ETHYI, C ~ . 4 S O ’ r A R ’ I ’ R O ~ . \ AND ~ r ~ ITS RI$AC’I’TOSUS IVITII A X I I N G S .
88.j
Precipitated by Xaper’s reagent, of which about 16.9 cc. were required, a white flocculent mercury salt was obiained which yielded 0 . 2 2 5 5 gram of alkaloid equivalent to 0 . 5 2 per cent. The leaf of D. glaucum when assayed by this method yielded b u t one crop of d-mannitol that weighed 0.18 gram and melted a t about 160’. Recrystallization from 95y0 of alcohol raised the melting point to 165’. The yield is therefore 0 . 3 6 7 ~ . The determination of crude alkaloid in 43 grams of the plant showed that ether extracted 0.160s gram that required I . 87 cc. o . I N sulfuric acid, after which chloroform extracted 0.0388 gram requiring 0 . j I cc. 0 . I N sulfuric acid. These were purified in the usual manner and there was obtained 0.1358 gram, equivalent to 0.32%. The resin precipitat‘ed weighed 0.g802 gram or 2 . 2 8 7 6 . An analysis of the ash of the leaves of D. geyeri by l l r . Fred V. Skinner gaye the following results: co,. . . . . . . . . . . . . . . . . 22.38 Sand . . . . . . . . . . . . . . . . . Carbon . . . . . . . . . . . . . . . . . . . . . . . . 0.33 SiO, (soluble) 11.88 Fe,O, A1,O1. . . . . . . . . . . . . . . . . . 5.36 CaO . . . . . . . . . . . . . . . . . . . . . . . . . . . 24.49
I . 13
0.33
11.72 5.28 24.34 0.05 22.39
+
I .9.3
c1. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.44 3.38 0.42
0.42
3.36 __
3.36 -
Summation.. . . . . . . . . . . . . . . . . . . . 9 8 . 2 4
98.15
[COSTRIBXTIO?;F R O Y TIIB CIIEMICAL I..~~OR.’LTORY O F THE vXIVl3RSITY OF I L L I S O I S . ]
ETHYL CYANOTARTRONATE AND ITS REACTIONS WITH AMINES. BY
R I C H A R D S Y D N E Y CURTISS A N D LLOYII
F.
KICKELL.
Received April 2 6 , 1913.
For some time the senior author and his co-workers have been interested in the reactions of the oxomalonic esters with substances having dissociable hydrogen, such as alcohols, amines, and halogen acids. In continuation of this work we have tried the action of prussic acid on ethyl oxomalonate, and have studied the action of the cyanhydrin thus formed with different types of amines. Ethyl oxomalonate, 0 = C : (COOCZH5)Z,is a greenish yellow oil which reacts vigorously with water, hence the reaction between it and 400;
Curtiss arid Spencer, THISJOURNAL, 31, 10j3; Curtiss, Hill and Lewis, Ibad., 33, Curtiss and Strachan, Ibid., 33, 396.
886
RICHARD S. CURTISS AND L1,OYD F. NICKELL.
prussic acid must be carried out under anhydrous conditions. Pinner and Bischoffl tried the reaction of anhydrous prussic acid on chloral, which is an analogue of ethyl oxomalonate, but noted no action. We have found, however, that anhydrous prussic acid completely discharges the color of ethyl oxomalonate, showing that a reaction occurs.2 This action is as follows: HNC
+0=C
COOC,H,
