August;  issT"*}      Conversion  of  Morphine  into  Codeine.  411 
rotatory  power.  M.  Grimaux  considers  that  this  divergence  must  not 
be  taken  as  proving  any  difference  in  the  alkaloids,  but,  judging  from 
their  exact  agreement  in  other  respects,  is  probably  only  an  error  of 
experiment.  Hesse  attempted  to  prepare  codeia  by  acting  with  methyl 
iodide  on  a  methylic  alcohol  solution  of  morphia  potassium.  By  this 
means  he  obtained  /9-methyl -morphia,  isomeric  with  codeia.  Accord- 
ing to  Hesse's  description,  this  alkaloid  is  amorphous,  and  its  hydro- 
chloride differs  in  some  important  respects  from  that  of  codeine.  For 
instance,  it  loses  all  its  water  of  crystallization  at  100°C.,  while  hydro- 
chloride of  codeia  loses  only  half  a  molecule  under  the  same  circum- 
stances. The  solubility  of  the  artificial  salt  at  18°C.,  in  water,  is  1  in 
10*8,  while  that  of  codeia  muriate  is  1  in  23-8.  A  saturated  solution 
of  the  former  gives,  with  potash,  an  oily,  permanently  amorphous  pre- 
cipitate, but  the  codeine  salt  gives  at  once  a  crystalline  precipitate.. 
The  specific  rotatory  power  of  both  was  found  to  be  the  same.  Hesse 
holds  that  the  idea  of  the  identity  of  these  two  salts  cannot  be  main- 
tained on  account  of  the  differences  above  referred  to,  especially  the 
fact  of  the  ^-methyl-morphia  being  only  obtained  in  the  amorphous 
state.  As,  however,  M.  Grimaux  did  not  employ  morphia-potassium,, 
but  morphia-sodium,  Hesse  repeated  his  experiment,  using  the  latter 
instead  of  the  potassium  compound,  but  in  other  respects  conducting 
the  experiment  as  before.  By  this  means  he  obtained  a  mixture  of 
/9-methyl-morphia  and  a  base  having  a  great  similarity  to  codeia," 
differing  indeed  therefrom  only  in  its  optical  behavior. 
In  my  first  experiment  I  conducted  the  operation  of  converting  the 
mor23hia  into  codeia,  according  to  the  process  described  by  Grimaux, 
using  molecular  proportions  of  morphia,  soda,  and  methyl  iodide.  The 
alcohol  was  distilled  off  and  the  residue  exhausted  with  ether.  The 
ether,  on  evaporation,  deposited  well-defined  crystals,  resembling  the 
ordinary  hydrate  of  codeia.  These  crystals  were  converted  into  hydro- 
chloride, which  was  purified  by  recrystallization  from  water.  An 
aqueous  solution  was  prepared  by  digestion  at  the  ordinary  temperature, 
and  the  solubility  of  the  salt  determined  by  evaporating  a  weighed 
portion  of  the  solution  to  dryness,  the  weight  of  the  residue  plus  2'42 
per  cent,  being  taken  as  the  weight  of  crystallized  salt  dissolved.  At 
12°C.  the  solubility  indicated  Avas  1  in  27*0.  As  regards  its  rotatory 
power,  the  result  obtained  was  («)o=  — 109'9.  Codeia  hydrochloride 
prepared  from  opiuni  gave  a  solubility  of  1  in  28  2  at  12°C.,  and  a 
specific  rotatory  power  (determined  as  above)  of  —  IH'O. 
