784. REPORT—1890. 
Important results were got by the dry distillation of veratrin, which yielded tiglic 
acid and 8-picoline, and by the distillation of veratrin with lime, which yielded par- 
ticularly isobutylene, 8-picoline, and 8-pipecoline. The picoline so formed has this 
peculiar property, that it is not miscible with water in all proportions, and is more 
soluble in cold than in hot water—a cold, saturated, aqueous solution becomes milky 
when very gently warmed. The picoline prepared from strychnine by Stoehr has 
the same properties, whereas the picoline prepared synthetically by Zanoni dissolves. 
in water in all proportions. The boiling-points of the two picolines also differ by 
6° C. Ladenburg found that the double salts formed by these two picolines with 
platinic chloride when boiled with water, both yield yellow crystalline sediments ; 
these are identical in composition, but differ by 16° C. in their melting-points. 
Ladenburg concludes that two isomeric 8-picolines must exist, and draws attention 
to the important theoretical consequences of this discovery. 
2. The Action of Phosphorus Trichloride on Organic Acids and on Water. 
By C. H. Botnamuey and G. R. THompson. 
The action of phosphorus trichloride on organic acids is given in all text-books 
as a general method for the preparation of acid chlorides, and, with scarcely any 
exceptions, the reaction is represented by the equation, 3RCOOH + PCI, =8RCOCI 
+H,PO,. Some years ago, in his paper on ‘ Specific Volumes of Liquids,’ Thorpe 
showed that in the case of acetic acid the reaction is properly represented by the 
equation, 3CH,COOH + 2PCl, =38CH,COC]+8HCl+P,0,; but this fact has been 
overlooked, and the incorrect equation may be found in the most recent text- 
books. 
The authors find that in the case of propionic and butyric acids the change is 
represented by a precisely similar equation, but that the reaction is liable to become 
complicated in presence of excess of one or other of the compounds. As a rule, a 
small quantity of the phosphorous oxide decomposes, with formation of P,O and 
other products. 
In the case of benzoic acid the reaction is much more complicated, the yield of 
benzoyl chloride being always lower than the calculated amount. Hydrochloric 
acid is evolved in large quantities in this case also. 
It would seem that, although the chief reaction is expressed by the equation, 
8RCOOH + 2PCl, =38RCOC1+ P,O,+3HCl, and though, under certain conditions, 
this equation may be strictly true, especially with the acids of the acetic series of 
low molecular weight, many other changes may take place, to an extent depending 
on the conditions. Some of these changes are, interaction of the acid chloride with 
the unaltered acid; decomposition of the phosphorous oxide, which takes place 
more readily in presence of organic compounds, &e. Possibly, with acids of higher 
molecular weight some phosphorous acid may be formed, and this will interact 
with the phosphorus trichloride still present, forming phosphorous oxide and 
hydrochloric acid. This reaction, together with the subsequent decomposition of 
the P,O,, would explain the greater formation of P,O in the case of acids of higher 
molecular weight. Direct evidence was obtained of the formation of benzoic acid 
by the interaction of phosphorous acid and benzoy] chloride. 
The action of phosphorus trichloride on water takes place in accordance with 
the ordinary equation, PCl, +3H,0=H,PO,+3HCl, so long as the water is in 
considerable excess ; but if the chloride is in excess it reacts with the phosphorous 
acid, with formation of hydrochloric acid and yellow phosphorous oxide mixed 
with other oxides, and, in some cases, with free phosphorus. In the interaction 
of water and excess of phosphorus trichloride, the authors obtained the soluble 
form of P,O or P,OH in the cooler parts of the vessel; but if exposed to a tem- 
perature above 70° it became insoluble, a result which agrees with an early state- 
ment of Gautier. 
In the interaction of phosphorus trichloride and organic acids we may, therefore, 
have several reactions taking place simultaneously, and the extent to which any 
one of them proceeds will depend largely on the temperature. The action of 
