216 



Aldehyde A . 



Aldehyde A separated from the crude oil in Experi- 

 ment c (see Table 1) had the following constants: — Refractive 

 index at 20° C. = I'SllO; dispersion, 0-01685. 



As the amount of aldehyde separated from the crude 

 oil f Tactions was very small, the aldehyde A from Experiments 

 a, b, and d were mixed. These mixed aldehydes gave the 

 following constants: — Specific gravity at 17*7° C. =0*9724; 

 corrected for || °C.=0'9744; rotation, —52° refractive 

 index at 20° C. = 1*5096 ; dispersion, 0-01673. 



Aldehyde A separated from the residual oil (Experi- 

 ment g. Table 2) gave the following constants: — Specific 

 gravity at {|°C. -0-9720; corrected for |4 ^ C. = 0*9742; rota- 

 tion, -12-75°; refractive index at 20° C. = 1-5203 ; disper- 

 sion, 0-01876. 



Preparation of the Oxime. — 5 ccs, of the latter sample 

 were dissolved in 10 ccs. absolute alcohol, and to the solu- 

 tion were added 10 ccs. of a saturated aqueous solution of 

 hydroxylamine hydrochloride. The mixture was then made 

 alkaline with sodium carbonate solution and heated on the 

 water bath for five hours, and then poured into cold water. 

 The oxime should crystallize under these conditions. It was 

 found that by changing the water into which the heated mix- 

 ture v/as poured, the crystallization of the oxime was 

 facilitated. Although, in this instance, the water was changed 

 several times, great difficulty was experienced in obtaining 

 the oxime in a crystallized condition. 



After crystallizing by this method and recrystallizing from 

 alcohol, the oxime melted constantly at 57*2° C. Attempts 

 to obtain a crystalline oxime from the aldehyde A samples 

 having a high rotation always proved unsuccessful, as a pasty 

 mass always resulted on pouring the heated liquor into water. 

 A sample of this aldehyde A having a high rotation ( — 44°) 

 was recombined with sodium bisulphite, filtered, well washed 

 with aloohol-ether mixture, and decomposed with hot sodium 

 carbonate solution. By this treatment, one-half of the alde- 

 hyde was lost, and the rotation of that separated had 

 diminished to —14*5°. The specific gravity was 0*977. As 

 the loss of aldehyde on recombining with sodium bisulphite 

 seemed inordinately great experiments were performed to 

 account for the loss, and it was found that the washing with 

 alcoholic-ether mixture dissolved a considerable amount of 

 the bisulphite compound. These alcohol -ether washings were 

 evaporated to a low bulk, and decomposed with a solution of 

 sodium carbonate. The aldehyde thus separated had a high 

 rotation ( — 44°). It therefore appears highly probable that 



