AxMarch"  mi™' }    Ur  ethane  s  of  Thymol  and  Carvacrol.  221 
The  reaction  was  next  carried  out  with  the  alkali  derivatives  in 
alcoholic  solution;  4.5  g.  nitrosophenol  were  treated  with  1.5  g. 
potassium  hydroxide  in  15  cc.  methyl  alcohol  previously  distilled 
over  potassium  hydroxide.  To  this  were  added  3.6  g.  methyl  iodide 
and  the  mixture  tightly  stoppered  and  shaken  frequently.  By  morn- 
ing crystals  had  deposited  and  the  reddish-brown  color  of  the  solu- 
tion remained  but  the  odor  of  methyl  iodide  had  disappeared.  The 
crystals  were  easily  proven  to  be  potassium  iodide,  and  the  alkaline 
reaction  had  disappeared  from  the  solution.  The  reaction  mixture 
was  allowed  to  evaporate  spontaneously  and  the  white  crystals 
washed  free  from  adhering  liquor  with  ether.  Both  of  the  phenols 
gave  brown  oils  at  this  point.  Carvacrol  gave  a  yield  of  potassium 
iodide  of  87  per  cent.;  while  that  for  thymol  was  lost.  The 
brownish-black  ethereal  solution  was  shaken  with  dilute  hydro- 
chloric acid  to  remove  basic  constituents.  This  was  made  alkaline 
and  again  shaken  with  ether.  Both  ether  solutions  were  evaporated 
spontaneously.    Nothing  appeared  from  the  acid  wash  liquors. 
The  oil  obtained  from  carvacrol  solidified.  The  compound  is 
probably  the  oxime  ether.  The  crystals  were  pressed  between  paper 
and  melted  at  390  and  were  stable  up  to  144°.  They  are  bright  yel- 
low or  orange  crystals  of  needle  shape.  The  oil  from  thymol  re- 
mained liquid.  It  was  accordingly  steam  distilled.  It  formed  a 
yellow  layer  in  the  distillate  lighter  than  water  and  came  over  about 
as  fast  as  the  methyl  ether  of  carvacrol,  and  accordingly  cannot  be 
considered  readily  volatile  as  the  acetone  derivatives  have  been  de- 
scribed.25 The  later  distillate  came  over  red  and  was  heavier  than 
water.  The  aqueous  portion  was  extracted  with  ether  and  dried 
over  calcium  chloride  with  no  apparent  change  in  the  chloride.  The 
separated  oil  was  also  dried  over  calcium  chloride  when  the  lumps 
of  chloride  began  to  disintegrate  and  formed  a  fine  powder  somewhat 
in  the  manner  that  calcium  chloride  forms  alcoholates.  When  the 
oil  itself  was  diluted  with  ether  and  allowed  to  stand  over  the  chlo- 
ride, the  same  change  was  noticed  after  ten  days. 
The  analysis  of  the  crystalline  methyl  derivative  of  carvacrol 
gave  the  following  results  by  Dumas'  method : 
0.2222  g.i  gave  15.3  cc.  'Nu  at,25°  and  708  mm. 
Found    Calculated  for  CnHlsN02 
Nitrogen,  7.40  p.  c.  7.26  p.  c.t 
25Diels  and  Plaut,  Ber.,  38  (1905),  p.  1917. 
