Aru.  Jour.  Ptaarm. ) 
January,  1899.  ) 
The  Chemistry  of  Sassafras. 
29 
or  heliotropine,  and  by  further  oxidation  piperonylic  acid.  When 
safrol  is  boiled  with  alcoholic  potash,  its  allyl  group,  CH2  ==  CH.CH2, 
is  transformed  into  the  isomeric  propenyl  group,  CH3CH  =  CH,  thus 
forming  iso-safrol,  a  substance  generally  similar  to  safrol,  but  of  a 
less  agreeable  odor,  a  higher  boiling  point',  2470  C,  higher  specific 
gravity  and  higher  refraction  to  light.  Upon  oxidation  it  also  yields 
piperonal  and  piperonylic  acid,  but  with  considerably  greater  ease, 
for  which  reasons  it  forms  the  base  for  the  technical  manufacture 
of  heliotropine, 
Those  parts  of  sassafras  oil  which  remain  liquid  even  in  a  freez- 
ing mixture,  can  be  separated  into  their  constituents  by  fractional 
distillation.  In  this  way  a  considerable  fraction  is  obtained,  boil- 
ing between  1 5  5  0  and  1 75  °,  which  consists  chiefly  of  pinene,  C10H16, 
that  terpene  which  is  found  so  generally  in  volatile  oils,  and 
which  forms  the  greater  part  of  oil  of  turpentine.  It  can  easily 
be  identified  by  its  crystalline  nitrosochloride  and  by  the  easily 
crystallizable  benzylamine  and  piperidine  compounds  of  the  latter. 
Besides  pinene,  a  small  amount  of  another  terpene,  C10H16,  is  pres. 
ent,  which  forms  a  solid,  but  very  unstable  addition  product  with 
nitrous  acid,  by  which  reaction  it  is  recognized  as  phellandrene,  a 
terpene  also  very  frequently  met  with  in  essential  oils. 
The  higher  boiling  fractions  of  sassafras  oil  contain  about  0-5  per 
cent,  of  a  body  which  can  be  extracted  by  means  of  a  diluted  solu- 
tion of  alkali.  When  set  free  from  this  solution  by  sulphuric  acid, 
it  forms  an  oil,  which  by  its  clove-like  odor  and  the  formation  of 
a  benzoyl  compound  melting  at  690  C.  can  be  identified  as  eugenol, 
the  characteristic  constituent  of  oil  of  cloves.  Eugenol  C10H12O2,  is 
distinguished  from  safrol  only  by  possessing  two  additional  atoms 
of  hydrogen  in  its  empirical  formula.  In  its  structural  composition 
it  is  also  closely  allied  to  the  latter,  being  the  methylic  inste  d  of 
the  methylenic  ether  of  the  same  phenol : 
CH2  =  CH  .  CH2 
C 
Eugenol:  HC /\CH 
HC\/C.O.CH3 
COH 
We  therefore  are  led  to  suppose  that  safrol  and  eugenol  are  gene- 
rated in  the  plant  by  nearly  allied  processes. 
