— 151 — 



most energetically when heat was applied, but when the reaction is allowed 

 to take place in the dark and with water-cooling, equimolecular quantities 

 of safrol and nitroso benzene give rise (in addition to azoxybenzene) to a 

 body Ci 6 Hi 3 3 N, which crystallises in yellow needles, m. p. 193°, and 

 which resolves itself on exposure to light into nitrosobenzene and 

 carbylamine. The first-named of these products is also generated under 

 the action of oxidising agents. With permanganate in alkaline solution 

 it yields piperonylic acid, with dilute mineral acids the isomeric Schiffs 

 base Ci 6 Hi 3 3 N, which is stable towards alkalies, a transposition which 

 corresponds with that of phenylhydroxyl amine into p-aminophenol. 

 With acids the Schiffs base can only be hydrolysed with difficulty, 

 forming small quantities of methylene dihydroxy cinnamic aldehyde, 

 which last-named body is generated in large quantities when hydroxyl- 

 amine was allowed to react with the original yellow compound melting 

 at 193° and the resulting oxime (CH 2 2 )-C 6 H 3 -C 3 H 3 : NOH was treated 

 with nitrous acid. The atomic structure of the yellow compound is 

 either that of Formula I or of Formula II, the readiness with which it 

 is generated from methylene dihydroxy cinnamic aldehyde (piperonyl 

 acroleine) and phenylhydroxylamine pointing towards the latter: 



(CH 2 2 )C 6 H 3 CH:CHCH-NC 6 H 5 (CH 2 2 )-C 6 H 3 CH:CHCH:N.C 6 H 5 . 



1 o 11. u 



The course of the reaction is explained by the authors as follows: First 

 the saturated product (CH2 2 )C6H 3 CH 2 CH 2 CH:NC 6 H5 is generated, 



6 

 (a hydrogen atom of the allyl side-chain migrating!); to this product 

 a second nitrobenzene molecule becomes attached, yielding the body 

 (CH 2 2 )-C 6 H 3 -CH 2 CHCH:NC 6 H5. From the last-named, phenyl- 



C 6 H 5 NOH O 



hydroxylamine is splitt off (yielding, with an excess of nitrobenzene, 

 azoxybenzene), giving rise to the yellow product melting at 193°. The 

 analogous product from eugenol ethyl ether had m. p. about 155°. 

 Allessandri x ) maintains that the compounds acquire their yellow colour 

 from the presence of the carbon-carbon double bond, for the analogous 

 compounds from benzaldehyde and phenyl acetic aldehyde are white, and 

 so is the corresponding derivative from /?-c^/cZocitral, in which, it is true, 

 the double bond lies in the nucleus. When hydroxylamine is allowed 

 to react with the above-mentioned phenyl ether this body is split up into 

 the phenylhydroxylamine and the oxime of the fundamental aldehyde of 

 the phenyl-ether : R • CH : NO • C 6 H 5 + NH 2 OH = R ■ CH : NOH + C 6 H 5 NHOH. 

 When exposed to light for a short time, the phenyl ethers of the oximes 



J ) Rendiconti della R. Accad. dei Lincei Vol. 19, Ser. 5, 2 nd Half-year, no. 3, p. 122 

 (August 1910). From a reprint kindly sent to us. 



