current machine using 2 X acetate buffer pH 5.5 inclusive of the infrared characteristics over the and benzene. The known triester, neogermitrine,3 whole measurable range, with the oxidation product was obtained by crystallizing the material recovered from triacetyldihydroveratramine (m.p. 242-245", [ a ] 2 3+57.5"; ~ final. Calcd. for C33H4506N: C, from tubes 6-10 from acetone-water. The hypotensive activity4p5of germanitrine, ger- 71.83; H, 8.22. Found: C, 71.94; H, 8.26) niaiiidine, and germanitrine was found to be The respective N-acetates (V), prepared by hy0.12 pg. [O.ll-O.14], 0.77 pg. [0.4G-2.3], and 0.41 drolysis with methanolic potassium hydroxide, were likewise identical (m.p. 2G4-266.5', [o!]'~.~D +71.7", pg. [0.36-0.49], respectively. t 6 8 . S " ; Anal. Calcd. for Cz9H4104N: C, 7'4.46: (3 J I ried 1' \umrrof and Y 11 Lus I J O L R \ % L 74, JU41 If. 8.84. Found: C, 74.57; H, 8.64). The 1932) (4) Edward I> Swiss and George I V a i w n , b ederatiun I'roceediiig\ vicinal effect of the indanone grouping on the 1 ol 11, S o 1. March, 1052 contribution to molecular rotation of Cg is evident ( 5 ) Expressed ds micrograms per kilogram of dnesthetrzed dog per in the abnormally high A [ \ I ] D for the saturation minute required for a ten-minute intravenous infusion t o lower t h e mean of the double bond (+481O for I1 --t IV, 1-493' arterial blood pressure ?(IL?, when administered according t o the method of G L Maison and J Vv Stutzman l h c bracketed numfor 0-desacetylated I1 -+ V) as compared with the hcrs express t h e %C-, confidence limits values +399" for triacetylveratramine + triacetyl11 \\ KLOHS dihydroveratramine, +404" for N-acetyheratra\I D DRAPER mine -+ S-acetyldihydroveratramine, and +243 O KIKERLABORATORIES, h c 17 KELLER 9480 BEVERLY BOULEVARD S KOSTER for normal A5-stenyl acetates5 The significance of this result lies in the fact that I os A\GELES48, CALIFORMA \! M A L E S H 1 J PETRACEKi t renders extremely remote the possibility of a R E C ~ I P EJ D L I 1 28, I%.! rearrangement of the carbon skeleton in the formation of the acetolysis product I1 from diacetyljervine, since ( 1 ) the presence in 1-eratramine of a THE STRUCTURAL CORRELATION OF JERVINE AND preformed benzenoid ring has been assured not only VERATRAMINE by ultraviolet spectrophotometry6 but also by Sir: chemical ~ n e a n s ,(2) ~ the conversion of triacetylAs reported in preliminary communications from dihydroveratramine to IV obviously cannot involve this Laboratorv.' 0.N-diacetvliervine (1) on ace- a change in the skeleton, and ( 3 )i t is reasonable on tolysis with acgtic anhydrideiLcetic acid .IC containing a catalytic amount of sulfuric 0 acid gave rise to a triacetate, CS3H4306K, (map. 239-240", [ a I z 4 D -29'9, which on the basis of its ultraviolet and infra red characteristics 251 rnp, log c 1.08; 300 mp, log E 3.30; I K : intense bands a t 5.75, 3.88 and 6.09 p, indicative, respectively, of 0-acetyl, ketonic carbonyl and N-acetyl) and other evidence was assigned the indanone structure 11. On the other hand, there has been obtained b y chromic acid oxidation of triacetyldihydroveratrarnine (C3YH4705K, now assigned structure 1113)a compound C33H4506N (rn.p.241-245", [ c r I 2 l ~+5Sc) which likewise exhibited the above spectral properties, and the new keto group I\-, K = Ac of which. like that of 11. was unreactive T', R = H to ketone reagent^.^ 'Lye have now reduced I1 catalytically with palladiuin---calciuni biogenetic grounds to accord also to jervine the carbonate in ethanol to its 3,(i-dihydro derivative abnormal ring structure which has now been shown W , 4arid found the latter ic1entic:il i i i :ill respects, to pre-exist in ver:i tr;iniine. \
( 1 j J. Fried, 0. Wiutersteinrr, A . L l i i i y s l x r p . AI h l w r e :r t x r u i i i : t i t v j 1%it ii l r i c ri
0 . \\-INTERSTEI.UEK .
RECEIVED JLTS
SORMAN HOSANSKY' 21, 1952
parently for t h e most part unchanged starting material), which could not always be completely removed by recrystallization or eliminated by rehydrogenation. so t h a t t h e yield of pure dihydro product was always iorv ( 5 ) D . €1. R. Barton, J . C / ~ P ?SOC., I L , 512 (1946). 16) TV A Jacobs and 1, C Craig, J . Biol. Chem., 160, 555 (1945). ' 7 ) This paper is part of the dissertation t o be presented by Norman 1Iosansky in partial fulfillment of t h e requirements for the Ph.D. de~ r t . ? i n tlic ( k ~ c l u : ~ tSrlim~l t, i,i R i i l p e r s University.
