_Cineol._--Fraction 1, 175° C., possessed a strong eucalyptuslike odor
and was tested for cineol by means of iodol. The tetraiodopyrol (iodol)
addition product of cineol formed into well-defined, nearly colorless
crystals, melting at 110° to 113° C. This crystalline addition product
of iodol formed in the first four fractions; in fraction 5, however,
only a trace of crystals appeared.
The presence of cineol having been proved, a quantitative estimation
of the compound was made in fractions 1, 2, 3, and 4. Fraction 5,
which contained only a very small quantity of cineol, did not admit of
estimation by the phosphoric-acid method, which is reliable only when
large percentages of cineol are present.
The fractions yielded the following percentages of cineol: 1, 40 per
cent; 2, 70 per cent; 3 and 4, 43.7 per cent. Calculating from the
original oil as a basis, the above results correspond to 19.7 per cent
of cineol in the original oil.
_Fenchone._--Fraction 5, boiling from 190° to 195° C., was a heavy
liquid with a strong camphorlike odor. Pure levo fenchone[32] from
thuja oil is an oily liquid with a strong camphoraceous odor; boiling
at 192° to 194° C.; specific gravity at 19° C., 0.946; (A_{D}) -66.9°.
An oxime was prepared from the fraction by reaction with hydroxylamine
hydrochlorid according to the method of Wallach,[33] which is as
follows: To 5 grams of fenchone dissolved in 80 cubic centimeters of
absolute alcohol is added a solution of 11 grams of hydroxylamine
hydrochlorid in 11 grams of hot water. Six grams of powdered potash are
added. The oxime separates in the form of crystals, upon standing for
some time. Recrystallized from alcohol it melts at 164° to 165° C.
The oxime formed from the fraction by the above method, after
recrystallization from ethyl acetate, melted at 170° C.
Provided that fraction 190° to 195° C. consists chiefly of fenchone the
oil should contain 8 to 10 per cent of this compound.
_Borneol._--The total amount of borneol contained in the oil was
determined by the saponification of a small quantity of the original
oil and subsequently fractionating the saponified oil. Twenty-five
grams of the saponified oil were carefully fractionated and then
refrigerated, 7.5 grams of borneol separating out. This corresponds to
a total of 30 per cent borneol. After the separation of the borneol
the oil was again fractionated, and the portion above 195° C. yielded,
when frozen, an additional 2 grams of borneol, making a total of
9.5 grams, or 38 per cent, of total borneol separated from the oil.
The theoretical quantity of borneol in the oil, as shown by the
acetylization value, is about 43 per cent, the lower percentage which
was actually obtained being caused by incomplete separation due to the
smallness of the amount saponified.
_Esters of borneol._--A careful examination of Table IV shows that the
esters of borneol, possibly chiefly bornyl heptoate and valerianate,
are found in the fractions boiling above 190° C., principally in the
highest boiling fractions; a perfect separation of these esters was
not feasible because of the existence of the esters as mixtures of
several acids. The ester numbers of the fractions, however, show the
distribution of the esters at the different temperatures.