For the purpose of accomplishing a separation of the constituents, 50
grams of the oil, after saponification, were dried and subjected to
fractional distillation in a three-bulb Ladenburg flask. The results
are given in Table V.
+Table V.+--_Fractionation of saponified oil of swamp bay and
description of fractions._
---------+-------------+-----------+----------------------------------
Fraction.| Temperature.|Distilled. | Remarks.
---------+-------------+-----------+----------------------------------
| _Degrees C._|_Per cent._|
1 |Below 170 | 1.1 | Penetrating odor; largest portion
| | | of the fraction distilled over
| | | below 80° C.; temperature rose
| | | rapidly to 170° C.
2 |170 to 182 | 8.8 | Camphoraceous cineol-like odor;
| | | largest portion distilled 175°
| | | to 180°.
3 |182 to 185 | 9.2 | Strong cineol-like odor;
| | | temperature rose uniformly.
4 |185 to 190 | 13.5 | Cineol-like camphoraceous odor;
| | | temperature rose uniformly.
5 |190 to 195 | 13.0 | Strong camphoraceous odor;
| | | temperature rose uniformly.
6 |195 to 200 | 5.8 | Strong camphorlike odor; crystals
| | | appeared in condenser;[34]
| | | largest portion distilled
| | | between 198° to 200° C.
7 |200 to 205 | 12.5 | Strong camphorlike odor; fraction
| | | semisolid upon cooling;
| | | temperature rose uniformly.
8 |205 to 215 | 14.0 | Strong camphorlike odor; fraction
| | | almost solid upon cooling;
| | | distilled largely between 205°
| | | to 210° C.
9 |215 to 225 | 12.5 | Strong camphoraceous odor;
| | | fraction semisolid; temperature
| | | rose uniformly.
10 |225 and above| 9.0 | Heavy yellow oil with
| | | camphoraceous odor.
---------+-------------+-----------+----------------------------------
Beginning with fraction 6 each successive fraction was refrigerated
in a freezing mixture of ice and salt and the crystals separated by
centrifuging in a platinum Gooch crucible. A total of 13.7 per cent of
crystals was obtained.
In order to obtain a further separation of crystals the portions of
the oil beginning with fraction 5 were fractionated into the following
fractions: 190° to 195° C.; 195° to 200° C.; 200° to 205° C.; 205° to
215° C.; 215° to 233° C.; 233° to 260° C. A total of 4 per cent of
crystals was obtained by refrigeration and centrifugation of those
fractions in which crystals appeared. The portion between 190° and 215°
C., and also fraction 4 of the original, were further fractionated into
four parts: 185° to 190° C.; 190° to 195° C.; 195° to 205° C.; 205° to
215° C., an additional yield of 3.3 per cent of crystals being obtained.
By the above method of successive fractionation and refrigeration
a total of 21 per cent of crystals was obtained from the oil. This
represents only approximately the total percentage of stearoptene in
the oil. The separation was not at all quantitative, as a considerable
proportion was lost in the manipulations incident to the separation.
Since the quantity of oil at hand was so meager the fractions were
reduced to such small quantities that further separation of crystals
was impossible, and as unavoidable losses were encountered in
transferring to and from the centrifuge the final percentages were
materially affected and the true amount of stearoptene may be assumed
to be considerably more than is shown above.
After the fractionation and refractionation of the oil and the
separation of the stearoptene portion, the remaining elaoptene
portion grouped itself into fractions, whose physical properties were
determined and qualitative tests for their constituents applied, as
shown in Table VI.
+Table VI.+--_Refractionation of the oil of swamp bay, showing the
physical properties of the fractions._
---------+------------+-------------+-------------+-----------+----------------
| | Specific | Rotation |Re-fraction|
Fraction.|Temperature.| gravity | in 50 mm. | N_{D} | Tests applied.
| | at 25° C. | tube. | 25°. |
---------+------------+-------------+-------------+-----------+----------------
|_Degrees C._| | _Degrees._ | |
1 |Below 170 |Insufficient.|Insufficient.| 1.4648 | When shaken
| | | | |with water the
| | | | |aqueous solution
| | | | |strongly reduced
| | | | |magenta solution
| | | | |to violet color;
| | | | |also produced
| | | | |silver mirror
| | | | |with ammoniacal
| | | | |silver nitrate.
2 |170 to 182 | 0.9011 | +22.5 | 1.4630 | Iodol
| | | | |(tetraiodopyrol)
| | | | |dissolved in oil
| | | | |by gentle
| | | | |warming yielded
| | | | |yellow crystals
| | | | |melting at
| | | | |115° C.; cineol
| | | | |iodol melts at
| | | | |112° C.
3 |182 to 185 | .9012 | +21.5 | 1.4628 | Treated with
| | | | |iodol and the
| | | | |yellow crystals
| | | | |recrystallized
| | | | |from benzol
| | | | |melted sharply
| | | | |at 112°.
4 |185 to 190 | .9075 | +23 | 1.4628 | Cineol-iodol
| | | | |crystals melted
| | | | |at 113° C.
5 |190 to 205 | .9228 | +31 | 1.4653 | Do.
6 |205 to 215 | .9351 |.............| 1.4706 | Negative test
| | | | |with iodol.
7 |215 to 233 | .9358 |.............| 1.4765 | Do.
8 |233 to 260 | .9360 |.............| 1.4830 | Oxidized with
| | | | |3 per cent
| | | | |potassium
| | | | |permanganate
| | | | |in cold yielded
| | | | |camphor
| | | | |crystals.
---------+------------+-------------+-------------+-----------+----------------