290 SCIENCE PROGRESS 



The Positions of the Oxygen Atoms of Morphine 



To gain a deeper insight into the constitution of morphine, 

 it was very important to determine which of the two hydroxyl 

 groups of morphol corresponds to the phenolic hydroxyl of 

 morphine, or, in other words, the methoxyl group of codeine. 

 To this end, Pschorr and Sumuleanu prepared 3-acetoxy- 

 4-methoxyphenanthrene by a reaction analogous to the above, 

 and from this they obtained 3-hydroxy-4-methoxyphenanthrene, 

 which they found to be quite different from Vongerichten's 

 methylmorphol. Hence it follows that the non-nitrogeneous 

 decomposition product obtained from a-methylmorphimethine 

 can only be 3-methoxy-4-hydroxyphenanthrene, and that con- 

 sequently the phenolic hydroxyl of morphine occupies position 3 in 

 the phenanthrene complex. 



That the alcoholic hydroxyl of morphine occupies position 6 in 

 the phenanthrene complex is proved by the following considera- 

 tions. A hydroxymethylmorphol was obtained by the action of 

 acetic anhydride on codeinone: 1 



CH 3 



cm y H HO 



^C l7 H,ON — > HO.C,H 4 .N< 

 CH3O.J \CH 3 + 



Codeinone 



HO 



This body has been synthesised in a manner entirely analogous 

 to that described for dimethylmorphol. Instead of vic.o- 

 nitrovanillin-methylether and sodium phenylacetate, Pschorr 

 started with w'c.o-nitrovanillin and the sodium salt of p-methoxy- 

 phenylacetic acid — 



CHO CH.COOH 



+ 

 CH,OL 'NO, 



OH OCH3 



OCH, 



whereby he obtained 3, 6-dimethoxy-4~hydroxyphenanthrene, 

 and ultimately arrived at 3~methoxy-4, 6-dihydroxyphenan- 

 threne, the identity of which with the hydroxymethylmorphol 

 obtained from codeinone is beyond question. 



1 Ber. 36, 3074. 



