322  Lloyd  Reaction  as  Applied  to  Heroin.     { Am-jJu0^if^rm- 
especially  the  pink  and  reddish-brown  colors,  may  serve  to  distin- 
guish heroin  from  morphin  and  apomorphin  when  applying  the 
Lloyd  reaction  to  alkaloids. 
According  to  my  experiments  the  delicacy  of  the  Lloyd  reac- 
tion for  heroin  is  not  as  great  as  for  morphin  or  apomorphin.  A 
mixture  composed  of  o  oi  mgm.  each  of  hydrastin  and  morphin 
yields  a  pale  blue-violet  color,12  and  a  mixture  of  o-ooi  mgm.  each  of 
hydrastin  and  apomorphin  yields  a  pale  red-violet13  at  room  tem- 
perature. A  mixture  composed  of  o-oi  mgm.  each  of  hydrastin 
and  heroin  yields  no  coloration  at  room  temperature,  but  between 
8o°  C.  and  900  C.  a  momentary,  very  pale  blue-violet  color  is  pro- 
duced. 
That  heroin  produces  results  somewhat  similar  to  morphin  is'not 
surprising,  it  being  a  substitution  product  of  morphin  produced  by 
substituting  the  hydroxyl  groups  in  morphin  by  the  acetic  acid 
complex  as  shown  by  the  following  equation  : 
OH  HOOCCH3  OOCCH3 
/      \  /  \ 
C17H17  NO  +  =  C17H17  NO  +  2H20 
\      /  V  / 
OH  HOOCCH3  OOCCH3 
Morphin.         Acetic  acid.        Heroin  (diacetyl  morphin). 
To  ascertain  to  what  extent  the  colors  produced  were  due  to 
heroin  alone  the  following  experiments  were  made : 
Dry  residues  of  heroin  containing  respectively,  01,  0-5  and  ro 
mgm.  were  treated  with  sulphuric  acid  and  produced  a  pale  yellow 
or  brownish  to  pink  solution  in  two  to  five  minutes.  The  same 
quantities  of  heroin  treated  with  sulphuric  acid  and  potassium 
dichromate  yielded  only  a  pale  yellowish-brown  color,  changing  to 
the  yellow  and  greenish  colors  of  the  acid  and  dichromate  alone. 
A  residue  containing  0.01  mgm.  of  heroin  treated  with  acid 
alone,  and  with  acid  and  dichromate,  was  unaffected. 
Ten  milligrams  of  solid  heroin  (not  previously  dissolved)  treated 
with  sulphuric  acid  yielded  a  pale  yellow  solution  at  room  tempera- 
ture, and  between  8o°  C.  and  90°  C.  a  pale  yellow  solution  changing 
to  pale  pink  in  ten  seconds.  When  treated  with  sulphuric  acid  and 
potassium  dichromate,  nothing  but  the  yellow  of  the  acid  and 
dichromate  was  produced  at  room  temperature,  and  between  8o°  C. 
