668    Monobromated  Camphor  in  Migraine  Tablets.  { A^J0°kerr'  ^JJ-* 
by  Schiff,6  who,  operating  with  sodium  on  a  solution  of  the  camphor 
derivative  in  toluene,  showed  the  result  of  such  action  to  be  sodium 
bromide  and  sodium  camphor.  Taking  advantage  of  this  observa- 
tion and  subjecting  the  resulting  products  to  titration  via  Volhard, 
Andre  and  Leulier7  report  satisfactory  results  in  the  examination  of 
several  commerical  samples  of  the  drug. 
In  medicaments  like  migraine  tablets,  however,  the  problem  of 
evaluating  the  camphor  derivative  becomes  more  complicated.  In 
addition  to  vehicular  and  other  more  or  less  inert  materials  peculiar 
to  such  products,  we  have  here  a  preparation  consisting  essentially 
of  acetanilide,  caffeine,  and  monobromated  camphor,  with  sometimes 
salicylates  and  plant  extractives.  From  mixtures  of  this  character 
monobromated  camphor,  on  account  of  its  physical  properties,  is 
hardly  susceptible  of  quantitative  isolation  by  means  of  immiscible 
solvents,  although  a  gross  separation  of  the  drug  in  solution,  along 
with  acetanilide,  caffeine,  and  other  extractable  material  eventually 
present,  may  indeed  be  made  by  a  systematic  treatment  of  the  pow- 
dered tablets  with  alcohol,  benzene,  or  toluene.  Such  procedure, 
however,  almost  invariably  gives  rise  to  solutions  of  so  unwieldy 
and  varying  a  volume  as  to  render  any  subsequent  reduction,  with 
sodium  for  example,  quite  valueless,  owing  to  the  uncertain  quantity 
of  metal  required  and  consequent  unsatisfactory  results.  Even 
when  operating  with  like  volumes  of  solvent,  and  in  strict  accord 
with  the  latest  approved  method  comprehending  the  Stepanoff  prin- 
ciple,8 the  amount  of  sodium  required  for  complete  reduction  is  gen- 
erally variable  and  always  relatively  large,  in  fact,  more  than  twenty 
times  that  of  the  bromine  derivative  involved.  This  comparatively 
low  efficiency  from  the  standpoint  of  sodium  consumption  arises 
from  the  phenomenon,  familiar  to  most  chemists,  whereby  metallic 
sodium  when  applied  to  heated  alcohol  immediately  assumes  the 
spheroidal  state,  moving  about  very  actively  on  the  surface  of  the 
liquid,  but  separated  therefrom  by  a  film  or  cushion  of  hydrogen  and 
alcohol  vapor,  all  conditions  clearly  favoring  incomplete  reduction. 
Any  objection  to,  or  uncertainty  attendant  upon,  the  use  of  the  free 
metal  may  be  entirely  eliminated  by  recourse  to  the  procedure 
whereby  the  powdered  tablet  itself  in  alcoholic  solution  and  suspen- 
sion is  subjected  to  the  action  of  sodium  in  the  form  of  its  mercury 
8  Ber.,  13  (1880),  1407. 
7  J.  pharm.  chim.,  [7]  2  (1910),  64. 
8  Loc.  cit. 
