TRANSACTIONS OF SECTION B. 637 



6. The Action of Oxides of Nitrogen on Oximido- compounds. 

 By W. Sloan Mills, M.A. 



In connection with tlie study of the chemistry of indiarubber, in which 

 Professor Harries, of the University of Berlin, is at present engaged, and which 

 takes the form in the first place of an investigation into its behaviour towards 

 oxides of nitrogen, I was intrusted with the simpler preparatory problem of investi- 

 gating the action of oxides of nitrogen on oximido-compounds. For this purpose 

 benzalisonitrosoacetone was prepared, which on being treated witli free hydroxyl- 

 amine under certain conditions in metbyl-alcohol solution yielded long colour- 

 less prism-shaped crystals of benzalisonitrosoacetoxime (C,.H.CH = CH'C 

 = NOH-CH. = NOH) melting at 201°-202° C. These were sparingly soluble in alcohol, 

 chloroform, and acetone, soluble in glacial acetic acid, and insoluble in absolute 

 ether. When the oxime was suspended in absolute ether, and treited at a low 

 temperature with nitrogen peroxide, a light flocculent precipitate of the nitrate of 

 benzalmetbylglyoximehyperoxide 



CgH-CH • CH,,- C • CH 



I " '! •! 



U • NO,, N N 



' I ! 

 0-0 



was formed, which melted when pure at 101°-102° C. It was insoluble in dilute so- 

 dium hydroxide and did not reduce Fehling's solution in the cold. When this sub- 

 stance was slightly heated in benzene solution, or in glacial acetic-acid solution it 

 was decomposed with the evolution of red fumes and the formation of benzalmethyl- 

 glyoxalketoxime (C,HjCH = CH ■ C = NOH • CHO). When recrystallised from 

 absolute alcohol, and subsequently from benzene, benzalmethylglyoxalketoxime 

 separated in the form of slightly brown needle-shaped crystals melting at 

 103°-104° C. It was easily soluble in chloroform, acetone, benzene, and glacial 

 acetic acid, and was soluble in ether. It reduced Fehling's solution in the cold 

 and was soluble in dilute sodium hydroxide and in dilute nitric acid. When 

 acted on by semicarbazide it yielded two isomeric semicarbazones, one of which 

 was easily soluble in glacial acetic acid, and melted at 225°-226°C.,and the other 

 which was insoluble in all the usual organic solvents, melted at 242° C. 



Hence by preparing the oxime of benzalisonitrosoacetone, treating this with 

 nitric peroxide and decomposing the resulting compound by heatino- it in benzene 

 solution, the interesting transformation of benzalisonitrosoacetone (C.H CH 

 - CH • CO • CH = NOH) into the isomeric benzalmethylglyoxialketoxime CC^H^CH 

 = CH-C = NOH- CHO) was accomplished. ^ ' ' 



When benzalisonitrosoacetone was dissolved in absolute ether and treated in a 

 freezing mixture with nitrogen peroxide benzalisonitrosoacetone pseudonitrole 

 (C,H,CH = CH-CO-CHNO-NO,) was formed. It was obtained crystalline 

 Irom benzene in the form of yellow plates, melting at 123°-124° C, and was very 

 soluble in most organic solvents. It gave Liebermann's nitroso-reaction and did 

 not reduce Fehling's solution in the cold. ' 



Isonltrosoacetone semicarbazone (CH, • C( = N • NH-CO • NH )-CH = NOH> 

 was prepared and gave white crystals, melting at 219°-220° C. It gave Lieber- 

 mann's nitroso-reaction, and was insoluble in concentrated sodium hydroxide and 

 soluble in dilute sodium hydroxide. When heated on a water-bath with acetic 

 anhydride acetylisonitrosoacetone semicarbazone was obtained, which when 

 recrystallised from glacial acetic acid gave cubic crystals meltino- at 186° C. It 

 dissolved in dilute sodium hydroxide, and when repreeipitated with dilute' sul- 

 phuric acid needle-shaped crystals melting at 218°-219° C. separated. Hence it 

 was reconverted into the original semicarbazone by elimination of the acetyl 

 group. When isonitrosoacetone semicarbazone was treated with nitrogen peroxide 

 at a low temperature the pseudonitrole of isonitrosoacetone semicarba/onf. 

 (CH3C ( = N • NH • CO • NH,) • CH = NO • NO,) was formed. It melted at 163°! 

 164 C. with sudden decomposition and gave Liebermann's nitroso- reaction. It 



