noting that large doses were required. Leyva and Gutierrez
noted similar toxi-cological effects with the alkaloid of
but unfortunately their finding that amonkey dying after a large dose
the alkaloid had dilated pupils has been misused asevidence for a mydriatic effect, resembling that of tropine, when
might have been betterregarded as due to asphyxia or some other agonal effect. There
therefore no pharma-cological data to indicate that the alkaloid
investigated in this laboratory isdifferent from dioscorine itself.
Most of the analyses are by Mr.
C. Hall. Spectral measurements are by Dr.
Strauss,with the assistance of
Hofman Degradation of the
AZkaZoid.-The crystalline alkaloid (2.0
in dry methanol (10
and methyl iodide (5 c.c.) were refluxed on the water-bath for 3 hr. After removal of thesolvent and excess of methyl iodide in
the residual crystalline methiodide (3.3
100%)was dissolved in water (15 c.c.) and the solution treated with freshly precipitated silver oxide,prepared from silver nitrate (3.0
and N-sodium hydroxide (50
After 12 hr. withoccasional shaking the solution was filtered and the filtrate evaporated to dryness
on thewater-bath. The foamy methohydroxide (2.1 g.)
obtained decomposed smoothly at 180-220°/12 mm., giving an aqueous distillate (1-4
which was heated under reflux on the water-bath with
aqueous potassium hydroxide
hr. The cooled solution was ex-tracted several times with ether, and the combined extracts were dried (KOH) Removal of theether through
short Vigreux column gave an oily base, which distilled at 125" (bath)/8mm.(0.6
1.0 in CHC1,) (Found
81.9; H, 11.25; N, 7-55; CMe,
Calc. for C,,H,,N:
7.3; 1C-Me, 7.85%). Gorter
reports b. p.
Hofmann base from dioscorine 1l.6--12O0/Smm.Ultra-violet absorption in ethanol
17,500. Infra-red absorption (liquid film)
Bands at 3-23, 5.61, 5.73, 5-80, 6.11,and 11.26
was obtained by refluxing the Hofmann base
with methyl iodide (2 c.c.)for 10 min.
it separated from ethanol-ether in clusters of glistening prisms, m. p. 120-122"(Found
I, 38.0.A picrate,prepared in the usual manner in methanol] separated from methanol in rhombic prisms, m. p.129-130" (Found
54-3; HI 5.7%).Acidification of the potassium hydroxide solution above, followed by basification withsodium carbonate and extraction with chloroform, gave a base distilling at 140-150" (bath) O-06mm. (0-7
which was mainly unchanged alkaloid (picrate, m. p. and mixed m. p. 187"), butthe appearance in the ultra-violet absorption spectrum of a peak at 2650
1,700) indicatesthat the product contains some of the normal methine base of the alkaloid.
C1,H,,N.-A solution of the base
in purified chloro-form (20c.c.)was ozonised at room temperature for 3 hr. Evaporation
the solvent in
at room temperature gave an oily ozonide, which was decomposed by distillation with normalhydrochloric acid (50 c.c.), about
of distillate being collected. The distillate, with anexcess of
saturated solution of 2
4-dinitrophenylhydrazine in 2~-hydrochloric cid, gaveformaldehyde
yellow needles (from ethanol) (0.20 g.), m. p. andmixed m.
C13H, N.-Adams' platinum oxide catalyst
mg.)was suspended in N-hydrochloric acid
c.c.) and pre-reduced by shaking in hydrogen at roomtemperature and pressure for 30 min. A solution of the base Cl3HZ1N
in N-hydrochloricacid (10 c.c.) was then added and the shaking resumed. After
hr. absorption had ceased (at17"/760 mm., 78
calc. for 3H,,
c.c.). The solution was filtered and basified with potas-sium hydroxide] and the product isolated with ether. The dried ethereal solution was evap-orated through a short Vigreux column, and the residual oily
p. 125-128"(bath)/l2 mm., 110" (bath)/g-lO mm. (0.20
1.5 in CHCl,)(Found
CMe, 6.55, 7.05.
1C-Me.7.6%). The base did not decolorise dilute, aqueous permanganate at room temperature in 30sec.A
was obtained by refluxing the base (0.1 g.) with methyl iodide
c.c.) for 10min.
evaporation of volatile matter furnished a syrup, which crystallised
trituration withacetone. The salt separated from the same solvent in clusters of elongated prisms, m. p.182-183" (Found, on material dried at 100" in
37.5%).C,,H,,NI requires C, 50.45
H, 7-2 I, 38.1%).Infra-red absorption (liquid film)
Band of medium intensity at 11.75-12-1
D o w n l o a d e d b y U n i v e r s i t y o f M i s s o u r i - C o l u m b i a o n 2 0 S e p t e m b e r 2 0 1 0 P u b l i s h e d o n 0 1 J a n u a r y 1 9 5 3 o n h t t p : / / p u b s . r s c . o r g | d o i : 1 0 . 1 0 3 9 / J R 9 5 3 0 0 0 1 8 2 5