210 REPORT—1904. 
The solid alkaloid appears to be the neutral carbinol, and persists in 
this form when dissolved in ether or chloroform. When dissolved in 
water or alcohol, however, it is converted largely into the ammonium-base 
from which the acid salts are derived. The addition of methyl alcohol to 
the ethereal solution causes a gradual change from the carbinol to the 
basic form, but a reverse change is brought about by adding sodium 
hydroxide to the aqueous solution. 
A similar equilibrium is possible in the salts derived from cotarnine, 
but the chloride is known only in the ammonium form and the cyanide only 
in the carbinol form : 
: ye 
ee aaah Hom CH : NMe | ON 
: 0,5,0 
60x mes 3 
CH, =“- CH, \CH,.CH, 
+ aa 
CHC]. NMe oe : NMe | Cl 
[ cating | ts CHO | 
CH, . CH, CH,. CH, 
11. Influence of Catalytic Agents Unlike the isomeric changes of 
Group A, which usually take place only in presence of an acid catalyst, 
those involving the transference of a mobile hydrogen atom are cha- 
racterised by an extraordinary sensitiveness to the catalytic action of 
traces of alkalies. The instantaneous fall of rotatory power on adding a 
small amount of ammonia to freshly prepared solutions of glucose was 
noticed by O'Sullivan and Tompson in 1890," but it was not until some 
years later that the dependence of the mutarotation on isomeric change 
was demonstrated. Similar effects have been observed in the case of 
nitrocamphor,? nitrocamphane,? benzoyleamphor,’ menthy] acetoacetate, 
camphorquinone phenylhydrazone,” and the azo- derivatives of menthyl 
acetoacetate,® and no exception has yet been discovered. The smaller 
catalytic action of acids was first noticed in the mutarotary sugars,’ and 
Osaka® has shown that whilst the influence of alkalies is proportional 
to the concentration that of acids is proportional to the square root 
only. The influence of acids on nitrocamphor was at first overlooked,° 
though it is well marked in decinormal and centinormal solutions ; Lap- 
worth was the first to show that acceleration by acids is character- 
istic of this group of isomeric changes. An apparent exception occurs 
in the case of camphorquinone phenylhydrazone, the mutarotation of which 
is stopped by traces of acid. Neutral salts have no influence on the iso- 
meric change of glucose,'? but greatly accelerate that of nitrocamphor.!! 
This difference is probably due to the fact that pseudo-nitrocamphor is a 
strong acid, and is able to compete for a base even against a mineral 
acid. 
1 Trans. 1890, 57, 920. 2 Loe. cit. p. 221. ; 
3 Forster, Zrans. 1900, 77, 259. 4 Forster, Zrans. 1901, 79, 999. 
5 Lapworth and Hann, Trans. 1902, 81, 1499 and 1508. 
6 Lapworth, P7oc. 1903, 19, 149. 
7 Levy, Zeit. phys. Chem. 1895, 17, 301; Trey, Zeit. phys. Chem. 1895, 18, 193; 
1897, 22, 424. 
8 Zeit. phys. Chem. 1900, 35, 661. ® Loe. cit. p. 221. 
1 Lowry, Zrans. 1903, 83, 1317. 1 Loe, cit. p. 221. 
