OD Laas J 
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34 REPORT OF SCHIMMEL & Co. APRIL 1914. 
depend upon the ester-content. Generally speaking the properties of the sample agreed . 
with those of a normal oil, except that ester-value was too high: dis0 0,9628, ap -+ 11°52’, 
acid v. 0,9, ester v. 89,4, soluble in any proportion of 90 p.c. alcohol. 
The ester value of normal calamus oil ranges from 6 to 20, hence the suspicion 
at once arose that an artificial ester had been added to the sample under examination. 
It is true that the first test which was applied, that for terpinyl acetate and the esters 
of sparingly-soluble acids, was without result, but the presence of glycerol ester was 
established. Extraction with 5 p.c. alcohol resulted in the removal of 5 p.c. of glycerol 
acetate with the following constants: b.p. 114 to 116° (3 mm.), diso 1,1677, acid v. 0,6, 
ester v. 737,8. From these constants it was to be inferred that the substance consisted 
chiefly of triacetine. For the purposes of further identification the ester was split up 
into its constituents, when the glycerol was identified by the acroleine-reaction and 
the acetic acid by conversion into acetic ester. In the course of further examination 
it was shown that by no means the whole of the glycerol ester in the calamus oil 
had been taken up by the 5p.c. alcohol, for when the extracted oil was fractionally 
distilled, further considerable quantities of glycerol ester were isolated. The total 
addition was estimated at probably about 10 p.c., a percentage which would also 
correspond with the ester value of the sample. 
The fact that the oil possessed a subsidiary odour of caraway induced us to treat 
it with a 40 p.c. sodium sulphite solution. By this manipulation we succeeded in 
isolating a certain proportion of carvone, which was identified from the oxime. Un- 
fortunately we obtained only such a small quantity of this oxime that is was impossible 
to recrystallise it; and it was therefore necessary to determine the m.p. from the 
crude product. It was 69° instead of 72°. We have convinced ourselves that carvone 
is not a constituent of pure calamus oil. But as the sample under examination only 
contained traces of carvone we cannot ascribe its presence in this case to adulteration, 
but only to contamination. 
It is true that no other foreign bodies could be detected in the sample, yet the 
specific gravity of the oil, after the extraction with 5 p.c. alcohol, was much too low 
to enable us to class it as a normal calamus oil. We therefore suspect that it con- 
sisted of a by-product in the manufacture of terpeneless calamus oil, mixed with © 
glycerol acetate. 
In a sample of oil distilled from Russian calamus root grown in the Baltic pro- 
vinces, F. W. Semmler and K. E. Spornitz') have found several constituents not 
previously encountered in this oil. The low-boiling portions (b. p. 45 to 50°, 9 mm.; 
%p + 59°) contained «-pinene, which was identified by converting it into the nitroso- 
chloride (m. p. 108°). An earlier examination by A. Kurbatov2) had already pointed to 
the probability of the presence of this terpene. Kurbatov found the oil to contain 
5 p.c. of a hydrocarbon with b.p. 158 to 159°, which yielded a hydrochloride with an 
exceptionally low m. p. (63°). In addition to pinene, the authors succeeded in identifying 
camphene by conversion into isoborneol (m. p. 212°). Another fraction (b. p. not stated) 
contained camphor (m. p. of the oxime 115°). A fraction with b. p. 130 to 135° 
(12 mm.), after being boiled over sodium, afforded a sesquiterpene Ci;H24, calamene, 
which possessed the following properties: b. p. 123 to 126° (10,5 mm.), ds 0,9224. 
& + 5°, np 1,50572. By treatment with hydrogen in the presence of platinum black 
1) Berl. Berichte 46 (1913), 3700. — 2) Berl. Berichte 6 (1873), 1210. — Liebigs Annalen 178 (1874), 4, 
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