Am.  Jour.  Pharm.  > 
Oct.,  1878.  J 
Nitrite  of  A  my  I. 
5oi 
tion  is  one  of  considerable  difficulty,  requiring  for  its  elucidation  the 
consideration  of  a  number  of  facts.  In  the  first  place,  I  have  ascer- 
tained that  the  fractions  boiling  below  900  and  above  ioo°  are  for  the 
most  part  either  physiologically  inert  or  have  an  action  distinct  from 
that  of  nitrite  of  amyl.  There  may,  however,  be  several  isomeric  or 
metameric  nitrites,  whose  boiling  points  differ  and  yet  whose  physiolo- 
gical action  is  the  same.  That  this  is  the  case  seems  probable  from 
the  varying  boiling  points  given  for  amylic  nitrite  and  amylic  alcohol. 
Indeed  two  isomeric  alcohols  are  known  to  exist.  According  to  the 
authorities  cited  in  Watts'  "  Dictionary,"  the  boiling  point  of  the 
nitrite  varies  from  91 0  to  960.  Tanner  ("  Year-Book  of  Pharmacy," 
1872,  186)  gives  95°-ioo°  and  Umney  ("Pharmaceutical  Journal" 
[3],  i,  422)  98°-iOO°  as  the  temperatures  at  which  nitrite  of  amyl 
should  distil.  For  amylic  alcohol  Gmelin  gives  boiling  points  varying 
from  1270  to  134°,  and  even  the  more  recent  researches  record  appar- 
ently conflicting  accounts.  Schorlemmer  found  ("  Proceedings  of  the 
Royal  Society,"  xv,  131)  that  amyl  alcohol,  whether  prepared  from 
fusel  oil  or  from  American  petroleum,  boiled  at  1320.  On  the  other 
hand,  Pedler  ("Chemical  Society's  Journal"  [2],  vi,  74)  gives  1280 
and  1290  as  the  boiling  points  of  the  dextrogyrate  and  optically  inactive 
alcohols,  respectively.  Without  going  further  into  the  matter  at  pres- 
ent, I  may  say  with  certainty  that  there  is  an  amylic  alcohol  or  mix- 
ture of  alcohols  boiling  at  I28°-I29°.  This  I  have  proved  by  recti- 
fying a  fraction  repeatedly  until  it  distilled  entirely  at  I28°-I29°,  and 
then  oxidizing  the  same  with  potassic  anhydrochromate  and  sulphuric 
acid.  It  gave  a  yield  of  valerianic  acid  equal  to  14  per  cent.  Other 
matters  that  have  to  be  taken  into  account  are  possible  inapplicability 
on  the  large  scale  of  a  process  of  preparation  or  purification  that  may 
work  well  in  the  laboratory,  also  that  a  sample  honestly  prepared  by 
one  method  may  contain  impurities  not  existing  in  a  sample  prepared 
by  another  process.  Not  much  importance  need  be  attached  to  the 
spec,  grav.,  as,  on  account  of  the  lower  fractions  having  a  higher,  and 
the  higher  fractions  a  lower  spsc.  grav.  than  amylic  nitrite,  it  is  easy 
by  a  judicious  blending  to  produce  the  desired  density. 
For  the  preparation  of  the  nitrite  two  processes  are  given  in  the 
Pharmacopoeia,  "  by  the  action  of  nitric  acid  or  nitrous  acid  (N203)  on 
amylic  alcohol."  Of  these  two  I  have  no  hesitation  in  pronouncing 
the  latter  to  be  the  better.    Whether  it  is  the  more  economical  may 
