The solid alcohol regenerated from the acid phthalate has the odor of borneol and camphor and boils between 196 and 198°. M. p. about 58 to 62°. Its phenyl urethane is liquid. Upon oxidation with chromic acid santenone results.
l) Berl. Berichte 40 (1907), 1124. 2) Ibidem 43 (1910), 1722.
3) Arch, der Pharm. 918 (1900), 372.
4) Report of Schimmel & Co. October 1910, 118. 4) Berl. Berichte 40 (1907), 4465; 41 (1908), 125. 6) Ibidem 40 (1907), 4918.
7) Report of Schimmel & Co. October 1910, 120.
6. Teresantalol, C10H160. Upon heating the santalone-containing fraction (b. p. 210 to 220) with phthalic acid anhydride, Schimmel & Co.1) obtained an acid phthalic ester which, upon saponification, yielded an alcohol. Recrystallized from petroleum ether, it showed a great capacity to crystallize, forming well shaped prisms several centimetres in length. Thus purified it melted at 111 to 112°. It sublimed in long thin needles which melted at 112 to 114°. Elementary analysis agreed with the formula C10H16O. Comparison with the teresantalol obtained by Semmler by reduction of teresantalic acid established the identity of the two substances.
7. Nortricycloeksantalal, C11H160. When the fraction that boils higher than santenone is treated with bisulphite, there results a slimy mass'2) that is readily soluble in water and from which the aldehyde can be regenerated by means of soda. It has a spicy odor and the following constants: b. p. 86 to 87 (6 mm.), 222 to 224° (760mm.); d20o0,9938; aD - 38°48'; nD20o1,48393; mol. refr. found 47,20, computed for C11H180 46,409, for C11H16 0/148,142.
This aldehyde is identical with the nortricycloeksantalal obtained by Semmler and Zaar.3) as an "Abbau" product of tricycloeksantalal. Its semicarbazone melts at 223 to 224°, the liquid oxime boils at 135 to 137° (7 mm.). Upon oxidation with ammoniacal silver nitrate solution, the nortricycloeksantalal is oxidized to nortricycloeksantalic acid (m.p. 91 to 93°; [a]D - 33° 17' in 13,8 p. c. alcoholic solution). Upon treating the enolacetate of the aldehyde with permanganate, there results teresantalic acid (m.p. 154 to 156°).
By shaking the normal sandal wood oil with bisulphite solution the aldehyde can also be obtained and in small amounts it may be identified by its semicarbazone.
8. Santa/one, C11H160. The second ketone occurring in the lower boiling portions of sandalwood oil is santalone. According to F. Muller4), it boils at 214 to 215°, 88 to 89° under 15 mm. pressure (?); d15o 0,9906; aD - 62°. Schimmel & Co.5)
1) Report of Schimmel & Co. October 1910, 125; April 1911, 105.
2) Ibidem October 1910, 122.
3) Berl. Bericht 43 (1910), 1890.
4) Arch, der Pharm. 238 (1900), 373.
5) Report of Schimmel & Co. October 1910, 124.
found the following constants: b. p. 213 to 216°; d15o 0,9909; aD - 41° 32'; nD20o 1,50021.
Santalone semicarbazone melts at 174 to 176°, santalone oxime at 74,5 to 75,5°. From the latter santalone cannot be regenerated by treatment with dilute sulphuric acid.
9. ketone, C11H160. The santalone fraction contains a second, presumably isomeric ketone, the difficultly soluble semi-carbazone of which melts at 208 to 209°, the oxime at 97 to 99°.
10. Santalene, C15H24. The occurrence of sesquiterpenes in sandal wood oil was first pointed out by H. von Soden and F. Muller1). M. Guerbet2) then showed that two sesquiterpenes were present which he designated as o- and B-santalene. Properties and derivatives of both are recorded in vol. I, p. 336. There should be added, however, the physical constants of both which have since been determined more accurately by Schimmel & Co.3).
a-Santalene: b.p. 252° (753 mm.) and 118° (7 mm.); d15o0,9132; aD - 3° 34'; nD15o 1,49205; mol.-refr. 64,87, computed for C]15H24/1 64,45.
B-Santalene: b.p. 125 to 126° (7 mm.); d20o0,8940; aD - 41°3'; nD20o 1,49460; mol.-refr. 66,53, computed for C15H24/2 66,16.
In their attempt to hydrate santalene by means of glacial acetic acid-sulphuric acid, von Soden and Muller1) obtained small amounts of a sesquiterpene alcohol with a strong cedar wood odor (b.p. 160 to 165° under 7 mm.; d15O0,978; aD inactive).
For the hydration Schimmel & Co. used a fraction, the molecular refraction of which showed that it consisted mostly of the tricyclic santalene, and from it obtained 5 to 10 p. c. of an alcohol with the odor of cedar wood: b.p. 154 to 157° (5 to 6 mm.); d15o0,9787; d20o0,9753; nD20o1,51725; mol. refr. found 68,81, computed for C15H260/; 68,07.
With concentrated formic acid the alcohol readily gave off water even at body temperature. It could not be oxidized with chromic acid. Hence it probably is a tertiary alcohol.
1) Pharm. Ztg. 44 (1899), 258. - Arch, der Pharm. 288 (1900), 363.
2) Compt. rend. 180 (1900), 417.
3) Report of Schimmel & Co. October 1910, 126.
The hydrocarbon which, in the hydration experiment, was not converted into an alcohol possessed properties different from those of the hydrocarbon employed.