142 



Report of Schimmel § Co. 1922. 



p. 238 to 239° [corr.], on slow heating) resulted as by-product, the isocyanate formed 

 in the main reaction acting with some of the unattacked amide: — 



C 9 H 13 N : C : O + H 2 N • CO • C 9 H 13 = C 9 H 13 • NH • CO • NH • CO • C 9 H 13 . 

 Careful saponification, performed by fusing with solid caustic potash, yielded apo- 

 tricyclylamine C 9 Hi 3 NH 2 , m. p. 104° (unsharp), besides camphenilone and camphenilol. 

 With the object to characterise the unstable apotricylylamine, the authors brought 

 toe body in reaction with, inter alia, phosgene, obtaining thereby as primary reaction- 

 product a liquid compound, probably apotricyclyl isocyanate. The latter was transformed 

 by aniline into apotricyclyl-phenyl-urea, partly also into symm. di-apotricyclyl-urea: — 



C 9 H 13 • NH 



>CO 

 C 6 H 5 • NH 



Apotricyclylphenylurea. 



C 9 H 13 N:CO 



Apotricyclyl isocyanate. 



C 9 H 1S NH 



>CO 

 C 9 H 13 - NH 



Di-apotricyclylurea. 



On diazotising the hydrochloride of apotricyclylamine with sodium nitrite, apo- 

 tricyclol resulted, the reaction passing off fairly well; intermediarily, a comparatively 

 stable nitrite was formed. The alcohol apotricyclol (m. p. 75 to 80° [unsharp], 

 b. p. 82 to 86° at 12.5 mm.; phenylurethane, m. p. 121.6 to 122° [corr.]), on exposure 

 to the air, deliquesces in the course of a few hours forming a viscid oil. When boiled 

 with a dilute mineral acid, equally when heated (without water, by ketisation) in a 

 current of dry hydrogen, opotricyclol yields quantitatively camphenilone. With phos- 

 phorus pentachloride, apotricyclol passes over into camphenilone dichloride (IV), 

 m. p. 168 to 169°. Ethereal solutions of the alcohol, on treatment with metallic 

 sodium, yielded, without evolution of hydrogen, the sodium compound of camphenilone 

 pinakone (V) from which the methyl ether was obtained, dimethyl sulphate reacting 

 quantitatively, and methyl iodide only partly. 

 H 2 C -CH— CH 2 H 2 C CH- CH* 



■ I 

 CHs-C'CHj 



CH S 



CH 2 



CH 



HC^- 



C 



I 

 OH 



(I) Apotricyclol. 



H 2 C CH CH 2 



I 

 CH 3 C-CH 3 



CH-OH 



(II) Cyctopropanol. 



H 2 C~ — CH 



CONH 2 



(III) Tricyclenic acid amide. 



HC 



H 2 C 



CH 



Cl-C 

 CI 



(IV) Camphenilone dichloride. 



HC 



I 

 H*C- 



CH 3 



C 



I 

 CH 3 



\ 



/ 



/ 

 NaO 



ONa 

 CH 2 H 2 C 



(V) Sodium compound of camphenilone pinacone 



— CH 2 



CH 3 I 



I I 



C CH 



CH3, 



CH S 



As to optical investigations of geraniol and citronellol, vide p. 116 of this Report. 



The publications by Fromm and Klein on olibanol (see p. 36 of this Report) and by 

 Muller on the constitution of reuniol (see p. 116 of this Report) are discussed by H. Heller 1 ). 



*) Deutsche Parf.-Ztg. 7 (1921), 22. 



