Messrs Jones and Millington, The Spatial, etc. 489 



The Spatial Configuration of Trivalent Nitrogen Compounds. 

 By H. 0. Jones, M.A., Clare College, and J. P. Millington, B.A., 



Christ's College. 



[Received 17 May 1904.] 



Ever since the hypothesis of Hantzsch and Werner was proposed 

 to explain isomerism of the oximes and allied compounds the 

 problem as to whether trivalent nitrogen compounds of the type 

 N-R/R/'B/" were capable of showing optical activity or not has 

 attracted considerable attention. Since in the cases mentioned 

 above the isomerism is explained by supposing that when a 

 nitrogen is doubly linked to a carbon atom, the third valency is not 

 in the same plane with the other two and the nitrogen atom, it 

 has been assumed that the three valencies do not lie in the same 

 plane as the nitrogen atom when all three are attached to different 

 atoms or groups. This is not necessarily so. Whatever the nature 

 of the forces acting in a chemical compound may be, the arrange- 

 ment of three atoms or groups around one atom all in one plane 

 being the most symmetrical would probably be the most stable of 

 the possible arrangements. This view is not incompatible with 

 the Hantzsch- Werner hypothesis, since it is quite conceivable 

 that the strain caused by the formation of a 'double union' 

 might cause a displacement in the equilibrium position of the 

 group attached to the third valency. 



Several attempts have already been made to obtain optically 

 active trivalent nitrogen compounds, thus Kraft (Ber., XXIII. 2780) 

 tried to resolve benzylethylamine and p-tolylhydrazine by means 

 of their acid tartrates. Behrend and Konig (Ann., 263. 175) 

 made similar attempts with /3 benzylhydroxylamine, and Reychler 

 (Bull.Soc.Chim.l902[S], xxvu. 979) submitted the dextro-camphor- 

 sulphonate of methyl-ethyl-/3-naphtylamine to fractional crystalli- 

 sation in the hope of effecting a separation into two isomerides. 

 The above attempts were all unsuccessful, and it was therefore 

 concluded that trivalent nitrogen compounds could not exist in 

 optically active forms, and that the three valencies lay in one 

 plane. 



Pope and Harvey (Trans. Chem. Soc. lxxix. 838) point out that, 

 since during a change in valency, a rearrangement of the positions 

 of equilibrium of the various groups or a change in ' valency- 

 direction ' sometimes occurs (a view fully confirmed by experiments 



