880
F . W . HEYL, F. E. HEPNER AND S. E;. LOY.
tated by hydrazine hydrochloride were distilled separately in hydrogen and the atomic weight determinations gave the following : Fraction Nos. I , 2, 3 and 4.... Fraction Nos. I , 2, 3 and 4.. .. B Fraction Nos. I, 2, 3 and 4.. .. B FractionNos. I, 2, 3 and 4.... FractionNo. 19.................. FractionNo. 19. . . . . . . . . . . . . . . . . .
A A
Det. W t . of Te. W t . of TeBra. 70of No. Gms. Gms. Te. I 0.300558 I .054251 28,509 2
I
2
I
2
0.199807 0.22032 0.158161 0.436907 0.29811
0.700947 0.773048 0,554717 1.532360 1.045485
Average ........................
28.505 28.500 28.512 28.512 28.514
At. wt, of Te.
127.481 127.456 127.425 127.500 127.500 127.512
28.509 127.479
These determinations show that there is no separation of the after I g fractional precipitations by hydrazine hydrochloride there is no difference between the tellurium which crystallized nitric acid solution in the octahedral crystals as the dioxide separating in the orthorhombic crystals as the basic nitrate.
tellurium and that from the and that
VANDERBILT UNIVERSITY, NASHVILLE, TENN.
CORRECTION. The papers from this laboratory which appeared in the June JOURNAL require the following corrections :
P. 712, equation 75, for 2RT read for mm. read cm.
zn,RT __ , and p. 739, lines 33 and 37, F EDWARD W. WASHBURN.
LABORATORY OF P€iYSICAL CHEMISTRY, UNIVERSITY OF ILLINOIS.
[CONTRIBUTIONSFROM THE CHEMICALLABORATORY OF THE UNIV~RSITY OF WYOMING.]
ANALYSES OF SOME WYOMING LUKSPURS. I. BY F.W. HEYL,P. E. HEPNERAND S. K . LOY. Received M a y 17, 1913.
The poisonous character of some of the various larkspurs whiih are widely and abundantly distributed in the states of the Northwest has been the d b j e c t of several experimental studies. Chestnut and Wilcox' studied the influence of D e l p h + w t glaucum and of Delphinium bicolor upon animals which were fed with these plants or with extracts prepared from them. These workers also had the opportunity for observing, to some extent, the economic importance of these particular species in Montana. During the season of 1900, one hundred cases of cattle poisoning produced by Delphinium glawcum were brought to their attention and of these fifty-six proved fatal. Because of the habitat of this plant on the mountain ranges, cattle alone are poisoned by it. The figures given are Div. Bot., U. S. Dept. Agr., Bull. 26, 65 (1901).
ASALYSES OF SOME R'I-OMIYC; LARKSPURS. I.
881
stated to be approximately one-fourth of the total loss caused by this plant in Montana. LA study of the laikspuis of Colorado by Dr. Geo. H. Glover1 and C. Dwight hlarsh indicates that this genus is coiisidered second only to loco fioiti the st.andpnint of the economic loss produced in that state through poisonous plants. 'I'hese workers coiisider Lklphiniurrt Selsonii, D. elorigutiiuc ( g l u i i ~ i o u )13. , g i and D. burbcyi as the most poisonous to stock, and oi' decreasing t ity in the order named. One other study2 of the poisonous propertir.; o f I). glnziciiiri has been cairied out by Dr. B. Kennedy of tlic N e \ d a Experiment Station. I n \.l'y~~iningthe three important larkspurs are Delphinium geyeri, D. g l a i i ~ ~ i i , cand 11. LYdJoiLiz'. The only chemical work that has been carried out upon any of these is confined to the report3 of an alkaloidal assay upon the roots of D. itiel.cotiii. ,This showed the presence of 0 .72%) of crude alkaloid. I n the same work, the isolation of an alkaloid from the roots of 11. r c o ~ ~ d o r z oisn described. I t is a crystallin substance, melting at 1 & + ~ ) - 1 8 5and ~ has the formula C,,,H,,NO,. I t is now placed upon the market by Merck, but the commercial product as described in 1Icrck's " Index" is ar, amorphous white powder. I t is used as a substitute for curare. In another comrr~unication~ it is reported that the cheinical e ~ a i r i i n a t i o nof the roots of the i.arious species of Delphinium proved the alkaloidal material to be similar. These larkspurs a r e t o be distinguished from those of European and .lsiatic origin> upon ivhich considerable chemical Ivork has been carried out. In thc: prcseiit paper \IC report tlie prvsiiiiatc analyses of the different 1 ~ ~ : of t s tlic several spwies \vhich arc iniportant in this state. Unless i 11rIe is a iirarked tliffercnce i t i the pliysiologiwl activities of the alkaloids est: :species, it ~ . o u l dseem from the results of o u r assays that I). i i s the niosl dangerous. In order to gain some idea as to the toxicity of tlic crude alkaloidal mixture obtained Ironi tlic leaves oi 11. geycri a i i intraperi!oiie;al iiijection of 0 . o < ~ h q grain of the alkaloid as sulfate \\'astiiade upon a guinea pig weighing 6 75 grams. Death followed iii :iinc niiiiti tes. In another experinlent an intraperitoneal injection of I.). 02 gratri as sulfate killed a guinea pig weighing 623 grams iii thirty! i \ ~ minutes.j Iion.e\w, the preirailing opinion as to the toxicity of these larkspurs clf
Bull. Co. i l g r . En-pt. Stntioii, 113,2.4. Bull. .Vez. A g r . Ez.pt. S t c , 55, 53, and others. Gco. Heyl, Siiddeufsclze Aputhckev Zeztung, 43, " 9 (1903). .Sitdd. .Afiofhckcr Z ~ z t u x g ,43, 28 (1903). The study rif thc physiological action of thcse alkaloidal preparations is being conducted by Dr. K. 1%.Pricn and will be reported in a Bulletin from the Experiment -I
"
Station.
882
F. W . HEI’L, P . E. H E P N E R AND S. K . LOT
does not ascribe to D.geyeri the position which our results would seem to indicate. Pammel,’ for example, states that,D. elongatum (gdaucum) and D. Nelsonii are the only ones that contain a sufficient quantity of deleterious substance to produce poisoning. The leaves of the three species have been subjected to a complete proximate analysis. Since the leaves of D. geyeri contain a comparatively high alkaloid content, and furthermore since it is the most abundant species in Wyoming, a complete chemical investigation of the constituents will be carried out in this laboratory by Dr. Loy. Experimental Part. The tall larkspur (D. glazccum) was collected while in f u l l bloom during the first week in August. The collection was macle upon the Snowy Range near Centennial in the 11. S. forest reservation. Thc leaves and stems were prepared as a single sample. The flowers and roots were separated and these were prepared in the usual manner. The sample of D. Nelsonii was collected about the middle of June a t Medicine Bow. Some of the plants were in full bloom and some were mature. The various parts were separated, dried in the air, and prepared for analysis in the usual manner. Delphinium geyeri was collected in large quantities ( 1 2 0 kilograms) between May 15 and June IO, 1912, just east of Laramie. The plants did not flower during this period because of the exceedingly dry spring. We were, therefore, unable to carry out any analytical work beyond that described on the roots and leaves. The samples were analyzed according to the usual2 methods. The alkaloidal assays in the following table were made according to the method3 given in the United States Pharmacopoeia for the assay of the b t k donna leaves. The Isolation of d-Mannitol.--The leaves of Delphinium Nelsonii were now assayed by a second method. A portion weighing 50 grams was extracted with one liter of 95 per cent. alcohol for several days. The mixture was occasionally brought to the boiling point. The tincture was removed by filtration on a Biichner funnel and the residue washed several times with alcohol and pressed dry. The filtrate was concentrated under reduced pressure to a small volume and allowed to stand over night, whereupon a poorly crystallin deposit weighing I . 37 grams separated. The partially exhausted drug was boiled with alcohol exactly as before and upon concentrating this extract 0 . 9 5 grams of beautiful, colorless needles separated. The melting point was 158*-162 ’. Upon further recrystallization from alcohol the melting point remained constant a t
* “Manual of a
*
Poisoning Plants,” 467 (1911).
U. S. Dept. Agr., Bur. of Chem., Bull. 107 (Revised). U. S. Dispensatory, 19th Ed., p. 228.
ANALYSES OF SOME WrTOMINC, LARKSPURS. I.
..18 . : : ' : ,: .. ... .. . .' .., 8 ' ' . . . . .
.. .. ..
,
.
884
F. W . HEYL, F. E. HEF'NER A S D S.
I(. LO';.
165'. Analysis showed that the two crops consisted of d-mannitol. The following analyses were conducted upon samples ohtained from D. N e l s o n i i , D. geyeri and D. glaucum,, respectively : Calculated for C,H,,O,: C, 39.6; H, 7 . 7 . Found : C,39.77, 39.36, 3 9 . 5 ; H , 7 . 9 , 7 . R , i 'I.
The yield obtained is equivalent to 4.62',; of the plant. The alcoholic mother liquors were joined ant1 macle up to a ~ o l u m r of 250 cc. and the dissolved solids and carbohydrates \$'ere determined upon an aliquot portion. The remainder of this solution equi\~:tlent to 43 grams of the plant was used for an alkaloidal assay. The soltition was concentrated to the consistency of a fluid extract atid diluted \ \ i t 1 1 a mixture of I O cc. of iV sulfuric acid and 2 0 0 cc. water. The resin \vhich Precipitated weighed 0 . 8 6 2 7 gram equi\dent to 2 . oo solution was extracted several times with the ether and then, it strongly ammoniacal, the alkaloid was extracted rvith etlier. I>roii-j the etiier the alkaloid !vas rernoved by repeated extraction with 0 . I r\l sulfuric acid, from which it was again extracted after neutralization with ammonia, hy repeated extraction with ether and the11 with c1iloi.oform, un,til at length complete extraction was indicated l)y the F:iilure of the aqueous solution to respond to a test with h h y e r ' s reagent. 'l'hc extracts, upon evaporation, left a residue weighing o . 0828 grain. The original ammoniacal liquid gave a positive test f o r alkaloid nnd a second series of extractions was carried 011t as before, using clllornfortn instead of ether. The residue here obtained weighed ( . I . u~12I grani. When the residues were titrated they required, respectively, 1.14cc. and 0 , 3 I cc. 0 , I N sulfuric acid. These crude alkaloidal products contained a small amount of resin. A quantity of normal sulfuric acid was added to each of the solutions which had been titrated as described above, and after filtering :ind uniting the filtrates, the alkaloid was precipitated with hlayer's reag-ent, of \rhich about 3 . 3 cc. were required. The mercury salt was filtered off, washed with water, suspended in dilute sulfuric acid and decomposed with hydrogen sulfide. The mercuric sulfide was removed by filtration, the filtrate was warmed to expel the excess of hydrogen sulfide, and the alkaloiti was recovered by another series of extractions with ether aiitl with chloroform. The weight was 0.07.3.3 gram equivalent to o . I 7 The above-described method was employed in the assay of the leaves of D. geyeri. Thus two crops of d-mannitol were obtained. The first melted a t 164' and weighed 0 . 6 7 gram. The second melted at 156-158' and weighed 0 . 8 7 gram. The yield is therefore equivalent to ,i. o8qC. The resin precipitated weighed 0.9434 grani equivalent to 2 . 19:;. E;ther extracted 0.3444 gram and chloroform 0,0789 gram of crude alkaloid. These neutralized 3 . 2 4 cc. and I , 18 cc. of 0 . I N acid, respectively.
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
1.44
c1. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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, 3 1 , 10j3; Curtiss, Hill and Lewis, Ibad., 33, Curtiss and Strachan, Ibid., 33, 396.
