1980, Vol. 39, pp.

85-87, O Hippokrates Verlag GmbH phnta W'

medica Plant Research

4-Nerolidylcatechol from Potomorphe

umbeIlatal

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Anake Kijjoa", Astrea M. Giesbrecht*", Maria K. AkisueU**,Otto R. Gottlieb' and
Hugo E. Gottlieb**"
lnstituto de Quimica
" lnstituto de Ciencias Biomedicas
"' Faculdade de Ci6ncias Farmac6ulicas, Universidade de Sao Paulo, SP, Brasil
"" Department of Organic Chemistry. The Weizmann Institute of Science. Rehovot, Israel

Key Word Index: Potornorphe urnbellata; Piperaceae; 4-Nerolidylcatechol.

Abstract Results

Roots and leaves of Potomorphe Mm- Hexane extracts of the roots and leaves
bellata ( L . ) MI+ (Piperaceae) from S i o yielded, besides sitosterol, a novel com-
Paulo State, Brasil, contain 4-nerolidyl- pound, 4-nerolidylcatechol (la). Its for-
carechol. mula, C2,H,, O?,determined by HRMS,
was expanded to C,H, (OH),C,, H1,, af-
Introduction ter inspection of the PMR and CMR
spectra, and preparation of a diacetate
Roots and leaves of Potomorphe um- (Ib). T h e PMR spectrum also identified
bellata (L.) Miq. [syn. Heckeria umbel- the aromatic and aliphatic portions as ca-
lata ( L . ) Kunth. [2], Piper umbellaturn techyl and nerolidyl groups respectively;
L., Piper hilarianum Stend. (Pipera- the former by the chemical shifts and
ceae)], known as pariparoba or caapeba, coupling constants of the 3 relevant pro-
are used in Brasil in popular medicine for tons, and the latter by revealing the exi-
the treatment of liver diseases [3] or epi- stence of 2 methyls on unprotonated sp2-
Iepsy. C, as well as an additional methyl and a
terminal vinyl on fully substituted sp'-C.
' Part I1 in the series "The Chemistry of Brazi- Confirmation of the structure of the ses-
lian Piperaceae". For Part I see ref. [I]. Basetl o n quiterpenic group was achieved by de-
part of the Doctorate thesis to be presented by A . coupling experiments: double irradiation
K . (on leave of absence from Chulalongkorn Uni- at the freqi!ency of t w o olefinic proton
versity, Bangkok, Thailand), graduatc fellow of the
Brazilian IForeign Office Itamaraty; to Universida- triplets (6 5.088 and 5.092), as well as, in
de d c S i o Paulo. Sponsored by F u n d a ~ i ode Ampa- a separate experiment, of a 4 proton mul-
ro i Pcsquisa d o Estado de S i o Paulo. tiplet (6 1.9-2.1), both affected the shape
86 Kijjoa et al.

of an additional 4 proton multiplet (6 o f the catechol derived la could involve

1.6-I.9), giving evidence for two = alkylation of caffeic acid by farnesol o r
CHCH2CH, sequences. nerolidol to the intermediate 111 and loss
The CMR spectrum also showed the o f the 3 carbon unit as indicated.
presence of a catechol substituted at C-4;
the large chemical shift of this carbon re-
lative to catechol [4] indicated the substi-
tuent to be a tertiary o r a quaternary car- ?\o /

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bon [S]. The remaining signals corre-
OH
spond to an aliphatic chain whose chemi- 11
cal shifts are almost identical to those of
nerolidol[6] except for the vicinity of the 0
sp', non-protonared center, which is
now linked to carbon, instead of oxygen.
T h e connection between the two moie-
ties is thus confirmed.
The MS was consistent with 'the pro-
posed constitution la. All proeminent
#
ions can be accounted for by cleavage of 111
bonds 3; 4'(m/e 151, 163), 4; 5'(137,
177), I , 3'(109), 8; 9'(69) and losses of
CH? of the resulting aliphatic fragments. Experimental

Iroluriorr o/rhc, co~~srirrrc,rrrj.

Pororno~phcirrrrLt.1-
I6trrr ( I ) . MIQ. nas collrc~cd nc.lr Ir.~nhncni,Sdo
Paulo State. Pon.tlcrrd roots (I kg) were pert~olalril
with hcsane ar room rcnip. rhc exrrxr ( 5 g) was
c l i r o m . ~ t o ~ r a ~ hon
e da Si gcl (120 g) column, elu-
ting in order \virh light - C,-H,, h:4 2nd 2:s.
The 1st eluatc was crys~allizrtlro sitosrerol (0.9 g).
The Znd*cluatc (2 g) was separated b! prcp.ar.lrivc
T L C (Si C(,H,-AcOEt 8:2) into nlore pol.ir 1.1
(0.5 g) and a lehs polar misture (0.2 g). A h e s ~ n c
ehrracr of leaves also conrained sitostrrc>l ~ n 1.1. d
Discussion J-Ai'c~roli~r~Ic~~~c~cI~ol (la). chrorna~ogr~~phi~~all~
pure viscor~soil (Found: M. 314.2184. C2,H,,cQ
Prenylated simple phenols seem to be requiro: 314.2247). [a]$ + l (CHICI:). \.,,,,,
(film. c m '): 3106. 1600. 1515. 1439. 1379. 129C.
very rare constituents of higher plants. 1126. 930. PMR (170 MHz. CDCI,. h): 1.30 (s.
O n e further example is alliodorin (It) Me-3'). 1.51 and 1.59 ( 2 3 . 2 Mc-l I '). I .67 (F. MI,-
from Cordia alliodora (R. et P . ) CHAM.7'). 1 . 6 1 . 9 ( m . 2 H-5'.2 H-9.). 1.9-2.1 (n1.2H-

-
(Boraginaceae), a species resistent against 4'. 2 H-8'). 5.00 (dd. J = 17. 1.3 H7.. H-1'). 5.05
attack by marine boring organisms, ter- (dcl. J 10.5. 1.3 HI. H-I '). 5.088 .~nd5.092 (21.
J - 7.5 Hz. H-6'. H-10'). 5.97 (iIi1. J :17. 10.5
mites and terrestial fungi [4]. This com- Hz. H-2'). 6.73 (dd. J = 8. 2 HY. H-5). 6.78 (d.1
pound, as well as the ubiquinones, derive - . 8 H 7 . H - h ) . 6 . 8 3 ( t l . J = 2 H z . H 2).CMR(22.6
formally from quinol. The biosynthesis MHz. CI)CI,. h ) : 15.9 (q. MI.-7'). 17.7 .mil 25.7
4-Nerolidylcatechol f r o m P o t o m o r p h e umbellata
(Zq, 2 M e - I I,), 23.2 (t, C-5'), 25.0 (q. Me-3'). 26.8
(I, C-9'), 39.7 (I, C-8'), 4 1.2 (I, C-4'), 43.8 (s, C -
3'). l I l . 6 ( r 3 C - 1 ' ) . l l 4 . 4 ( d , C-6). 115.1 (d.C-3),
1 19.3 (d, C-5). 124.5 and 124.7 (2d, C-6' and C-
lo'), 131.4 (s, C - l l'), 135.1 (s, C-7'), 141.1 and
14 1.4 (2s. C - l and C-4). 143.2 (s,, C-2). 147.1 (d,
C - 2 ' ) . T h e assignments o f the sp--methine signals
w c r e made unambiguous b y correlating the residual
couplingc in the single-frcqucncy off-rcsonancr de
coupled spectrum w i t h the correspontlinR p r o t o n
shifts. M S (m/c): 314 (25 %) M+. 177 (14). 163
(94), 151 (39), 145(31), 137(18), 123 (39). 109(22),
9 5 (100). 8 I (39). 69 (22), 55 (27). 4 1 (22). 1)iacetatc
(Ib). Acctylarion (AclO, CiH;N. 24 h. r o o m
~ e m p . )gave 'b. v,,,,, (film, cm-'): 1770, 1493, 1370,
1205, 11 12, 1010. P M R (60 M H z . CDCI,. h): 2.2
(s, 2 O A c ) . 7.25 (br. s, H-3,5.6), other bands prac-
tically unchanged.
References
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Mcdica .1j, 190 (1979).
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2. Silva. R. A. L).: Pharmacopeia do.; Fcrndos
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