— i77 — • 



The oxime of the ketone boils at 16 mm. pressure about 138 to 

 140 , and when recrystallised from a mixture of ether and petroleum 

 ether, melts at 150 to 151 . Barbier and Grignard ascribe to 

 this ketone the following formula: 



CH, 



1 







-co 





1/ 



CH: 



CH 2 



= CH 



\CH 

 -CH 2 



• C\ 



CH, 



CE 



(6) (5) 



CH CH 



(l)/(7) (8) \(4) 



CH3.C — CH 2 — CH 2 — CH 



\ / 



CO c 



(2) /(3)\ 



CH 3 CH 3 

 and they designate it as trimethyl- 1, 3, 3-bicyclo- 1, 7, 8,4-hexene-5-one-2 ; 

 they consequently look upon the bridge as a special substituent, the 

 original ring thereby becoming more manifest. 



Nitrogenous Bodies. 



The generally accepted view that the nitrites of primary amines 

 of the aliphatic series are unstable compounds which decompose the 

 moment they are formed, is opposed to by Wall a ch 1 ) in his treatise 

 On the behaviour of nitrites of primary bases, and on the ring- 

 enlargement of carbocyclic systems. He proves that these bodies, 

 and particularly those of the primary alicyclic bases, when every trace 

 of free acid is kept away, are partly so stable, that they can be 

 recrystallised from hot water. On the other hand, the smallest quantity 

 of free acid has in a high degree a decomposing action. For example, 

 the very stable recrystallised nitrites of 1-menthylamine (decomposing 

 point 1 39 ) and of pinylamine (decomposing point 125 ), are obtained 

 by bringing together concentrated aqueous solutions of the corresponding 

 hydrochloride and sodium nitrite. In the case of readily soluble 

 nitrites, comparatively stable nitrite solutions can be obtained. Of 

 aromatic bases, 4-amido-i, 3-xylene which Wallach employed for his 

 examination, forms a solid nitrite, which at the temperature of the 

 room gradually deliquesces. 



The view which is still largely held, that in converting primary 

 amines with sodium nitrite, the corresponding alcohol must always be 

 formed, does not, according to Wallach, apply, — a fact on which 

 O. Meyer 2 ) and M. Freund 3 ) have also laid stress. On the contrary, 

 there occur as reaction - products, in addition to hydrocarbon, one or 

 more alcohols isomeric with each other. The direction in which the 

 reaction chiefly progresses depends upon the bases employed and the 

 conditions of the experiment. For instance, 1-menthylamine nitrite yields 



3 ) Liebig's Annalen 353 (1907), 318. 



2 ) Berl. Berichte 9 (1876), 535. 



3 ) Ibidem 23 (1890), 2865; 24 (1891), 2150, 3350. 



12 



