= PAE Pee oe eee 
‘ a a 
82 REPORT OF SCHIMMEL & Co. OCTOBER 1915. 
In a paper by G. Reddelien') on the addition products of nitric and picric acids E 
with unsaturated organic compounds we find the description of the picrates of benzal- — 
dehyde and cinnamaldehyde. The picrate of benzaldehyde forms when picric acid is — 
dissolved in benzaldehyde under heating; it crystallizes in splendid light-yellow prisms 
of about 1 cm. in length, melting at from 70 to 72°. It is fairly unstable, the crystals 
decay quickly, losing benzaldehyde. In order to prepare the picrate, cinnamaldehyde 
is saturated with picric acid at about 70° and then cooled in a freezing mixture. It 
forms light-yellow prisms melting at 66 to 67°, which after some time gai the smell 
of cinnamaldehyde but are very stable, generally speaking. 
As to the formation of benzaldehyde by means of tyrosinase, see p. 68. 
; - 
Cinnamaldehyde. In order to reduce cinnamaldehyde, E. Rona?) added yeast to 
a sugar solution and, after the fermentation had started, cinnamaldehyde, when cinnam- 
alcohol resulted. 
o-Vanillin. Whilst the derivatives of vanillin and piperonal (heliotropin) are well 
investigated, little is known regarding those of o-vanillin and o-veratraldehyde, as 
they are accessible only with difficulty. In order to fill this gap at least in part, 
W. H. Perkin and R. Robinson®) prepared some derivatives of these aldehydes, viz., 
those of benzoic acid, benzyl alcohol, cinnamic acid, phenylpropionic acid, hydrindone, 
and other simple derivatives of the o-veratric series. 
Homovanillin. As stated on p. 103 of our previous Report, C. Harries and R. Haarmann 
obtained on reduction of normal eugenolozonide homovanillin as a thick oil, which, 
as per the results of the analysis, was not pertectly pure. When distilled under 
reduced pressure (0,25 mm.), as Harries*) says in a later publication, homovanillin 
boiled between 105 and 106° and congealed on standing at a low temperature to a 
white crystalline mass, from which homovanillin in a chemically pure state could be 
obtained by treatment with carbon disulphide and carbon tetrachloride. It melts at 
from 50 to 50.5° and smells agreeably, flower-like, somewhat less strongly than vanillin 
but perhaps more like vanilla. The p-nitrophenylhydrazone melts at 154.59. Homo- 
vanillin is a very sensitive body which, on distillation in vacuo, leaves a sytupy, 
red residue. 
Ketones. | 
Anhydroxylamines of unsaturated ketones. 
As Semmler®) found at the time, an anhydro-compound, the imino-base CioHi,NO, 
results from pulegonehydroxylamine by splitting off water. Harries obtained in a similar 
way an anhydro-compound from diacetonehydroxylamine; santolinenone‘), the structure 
of which is analogous with that of pulegone, likewise yields an imino-base in this way. _ 
L. Francesconi and G. Sanna’) conjecture therefore that anhydro-bases generally result 
from the hydroxylamino compounds of cyclic «-unsaturated ketones, the double-linking 
1) Journ. f. prakt. Chem. Il. 91 (1915), 239. — °) Biochem. Zeitschr. 67 (1914), 137; Chem. Zentralbl. 1915, 
1. 619; comp. Report April 1915, 91. — #) Journ. Chem. Soc. 105 (1914), 2376. — 4) Berl. Berichte 48 (1915), 
868. — 5) Berl. Berichte 37 (1904), 305, 134; Report October 1904, 124. — *) Comp. Report April 1915, 41. — : : 
*) Gazz. chim, ital. 45 (1915), 1. 35; Chem. Zentralbl. 1915, 1. 1117. : 
