Am.  Jour.  Pharm. 
Jan.,  1888. 
Chlor  acetones. 
37 
and  with  aniline  it  yields  phenylcarbylamine  and  dichloracetanilida. 
It  may  also  be  prepared  in  large  quantity  by  the  action  of  dry 
chlorine  on  dry  commercial  acetone  in  direct  sunlight.  Pure  acetone 
seems  to  give  a  different  result,  since  Fittig,  and  Dumas  and  Kane, 
obtained  no  derivative  higher  than  the  dichloracetone  by  the  action 
of  chlorine  on  acetone  at  100°  or  in  sunlight.  Under  the  conditions 
given,  however,  the  acetone  is  converted  into  a  mixture  of  penta- 
chloracetone  and  hexachloracetone  w^hich  are  separated  by  fractiona- 
tion. 
Pentachloracetone  is  a  colorless  liquid  with  an  odour  resembling 
that  of  chloral,  which,  however,  is  only  observed  after  the  liquid  has 
been  exposed  to  air.  It  boils  at  192°,  and  is  readily  volatile  in  water 
vapor;  sp.  gr.  at  14°  =1-576.  It  dissolves  in  10  parts  of  water, 
from  which  it  separates  completely  at  50 — 60°.  At  low  temperatures, 
the  solution  deposits  a  tetrahydrate  in  small,  rhomboidal  plates  melt- 
ing at  15°  with  decomposition.  With  ammonia,  it  yields  chloroform 
and  dichloracetamide. 
The  action  of  chlorine  in  sunlight  on  the  pseudodichloracetone 
from  dichlorhydrin  yields  a  liquid  which  has  a  pungent  smell,  and 
boils  at  185°;  sp.  gr.  at  8°  =1*617.  With  ammonia,  it  yields  tri- 
chloracetamide  but  no  chloroform,  and  hence  it  is  not  a  derivative  of 
acetone.  The  action  of  chlorine  on  dichloropropylene  oxide  yields  a 
strongly  fuming  liquid  which  boils  at  about  178°.  Its  composition 
does  not  agree  very  well  with  that  of  pentachloropropylene  oxide,  and 
when  treated  with  ammonia,  it  yields  trichloracetamide  but  no  chloro- 
CCl 
form.    It  therefore  has  the  constitution  CHC12'CC1<_q^>.  From 
these  results,  it  is  evident  that  there  are  three  isomeric  compounds 
having  the  composition  of  pentachloracetone,  but  only  one  of  these  is 
really  a  derivative  of  acetone. 
Hexachloracetone  was  obtained  by  Plantamour  by  the  action  of 
chlorine  on.a  solution  of  citric  acid  in  sunlight,  and  has  been  described 
under  different  names  by  Laurent,  Staedeler,  and  Cloez,  sen.  A 
solution  of  citric  acid  is  treated  with  chlorine  in  sunlight  until  the 
gas  is  no  longer  absorbed.  Carbon  dioxide  is  given  ofp,  especially  in 
the  later  stages  of  the  reaction.  The  yield  is  about  one-fourth  of  the 
weight  of  the  citric  acid  taken.  .  Hexachloracetone  can  readily  be  ob- 
tained by  the  action  of  chlorine  on  acetone  in  sunlight.  The  fraction 
of  the  product  which  boils  at  185 — 220°  is  collected  and  purified. 
