127 — 



(15 mm. pressure). Its odour is powerful and reminds of camphor; 

 m. p. of the semicarbazone 137 to 13 8°. In the same manner were 

 formed m-methylhexahydrobenzaldehyde from m-methylcyclohexanone ; 

 and p - methylhexahydrobenzaldehyde from p - methylcyclohexanone. 

 This method is said to give good yields. 



Citronellal. If, according to A. Klages and R. Sautter 1 ), by 

 the action of bromobenzene magnesium on citronellal the benzene 

 nucleus is introduced into the asymmetric molecule of citronellal, the 

 fatty-aromatic carbinol formed can be converted by suitable operations in 

 active dimethooctylbenzene, (CH 3 ) 2 : CH • CH 2 • CH 2 • CH 2 • CH(CH 3 ) 

 • CH 2 • CH 2 • C 6 H 5 . An interesting insight is thereby obtained in the 

 changes of the rotatory power of the substances. 



Ketones. 



Carvone. According to Goldschmidt and Kisser 2 ), the 

 treatment of carvoxime hydrochloride or hydrobromide with alcoholic 

 alkali leads to the so-called isocarvoxime (m. p. 142 to 143 ), which 

 according to its constitution must be regarded as the oxime of a 

 carvone- isomeric with regard to the position of the double linkings. 

 When isocarvoxime is heated with dilute sulphuric acid, there is 

 formed, besides carvacrol, a basic compound melting at 94 , also 

 isomeric with carvoxime, which was designated by Goldschmidt 3 ) 

 as "carvoline", and was regarded as the product of a Beck- 

 mann's transposition. Wallach 4 ) has now obtained abundant 

 quantities of carvoline (4O°/ ) both by heating isocarvoxime with dilute 

 mineral acids, and by boiling with aqueous oxalic acid, that is to say 

 under conditions, under which a genuine Beckmann's re-arrangement 

 has not yet been observed. The isocarvoxime used as crude material, 

 m. p. 143 to 1 44 , b. p. 157 to 1 59 (12 mm. pressure) which re- 

 generates carvoxime hydrochloride by absorption of hydrochloric 

 acid, was identified by its dibromide (m. p. 126 to 127 °), better 

 by its tetrabromide (m. p. 134 to 135 °). From the isocarvoxime 

 the carvoline was then produced by heating with dilute sulphuric 

 acid; it melts at 94 (its hydrochloride at 189 to 190 ), and boils 

 at 12 mm. at 158 to 163 , at ordinary pressure at 289 to 290 

 (not corr.). The base is isomeric with carvoxime, and represents a 

 primary aromatic hydroxy base. The aromatic amido-character appears 

 from the diazotising. The oxygen is present in the form of hydroxy], 



x ) Berl. Berichte 39 (1906), 1938. 



2 ) Berl. Berichte 20 (1887), 2073; 22 (1889), 3104; 26 (1893), 2o8 5- 



8 ) Ibidem 29 (1896), 12. 



4 ) Liebig's Annalen 346 (1906), 266. 



