106 Report of Schimmel 8* Co. 1921. 



phthalic acid-d-monomenthylester (m. p. 207 to 208°; [a] D — 11.70°); the phthalic acid- 

 d-monomenthylester (m. p. 107 to 108°; [a] D — 107.50°); the phthalic acid-d-mono- 

 menthylester (m. p. 107 to 108°: [«] D -f- 18.40°); the phthalic acid-Z-monopulegylester 

 (m. p. 212°; [a] D — 86.80°). The bromination of Z-pulegol yielded a product, the bromine 

 percentage of which was slightly diminished by the distillation to less than would 

 correspond to the formula Ci Hi 6 OBr 2 . This peculiarity stands in need of an explanation. 



Carvomenthol. — Since carvomenthol contains three asymmetric carbon atoms, eight 

 optically-active modifications are possible, as in the case of menthol. V. Paolini 1 ) 

 succeeded in decomposing inactive carvomenthol (b. p. 218°) which he had obtained 

 from carvone (b. p. 224 to 225°; d 20 o 0.9596; -[«] D + 62.4°) into I- and d-carvomenthol. 

 The author applied the same method which he had found useful in the investigation 

 of other terpene alcohols 2 ). The method is briefly this: — Work without any heating 

 and prepare characteristic crystallisable double salts of the acid phthalate and various 

 bases of organic or inorganic character. 



Thus Paolini prepared from the inactive carvomenthol the strychnine salt of 

 /-monocarvomenthyl phthalate (m. p. 155 to 156°; [a] D — 14.76°) and from this further 

 the /-monocarvomenthyl phthalate (m. p. 125°; [a] D — 3.80°) and Z-carvomenthol 

 (b. p. 218° [corr.]; d 15o 0.9082; [«] D — 1.82°; n D15 o 1.461). He further isolated the 

 silver salt of the d-monocarvomenthyl phthalate (m. p. 109°; |>] D + 4.62°) and ^-carvo- 

 menthol (b. p. 218° [corr.]; d 15o 0.9082; [«] D + 1.82°; n D15 o 1.461). 



Terpin. — According to O. Fernandez and N. Luengo 3 ) only one of the hydroxyl 

 groups of this glycol is acetylated when terpin is treated with acetic anhydride and 

 anhydrous sodium acetate. When, however, a solution of terpin in oil of turpentine is 

 treated in the same way, the acetylation is complete. 



As regards piperitol, see page 23 of this Report. 



Aldehydes. 



The process for the preparation of aldehydes and ketones from primary and secondary 

 alcohols, which is described by Ch. Moureu and G. Mignonac 4 ) and which is very 

 suitable in the case of alcohols of low molecular weight, gives less good yields with 

 compounds of higher molecular weights. The authors have now 5 ) succeeded in getting 

 over this difficulty by treating the alcohols with oxygen, as before at 230 to 300° and 

 in the presence of a catalyst, but at diminished pressure (20 to 40 mm.). 



By this modified method the authors have obtained benzaldehyde and cinnamic 

 aldehyde (yield 80 to 90 per cent), methylhexyl ketone and dodecyl aldehyde (yield 

 80 per cent.) further from geraniol, without any noticeable decomposition, citral. 



In a paper on the Doebner reaction R. Ciusa and G. Zerbini 6 ) state that they 

 obtained by the action of an aldehyde upon pyroracemic acid and fi-naphthylamine, 

 in addition to the main product, a /2-naphthocinchonic acid, the corresponding tetra- 

 hydro compound and yet a second by-product. Thus they prepared from anisaldehyde: — 

 «-anisyl-/?-naphthocinchonic acid C21H15O3N (m. p. 283°), the tetrahydro derivative 

 C 2 iH 19 3 N (m.p. 234°) and 2>methoxybenzyl-/?-naphthylamine Ci H 7 NH • CH 2 • C 6 H 4 • CH 3 





*) Bend, della R. Accademia del Lincel, Roma 28 (1919), II. 82. Reprint kindly sent to us. — *) Cf. Report 

 October 1911, 142; October 1915, 79, 80; 1917, 149. — *) Journ. Soc. chim. Ind. 39 (1920), A. 704. — 

 *) Cf. Report 1920, 132. — 5 ) Compt. rend. 171 (1920), 652. — 8 ) Gazz. chim. ital. 50 (1920), II. 317. 



