RECENT WORK ON THE MORPHINE GROUP 285 



The Nitrogen-free Products of Exhaustive Methylation 



Morphol is obtained in the form of the acetyl derivative 

 of its monomethyl ether by heating methylmorphimethine with 

 acetic anhydride, as represented by the equation : 



CH 3 0\ 



XC 4 H 9 0)C,H, . N(CH 3 ), + 2(CH 3 CO),0 = 

 HO/ 



Methylmorphimethine 



CH 3 0\ 



>C'<H 8 + CH 3 . CO . O . C,H 4 . N(CH 3 ) 2 + 2CH3COOH 

 CH 3 . CO . 0/ 



Acetylmethylmorphol Acetoxyethyldimethylamine 



When acetylmethylmorphol is oxidised by means of a solution 

 of chromic acid in glacial acetic acid, it is converted into acetyl- 

 methylmorpholquinone which is readily shown to be a derivative 

 of phenanthraquinone : 



CH 3 0\ CHsOv 



>C 14 H 8 -> >C )4 H 6 2 



CH 3 CO . 0/ CH3CO . 0/ 



Acetylmethylmorphol Acetylmethylmorpholquinone 



In view of the fact that acetylmethylmorpholquinone is 

 obtained by this reaction, neither of the hydroxyl groups of 

 morphol can be attached to the " bridge " carbon atoms of the 

 pJienanthrene complex, for if such were the case they would 

 disappear in the process of oxidation. Hence they must either 

 be distributed between the two remaining rings or be both 

 attached to one of them. The latter assumption has proved to 

 be correct since acetylmethylmorpholquinone, as also morphol- 

 quinone, yields phthalic acid on further oxidation. This 

 conclusion is supported by the fact that Barth and Weidel ' 

 obtained protocatechuic acid by fusing morphine with caustic 

 alkali. 



Morphenol may be obtained as a methyl ether by heating 

 a-methylmorphimethine methohydroxide, but a better yield is 

 secured if, as mentioned above, the corresponding /3-derivative 

 is employed. According to Vongerichten, 2 the decomposition 

 takes place as follows : 



CH,0\ 



>(C,<H 9 0)C 2 H 4 . N(CH 3 ) 3 OH = (CH 3 0)C H H 7 + 2H,0 + C 2 H, + N(CH a ) s 



HO/ 7 



0-Methylmorphimethine Morphenol Eth)lene 



methohydroxide methylether 



Wien. Monatsh. 4, 700. 2 Ber. 29, 67. 



