- 1 8 3 - 



mass which cannot be easily purified. Judging by the melting-point 

 curve this is a combination C 6 H 5 • CHO • HN0 3 , m. p. -(-5,4°. (Ac- 

 cording to Germ. Patent 206 695, the m. p. lies at about — I °) 1 )- 

 Crystalline compounds were also obtained from cenanthol and from 

 methylnony Ike tone. 



It is known from the work of Thorns 2 ) and his collaborators that 

 nitric acid also acts in another manner by displacing aggregations 

 of atoms, 



A similar process of reaction was observed by A. H. Salway 3 ) in 

 the course of the action of nitric acid upon myristicinic aldehyde. In 

 this process, in addition to nitro-myristicinic aldehyde, there is formed, 

 owing to substitution of the aldehyde groups, 5-nitro-i-methoxy-2, 

 3-methylenedioxybenzene, as shown by the following equations : — 

 CH CH CH 



/OcAccho /OcAccho /OcAc_no 2 



H 2 C< II I H 2 C<( II I H 2 C< || I 



x OC ^CH x OC .C-N0 2 X)Cv /H 



COCH3 . COCH s COCH 3 



Myristicinic aldehyde Nitromyristicinic aldehyde 5-Nitro-i-methoxy- 



2, 3-methylenedioxybenzene 



It was clear from the analogous processes of acting with nitric 

 acid upon anisic aldehyde, piper onal, and vanillin-methyl ether, that 

 the reaction described above, viz., the displacement of the aldehyde- 

 group by the nitro-group, applies generally to the ethers of the aromatic 

 hydroxy-aldehydes. Accumulation of alkoxyl groups facilitates the sub- 

 stitution. 



As Semmler 4 ) has shown, aldehydes which have in adjacent 

 positions one or more H-atoms of the CHO-group, when boiled with 

 acetic acid anhydride and sodium acetate, give mono-esters, by reacting 

 in the enolic form. By means of this reaction, Semmler 5 ) was able 

 to show that for camphenilanic aldehyde only the camphene formula 

 applies, which contains a tertiary H-atom vicinal to the CHO-group. 



>C H 2 C H 2 



CH CH 2 ^CH 



\cH(CHO)-C(C 3 H) 2 

 Camphenilanic aldehyde 



When camphenilanic aldehyde was boiled for an hour with acetic acid 

 anhydride there was formed, in addition to a little di- acetate, enol- 



*) Chem. Zentralbl. 1909, I. 805. 



2 ) Comp. Report October 1903, 99. 



3 ) Proceed, chem. Soc. 25 (1909), 160. 



4 ) Berl. Berichte 42 (1909), 584; Report April 1909, 128. 



5 ) Berl. Berichte 42 (1909), 963. 



