(oio). 



to (liscoiiliiiiio this rescarcli 1 tried al I lic i'G(|iiesl of tlie lale Pro/'. 

 LoHHY DK l^RUYN to delemüiie this constitution. After a few trials 

 which led "to no result the method was followed which had f)roved 

 successful in the determination of the constitution of 2.3.4 trinitro- 

 phenetoP). The constitution of that substance was shown to be: 



C«H, (0C,HJ(N0J3 2.3.4 -^C„H,(00,H3)NH,(N0J., 1.3.2.4-^ 



C,H3(0C,H,)(N0J, 2.4. 



Oxymethyldinitrobenzonitrile was now treated in an analogous 

 manner; by the action of alcoholic ammonia one NO.^-group was 

 replaced by NH^ and this was then in turn removed by diazotation 

 and boiling with alcohol. In this manner was obtained an oxymethyl- 

 nitrobenzonitrile (m.p. 126°) C«H,(OCIIJ CN(NO,), -^ O.H.COCH,) 

 CN.NH.NO, -^ C.H^COCH^lCN.NO.,. 



This shows that the NO,-group at 3 is replaced by NH, as other- 

 wise the original oxymethylniti'obenzonitrile CgH3(OCH3)CN.NO., J.2.3 

 m.p. 171° would have been reobtained. Now it remained only to 

 determine the constitution of this substance. On treatment with nitric 

 and sulphuric acids an oxymethyldinitrobenzonitrile was obtained 

 which melts at 71° and which possesses the following constitution: 

 C„H,(0CH3)CN(N0J/1.2.4.6 ^). 



The constitution of this substance was determined in the following 

 manner. If this compound is treated in alcoholic solution with ammonia 

 or methylamine the OCH, group is readily substituted by NH, or 

 NHCHg and dinitrocyano-aminobenzene m.p. 219^ or dinitrocyano- 

 methylaminobenzene m.p. 161° is formed which substances were 

 prepared previously from the corresponding oxyethyl compound '). 



The oxymethylnitrobenzonitrile m.p. 126° was then heated at 150° 

 with hydrochloric acid for 5 hours. On opening the tube a gas 

 escaped which burnt with a green-bordered flame (CH3CI) whilst in 

 the lube there were present crystals which after recrystallisation 

 from water melted at 228° and proved to l)e 5-nitrosalicylic acid 

 (CeHjCOOH, OH, N0./1. 2. 5.) In the motherliquor the presence of 

 NH3 was detected, formed by saponitication of the cyano-group. 

 For the purpose of identifying the substance obtained a little of the 

 preparation was mixed with an equal quantity of 5-nitrosalicylic acid 

 (m.p. 228' prepared by nitration of salicylic acid '). The melting point 



1) Recueil 27, 49. 



2) This shows that in oxymethylnitrobenzonitrile m.p. 126° the nitro-group is 

 placed on 4 or 6. 



3) Blanksma. Rec. 20, 413. 21, 274. 

 'j HüBNER. Ann. 195, 31. 



