Am.  Tour.  Pharm. 
July,  191S. 
Analogues  of  Atropine. 
529 
dopelletierine  with  alcohol  and  sodium,  and  pseudotropine  is  pre- 
pared from  the  corresponding  ketone  tropinone  in  analogous  man- 
ner :  iso-methylgranatoline  and  tropine  are  both  prepared  from  the 
corresponding  ketones  by  reduction  with  zinc  dust  and  hydriodic 
acid.  These  results  show  the  uncertainty  of  associating  similarity 
of  chemical  and  physical  properties  of  compounds  with  similarity  in 
physiological  behavior. 
Experimental. 
Preparation  of  Methylgranatoline. — The  method  used  by  Cia- 
mician  and  Silber,3  slightly  modified,  was  followed.  Ten  Gm.  of 
pseudopelletierine  were  dissolved  in  200  Cc.  of  ethyl  alcohol,  and 
metallic  sodium  added  until  no  more  would  dissolve,  the  reaction 
being  carried  out  in  a  flask  heated  by  a  metal  bath.  Water  was  then 
added,  and  the  alcohol  distilled  off,  and  the  aqueous  alkaline  residue 
made  acid  with  hydrochloric  acid.  This  acid  solution  was  then  satu- 
rated with  sodium  bicarbonate,  and  the  unchanged  pseudopelletierine 
removed  by  shaking  out  with  chloroform.  The  solution  was  then 
made  strongly  alkaline  with  sodium  hydroxide  solution,  and  the 
methylgranatoline  shaken  out  with  chloroform.  Upon  drying  the 
chloroform  solution  over  anhydrous  sodium  sulphate,  the  methyl- 
granatoline was  obtained  as  a  crystalline  solid  upon  distilling  off  the 
chloroform.  Upon  recrystallizing  from  petroleum  ether,  the  pure 
compound  is  secured,  melting  at  ioo°  (uncorr.). 
Preparation  of  Iso-methylgranatoline . — The  method  used  was 
analogous  to  that  used  by  Willstaetter4  in  reducing  topinone  to  tro- 
pine. Ten  Gm.  of  pseudopelletierine  were  dissolved  in  120  Gm.  of 
cone,  hydriodic  acid  ( sp.  gr.,  1 .96) ,  and  was  then  cooled  to  0° .  Twenty 
Gm.  of  zinc  dust  were  then  added,  stirring  constantly,  and  the  tem- 
perature was  not  allowed  to  rise  above  o°.  The  reaction  required 
about  two  hours.  The  mixture  was  allowed  to  stand  for  24^ hours, 
and  then  an  excess  of  sodium  hydroxide  solution  added,  and  the 
mixture  shaken  out  with  chloroform.  This  chloroform  solution 
contained  both  pseudopelletierine  and  the  new  alcohol.  In  order  to 
separate  the  two,  the  chloroform  solution  was  shaken  out  with  an 
excess  of  dil.  hydrochloric  acid,  and  after  separating  from  the 
chloroform,  the  acid  solution  was  saturated  with  sodium  bicarbon- 
3  Ber.,  26,  2740  (1893). 
4  Ibid.,  33,  1 1 74  (1900). 
