AmAprifif97arm" }    Marrubiin  and  its  Dichlorine  Derivative.  203 
In  this  case  Harms  obtained  the  bitter  principle  by  treating  the 
herb  with  three  successive  portions  of  hot  water,  evaporating  the 
water  extractions  to  a  syrupy  consistence,  and  treating  them  with 
alcohol;  to  the  alcoholic  solution  he  added  a  large  quantity  of 
sodium  chloride  and  about  one-third  its  volume  of  ether ;  the  whole 
was  then  agitated  and  the  separated  ethereal  layer,  when  drawn  off 
and  allowed  to  evaporate  spontaneously,  left  tabular  crystals  of 
marrubiin,  which,  after  two  re-crystallizations  from  alcohol,  appeared 
pure.  From  25  pounds  of  herb  Harms  obtained  2  grammes  of  the 
crystalline  bitter  principle. 
With  reference  to  the  properties  of  marrubiin,  Harms  says  he 
found  them,  in  general,  to  agree  with  those  given  by  Kromayer. 
An  elementary  analysis,  which  Harms  made  on  a  portion  of  the 
crystals  presented  to  him  by  Mein,  yielded  from  0-313  gramme  of  the 
principle,  dried  at  90°-ioo°  C,  0-240  gramme  of  H20,  or  8.5  2  per  cent, 
of  H.  The  carbon  estimation,  unfortunately,  was  lost,  but  it  showed 
that  the  marrubiin  contained  more  than  69  per  cent,  of  carbon. 
Harms  also  stated  that  on  recrystallizing  marrubiin  from  hot  solutions 
a  portion  of  it  assumes  an  amorphous  form.  On  dissolving  the  amor- 
phous bitter  principle  in  alcohol,  and  allowing  the  solution  to  stand 
at  the  ordinary  temperature  in  the  air,  it  goes  over  into  its  original 
form,  and  separates  in  a  crystalline,  wart-shaped  mass.  Marrubiin 
crystallizes  easily — best  when  to  a  boiling  alcoholic  solution  boiling 
water  is  added  until  it  begins  to  become  turbid,  and  the  solution 
allowed  to  cool  slowly. 
In  the  American  Journal  of  Pharmacy  for  June,  1890,  Hertel 
published  the  following  experience  : 
On  making  a  fluid  extract  of  marrubium,  using  diluted  alcohol  as 
a  menstruum,  it  was  noticed  that,  after  standing  for  a  week,  a  de- 
posit of  well-defined  crystals  separated  from  the  extract.  The  de- 
posit from  10  pounds  of  herb  was  nearly  1  ounce,  the  extract, 
however,  still  being  as  bitter  as  before.  The  slight  yellow 
color  of  the  needle-shaped  crystals  was  removed  by  several  recrys- 
tallizations  from  alcohol.  The  crystals  still  retained  their  slowly- 
developing  but  persistently  bitter  taste.  When  heated  on  platinum 
foil  the  crystals  melted,  then  charred  and  finally  volatilized  without 
leaving  any  residue.  They  were  quite  soluble  in  chloroform,  alco- 
hol and  ether,  and  slightly  soluble  in  water.  The  principle  is  insolu- 
ble in  benzin,  is  not  colored  by  acids,  does  not  respond  to  Fehling's 
