150 Report of Schimmel $ Co. April/October 1917. 



benzine); [«] D — 14°63' (in methylalcohol ; c = 7.382). The acid phthalate produced 

 on saponification pure sabinol, boiling at 208°; d 15 o 0.9518; [«]d+7°56'; n D18 o 1.4895. 

 The strychnine salt of acid phthalic sabinol ester forms colourless needles melting at 

 200 to 201°. This investigations proved that savin oil contains no other isomeric 

 sabinols. 



Ketones. 



Condensation of methylethylketone with benzaldehyde. — Some times ago, already Harries 

 and Miiller 1 ) demonstrated that methylethylketone condenses with benzaldehyde in the 

 presence of alkali, forming thereby an «-benzylidene derivative, whereas in the presence 

 of muriatic acid a /-benzylidene derivative is produced. Accordingly to their opinion 

 the "-compound forms with benzaldehyde a further condensation product, namely a 

 pyrone compound, Ci8Hi 8 2 , melting at 68.5°. H. Ryan and A. Devine, 2 ) on repeating 

 these experiments, indeed obtained the same a-benzylidene compound, but instead of 

 the substance Ci 8 Hi 8 2 , melting at 68.5°, they got an isomeric compound or the same 

 one in a purer state, as it gave a melting point of 81 to 83°. They regard it as an 

 unsaturated ketone and not as a pyrone derivative because it produces an orange 

 colouring with concentrated sulphuric acid. 



Methylethylketone condenses with piperonal (heliotropine) in a solution of alcoholic 

 hydrochloric acid, producing a blue substance (an oxonium-salt?) which forms with 

 alkali a compound C 28 H 2 o07, melting at 212°. 



On the use of methylheptenone as an insecticide vide page 138 of this Report 



Transformation of tribromotetrahydrocarvone into dihydroxycitronellic acid. — G. Cus- 

 mano 3 ) described some time ago, in common with P. Poccianti, the transformation of 

 dibromotetrahydrocarvone into buchu camphor, whereby he assumed the formation of 

 two unsaturated intermediate products which he imagined were changed by means of 

 mutual reduction and oxidation between the double bond and the secondary carbinol into 

 a ketone tautomeric to buchu camphor. Cusmano 4 ) has now attempted to produce similar 



H 3 ( 

 H 2 C 



:-CBr 



CO 



H 3 C 

 H 2 C 



:cc 



)H 

 CO 



H3CCOH 



H.c/^SCHOH 



H 2 C 



CH 



CHBr 



H 2 C 



c 



CHOH 



H 2 cl J CO 

 C 



H 3 CCBr.CH 3 



HsC'C'CHs 



H.C-C.-.CH. 



(I) Tribrom 



tetrahy 



drocarvone. 



(II) Hy 

 mec 



Dotheti 

 iate pr 



:al inter- 

 oduct. 



(Ill) a, /3-Dihydroxy- 



citronellic acid. 



unsaturated carbinols by starting from halogenized terpene ketones' whose halogen he 

 removed by means of alkali, for which purpose the tribromotetrahydrocarvone (I), 

 described by Wallach, 5 ) seemed suitable to him. Contrary to his expectations, however, 

 alkali did not effect the formation of a double bond in the nucleus, but instead of 

 that the bromine atoms round the nucleus were substituted by hydroxyl. The resulting 

 compound (II) is then split up either directly or after rearrangement by the alkali into 

 a tautomeric substanc, an acid Ci Hi 8 O4, an «,/?-dihydroxycitronellic acid (III). The 



!) Berl. Beriehte 35 (1902), 966. — 2 ) Proc. Roy. Irish Acad. 32 (1916), 208; Journ. chem. Soc. 110 (1916), 

 I. 654. — ») Chem. Zentralbl. 1914, II. 481 ; Report April 1916, 104. — 4 ) Atti R. Accad. del Lincei, Rome (5) 

 24 (1916), II. 520; Chem. Zentralbl. 1916, I. 1146. — B ) Liebigs Annalen 286 (1895), 127. 



