( 660 ) 



important to furtlier eoiitiiiu tliis statement and as Dr. Beekman could 

 not undertake tliis himself, I have studied this subject once more 

 and now communicate the I'esults obtained. 



Tlie (Htïicullv wliicli presented itself was tluit we were unalile lo 

 obtain benzene orthonitrofluoride so lliat il was impossible to ajjply 

 tlie methods which, in the case of the products of nitration of the 

 other halogen benzenes, lead to the knowledge of the proportion in 

 which the isomers are foi-med. Two observations by Dr. Beekman 

 furnished us, however, A\ith a key to tind the said proportion. Tliese 

 were: J. the very ready traii^foi-niatio]! of benzene /3-nitrotlnoride 

 with sodium methoxide into the coirespojiding- anisol ; 2. the further 

 jiitration of the benzene orthonitrotluoride present in the nitrating 

 mixture to benzene dinitrotlnoride (Fl : XOg : NO^ = 1:2:4) which 

 compound lia> l»eeii obiaiiicd by Dr. Beekman in a pure coiKbtion. 



I con\inced myself in the tirst place of the quantitative course of 

 tlie transformation of benzene y>-nitrotlnoride with XaOCH,. 



1.8347 grams of p-NOo Cg H^. Fl = 13.01 millimols. were dis.solved in a very- 

 little pure methyl alcohol, an equivalent quantity of sodium metoxide dis- 

 solved in methyl alcohol to the concentration of 0.75 normal was added 

 and the mixture w-as heated in a reflux apparatus for fully one hour in 

 the boiling waterbath. The liquid still possessed a faint alkaline reaction 

 but became neutral on our adding a trace of dilute acetic acid. On pouring it 

 into water a very beautiful white mass was precipitated which was drained 

 and then air-dried. Without being reerystallised it exhibited a melting 

 point of 52 — 53", showing it to be pure pnitranisol. 



On the other hand in tiiis dilution benzene metanitrolluoride is 

 but very little affected by treatment with sodium methoxide for one 

 hour in the boiling waterl)ath : 



1.0842 grams »«-X0o Cg H^ Fl = 7.7 millimols. were mixed with Ittc.c. of 

 w/i.295 NaOCHg this being the equivalent quantity. After being diluted with 

 water, the liquid was titrated back with 7.50 cc, of n acid, theory requiring 

 7.7 cc. Only 0.2 millimols of the compound had therefore, been decomposed, 

 or 2.6% ^f the total amount. 



This renders it possible to (juantitati\"ely determine the amount of 

 benzene />- and /«-nitroflnoride in a mixture of the two com|»ounds 

 as shown by the following experiments : 



(/. 1.1040 grams = 7.83 millimols. of a mixture of 89 y/„ of the para and 

 no/,, of the meta compound were mixed with 10.1 cc. of n\.n,y, sodium 

 methoxide ;md heated in a retlux apparatus for one hour in the boiling water- 

 bath. After being poured into svater the liquid was titrated back with 0.8 cc. 



