﻿72 
  DR 
  ANDERSON 
  ON 
  CODEINE, 
  AND 
  

  

  8*670 
  grains 
  of 
  the 
  precipitated 
  salt, 
  dried 
  by 
  long 
  exposure 
  to 
  the 
  air, 
  lost, 
  

   at 
  212°, 
  0*569 
  grains 
  of 
  water 
  =6*56 
  per 
  cent. 
  

  

  Four 
  equivalents 
  of 
  water 
  require 
  6-14 
  per 
  cent. 
  The 
  formula 
  of 
  the 
  salt 
  is, 
  

   therefore, 
  C 
  36 
  H 
  20 
  (N0 
  4 
  ) 
  NO 
  G 
  HC1 
  + 
  Pt 
  Cl 
  2 
  + 
  4 
  HO. 
  

  

  When 
  nitrocodeine 
  dissolved 
  in 
  alcohol 
  is 
  treated 
  with 
  hydrosulphuret 
  of 
  

   ammonia 
  in 
  the 
  water-bath, 
  the 
  solution 
  gradually 
  acquires 
  a 
  dark 
  colour, 
  and 
  

   sulphur 
  is 
  deposited. 
  When 
  the 
  action 
  is 
  complete, 
  the 
  filtered 
  fluid 
  gives 
  with 
  

   ammonia 
  a 
  brown 
  amorphous 
  precipitate, 
  which, 
  when 
  dissolved 
  in 
  hydrochloric 
  

   acid, 
  and 
  boiled 
  with 
  animal 
  charcoal, 
  gives, 
  on 
  precipitation, 
  a 
  pale-yellow 
  base. 
  

   The 
  substance 
  so 
  obtained 
  is 
  very 
  different 
  from 
  nitrocodeine 
  ; 
  it 
  is 
  extremely 
  

   soluble 
  in 
  alcohol, 
  and 
  is 
  deposited 
  from 
  it 
  as 
  an 
  amorphous 
  powder. 
  Once 
  only 
  

   did 
  I 
  obtain 
  definite 
  crystals, 
  which 
  were 
  brownish 
  rhomboids, 
  but 
  in 
  too 
  small 
  

   quantity 
  to 
  admit 
  of 
  examination. 
  The 
  amorphous 
  base 
  did 
  not 
  give 
  satisfactory 
  

   results 
  ; 
  and 
  as 
  its 
  preparation 
  is 
  extremely 
  troublesome, 
  I 
  did 
  not 
  pursue 
  its 
  

   investigation 
  further. 
  Arguing 
  from 
  what 
  we 
  know 
  of 
  the 
  other 
  bases 
  formed 
  by 
  

   the 
  same 
  process, 
  its 
  constitution 
  ought 
  to 
  be 
  C 
  36 
  H 
  2 
  , 
  N., 
  6 
  , 
  and 
  it 
  might 
  be 
  called 
  

   azocodeine. 
  

  

  V. 
  Action 
  of 
  Bromine 
  on 
  Codeine. 
  

  

  Bromocodeine. 
  — 
  In 
  order 
  to 
  obtain 
  this 
  substance, 
  bromine-water 
  is 
  added 
  in 
  

   small 
  successive 
  portions 
  to 
  finely-powdered 
  codeine. 
  The 
  base 
  is 
  rapidly 
  dis- 
  

   solved, 
  and 
  the 
  solution 
  loses 
  its 
  colour 
  of 
  bromine, 
  but 
  acquires 
  a 
  peculiar 
  and 
  

   characteristic 
  red 
  shade. 
  After 
  a 
  certain 
  quantity 
  of 
  bromine 
  has 
  been 
  added, 
  

   small 
  crystals 
  make 
  their 
  appearance, 
  which 
  are 
  hydrobromate 
  of 
  bromocodeine 
  ; 
  

   but 
  these 
  are 
  only 
  observed 
  if 
  the 
  bromine-water 
  has 
  been 
  thoroughly 
  saturated, 
  

   and 
  are 
  deposited 
  in 
  small 
  quantity 
  only, 
  the 
  remainder 
  being 
  retained 
  in 
  solu- 
  

   tion. 
  When 
  the 
  whole 
  of 
  the 
  codeine 
  has 
  been 
  got 
  into 
  solution, 
  ammonia 
  is 
  

   added, 
  and 
  bromocodeine 
  is 
  immediately 
  thrown 
  down 
  as 
  a 
  silvery-white 
  powder. 
  

   In 
  this 
  state 
  it 
  contains 
  a 
  small 
  quantity 
  of 
  unchanged 
  codeine. 
  It 
  is 
  collected 
  

   on 
  a 
  filter 
  ; 
  washed 
  several 
  times 
  with 
  cold 
  water, 
  and 
  redissolved 
  in 
  hydrochloric 
  

   acid, 
  from 
  which 
  it 
  is 
  reprecipitated 
  by 
  ammonia, 
  and 
  finally 
  crj'stallised 
  from 
  

   boiling 
  spirit. 
  Bromocodeine 
  is 
  scarcely 
  soluble 
  in 
  cold 
  water 
  ; 
  but 
  by 
  boiling, 
  a 
  

   somewhat 
  larger 
  quantity 
  is 
  taken 
  up, 
  and 
  deposited 
  again 
  on 
  cooling 
  in 
  minute 
  

   prisms, 
  terminated 
  by 
  dihedral 
  summits. 
  It 
  is 
  readily 
  soluble 
  in 
  alcohol, 
  parti- 
  

   cularly 
  on 
  boiling, 
  and 
  is 
  best 
  crystallised 
  from 
  spirit 
  diluted 
  with 
  its 
  bulk 
  of 
  

   water. 
  The 
  crystals 
  in 
  which 
  it 
  is 
  deposited 
  are 
  always 
  very 
  small, 
  but 
  bril- 
  

   liantly 
  white. 
  It 
  is 
  scarcely 
  soluble 
  in 
  ether. 
  Exposed 
  to 
  heat, 
  it 
  melts 
  into 
  a 
  

   colourless 
  fluid, 
  which 
  is 
  destroyed 
  at 
  a 
  temperature 
  slightly 
  above 
  its 
  melting 
  

   point. 
  It 
  dissolves 
  in 
  cold 
  sulphuric 
  acid, 
  and 
  the 
  solution 
  when 
  heated 
  becomes 
  

   dark 
  coloured. 
  It 
  is 
  attacked 
  by 
  nitric 
  acid, 
  but 
  much 
  less 
  rapidly 
  than 
  

   codeine 
  itself. 
  

  

  