68 TReport of Schimmel % Co. 1922. 



In the next fractions we found after repeated, careful fractionation a new terpene 

 with a carrot-like odour and the following constants: — 



l.B.p. 155Q: d 15O 0.8533, « D +4°50', n D20 o 1.46201 



2. B.p. 155°: d 150 0.8535, « D -f-4°58', n D20O 1.46221 



3. B.p. 155 to 156°: d 15 o 0,8537, « D +4°35', n D20O 1.46231. 



The values obtained on combustion pointed to a terpene CioHi 6 : — 



0.1822 g. substance gave 0.5879 g. CO*, 0.1958 g. H 2 0. 



Found Calc. for Ci H 16 



C 87.98 per cent. 88.23 per cent. 



H 11.93 per cent. 11.77 per cent. 



Mol. refr. found calc. for CioHieT 



43.89 43.51. 



The nitrosochloride, purified by means of chloroform and methyl alcohol, shows 

 a strong tendency to decompose and can therefore be prepared and purified only in 

 small amounts. Decomposition starts at about 85° in a very sudden and violent 

 manner. The piperidide melts at 194 to 195°, the nitrolbenzylamine indistinctly from 

 105 to 108°; the anilide was not obtainable, neither a solid nitrosate. When dissolved 

 glacial acetic acid and cooled down the terpene adds somewhat more than two atoms 

 of bromine; the resulting bromide remains oily. Likewise, the hydrochloride obtained 

 by saturating, in glacial acetic acid solution, the terpene with hydrogen chloride gas 

 was liquid. On trying to hydrate the terpene by action of acetic and sulphuric acids 

 resinification resulted. When oxidized by means of permanganate solution, with 

 cooling by ice (according to the method for obtaining pinonic acid), the terpene gave 

 rise to a neutral oxidation product soluble in water and chloroform, which did not 

 distil without decomposing and was therefore not yet obtainable in the crystalline 

 state. On further oxidation with neutral permanganate at 100° there was obtained, 

 in addition to oxalic acid, m. p. about 100°, and acetic acid (Ag estimated in the 

 silver salt 64.20 per cent), an acid which decomposed on distillation in vacuo and 

 which evidently was not a ketonic acid. Treatment with dimethyl sulphate yielded no 

 ester. Details as to the chemical structure of the terpene are to be expected only 

 after closer investigation. We wish to add that this oil offered no clue for the presence 

 of «-pinene, in contradiction to another oil which years ago 1 ) we found to contain 

 that terpene. Considering the great variety in the botanical origin of the Spanish 

 thyme oils this different behaviour is by no means surprising. 



A very small amount of camphene is present in the Spanish oil. It was identified 

 by treating the fractions boiling above 157° in the usual manner with acetic-sulphuric 

 acid, when a trifle of isobornyl acetate (b.p. 82 to 88° at 6mm.; sap. 4 value 202) was 

 isolated by fractionation. The free zsoborneol obtained therefrom by saponification 

 melted at 208 to 212°. 



fi-Pinenc was likewise a constituent of the oil. After oxidising a fraction b.p. 165 

 to 169° with alkaline permanganate a hydrocarbon with the following constants was 

 regenerated: — b.p. 163 to 167°, d 20 o 0.8520, « D +3°45', n D20o 1 .46609, mol refr. found 

 44.02, calc. 43.5. On further oxidation with permanganate is yielded nopinic acid, 

 m. p. 126 to 127°. The hydrocarbon occurs in minute quantity only. 



A hydrocarbon fraction, b.p. 165 to 168° (di 5 o 0.8567, « D +3°57', n D20O 1.47141) 

 which on saturating with hydrogen chloride gas and after some standing had yielded 



l ) Report October 1894, 57. 



