RECENT WORK ON THE MORPHINE GROUP 293 



chlorethyldimethylamine are heated with an excess of caustic 

 soda. 



The decomposition of a- or /3-methylmorphimethine with 

 sodium ethoxide gives, in addition to methylmorphol, the 

 hitherto unknown dimethylamino ether, (CH 3 ) 2 N . CH 2 . CH 2 . O . 

 CH 2 . CH 3 , which, according to Knorr, may be obtained synthe- 

 tically by the interaction of dimethylamine and iodo-ether, 



CH 3 \ CH 3 \ 



)nh + ich, . ch 2 . o . c 2 h 5 = > n . ch 2 . ch 2 . o . c 2 h s 

 ch 3 / ch/ /\ 



H I 



or by heating chlorethyldimethylamine with sodium ethoxide, 



CHa CHa 



>N . CH 2 . CH 2 C1 + NaOC 2 H 5 = >N . CH 3 . CH 2 . O . C,H 5 + NaCl 



CH 3 / CH 3 / 



When codeinonemethiodide or thebainemethiodide is heated 

 with alcohol at 160 — 165 , they yield respectively a mixture of 

 3-methoxy-4, 6-dihydroxyphenanthrene and dimethylaminoethyl 

 ether in the first case and thebaol and dimethylaminoethyl 

 ether in the second. These reactions suggest that the meth- 

 iodides of codeinone and thebaine possess a very labile 

 linkage, from which the three-membered complex, C.C.N, may 

 be expelled with great ease. It is of great, interest to note 

 that this three-membered complex is obtained in the form of 

 dimethylaminoethyl ether in the two reactions described above, 

 for it is clear that this substance cannot be the primary decom- 

 position product. According to Knorr, the only reasonable 

 assumption is that the three-membered complex is first liberated 

 in the form of an unsaturated compound — probably a vinyldi- 

 methylamine, and that this, in the nascent state, combines with 

 alcohol to form the ether base : 



(CH,) 2 N . CH : CH 2 + C 2 H 5 OH = (CH 3 ) 2 N . CH 2 . CH 2 . O . C 3 H 5 



In a similar manner, the formation of the acetic ester of a 

 hydramine in the case of an acetic anhydride decomposition 

 may be accounted for by the combination of acetic acid and the 

 originally formed vinyl base : 



(CH,),N . CH : CH 2 + CH s COOH = (CH 3 ).,N . CH 2 . CH, . O . COCH 3 



