2242
NOTES
VOl. 69
To the ester (50 g.) was added 5 g. of catalyst and the from the mother liquor after the separation of diosmixture placed under a pressure of 1810 lb. of hydrogen. genin (yield, about 1.0 g./kg. dry seed),4two more The temperature was then slowly raised. Hydrogenation of the double bond took poace at'a pressure of 2550 lb. sapogenins, namely, tigogenin (trace) and gitoand a temperature of 146 . If the hydrogenation were genin (yield, 0.1 g./kg. dry seed). The last two interrupted a t this point, an approximately quantitative sapogenins have occurred jointly in other plants, yield (98yo) of ethyl 2,3-dimethoxydihydrocinr~amate, namely, Yucca Whipplei Torr. subsps. intermedia, b. p. 174-176" a t 13 mm., could be obtained. Agave gracilipes Trel. and Agave Schottii Engelm. Anal. Calcd. for .C13H180(: C, 65.6; H , 7.57. Found: However, this is the first and single case of the C, 65.6; H , 7.55. At a pressure of 2680 lb. and a temperature of 224O, occurrence of all three in the same plant. The significance of this finding has been discussed.3b further hydrogen was consumed and the principal product weighing 34 g. (86%), distilled a t 160-165' a t 13 mm. Lilagenin has been isolated from the sapogenin The product failed to crystallize. For identification, a fraction of Lilium rubrum magni$c~m.~In addiphenylurethan was prepared. This compound melted tion, a small amount of yuccagenin was found. a t 62.7-63.2' after crystallization from petroleum .:her. In our preliminary paper,3a vye erroneously reAnal. Calcd. for C18HZlOaN: C, 68.6; H , ti 70. ported Samuela Faxoniana Trel. to be a source for Found: C, 68.4; H, 6.67. 2,3-DimethoxydihydrocinnamylChloride and Bromide. smilagenin. Actually, i t is a new source for sarsa-The halides corresponding to 2,3-dimethoxydihydrosapogenin. cinnamyl alcohol were prepared by the action of .thionyl Other new sources are listed in the accompanychloride or hydrogen chloride, and hydrogen bromide or 48% hydrobromic acid. They were separated artd sub- ing tables. jected to a variety of demethylation procedures without TABLEI further identification. The dihydric phenols could not be PLANTS CONTAINING DIOSGENIN AND KRYPTOGENIN isolated; resins were frequent products. Nor was it Yield . per kg. found possible to prepare by demethylation the 2,3(dry? plant dihydroxybenzyl halides. Holirever, during sealed tube Plant Location Dios. Krypt. demethylations in the presence of concentrated hydroBalanites aegyfitica Wall. Southern Mexico 5.0 1.0 bromic and hydriodic acids, catechol itself was formed Dioscorea loridiana Bartlett Southern Georiga 1.7 , .. and isolated in yields up to 18% from these 3-substituted Dioscorea glauca Muhl. North Carolina, 1.0 ,.. catechol ethers. This has also been encountered during Trillium Catesbaei Ell. North Carolina .. . 0.1 acid demethylation of 2,3-dimethoxy-n-pentadecylben- Tvillium cernum L, North Carolina . , , 1 .O zene,' ant1 by Hawortli12 during the acid demethylations Trillium decumbens Harbison North Carolina . . . 0.5 of 3 - :tntl 4-substituted catechol ethers. Lability of Trillium declinatum Gleason Tennessee 5.0 1.0 alkyl substitucnts it]. the veratrole molecule under these Trillium erectum L. h'orth Carolina 3.0 0.2 conditions is thus indicated. Trillium Hugeri Small North Carolina 3.0 ...
Acknowledgment.-I am indebted to Dr. rlrthur T. Ness and to Mr. Charles A. Kinser for the microchemical analyses. (12) Haworth and Woodcock, J . Chem. Soc., 999 (1947).
CONTRIBUTION FROM THE OFFICEOF DERMATOLOGY INDUSTRIAL HYGIENE DIVISION ITSITED STATE$, P u ~ r HEALTH x SERVICE I3ETH E SDA , bZD . RECEIVED FEBRUARY 14, 1947 [CONTRIBUTION FROM THE SCHOOL OF CHEMISTRY AND PHYSICS OF THEPENNSYLVANIA STATE COLLEGE]
Trillium ludovicianum Harbison TriElium recurvalum Beck Trillium simile Gleason Trillium stamineum Harbison Trillium Vascyi Harbison Trillium viride Beck
Georgia Mississippi North Carolina Georgia North Carolina North Carolina
5.0 4.0 4.0
..,
...
Trace
..,
0.8
0.4
.. .
,
0.5
..
PLANTS CONTAINING SITOSTEROL Plant Areca Catechu L. Arisaema triphyllum Schott Jatrorrhiza palmata hfiers Smilacina raccmosa Desf. Zanlhorhiea apiifolia L'HCrit
Location Commercial Commercial Commercial State College, Pa. Commercial
Yield, g. per kg. dry plant Trace 0.5 Trace Trace Trace
The identities of the above compounds were established by analyses.of the genins and their aceBY RUSSELLE. MARKER, R. B. WAGNER, PAULR . ULSHAFER, EMERSOS L. M'ITTBECKER, DALEP. J. GOLDSMITHtates along with melting point and mixed melting point determinations on both. Generalized isoASD CLARENCE H. RUOF lation procedures have been reported.3b The isolations of various steroidal sapogenins SCHOOL OF CHEMISTRY AND PHYSICS from many plant sources have been reported pre- THE PENNSYLVANIA STATECOLLEGE viously from this L a b o r a t ~ r y . ' The ~ ~ ~results ~ of STATECOLLEGE, PENNA. RECEIVED MARCH^ 11, 1947 our studies on additional plants are now summar( 4 ) Marker, Wagner, Ulshafer, Goldsmith and Ruof, ibid., 68, ized. 1247 (1943). ( 5 ) Marker, Turner, Shabica, Jones, Krueger and Surmatis, ibid., Among the new sources for steroidal sapogenins 2620 (1940). is the seed of Trigonella Foenum-graecu& L. 62,(6) Original manuscript received June 26, 1914. (Foenugreek). For their isolation 460 kg. of seeds were processed. There has been isolated The Use of a Fluorescent Adsorbent for the (1) Marker, Turner and Ulshafer, THISJ O U R N A L , 62, 2542 (1940). Chromatography of Colorless Compounds (2) Marker, Wagner and Ulshafer, ibid., 64, 1283 (1942). New Sources for Sapogenins
(3) (a) Marker, Wagner, Ulshafer, Wittbecker, Goldsmith and Ruof, ibid., 66, 1199 (1943); (b) 69, 2167 (1947); (c) for suppltrmentary tables, order Document 2384 from American Documentation Institute, l i l 9 N Street, N. W . , Washington 6 , D. C., remitting 506 f o r microfilm or $ 2 1 0 f u r phqtocopies.
BY JOHN W. SEASE
When colorless compounds which absorb ultraviolet light are chromatographed on a fluorescent
