402  Contributions  to  Pharmacy. 
1  Am.  Jour.  Pharm. 
t      August,  1894. 
obtained,  for  the  purification  of  which,  solution  in  petroleum-ether 
had  to  be  resorted  to ;  the  small  quantity  of  resin  which  did  not 
dissolve  in  this  solvent  was  filtered  out  and  the  solution  evaporated, 
when  it  left  a  pale-yellow  colored  liquid  which  was  freed  from  the 
persistent  odor  of  the  petroleum-ether  by  repeated  solution  in  ether 
and  evaporation.  Cinnamein,  the  name  given  by  previous  investi- 
gators to  this  oil  from  Peru  balsam,  because  it  was  considered  to 
consist  chiefly  of  benzyl-cinnamate,  is  present  to  the  extent  of  62-64 
per  cent,  in  the  balsam ;  the  physical  properties  and  behavior 
towards  reagents  of  this  oil  being  well  known,  attention  was 
directed  to  its  composition.  Dried  over  calcium  chloride  it  was 
submitted  to  fractional  distillation  at  ordinary  pressure  in  a  current 
of  carbon  dioxide ;  by  applying  heat  very  carefully  the  tempera- 
ture rose  steadily  to  nearly  3000  C.  without  anything  distilling  over; 
(no  indications  of  free  benzyl-alcohol  boiling  at  about  200°  C.  were 
obtained,  although  this  has  been  claimed  to  be  present);  between 
298°-302°  C.  almost  the  entire  quantity  distilled  over,  leaving  only  a 
small  quantity  of  a  tarry  mass,  which,  upon  cooling,  became  solid. 
The  too  rapid  application  of  heat  or  an  irregular  current  of  carbon 
dioxide  caused  decomposition,  producing  discoloration  and  a  very 
penetrating  odor.  This  fraction,  at  about  3000  C,  was  obtained 
almost  colorless  and  without  empyreumatic  odor,  had  a  slightly  dif- 
ferent odor  from  that  of  the  material  distilled,  it  now  being  honey- 
like ;  the  reaction  was  slightly  acid,  due  to  traces  of  cinnamic  acid, 
produced  by  a  slight  decomposition,  and  which  was  carried  over  in 
the  distillation  ;  by  saponification  with  strong  potash  solution  and 
extracting  with  ether,  the  latter  solution  left,  upon  distillation,  a 
colorless  liquid,  boiling  constantly  at  20i°-202°  C,  yielding  benz- 
aldehyde  when  heated  with  potassium  permanganate  solution,  and 
only  benzoic  acid  with  chromic  acid  ;  these  properties  are  charac- 
1  teristic  of  benzyl  alcohol.  The  alkaline  liquid,  which  was  agitated 
v  with  ether,  was  acidified  with  hydrochloric  acid  ;  the  separated  acid, 
.  decolorized  with  animal  charcoal  and  recrystallized,  melted  at  1210 
C,  and  gave  no  test  for  cinnamic  acid  with  potassium  permanga- 
nate ;  therefore,  only  benzoic  acid  was  present  in  the  precipitated 
acid,  and  the  chief  constituent  of  cinnamein  is  benzyl-benzoate.  The 
small  quantity  of  tarry  residue  left  in  the  fractional  distillation  of 
cinnamein  saponified,  and  the  products  isolated  yielded  benzyl- alco- 
hol and  cinnamic  acid,  boiling  constantly  and  entirely  at  2020  C.  Cin 
