﻿76 
  DR 
  ANDERSON 
  ON 
  CODEINE, 
  AND 
  

  

  mating 
  to 
  the 
  experimental 
  numbers, 
  and 
  the 
  recurrence 
  of 
  the 
  results, 
  in 
  portions 
  

   prepared 
  at 
  different 
  times, 
  leaves 
  no 
  doubt 
  that 
  this 
  is 
  their 
  real 
  constitution 
  ; 
  

   and, 
  in 
  all 
  probability, 
  the 
  error 
  may 
  be 
  due 
  to 
  the 
  salt 
  retaining 
  a 
  small 
  excess 
  

   of 
  hydrobromic 
  acid. 
  The 
  constitution 
  is 
  therefore 
  remarkable, 
  and 
  I 
  am 
  not 
  

   aware 
  of 
  any 
  similar 
  salt 
  having 
  been 
  before 
  observed. 
  

  

  Platinochloride 
  of 
  Tribromocodeine. 
  — 
  Bichloride 
  of 
  platinum 
  throws 
  down 
  

   from 
  solution 
  of 
  tribromocodeine, 
  in 
  hydrochloric 
  acid, 
  this 
  salt, 
  in 
  the 
  form 
  of 
  a 
  

   brownish-yellow 
  powder 
  soluble 
  in 
  water 
  and 
  alcohol. 
  

  

  5-142 
  grains 
  of 
  platinum 
  salt, 
  dried 
  at 
  212°, 
  gave 
  0-669 
  grains 
  of 
  platinum. 
  

  

  Experiment. 
  Calculation. 
  

  

  Carbon, 
  

  

  

  29-10 
  

  

  c 
  86 
  

  

  216 
  

  

  Hydrogen, 
  

   Bromine, 
  

  

  . 
  

  

  2-55 
  

   32-33 
  

  

  H 
  19 
  

   Br 
  8 
  

  

  19 
  

   240 
  

  

  Nitrogen, 
  

  

  . 
  

  

  1-88 
  

  

  N 
  

  

  14 
  

  

  Oxygen, 
  

   Chlorine, 
  

  

  . 
  

  

  6-57 
  

   14-34 
  

  

  o 
  3 
  

  

  Cl 
  3 
  

  

  48 
  

   106-5 
  

  

  Platinum, 
  

  

  13-07 
  

  

  13-29 
  

  

  Pt 
  

  

  98-7 
  

  

  100-00 
  742-2 
  

  

  I 
  have 
  reason 
  to 
  believe 
  that 
  the 
  action 
  of 
  bromine 
  upon 
  codeine 
  does 
  not 
  ter- 
  

   minate 
  with 
  the 
  production 
  of 
  the 
  base 
  now 
  described 
  ; 
  but 
  its 
  further 
  action 
  did 
  

   not 
  appear 
  to 
  afford 
  any 
  products 
  of 
  a 
  sufficient 
  interest 
  to 
  induce 
  me 
  to 
  prose- 
  

   cute 
  the 
  investigation 
  in 
  this 
  direction. 
  There 
  must 
  also 
  no 
  doubt 
  exist 
  a 
  dibro- 
  

   mocodeine, 
  C 
  3fi 
  H 
  in 
  Br 
  2 
  N 
  6 
  , 
  but 
  I 
  did 
  not 
  meet 
  with 
  it 
  in 
  the 
  course 
  of 
  my 
  ex- 
  

   periments, 
  and 
  have 
  not 
  made 
  any 
  special 
  attempts 
  to 
  obtain 
  it. 
  

  

  VI. 
  Action 
  of 
  Chlorine 
  upon 
  Codeine. 
  

  

  We 
  might 
  anticipate 
  that 
  the 
  action 
  of 
  chlorine 
  upon 
  codeine 
  should 
  be 
  exactly 
  

   similar 
  to 
  that 
  of 
  bromine 
  ; 
  but 
  this 
  is 
  not 
  the 
  case, 
  as 
  in 
  place 
  of 
  a 
  simple 
  

   and 
  definite 
  action 
  complex 
  products 
  are 
  immediately 
  obtained. 
  When 
  a 
  current 
  

   of 
  chlorine 
  is 
  passed 
  through 
  an 
  aqueous 
  solution 
  of 
  codeine, 
  the 
  fluid 
  immedi- 
  

   ately 
  acquires 
  a 
  brown 
  colour, 
  which 
  soon 
  becomes 
  very 
  deep, 
  and 
  eventually 
  

   almost 
  black. 
  From 
  this 
  solution 
  ammonia 
  throws 
  down 
  an 
  amorphous, 
  resinous 
  

   base. 
  With 
  chlorine-water 
  the 
  solution 
  also 
  becomes 
  rapidly 
  brown, 
  and 
  a 
  

   similar 
  precipitate 
  is 
  obtained. 
  As 
  there 
  was 
  no 
  method 
  of 
  determining 
  in 
  either 
  

   of 
  these 
  cases 
  when 
  the 
  action 
  was 
  complete, 
  I 
  did 
  not 
  attempt 
  to 
  examine 
  the 
  

   product. 
  I 
  succeeded 
  better, 
  however, 
  by 
  the 
  action 
  of 
  chlorate 
  of 
  potash, 
  and 
  

   obtained 
  a 
  base 
  corresponding 
  to 
  bromocodeine. 
  

  

  Chlorocodeine. 
  — 
  For 
  the 
  preparation 
  of 
  chlorocodeine 
  a 
  sufficient 
  quantity 
  of 
  

   codeine 
  is 
  dissolved 
  in 
  an 
  excess 
  of 
  dilute 
  hydrochloric 
  acid, 
  at 
  the 
  temperature 
  of 
  

   about 
  150° 
  or 
  160°. 
  Finely-powdered 
  chlorate 
  of 
  potash 
  is 
  then 
  added, 
  and 
  the 
  solu- 
  

   tion 
  agitated. 
  In 
  the 
  course 
  of 
  a 
  few 
  minutes 
  a 
  small 
  quantity 
  of 
  the 
  fluid 
  is 
  

  

  