Am.  Jour.  Pliarm. 
Jan.,  1888. 
Chlor  acetones. 
35 
mine,  which  is  doubtless  derived  from  the  compound  CHCla'CO'CHs 
.NH2.  It  would  follow  that  the  trichloracetone  has  the  constitution 
OHCl2*CO"CH2Cl,  but  the  formation  of  chloroform  and  phenylcar- 
bjlamine,  and  the  variable  boiling  and  melting  points  of  the  com- 
pound, show  clearly  that  it  is  a  mixture  of  a  solid  trichloro-derivative 
which  melts  about  — 5°,  with  an  isomeride  which  is  liquid  even  at 
low  temperatures. 
U asymmetrical  tetracrdor acetone  was  obtained  by  Bonis  by  the  action 
of  chlorine  on  wood-spirit  in  diffused  daylight  {Ann.  Chim.  Phys.  [3], 
21 — 111),  and  by  BischofP  by  the  action  of  chlorine  on  a  mixture  of 
acetone  and  methyl  alcohol  (1876).  It  is  most  readily  obtained  by 
passing  chlorine  into  commercial  acetone,  the  temperature  being 
allowed  to  rise.  Tetrachloracetone  is  a  colorless  liquid  which  boils 
at  180° — 182°,  and  becomes  brown  when  exposed  to  air  and  light ; 
sp.  gr.  at  17°=1'482.  When  distilled  under  the  ordinary  pressure, 
it  undergoes  partial  decomposition.  It  is  very  hygroscopic,  and 
forms  a  tetrahydrate  which  melts  without  decomposition  at  30°. 
With  aniline  and  potash  it  yields  phenylcarbylamine,  and  with 
aqueous  ammonia  at  a  low  temperature  it  yields  chloroform  and  mo- 
nochloracetamide.    It  therefore  has  the  constitution  CClg  CO'CHgCl. 
By  the  prolonged  action  of  chlorine  on  pure  acetone  at  first  cooled 
and  afterwards  heated  on  a  water-bath,  Grabowsky  (1876)  has  ob- 
tained trichlorom ethyl  propyl  ketone,  boiling  at  186°.  The  author 
has  been  unable  to  obtain  this  result.  Probably  the  nature  of  the 
reaction  depends  on  the  purity  of  the  acetone. 
Symmetrical  tetrachloracetone. — Dichlorodibromacetone  prepared  by 
the  action  of  bromine  on  unsymmetrical  dichloracetone  is  heated  with 
alcohol  and  mercuric  chloride  in  sealed  tubes  at  100°.  The  product 
is  distilled,  and  is  purified  from  mercury  by  conversion  into  a  hydrate 
which  is  repeatedly  recrystallized,  and  then  decomposed  by  hydro- 
chloric acid.  The  product  is  dried  over  calcium  chloride,  and  boils 
at  179° — 181°  ;  its  sp.  gr.  is  the  same  as  that  of  the  preceding  com- 
pound. With  water,  it  forms  a  hydrate  crystallizing  in  needles  which 
melt  at  47° — 48°.  With  ammonia  or  aniline,  it  yields  no  distinct  re- 
sult, but  neither  chloroform  nor  phenylcarbylamine  is  formed.  The 
compound  therefore  does  not  contain  the  group  CCI3,  and  must  have 
the  constitution  CHCl2'CO-CHC]o. 
The  dichlorodibrom-derivative  obtained  by  the  action  of  bromine 
on  dichlorhydrin  yields  with  mercuric  chloride  an  oily  liquid  which 
