186 Short Cornmunicati~ns

Some Chemical Constituents of Morinda citrifolia

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Oscar Levand* and Harold 0.Larson**

* Department of Chemistry, University of Guam, Agana, Guam.

'* Department of Chemistry, University of Hawaii, Honolulu, Hawaii.

Key Word Index: Morinda citrifolia; Rubiaceae; Asperuloside.

From extracts of the dried fruit of Mo- fruit pulp was complicated by the extreme
rinda citrifolia L. asperuloside and glucose .instability of the products and losses of
were identified b y their acetyl derivatives. organic products during isolation were
Caproic and caprylic acids. were also iso- high. It is possible that the substantial ma-
lated. terial accompanying asperuloside tetraace-
Morinda citrifolia L. (Rubiaceae), is a tate contained related compounds contai-
tree that is widely distributed throughout ning the cyclopentanoid ring system of the
the warm regions of the Pacific [I]. I t was iridoid glucosides in which there is some
called NONIin Hawaii [2] and LADAin interest [IO]. The presence of asperuloside
Guam [3]. The fruit was used for medici- was first noted in Morinda citrifolia b y a
nal purposes by the Polynesians [3, 41 and characteristic color test [Ill, and the distri-
for food in time of famine. More .recently bution of asperulosidic glycosides in the
a survey [5] for antibiotics indicated posi- Rubiaceae has been reported [12].
tive tests from concentrates of the ripe
fruit. Although we were unable t o confirm The ripe fruit was pressed through a colan-
this report, several compounds were'identi- der to remove numerous seeds. After filtration
fied. Aucubin has been reported to posses the pulp was dried at 60-70° and was extrac-
antibacterial activity 161. Although aspe- ted successively with hexane and methanol. The
resdiue from the methanol extract was adsorbed
ruloside is structurally similar to aucubin
on Darco and Celite in an aqueous system simi-
[ 7 , 81, our asperuloside tetraacetate was lar to TRIM'Sprocedure [13]. The adsorbed ma-
completely inactive. Asperuloside does not .teriaI was removed with hot ethanol. After
have outstanding bacteriological proper- removal of the solvent, the unstable residue was
ties [9]. treated with pyridine and acetic anhydride.
Isolation of compounds from the dried . The acetylated mixture of products was iso-
Short Communications
lated in the usual way [14] and was suffi-
ciently stable t o permit column d-tromatogra-
phy. The acetylated mixture (70 g) was chro-
matographed on a column of Silica gel G
(500 g). Benzene was used as the initial eluent.
8-D-Glucopyranose penta-acetate (6 g) was the
first compound eluted mp 132-133O, mrnp with
a known sample was not depressed; satisfactory
C and H analyses were obtained.
Elution of the column with a mixture of
benzene and ethyl acetate (80:20) yielded 15 g
of material that was chromatographed again.
Asperuloside tetraacetate (3.3 g) was isolated
mp 152-153O from ethyl acetate and hexane
(lit. [9] 154.5-1559), mmp with an authentic
sample (mp 151-152') was not depressed.
Found: C, 53.8; H; 5.2; 0 , 41,2; Acetyl, 36.3;
C-methyl, 12.0. C,,H,,O,, requires: C, 53.6;
H, 5.2; 0, 41,2; 5 acetyl groups, 36.9; 5 C-
.methyl groups, 12.9. I,":; 5.66 (a$-unsatura-
ted-y-lactone), 5.74 (acetate), and 6.01 ,u (en01
ether) [8, 91 identical t o IR of authentic
sample; 1 :;?OH 232 nm (log r 3.89).
Steam distillation of the ripe, sliced fruit
gave a distillate that was extracted with ether. 10. Bobbitt, J. M. and K.-P. Segebarth: in
The acidic components were separated by frac-
tional distillation. Caproic and caprylic acids
were identified by preparation of their amides
and anilides for which satisfactory C, H, and
N analyses and melting points were obtained.
Acknowledgements
We thank Professor Charles H. LAMOUREUX 14. Levand, 0 . : Ph. D. Thesis, University of
from the Department of ~ o t a n yof the Univer-
sity of Hawaii for the idedtification of plant
material. The research was generously suppor-
ted by the National Institutes, of Health (Grant
E-3163). An authentic sample of asPeruloside
tetraacetate was provided by Professor L. H.
BRIGGS.
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Hawaii, 1963.
Address: Dr. Oscar Lewand,
College of Arts and Sciences,
University of Guam,
Agana, Guam 96910