3o 4 SCIENCE PROGRESS 



Now naphthalanemorpholine, when subjected to exhaustive 

 methylation, gives as ultimate products naphthalene and 

 hydroxyethyldimethylamine — morphine, it will be remembered, 

 gave under similar treatment a derivative of dihydroxy- 

 phenanthrene and also hydroxyethyldimethylamine — and it was 

 on these grounds and also the close similarity in properties 

 shown by naphthalemorpholine and morphine that Knorr 

 originally suggested 



OH 

 CH o 



(C, H S OH)( 



CH 2 N.CH 3 



as the constitutional formula for morphine— a formula which 

 was disproved by his own subsequent work. 



ISOMERIDES OF MORPHINE AND CODEINE 



It has been shown by Vongerichten 1 that by the interaction 

 of codeine and phosphorus pentachloride, the alcoholic hydroxyl 

 group of the former is replaced by chlorine and a crystalline 

 base, chlorocodeide C 18 H 2 o0 2 NCl, obtained. Recently, Schryver 

 and Lees 2 have made an extended study of this and similar 

 compounds and have prepared chloromorphide Ci 7 H 18 2 NCl, 

 bromomorphide Ci 7 H 18 2 NBr, and bromocodeide C^rl^ONO by 

 the interaction of morphine and codeine with phosphorus 

 halides ; the same two investigators have also demonstrated 

 that when these halogen derivatives are hydrolysed by water, 

 morphine and codeine are not simply regenerated, but that in 

 each case at least two bases isomeric with, but not identical 

 with, morphine and codeine respectively are produced. 



Vongerichten 3 (and independently Knorr and Horlein 4 ) has 

 proved that chlorocodeide on hydrolysis yields an isomeride 

 of codeine which is identical with the so-called " /wwafocodeine " 

 first obtained by Merck 5 by the interaction of dilute sulphuric 

 acid and codeine. Lees 6 has also shown that when chloro- 

 morphide is methylated, a chlorocodeide identical with the 



1 Annalen, 210, 107. 4 Ber. 39, 4409. 



2 Trans. 77, 1024 ; 79, 563. 5 Arch. Pharm. 229, 161. 



3 Ber. 36, 159. 6 Trans. 92, 1408. 



