Chemistry of Essential Oils

90 THE CHEMISTEY OF ESSENTIAL OILS

with were cultivated at Madison, Wis., U.S.A. The oil distilled fron
the fresh tops of this material was straw-yellow, with a pleasant cam-
phor-like odour and an aromatic bitter taste : specific gravity O9509 at
23° C.; aD + 12-2°; nD23o1 5035; acid value nil; ester value 12-6;
acetyl value 5305. The oil from the rhizomes was reddish-brown ;
the odour aromatic and somewhat camphoraceous, the taste acrid and
bitter : specific gravity 09547 at 23° C.; aD + 217°; nD23o 14990; acid
value 0; ester value 15

• 3 ; acetyl value 384. The root oil was golden-
  yellow and had a pleasant camphoraceous odour; specific gravity 09491
  at 23° C.; aD + 187°; RAD 23 O 15063, and value 0 ; ester value 23*7; acetyl
  value 42. The rhizome oil was soluble in all proportions of ethyl
  alcohol 90 and 70 per cent. The herb oil was soluble 1: 5 in ethyl
  alcohol with turbidity ; and 1:8 in ethyl alcohol 70 per cent. The root
  oil was soluble 1:6 in ethyl alcohol 90 per cent, and 1: 40 in ethyl
  alcohol 70 per cent. None of the oils contained phenols : all indicated
  the presence of one or more aldehydic constituents.

In the oil from the fresh tops butyric and oenanthylic acids in the

form of esters were found.

A genuine calamus oil has the following characters :—

Specific gravity

Optical rotation

Refractive index

Acid value.

Ester

(after acetylation)

0-958 to 0*970 (rarely 0*950)

+ 9° to + 35°

1-5000 „ 1-5080

0 „ 3

5 „ 20

30 „ 55

The oil is easily soluble in 90 per cent, alcohol.

Kurbatow^1 was the first chemist to examine this oil. He found about

5 per cent, of a terpene boiling at 158° to 159°, which was probably

pinene, whose presence has since been confirmed by Semmler and

Spornitz.

Thorns and Beckstroem? isolated n-heptylic acid, palmitic acid, an.

unrecognised unsaturated acid, eugenol, and asarylic aldehyde. There

is also present a body of the formula C 15 H 26 O 2 melting at 128°, which

was termed calamus camphor by Schimmel & Co., but has been named

calameone by Thorns and Beckstroem. There are present two hydro-

carbons of the formula C 15 H 22 having the following characters :—

Boiling-point

Specific gravity

rotation

1.

. 146° at 19 mm.
. 0*933 at 18°

• 34'83°

2.

151° at 22 mm.

0-9336 at 12°

• 1338°
  A sesquiterpene of specific gravity 0931 and boiling at 255° to 258°
  is present in the oil in small amount.
  F. W. Semmler and K. E. Spornitz
  3
  have recently isolated several
  new constituents from this oil. The low-boiling portions (boiling-
  point 45° to 50°, 9 mm.; <XD + 59°) contained a-pinene, which was
  identified by converting it into the nitrosochloride (melting-point 108°).
  In addition to pinene, these chemists succeeded in identifying camphene
  by conversion into isoborneol (melting-point 212°). Another fraction
  contained camphor (melting-point of the oxime 115°). A fraction with
  boiling-point 130° to 135° (12 mm.), after being boiled over sodium,
  afforded a sesquiterpene C 15 H 24 , calamene, which possessed the following,

(^1) Bericht, 6 (1873), 1210. (^2) Ibid., 34 (1901), 1021.
•> Ibid., 46 (1913), 3700 ; and Schimmel's Report.