Three New Flavonoid Glycosides, Kaempferol 3-O-(caffeoylrhamnoside), Apigenin 4′-O-(caffeoylglucoside) And 4′-O-(feruloylglucoside) From Dryopteris villarii

2007·2.6 MB·English

by  Filippo Imperato

—
SHORTER NOTES
2 3 3
Amer. 66:1138-1150. Canad. 55:563-567.
Bot. 1976; Whittier, Bot. 1977).
J. J.
The &
gametangia of Lycopodiella appressa (F.Lloyd Under.) Cranfill and
L.
Lycopodiella cernua Pichi-Serm. have essentially the same sizes as those
(L.)
The
gametangia
of L. prostrata. of L. prostrata are typical for Lycopodiella.
The development of the other types of gametophytes of the Lycopodiaceae
is
from found The mature gametophyte
quite different that in Lycopodiella. of
Phylloglossum photosynthetic but starts out as a subterranean, mycorrhi-
is
it
zal gametophyte that is negatively gravitropic. After its exposure to light at the
soil surface becomes a green, bilaterally symmetrical, tuberous gametophyte
it
&
lacking photosynthetic lobes (Whittier Braggins, Amer. Bot. 87:920-924.
J.
2000).
The
remaining gametophytes Lycopodiaceae
of the are subterranean,
mycorrhizal, and nonphotosynthetic. Their development un-
initiated
is
derground by the dark germination of their spores and requires a mycorrhizal
association for continued growth. Early growth forms a solid, teardrop-shaped
gametophyte that gives rise to the four other gametophyte shapes found in the
Lycopodiaceae. Larger teardrop-shaped gametophytes develop meristems
ring
that form the radially symmetrical disk- and carrot-shaped gametophytes of
Lycopodium
(Whittier, Canad. Bot. 55:563-567. 1977; Whittier, Bot. Gaz.
J.
142:519-524.
1981).
The
gametophyte
uniaxial, dorsiventral, strap-shaped of the
terrestrial
Huperzia The
species lacks a ring meristem. meristem arises from a portion
of the apical region of a larger teardrop-shaped gametophyte (Bruchmann,
Flora 101:220-267. This meristem occurs subterminal groove
1910). in a
overarched by young dorsal tissue on these strap-shaped gametophytes. With
the epiphytic Huperzia species, the teardrop-shaped gametophyte enlarges
and grows into the branched, cylindrical, mycorrhizal gametophyte (Whittier
unpublished).
The
gametophyte and development
of prostrata has the typical structure
L.
of Lycopodiella gametophytes; thus different from the other gametophyte
it is
types of the Lycopodiaceae. Dean Whittier, Department of Biological
P.
TN
Sciences, Box 1634, Vanderbilt University, Nashville, 37235-1634, and
Richard Carter, Department of Biology, Valdosta State University, Valdosta,
GA
31698-0015.
New
Three Flavonoid Kaempferol
Glycosides, 3-0-(caffeoylrhamnoside),
Apigenin and from
4'-0-(caffeoylglucoside) 4-0-(feruloylgliicoside)
—
Dryopteris Ten flavonol O-glycosides (based on kaempferol and
villarii.
quercetin), two flavanone O-glycosides (based on naringenin and eriodictyol)
and and
three C-glycosylflavones vitexin, vitexin 7-O-glucoside orientin)
(
have previously been by Hiraoka (Biochem. 171-175.
identified Syst. Ecol.
6:
1978) in eighteen Dryopteris species whereas 3-desoxyanthocyanins have been
found Kuntze by Harborne
in red sori of Dryopteris erythrosora
(Eat.)
(Phytochemistry 589-600. 1966). In addition kaempferol 7-0-(6"-succinyl-
5:
VOLUME NUMBER
AMERICAN
PERN JOURNAL:
234 97 4 (2007)
was
glucoside) was found in four Dryopteris species and an unusual flavan
shown
review by
isolated from Dryopteris filix-mas Schott as in a
(L.)
Markham 427-468, Harborne The Flavonoids, Advances in
in ed.,
(pp. J.B.
New
Research since 1980. Chapman and Hall, London and York. 1988).
Eighteen flavonoids flavonol glycosides, one flavone glycoside and three
(14
aglycones) have been found recently in Dryopteris villarii by Imperato (Amor.
Fern 96: 93-96. 2006; Amer. Fern 97(2): 124-126. 2007; Nat. Prod.
J.
J.
Commun.
909-912.
2007).
2:
— from
This paper deals with identification of three flavonoids aerial
(I III)
parts of Dryopteris villarii (Bellardi) Schinz & Thell collected in the Botanic
Garden of the University of Naples The fern was identified by Dr. R.
(Italy).
[NAPEA
Nazzaro (Universita "Federico Naples); a voucher specimen 3496)
II",
has been deposited in Herbarium of Dipartimento di Biologia, Universita
"Federico IT, Naples, Italy (NAP).
Flavonoids were isolated From an ethanolic extract of aerial parts of
(I-III)
BAW
W
B E
upper °0
acid-water, phase), 15
acetic 4:1:5,
was by
butanol-ethanol-water, further purification carried out
4:1:2.2).
Sephadex LH-20 column chromatography with methanol.
eluting
UV+NH
Whatman
R
(brown yellow values on N.l
Color reactions to in
3 ),
f
UV
BAW; 15% AcOH;
and
paper 0.23 0.08 in water) spectral
(0.75 in in
(MeOH)
(nm)
presence usual flavonoid reagents
analysis in the of shift max
(A-
+NaOAc
+A1CVHC1
266, 324; +A1C1 274, 303, 347, 398; 274, 300, 343, 396;
,
:
+NaOMe may
suggested flavonoid be
272, 300, 370; 272, 325, 395) that
(1)
and
a flavonoid glycoside with free hydroxy] groups at positions 5, 7 4' (shifts
NaOMe
NaOAc
and addition flavonoid
with AICI3/HCI, respectively); in
(I)
UV
may hydroxycinnamic spectrum
be acylated with a acid since the of
shown
hydroxycinnamic acid superimposed on the flavonoid spectrum as in
is
W
M
Mabry
N
acid hydrolysis HC1; hr 100 C) and controlled acid hydrolysis (10%
(2 2 at
AcOH, under gave kaempferol and L-rhamnose whereas alkaline
3.5 hr reflux)
hydrolysis (2N NaOH, hr room temperature in a sealed tube) gave 4-
2 at 3,
CID
dihydroxycinnamic and kaempferol 3-O-rhamnoside.
acid (caffeic acid)
induced mass spectrum (negative mode) gave quasi-
(collision dissociation) a
molecular ion |M-H|~ m/z 593 and fragment ions m/z 431 (kaempferol 3-O-
at at
show
rhamnoside) and m/z 285 (kaempferol). These results that flavonoid
(I) is
new
product
kaempferol 3-0-(caffeoylrhamnoside), a natural (Fig.
1).
UV+NH Whatman
R
Color reactions (brown yellow in values on N.l
to
),
r
:i
UV
BAW, 15% AcOH,
and
paper (0.78 in 0.21 in 0.04 in water) spectral
nm
(MeOH)
analysis the presence of usual reagents 262, 322;
in shift max
(X,
( )
+AICI3 272, 305 340, 383; +A1C1 /HC1 270, 294 (sh), 326, 386 (sh);
(sh),
3
may
showed
4-NaOAc -f-NaOMe flavonoid be
268, 340; 271, 347) that
(II)
and
a flavonoid glycoside with free hydroxyl groups at positions 5 7 (shifts
NaOAc may
with AICI3/HC] and respectively). In addition flavonoid be
(II)
UV
hydroxycinnamic spectrum hydro-
acylated with acid since the of
a
SHORTER NOTES
235
rhamnose
Kaempferol
Fig. 3-0-(ctiffooylrhamnoside).
1.
xycinnamic
superimposed
acid on the flavonoid spectrum (Harborne and
is
Williams, Both
1975). total acid hydrolysis (2N HC1; hr 100°C) and
1 at
AcOH;
controlled acid hydrolysis (10% under
3.5 hr reflux) gave apigenin and
N
D-glucose whereas NaOH; room
alkaline hydrolysis
hr temperature
2
(2 at in
a sealed tube) gave apigenin 4'-0-glucoside and 4-dihydroxycinnamic
acid
3,
CID
(caffeic acid). (collision induced dissociation) mass spectrum
(negative
mode) showed
a quasimolecular ion m/z 593 [M-H]" and fragment m/
at ions
at
z 431 (apigenin 4'-0-glucoside), m/z269 (apigenin) and m/z 253
(glucosylated
These show
B-ring). results that flavonoid apigenin
4'-0-(caffeoylgluco-
is
(II)
new
side), a natural product
(Fig.
2).
UV+NH
Color reactions (brown to yellow in R values on Whatman
n.l
3 ),
r
BAW;
paper 15% HOAc; UV
(0.72 in 0.26 in 0.04 in water) and spectral
(M
305 +NaOMe
may
271, 351) suggested that flavonoid be a flavonoid glycoside with
(III) free
hydroxyl groups and NaOAc
positions with A1C1 /HC1 and
at 5 7 (shifts
3
may
respectively); in addition flavonoid be acylated with hydroxycin-
(III)
UV
namic
acid since the spectrum superimposed on the flavonoid spectrum
is
Will
X
apigenin and D-glucose whereas alkaline hydrolysis (2N NaOH; room
2 hr
at
temperature
in a sealed tube) gave 3-methoxy-4-hydroxy-cinnamic
acid
and apigenin The
(ferulic acid) 4'-0-glucoside. electrospray mass spectrum
+
pseudomolecular m/z
exhibits a ion 632 [(M+H)+Na] and fragment
at ions
at
m
new
flavonoid apigenin
is 4'-0-(feruloylglucoside), natural product
(III) a
(Fig
2).
O.M
Williams 749-856
(dd. in
Markham
eds., Flavonoids, Chemistry, Biochemistry and Applications, CRC
New
London,
Press, York. 2006) flavonoids having an group
acyl linked
to
carbohydrate
a attached position 4' of B-ring flavonoids and
at (as are
(II) (III))
Such compounds
rare natural products. have previously been reported by
VOLUME NUMBER
AMERICAN FERN JOURNAL:
97 4 (2007)
236
glucose
CH=CH
R=OCH
=
R OH; Apigonin 4'-0-(feruloylglucoside).
Apigenin 4'-0-(caffooylrhamnoside).
Fk;. 2. :) .
who
2621-2624. 1986) isolated 8-
Horie (Phytochemistry 25: 6,
et al.
3 4'-0-(6"-(3-hydroxy-3-methylglu-
-trimethy ether
dihydroxyluteolin
6, 8, ' 1
and
from sudachi green peel (Rutaceae)
glucoside) (sudachiin B) Citrus
taryl)
who
found
1223-1226.
(Phytochemistry 2001)
by Stockmalia 57:
et al.
4'-0-(2" feruloylglucuronosyl glucuronide) from aerial parts
apigenin (l-»-2)
The occurrence of these
Medicago (Leguminosae).
of sativa L. var. artal first
Commun.
compounds has been described by Imperato (Nat. Prod. 2:
in ferns
coumaroy
909-912
The presence acylated flavonoid glycosides
of
Dryopteris
parts of villarii.
93-96.
previously reported in Dryopteris villarii by Imperato (Amer. Fern 96,
J.
124-126.
Commun. 909-912. Amer. Fern
2007; 97(2):
2006; Nat. Prod.
2:
J.
2007) and identification of three further acylated flavonoid glycosides (I-III) in
number
show acylated flavonoid
has of
Dryopteris that this fern a
villarii
with the
which absent from Dryopteris species
generally
glycosides are
em Dryopteris species
" succinylglucoside) in four
shown review by
and Dryopteris filix-mas as in a
a flavan acetate in rteris (L.)
Markham
(1988). —
support
The author thanks Universita della Basilicata for financial
85100
Dipartimento Chimica, Universita della Basilicata,
di
Imperato,
Filippo
Potenza,
Italy.