398  The  Technical  Manufacture  of  Cocaine.  {^ASXt.wgT1, 
of  preparing  methyl-ecgonine  directly  in  the  decomposition  of  these 
alkaloids,  thereby  simplifying  the  technical  manufacture  of  cocaine 
from  this  source. 
We  have  found  that  this  problem  is  easily  solved  if  the  alkaloids 
be  boiled  for  several  hours  with  sulphuric  or  hydrochloric  acid  in 
the  presence  of  methyl-alcohol ;  this  gives  conditions  under  which 
methyl-ecgonine  is  not  decomposed,  but,  on  the  contrary,  tends  to 
be  easily  produced  or  formed. 
Fifty  gm.  of  the  cocaine  accompanying  alkaloids  are  boiled  on  a 
water-bath  for  three  to  four  hours  (using,  of  course,  a  reflux  con- 
denser) with  300  gm.  methyl-alcohol  and  100  gm.  pure  sulphuric 
acid ;  after  distilling  off  the  alcohol,  the  syrupy  residue  is  poured 
into  water  (the  quantity  of  this,  however,  must  not  be  excessive), 
the  aromatic  acids,  but  more  especially  their  esters  (methyl-esters), 
which  are  precipitated  are  removed,  and  the  acid  solution  extracted 
with  chloroform  ;  the  acid  solution  is  next  saturated  with  potassium 
carbonate,  and  the  methyl  ecgonine,  which  separates  as  an  oily  layer, 
extracted  with  chloroform. 
The  same  results  are  obtained  when  dry  hydrochloric  acid  gas  is 
passed  into  the  methyl-alcohol  solution  of  the  alkaloids  until  the 
solution,  which  at  first  becomes  warm,  again  becomes  cold ;  the 
solution  is  then  boiled  for  two  hours,  using  a  reflux  condenser,  and 
the  methyl-ecgonin  isolated  as  just  described.  The  ester,  methyl- 
ecgonine,  was  obtained  in  almost  theoretical  quantity ;  it  was  puri- 
fied by  conversion  into  the  hydrochlorate  which,  recrystallized  from 
alcohol,  had  the  melting  point,  as  stated  by  Einhorn  and  Klein,  of 
2120  C.  Distilled  in  a  vacuum,  methyl-ecgonine  gives  in  the  main  a 
distillate  free  from  decomposition  products,  boiling  at  1770  C,  under 
a  pressure  of  15  mm. 
If  in  the  process  as  described  ethyl-alcohol  be  substituted  for  the 
methyl-alcohol,  there  results  ethyl-ecgonine  instead  of  methyl- 
ecgonine.  A  similar  observation  was  made  by  Einhorn  and  Konek 
de  Norwall  when  in  heating  dextro- methyl-ecgonine  in  an  ethyl- 
alcoholic  solution  of  ammonia  in  a  sealed  tube  to  ioo°  C,  they 
found  that  there  was  produced  dextro-ethyl-ecgonine.  We  can  add 
that  cocaine  can  be  quantitatively  converted  into  it?  higher  homo- 
logue,  cocethyline,  by  boiling  for  two  hours  an  ethyl-alcohol  solution 
of  cocaine  which  has  been  saturated  with  hydrochloric  acid  gas. 
