‘Tet,rahedron
Tm
Letters
N0.51,
Ommmm
OF
pp.
of
a new
Pharmaceutical
cordata drug
DITmIIPEKE
acid
needles
(A
3%)
IN
Ltd.
AJTALIA
(TT),C21?3202,
giving
only an end absorption,
the presnnce
revealed
the absence
'117cm -l(.monosubstituted bond).
of three tertiary
orotons
c*xunlinq)), Mose pimarate
.
:;i.' Qalja
1 :1-Jr:_,.
double
bond
bsrds et IA“' -*.-.
counlinr: nattern
-,.Q., 1.W
(T 425 double
:)
of con.iupe+-eC s,..+~'-3,
COubl~~ bond!,
methyls(?
?65 sm-: -5:‘ r? - !. JC' . , T?(.;.,”
~7.i .'.73), ny
.- .:':n *
'b-oad sl~n-let)', " 1 4-‘--A.. bond (f %.0-S.?
c:=f + .‘--
is aili.tesimilgr to thet of ~et',--;l+ i .
(??I) (2).
fTO),
C20HJz0,
ester
(II) wit!? T,i.?lii, .r:elded 2n r?rO'-0‘‘c:
m.p. lC9-110".
w";h TiLlU _I^__ 4 wave an oily hydrocarbon of 1.9. end P.' .R. soectra, rotation,
of the roots
The T?T.T..D. ~:rect:-~~-: 'i- 77C1,'
on a monosubstituted
Qe,iuctlon of the methyl conoound
.Tenan
T>..c-'.i,'. s?Pc;ru'y:(?Y, ?+“ ,\ of
m.p.63~G4.5".
nroton on a trisubstituted olefinic
r~“~~9.
one of t'ce Or;:-i.na.:. -,lants ,J!'y31j -i're
"!,e T.'. s-nectrum (in CC1 ) of T showed absorn%ion 4
(trisubstitllted double
t ~:~n.
nlant drurs, r+:e: sol ??TWi
of the oriental
16 - 12c.c" m.o. 163-164°,[411D
ester
'l?c,
cORDATA
llri
The dit,'rnen:c ?c
(1).
methyl
(cnrboxyl),
xn ~;reaf
@samu Tanaka
(I) from the ethereal. extracts
(from hexane),
I’rint,rxd
i”, .r,,yp,. ~:: 11,?.r*
Thunb. (;r?nanese name: Wo),
"Duhuo"
I’r~s~
TJnivcrrit:.F of -0::yo :
Sciences,
a series of investigation
diterpenic
Pergamm
susumu Mihashi*and
:‘m.‘i”“l
During
1967.
(->PI?WWE-TYPE
Sho ji Shibata, Faculty
5241-5243,
'Tos;rl.atlon of ?I! fo'.?oV/iPSj :"z I'<' '!:cr,i on
2c (V), _&d
ll,.EO
ir-Tl_;).
-.> ,‘I’y; 8011
_'"i?c, , 1‘i.c thin layer and '
and C.P..D. curve of V with those of (+)~~ilRre-"(14\,~.5-~i?rc ,'Tr-'
(3) led to assipn this hydrocarbon The posir;ion of the carboxyl son of the methyl
signals
(V) as /-~nirnara-9(14),15-,1;~PP ‘:I:.
group of I has been established
of FT.bK.P.snectrum
pyridine with those of its methyl -Present address: molcyo Co?lese
of the oripinal
hp -'se co~-~=ri-
acid
T \/ iri
ester (IT). (see Table I') -----~-.--------.---.---_-of Dharmacy, Kashiwami, (jhin;iulr!l-L-l1,~o'~vo.
5241
No.51
5242
Table I Nethyl signals
Chemical shifts(cps) from TMS at 60 MC. Compd. I
a ';
54.0 62.0 82.0
C
Difference
II 40.0 62.5
-
0.5
72.5
+
9.5
Referring the reDort of Narayanan et al. (5),
+ 14.0
the signal a can be assigned
to the methyl group which is located in a 1,3-cis diaxial disposition with the carboxyl or the carbomethoxyl group.
The signal 2 can be assigned to
the methyl groun attached~to the carbon atom bearing the carboql methoxyl groun.
or carbo-
The axial conformation of the carboxyl group of I is also
demonstrated by the I.R. spectrum (KBr) of its methyl ester (II) (C-O bands at 1232 (strong), 1193,
1136 (weak), 1158 cm-l(strong)) (6), and by the
Cz20R signals of R.M.R. snectrum (in CDC13) of the corresponding alcohol (TV)
(q6.13 and 6.58 doublets, J= 11.5 CPS) (7). These evidences led to a conclusion that the carboxyl Froun of I must be present at C-4~ (axial) of (-)oimara-S(14),15-diene (V), and the N.M.R. signals a, 2 and 2 should correspond to the methyl at C-10,
fl
CHZOPP
C-13,
and C-4p (equatorial), resoectively.
)
\
19R
. ;
I II N V
R-COOH R = COOCl13 R--C&OH R =CH3
I
’ \ :
n
@ .J Ill Vl
OIBBERELUNS
__
R R =COOCH:, R=CH3
VW RrcOOH VIII R-CH3
No.51
,i24i
Conseouently,
the diterpenic
15-dien-19-oic
acid (I) can be formulated
acid.
The co-occurrence
of kau-lfi-en-l'+oic acid (VII or its anti-xode\ /c' 1.1 the
root of this slant has been shown by the qas-liquid methyl
ester.
The isolation
Aralia
cordata
would be noticeable,
a sisnificant
nrecursor
and pibberellins.
of I in a fairly !:ood yielii (O.,%# ) +,,I.-
by Aralia
since I or its '3:>mo'o-~1~,q wq _’3 -0
of the bins:Jnthesis of /--\'?a lre'le IvITI?
crude
ethereal
is beinp used as a western
same Dattern
chromato%ranh.: !>f ?+i
I;>rt v-t! vp?
(9,lO)
The methylated which
as (-)nimarn_~.<14),
of Pas-lioui?
extracts
of the ro3ts of Arnlia --
folk medicine
has ?efn found '7 ~~vc +-?e
and thin layer chro-ato-rams
cordata 'Chunb., indicating
racereDs; 1,.
the nreserce
vlit31t‘-at-:f -.'JCT
of T 2nd VT iz- ;*,c ,-,ti-
?ode). Acknowledgements: for
collectinq
authentic
We are qrateful
the
slant material,
samnle of (+)nimara-8(14),15-diene,
Dr. 1:. ""ori for sunrlying Thanks
to :r. T. Ando, "ohoku
CoIle'-c 0: ??r-acp,
to Yrof. S. ldenkert fov s*l?n?_:~i~.~t;:e and to mof.
'r. "'nti;i a+
the alithentic sam?!e of (+)ka!lr-1:.--e?--? a-o'c acjd.
are also due to Yakurikenkyukai
a?d $~i~akukensl~uf~~‘~~r~'li 'r?i f F
pants. Seferences 1.
J. Sato:@n
the Chinese
n"edical Dl~ants (,‘a,an Society: frr r?q*Yr;
' *f
Sciences.
2.
1059) PP.332. E. l$en':ert, and P.?eak, -,T. Am. Chem.
A. Afonso, c=.,
-.
Desk,
T?.V.J.
SOC., 2,
'9F (1 %l);
F. ‘~r?Lyc-‘c,
Carne,y, D.'I'..Teffs 4'1 ,?.7. "C?l'p
_.. -.z.
30 713 (1965). J. Crc. Chem., 2F, 6 (1365). and Sukh Dev, 7>etrzedron Tetterc,
z/.
E. Ireland
4.
A.FI. Yanadi, R.R.
5.
C.?. Narayanan
6.
(1965). S. Sory and r". Fgtizon,
7.
A. Gaudemer,
P2.
bust. J.Chem. 7 17 C.A. Senrick and P.R. Jefferies 9 L_-__’ 115 (19F4). E. Wenkert, &em. and Ind., 1955, 2?2. B.E. Cross, 2.TT.B. Gait and J.R. 'Ianson, J. Chem. Sac., w, '95:
9. 10.
and W. Scheirs, Sobti
em.,
'
and TT.I(.TJen~atasLlbra'"'tT;-;'., 'i-trahedron --_-ret'-erc.
,T. Polonsky
Sull.soc.chim.Fr., 1")Ei4,'?5C. and E. 'kJer?kert, Bull.~cc.c __--.Fr., 1,
'1%
.)\.
’
uhT1.
J.E. Graebe, D.T. Dennis, C.D. l:pner and C.8. l'iest,J. BiOl.",hem., 240, 1847 (1965); T.A. Seissman, -4.5. Verbicar, B.O. Phinney and A.J. Verhiscer, CT. Crac,z, ?.A. Phytochem., 2, 933 (1966). and B.O. Phinney, Phytochem., 2, SO7 (1967). z*D*-‘r-'pr: "*-?*“est+ ?k-, A^i^ J.Biol.Chem., 242, 3095 (1967). D.T.Dernis, C.4.'.;Ps+,z., = (1~967). -
G.rap;g, Geissman