oil and that from Reunion are the most important of the commercial oils.
The following amounts have been exported: from Reunion: from Algiers:
Amount in kg.
1901 .... 13953
1902 . . .
17 193 Year
Amount in kg.
1903 . . .
25323 1903 . .
. 31 200
1904 . . .
27 660 1904 . .
. 63 600
1905 . . .
38 334 1905 . .
. 52 600
1906 . . .
31 645 1906 . .
. 54 600
1907 . . .
31 247 1907 . .
, . 38 700
1908 . .
34 360 1908 . .
. 46 600
1909 . . .
59 788 1909 . .
. . 41000
1910 . .
61 792 1910 . .
. . 33 800
1911 . . .
44 620 1911 . .
. . 28 500
1912 . . .
43 138 1912 . .
. . 24 900
As already pointed out, southern France produces annually 2000 to 3000 kg., Spain 600 to 1000 kg. and Corsica 600 to 1300 kg. of oil.