498  Acid  Chlorides  and  Phenol- Ethers.  {Am-Jc0tu,ri8Sarm' 
methylic  or  ethylic  alcohol  at  135-140°C.  When  using  methylic 
alcohol  it  is  best  to  work  under  pressure  to  prevent  loss. 
Method  for  the  preparation  of  the  ketones. — To  a  solution  of  1  part 
phenolether  and  2  parts  acid  chloride 1  in  4  parts  carbon  bisulphide, 
2  parts  of  finely  powdered  anhydrous  aluminium  chloride  is  gradually 
added.  The  latter  is  dissolved  by  the  liquid  until  about  one- half  has 
been  added,  when  a  heavy  oil  falls  to  the  bottom.  The  reaction  is 
accompanied  by  a  copious  elimination  of  hydrochloric  acid  gas, 
which  usually  takes  place  without  applying  artificial  heat ;  but  should 
this  not  be  the  case,  the  flask  is  slightly  warmed  on  a  water-bath. 
As  soon  as  all  the  aluminium  chloride  has  been  added  the  super- 
natent  carbon  bisulphide  is  poured  off  and,  while  cooling,  the  residue 
is  decomposed  by  water.  The  liquid  is  acidified  with  hydrochloric 
acid  in  order  to  dissolve  the  precipitated  basic  aluminium  compound 
and  the  ketone  taken  up  with  ether.  This  solution  is  then  washed 
with  water  and  a  dilute  alkaline  solution  until  perfectly  neutral,  dried 
over  anhydrous  calcium  chloride  and  the  ether  recovered.  The  re- 
siduary oil  is  subjected  to  fractional  distillation,  the  colorless  portion 
distilling  above  200°  C.  is  collected,  brought  into  a  freezing  mixture 
and  the  crystalline  compound  subjected  to  pressure  between  absorbent 
paper  or  plates.  The  further  purification  is  accomplished  by  crystal- 
lization from  ether,  dilute  alcohol  or  glacial  acetic  acid. 
The  oxidation,  by  which  the  corresponding  acids  were  obtained, 
was  carried  out  according  to  the  method  of  Weith  (Ber.  vii.,  1874, 
1057)  by  means  of  alkaline  permanganate  of  potassium  solution.  By 
complete  oxidation  of  the  side  group  I  obtained  the  carbon  acids  and 
by  interrupting  the  action  as  soon  as  the  oil  drops  had  disap- 
peared, the  corresponding  glyoxylic  acids  were  usually  obtained  in 
such  an  impure  state  that  an  analysis  could  not  be  made  except  in  a 
few  instances.  The  acids  were  recognized  by  the  following  very 
characteristic  reactions  :  1,  with  active  benzol  and  concentrated  sul- 
phuric acid  (claisen);  2,  by  fusing  with  dimethylaniline  and  zinc 
chloride  (malachite  green). 
1.  Action  of  acetylchloride. 
Anisol  yields  a  body  which  in  a  pure  state  melts  at  38-39 °C.  and 
distils  at  258 °C.  This  compound  p-acetylanisol,  crystallizes  from 
ether  in  short  four-sided  prisms.  Olivieri  (Gazetta  Chimica  Italiana 
XIII,  p.  275)  obtained  a  body,  not  solidifying  at  — 15°C.  and  distilling 
xIn  the  reaction  with  benzoylchloride  the  theoretical  amount  is  best  used. 
