The occurrence of (−)pimarane-type diterpene in aralia cordata thunb

The occurrence of (−)pimarane-type diterpene in aralia cordata thunb

‘Tet,rahedron Tm Letters N0.51, Ommmm OF pp. of a new Pharmaceutical cordata drug DITmIIPEKE acid needles (A 3%) IN Ltd. AJTALIA (T...

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‘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