168 
DE. E. EEANKLAND ON A NEW SEEIES OF 
sion of the research to the homologous methyl compound, I much regret having been 
deprived of the cooperation of my friend and fellow-labourer who had rendered me 
such valuable assistance at the commencement of the investigation, but who was 
reluctantly compelled to abandon its further prosecution. 
The first attempt to replace oxygen by ethyl in boracic anhydride was made by 
exposing the latter in a finely pulverized condition to the action of zincethyl at various 
temperatm’es, but it was found that the zincethyl was utterly powerless to effect the 
desu’ed substitution; neither did the anhydrous acid yield in the slightest degree to 
Wajs^kltx’s compound of sodiumethyl and zincethyl, although it was digested and 
heated with it for several days. There could scarcely be a doubt that the intractability 
of the anhydride was due in great measure to its total insolubility in the surrounding 
liquid, and therefore, in order to place it under conditions more favourable for the action 
of the organo-metallic body, it was converted into boracic ether. 
The ether was prepared by Eose’s process*, which consists in distilling an intimate 
mixture of sulphovinate of potash and dried borax. The best proportions were found 
to be two parts by weight of borax, and three parts of the sulphovinate ; but the yield of 
ether was very small, the greater part of the product consisting of alcohol. The removal 
of the latter by rectification, as recommended by Eose, involved the loss of much ether ; 
recourse was therefore had to chloride of calcium for its abstraction, a method which 
gave very satisfactory results, the product of pure ether being more than doubled. 
The following is a sketch of the process finally adopted. About 3 lbs. of the mixed 
borax and sulphovinate of potash were put into an ordinary Papin’s digester, which was 
placed in a sand-bath and exposed to a very gradually increasing heat so long as volatile 
products came over. The crude distillate obtained from several such operations was 
then treated with about one-fourth of its weight of fused chloride of calcium, and 
agitated until the latter was dissolved. The liquid now separated into two layers, a 
lower one consisting of an alcoholic solution of chloride of calcium, and an upper one 
containing nearly all the boracic ether, which retained only a small proportion of alcohol 
in solution. The upper layer was decanted and submitted to distillation. It began to 
boil at about 85° C., but the thermometer soon rose to 118° C., between which tempe- 
ratm’e and 125° C. the greater part of the remaining liquid passed over and was reserved 
for the purposes of the investigation. A thick oily liquid remained in the retort, and 
appeared to consist of boracic acid united with a smaller proportion of oxide of ethyl. 
On adding zincethyl to the boracic ether thus prepared, a considerable elevation of 
temperature gradually occurred, whilst at the same time a most penetrating and peculiar 
odour was developed, due apparently to the vapour of some volatile body, that not 
unfrequently burst into flame, when the cork was removed from the flask in which the 
reaction took place. Some prehminary experiments showed that this volatile body 
could be distilled unchanged from the mixture, and that it was neither miscible with, 
nor apparently decomposed by, water. It was also spontaneously inflammable, and the 
* PoGGENDOErr’s ‘Annalen,’ Bd. xcviii. s. 245, 
