﻿ITS 
  PRODUCTS 
  OF 
  DECOMPOSITION. 
  77 
  

  

  tested 
  with 
  ammonia, 
  in 
  order 
  to 
  see 
  whether 
  a 
  precipitate 
  is 
  formed 
  ; 
  and 
  the 
  

   action 
  is 
  allowed 
  to 
  go 
  on 
  until 
  this 
  is 
  obtained, 
  and 
  the 
  chlorocodeine 
  is 
  then 
  pre- 
  

   cipitated 
  by 
  a 
  slight 
  excess 
  of 
  ammonia. 
  The 
  successful 
  performance 
  of 
  this 
  expe- 
  

   riment 
  requires 
  exactly 
  the 
  same 
  precautions 
  as 
  the 
  preparation 
  of 
  nitrocodeine 
  ; 
  

   and, 
  unless 
  the 
  action 
  is 
  stopped 
  at 
  the 
  right 
  moment, 
  further 
  products 
  of 
  decom- 
  

   position 
  are 
  obtained. 
  The 
  reaction 
  which 
  takes 
  place 
  is 
  represented 
  by 
  this 
  

   equation 
  : 
  — 
  

  

  3 
  (C 
  3G 
  H 
  21 
  N0 
  36 
  H 
  CI) 
  + 
  3 
  H 
  CI 
  + 
  KO 
  CI 
  5 
  = 
  K 
  CI 
  + 
  6 
  HO 
  + 
  3 
  (C 
  36 
  H 
  20 
  CI 
  N0 
  6 
  H 
  CI). 
  

  

  The 
  chlorocodeine 
  is 
  precipitated 
  in 
  the 
  form 
  of 
  a 
  silvery 
  crystalline 
  powder, 
  

   closely 
  resembling 
  bromocodeine 
  ; 
  it 
  has 
  generally 
  a 
  yellowish 
  colour, 
  and 
  the 
  

   fluid 
  from 
  which 
  it 
  has 
  deposited 
  is 
  coloured 
  dark-red 
  by 
  the 
  presence 
  of 
  a 
  small 
  

   quantity 
  of 
  some 
  products 
  of 
  the 
  further 
  action 
  of 
  chlorine. 
  It 
  retains 
  also 
  a 
  small 
  

   quantity 
  of 
  codeine, 
  from 
  which 
  it 
  is 
  purified 
  by 
  dissolving 
  in 
  hydrochloric 
  acid, 
  

   boiling 
  with 
  animal 
  charcoal, 
  and 
  reprecipitating 
  with 
  ammonia 
  ; 
  and 
  it 
  is 
  finally 
  

   obtained 
  in 
  crystals 
  from 
  its 
  solution 
  in 
  boiling 
  spirit. 
  

  

  In 
  its 
  general 
  properties 
  chlorocodeine 
  closely 
  resembles 
  bromocodeine 
  ; 
  so 
  

   much 
  so, 
  indeed, 
  that 
  they 
  may 
  be 
  easily 
  confounded 
  with 
  one 
  another. 
  It 
  is 
  

   sparingly 
  soluble 
  in 
  boiling 
  water, 
  and 
  deposited, 
  on 
  cooling, 
  in 
  minute 
  prisms 
  

   exactly 
  similar 
  to, 
  and 
  apparently 
  isomorphous 
  with, 
  those 
  of 
  bromocodeine. 
  It 
  

   is 
  readily 
  soluble 
  in 
  strong 
  alcohol, 
  especially 
  with 
  heat, 
  and 
  sparingly 
  soluble 
  in 
  

   ether. 
  It 
  dissolves 
  in 
  sulphuric 
  acid 
  in 
  the 
  cold 
  without 
  change, 
  but 
  the 
  solution 
  

   is 
  charred 
  by 
  heating. 
  Nitric 
  acid 
  dissolves 
  it, 
  and 
  the 
  solution 
  is 
  decomposed 
  by 
  

   boiling, 
  but 
  not 
  by 
  any 
  means 
  so 
  readily 
  as 
  codeine. 
  Red 
  fumes 
  are 
  evolved 
  

   along 
  with 
  a 
  peculiar 
  and 
  excessively 
  pungent 
  vapour. 
  

  

  Analysis 
  gave 
  the 
  following 
  results 
  : 
  — 
  

  

  {6-425 
  grains 
  of 
  chlorocodeine, 
  dried 
  at 
  212°, 
  gave 
  

   15*315 
  ••• 
  of 
  carbonic 
  acid, 
  and 
  

   3-601 
  ... 
  of 
  water. 
  

  

  {6-162 
  grains 
  of 
  chlorocodeine 
  gave 
  

   14-597 
  ... 
  of 
  carbonic 
  acid, 
  and 
  

   3-372 
  ... 
  of 
  water. 
  

  

  5-030 
  grains 
  of 
  chlorocodeine 
  gave 
  2*100 
  grains 
  chloride 
  of 
  silver. 
  

  

  

  Experiment. 
  

  

  

  Calculation. 
  

  

  

  

  I. 
  

  

  II. 
  

  

  "" 
  

  

  

  ~ 
  v 
  - 
  

  

  Carbon, 
  . 
  

  

  65-00 
  

  

  64-62 
  

  

  64-76 
  

  

  ^36 
  

  

  216 
  

  

  Hydrogen, 
  

  

  622 
  

  

  6-08 
  

  

  5-99 
  

  

  H 
  20 
  

  

  20 
  

  

  Chlorine, 
  

  

  

  10-32 
  

  

  10-64 
  

  

  CI 
  

  

  35-5 
  

  

  Nitrogen, 
  

  

  , 
  # 
  ... 
  

  

  • 
  • 
  • 
  

  

  4-19 
  

  

  N 
  

  

  14 
  

  

  Oxygen, 
  

  

  

  

  14-42 
  

  

  o 
  6 
  

  

  48 
  

  

  

  100-00 
  

  

  333-5 
  

  

  VOL. 
  XX. 
  PART 
  I. 
  

  

  

  

  

  

  X 
  

  

  