Am.  Jour.  Pharm. 
Jan..  1888. 
Chlor  acetones. 
31 
CHLORACETONES.i 
By  C.  Cloez. 
The  author  has  prepared  and  examined  all  the  chlorine  derivatives 
of  acetone  which  are  theoretically  possible  if  the  generally  accepted 
formula  is  correct.  A  short  history  of  the  derivatives  previously 
known  is  given,  together  with  full  bibliographical  references. 
The  material  employed  w^as  commercial  acetone  purified  b}^  frac- 
tionation and  conversion  into  the  hydrogen  sodium  sulphite  compound. 
The  author  investigated  the  action  of  chlorine:  (1)  on  cold  acetone; 
(2)  on  acetone  wdiich  at  first  was  cold,  but  afterwards  was  heated  to 
100°  ;  (3)  on  w^ell-cooled  acetone  containing  iodine  ;  and  (4)  on  boil- 
ing acetone  containing  iodine.  ]N"o  advantage  is  gained  by  the  presence 
of  iodine,  and  in  fact  the  iodo-products  which  are  formed  in  small 
quantity  decompose  during  distillation  and  render  purification  very 
difficult.  The  iodine  cannot  be  removed  by  means  of  iron  or  mercury. 
All  fractions  boiling  above  125-130°  should  be  distilled  under  re- 
duced pressure.  The  final  product  in  all  four  cases  is  tetrachlorace- 
ione. 
MonocMoracetone  is  most  readily  prepared  by  Barbaglia^s  method 
{Ber.,  vii,  467)  of  passing  chlorine  into  well-cooled  acetone  for  several 
days;  a  current  of  w^ater  is  sufficient  for  this  purpose,  a  freezing  mix- 
ture is  not  necessary.  It  boils  at  117-118°  ;  sp.  gr.  at  13°  =  1'158. 
It  is  very  slightly  soluble  in  w^ater,  but  dissolves  in  all  proportions  in 
alcohol,  ether,  and  chloroform.  It  does  not  form  a  crystalline  hydrate, 
and  volatilizes  readily  in  water-vapor.  When  freshly  prepared,  it  has 
no  irritating  odor,  but  after  exposure  to  air  for  some  days  it  gives  ofP 
irritating  vapors.  It  can,  however,  be  purified  by  w^ashing  with  a 
very  dilute  solution  of  an  alkali. 
Monochloracetone  is  readily  attacked  by  chlorine  in  the  cold.  Bro- 
mine has  little  effect  in  the  cold,  but  at  100°  energetic  reaction  takes 
place  with  formation  of  chlorotribromacetone.  With  potassium,  it 
forms  potassium  chloride,  together  with  red  and  brown  products  which 
probably  contain  the  acetyl  carbinol  obtained  by  Emmerling-  by  the 
action  of  potassium  or  potassium  carbonate  on  bromacetone.  Ammonia 
produces  ammonium  chloride  and  the  amido-derivative,  COMe'CHa'- 
^Ann.  Chim.  Phys.  [6],  ix,  145-221.  Reprinted  from  Jour.  Chem.  Soc,  1887, 
p.  1091-1099. 
