Jour

the same as No. III., as its boiling point was the same, its sp. gr. 0-8863 at 16° C., and its other physical properties identical.

No. V. from a dealer in New York was no doubt the same as III. and IV, as it only differed by having the sp. gr. of 0.8803 at 16° C.

No. VI. from a New York importing firm, marked "rectified," had a sp. gr. of 1006 at 16° C., and boiled at 210° C. Its color was a light yellow, and odor that of sassafras and slightly camphoraceous.

No. VII. from wholesale druggists of Philadelphia was similar to No. VI., with a sp. gr. of 0·9903, boiling point of 206° C., and somewhat darker color.

No. VIII., also from a wholesale drug firm of Philadelphia, was dark reddish brown, with an empyreumatic and camphoraceous odor, a sp. gr. of 0.9546 at 16° C., and a boiling point of 198° C.

They all had an acid reaction; all were miscible in all proportions with 95 per cent. alcohol.

As I. and II. appeared to represent the crude product, they were taken for analysis. No. I. we were able to get in considerable quantity, and in most of the following work it was used.

The remaining samples were submitted to fractional distillation in vacuo, and samples III., IV. and V. were found to contain from 1-3 per cent. of camphor in solution in the light fractions of camphor oil. Samples VI. and VII. consisted of the intermediate portions of the commercial oil, the lowest and highest boiling fractions being entirely absent. Sample VIII. contained all the fractions, the lightest in smaller quantity only, but it was quite empyreumatic, and yielded a considerable quantity of a solid residue at 235° C. Each sample was submitted to the action of polarized light, I., II. and VIII. being first decolorized with animal charcoal. The following readings were obtained with the 200 mm. tube in a Wild polaristrobometer:

The following results, it will now be understood, apply to sample No. 1. An alcoholic solution of ferric chloride produced no change when mixed with the oil, and negative results were likewise gotten with saturated solution of sodium bisulphite and with alcoholic ammonium sulphide. Alcohol and fixed oils were found to be absent from the sample.

Tour

On agitating the oil with water the latter absorbed the acidity, which was found by appropriate tests to be due to acetic and formic acids. The same portion of oil after agitation with water was boiled for some hours with an aqueous solution of potassium hydrate in a flask attached to an inverted condenser. The resulting potassium compound, decomposed by a mineral acid, separated into two layers. The aqueous layer was distilled, and in the distillate butyric acid was found, besides acetic and formic acids as above.

Three litres of the oil were fractionated in vacuo and the distillate collected in four portions as follows:

1.-20 per cent. obtained between 90°-110° C. in vacuo, or 180°-200° C. ord. pres.

A small amount of resinous residue remained.

A quantity of the oil was also distilled at ordinary pressure, but this method resulted in decreasing the amount of the higher boiling fractions and rendering them more empyreumatic. It was found, however, after the

original oil was once fractioned, that the lightest portions could with advantage be distilled at the ordinary pressure, but those of higher boiling points decomposed and the use of the vacuum was continued with them through all the rectifications. By redistilling the above four fractions, the lightest ones over sodium, until nearly constant boiling points were obtained, the following fractions resulted:

Jour. Pharm

, 1889

It had better be explained that the fractions P, Q, R and S were not the result of fractional distillation alone, but were obtained by treatment to be hereafter explained from fresh portions of the oil. Only those fractions having constant boiling points were examined. All the polariscope readings were made in the 200 mm. tube, confirmed by the use of the 100 mm. tube. The vapor densities were made with the Victor Meyer apparatus. The combustions were carried out in an open tube with cupric oxide and a stream of oxygen. Over ninety combustions were made during the progress of the work which has been carried on uninterruptedly since last December.

Fraction A. 145-155° C.-This fraction was found only in small quantity, having strong terebinthinate odor, of sp. gr. 0.8593 at 16° C., and dextro-rotary+53°. It was submitted to combustion with following results:

I. 0-100 gm. substance yielded 0-3235 gm. CO, and 0·106 gm. H2O.

II. 0141 gm. substance yielded 0.453 gm. CO, and 0.146 gm. H2O.

I. 0.1152 gm. subst. vaporized replaced 21 cc. air =4.70.

Fraction B. 158-161° C., b. p. 159° C.―This fraction of constant boiling point possessed fragrant and terebinthinate odor, of sp. gr. 0.8616 at 16° C., and dextro-rotary=+54°.

Combustions as follows:

I. 0.109 gm. subst. yielded 0·350 gm. CO2 and 0·114 gm. H2O. II. 0.111 " 0.358" CO2 and 0.1175" H2O.

Fraction D. 167-169°, b. p. 168° C.-In somewhat larger quantity than Fraction B, of fragrant odor, colorless, sp. gr. 0.8678 at 16° C., and dextro-rotary=+56.9°.

Combustions as follows gave results for a hydrocarbon :

I. 0.1185 gm. yielded 0-381 gm. CO, and 0.124 gm. H2O. 0'415 gm. CO2 and 0.1355 gm. H2O.

II. 0·129 gm.

66

Fraction E. 170-171° C., b. p. 171° C.-Of this fraction only a small quantity could be separated, but it consisted of a distinct fraction, with constant boiling point of 171° C. The specific gravity was found to be 0.8737 at 16° C., colorless, fragrant odor and dextrorotary=+584°.

Combustions gave results as follows:

June, 1889

Jour. Pharm

I. 0.116 gm. subst. yielded 0.3745 gm. CO2 and 0·1221 gm. H2O.

I. 0.1155 gm. subst. replaced 21 cc. air=4·67.

II. 0.1231 gm. 66

66 22.5 cc. air=4.65. Calculated for C10H16=4.71.

Fraction G. 175-177° C., b. p. 176° C.-This fraction was separated without much difficulty, in large quantity and very constant. It was colorless, strong pleasant odor, resembling cajeput, of sp. gr. 0.8824 at 16° C., and strongly dextro-rotary= +62°.4.

The following combustions and vapor densities give it the formula C10H18O:

I. 0.1635 gm. subst. yielded 0·467 gm. CO, and 0·168 gm. H2O. II. 01684 gm. 04813 gm. CO2 and 0.1733 gm. H2O.

5.28.

66

66 27.4 cc. air

= 5.35.

I.-0.164 gm. subst. replaced 26-4 cc. air II.-0.1724 gm.

Calculated C10H180 = 5·33.

Fraction J.-180-182°, b. p. 180° C.-Fraction of oil boiling between 185-200° C., on repeated distillation over sodium, gave a small