New depsides from the Lichen Neofuscelia depsidella

Article abstract of DOI:10.1071/C97091

The new depsides decarboxydivaricatic acid (3), decarboxy-2′-O-methyldivaricatic acid (4), decarboxynorstenosporic acid (5), decarboxynorimbricaric acid (6), decarboxystenosporic acid (7), decarboxy-2′-O-methylnorimbricaric acid (8), decarboxyanziaic acid (9) and decarboxyperlatolic acid (10), and the novel tridepsides depsidellin A (23), depsidellin B (27) and depsidellin C (29) have been detected in the lichen Neofuscelia depsidella and their structures determined by total synthesis.

Full text of DOI:10.1071/C97091

C S I R O P U B L I S H I N G
Australian Journal
of Chemistry
Volume 50, 1997
© CSIRO Australia 1997
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Aust. J. Chem., 1997, 50, 1145–1150
New Depsides from the Lichen Neofuscelia depsidella
John A. Elix and Judith H. Wardlaw
Department of Chemistry, The Faculties, Australian National University,
Canberra, A.C.T. 0200.
The new depsides decarboxydivaricatic acid (3), decarboxy-20-O-methyldivaricatic acid (4), de-
carboxynorstenosporic acid (5), decarboxynorimbricaric acid (6), decarboxystenosporic acid (7),
decarboxy-20-O-methylnorimbricaric acid (8), decarboxyanziaic acid (9) and decarboxyperlatolic acid
(10), and the novel tridepsides depsidellin A (23), depsidellin B (27) and depsidellin C (29) have been
detected in the lichen Neofuscelia depsidella and their structures determined by total synthesis.
R3
O
Introduction
C
O
OR4
Depsides form the largest group of lichen metabolites
and have primarily a phenyl benzoate structure. Minor
biosynthetic variations observed within a lichen or a
group of related species can produce a large number of
structurally related metabolites or a chemosyndrome.1
In the para-orcinol depsides (1) the structural varia-
tions within a chemosyndrome may take several forms;
for instance variations in the length and the degree
of oxidation of the alkyl side chains at C 6 and
C 60 (i.e. CH2COC3H7, C5H11, C3H7). Biosynthetic
elaboration of the parent depside (1) may proceed fur-
ther by O-methylation, C-methylation, C-chlorination,
decarboxylation or a combination of these processes.
In this report we describe the detection of anziaic
acid (2) and 11 new depsides in extracts of the lichen
Neofuscelia depsidella Elix, and the total synthesis
of these compounds. The cohort of new depsides
was found to comprise a chemosyndrome based on
decarboxyanziaic acid (9).
CO2R5
R2O
OR1
R6
(1)
O
C
C5H11
O
OH
CO2H
HO
OH
C5H11
(2)
R2
O
C
O
OR3
2'
6
1'
6'
3'
4'
5
1
2
4
5'
3
R1O
OH
R4
R1
R2
R3
H
R4
The New Depsides
(3) Me C3H7
C3H7
(4) Me C3H7 Me C3H7
Our preliminary chromatographic [thin-layer chro-
matography (t.l.c.) and high-performance liquid chro-
matography (h.p.l.c.)] and mass spectrometric exam-
ination of the lichen Neofuscelia depsidella indicated
that this lichen contained 12 phenolic compounds. A
minor constituent was readily identiꢀed as the known
depside anziaic acid (2), by comparison with authentic
material.2
Mass spectrometry indicated that one of the
major constituents of this lichen was the corre-
sponding decarboxy derivative, decarboxyanziaic acid
(9), and this was subsequently conꢀrmed by chro-
matographic comparisons with authentic (synthetic)
material. Indeed, seven of the remaining 10 new
depsides appeared to be homologues of (9), or of the
corresponding O-methyl derivatives. Subsequently we
(5)
(6)
H
H
C3H7
H
H
H
C5H11
C3H7
C5H11
(7) Me C3H7
C5H11
(8)
(9)
H
H
C5H11 Me C3H7
C5H11
H
H
C5H11
C5H11
(10) Me C5H11
undertook the synthesis of decarboxydivaricatic acid
(3), decarboxy-20-O-methyldivaricatic acid (4), decar-
boxynorstenosporic acid (5), decarboxynorimbricaric
acid (6), decarboxystenosporic acid (7), decarboxy-20-
O-methylnorimbricaric acid (8), decarboxyanziaic acid
(9) and decarboxyperlatolic acid (10), depsidellin A
(23), depsidellin B (27) and depsidellin C (29).
The synthetic strategy was to prepare suitably
protected benzoic acids and appropriately substituted
Manuscript received 10 July 1997
᭧ CSIRO Australia 1997
0004-9425/97/121145$05.00
10.1071/CH97091

1146
J. A. Elix and J. H. Wardlaw
phenols as A- and B-ring precursors respectively.2,3
Divarinol (5-propylbenzene-1,3-diol) (11) and olive-
tol (5-pentylbenzene-1,3-diol) (13) are well known
compounds, while 3-methoxy-5-propylphenol (12) was
prepared by decarboxylation of 4-hydroxy-2-methoxy-
6-propylbenzoic acid (14).4 The preparation of the pre-
cursor benzoic acids, namely 2-hydroxy-4-methoxy-6-
propylbenzoic acid (15),2 2,4-dibenzyloxy-6-propylben-
zoic acid (16),5 2-hydroxy-4-methoxy-6-pentylbenzoic
acid (17)2 and 4-benzyloxy-2-hydroxy-6-pentylbenzoic
acid (18),2 have been described previously. Depside for-
mation between the carboxylic acids (15)–(18) and the
phenols (11)–(13) was achieved by treatment with dicy-
clohexylcarbodiimide to yield the depsides (3), (4), (7),
(10) and (19)–(22). When 3-methoxy-5-propylphenol
(12) was used as precursor, a 1 : 1 mole ratio of the
benzoic acid and phenol were condensed. In order to
maximize the yield of monodepsides, 2 moles of the
requisite benzenediol (11) or (13) were condensed with 1
mole of the corresponding benzoic acid. Even so minor
quantities of the bis-condensation products, depsidellin
A (23) and depsidellin D (24), were isolated from the
appropriate condensation reactions, i.e. condensation
of 2-hydroxy-4-methoxy-6-propylbenzoic acid (15) with
olivetol (13) and divarinol (11) respectively.
O
C
C3H7
C3H7
O
C
O
O
HO
OMe
MeO
OH
R
(23) R = C5H11
(24) R = C3H7
Me
O
Me
C
O
OR
CO2R
OR
RO
OR
C
O
O
Me
(25)
extracts of N. depsidella appeared to be homologues
of depsidellin A. Consequently, we have undertaken
the synthesis of depsidellin B and depsidellin C as
illustrated in Scheme 1.
Thus, condensation of 4-benzyloxy-2-hydroxy-6-
pentylbenzoic acid (18) with olivetol (13) aꢁorded a
mixture of 4-benzyloxydecarboxyanziaic acid (22) and
4,40-di-O-benzyldepsidellin B (26). Subsequent conden-
sation of the ester (22) with 2-hydroxy-4-methoxy-6-
propylbenzoic acid (15) aꢁorded 4-O-benzyldepsidellin
C (28) in good yield.
R2
R3
CO2H
Catalytic hydrogenation of the O-benzyl depsides
(19)–(22) and depsidellins (26) and (28) proceeded to
give the corresponding deprotected depsides (5), (6),
(8) and (9) and tridepsides (27) and (29) in high
R1O
OH
R2O
OR1
R3
R1
R2
R1 R2
1
yield. The H n.m.r. and mass spectral data recorded
for these synthetic depsides were consistent with those
(11)
H
C3H7
(14) Me
(15)
(16) Bn Bn C3H7
H
C3H7
observed previously for related para-depsides.2,3
(12) Me C3H7
(13) C5H11
H
Me C3H7
H
The thin-layer chromatographic behaviour of the
depsides decarboxydivaricatic acid (3), decarboxy-20-
O-methyldivaricatic acid (4), decarboxynorstenosporic
acid (5), decarboxynorimbricaric acid (6), decarboxy-
stenosporic acid (7), decarboxy-20-O-methylnorimbric-
aric acid (8), decarboxyanziaic acid (9) and decar-
boxyperlatolic acid (10), and the tridepsides depsidellin
A (23), depsidellin B (27) and depsidellin C (29) in
three independent systems was identical to that of the
new depsides present in Neofuscelia depsidella, and
this was further conꢀrmed by comparative h.p.l.c.,
ultraviolet spectroscopy and mass spectrometry.
(17)
(18)
H
H
Me C5H11
Bn C5H11
Bn is CH2Ph
R2
O
C
O
OR3
BnO
OR1
R2
R4
R4
R1
R3
(19) Bn C3H7
H
H
C5H11
C3H7
(20)
H
H
H
C5H11
(21)
(22)
C5H11 Me C3H7
C5H11 C5H11
Experimental
H
1H n.m.r. spectra were recorded at 300 MHz on a Varian
Gemini 300 spectrophotometer. Mass spectra were recorded
at 70 eV on an Autospec mass spectrometer (e.i., positive).
To our surprise depsidellin A (23) also proved to
be a major metabolite of N. depsidella. As such, it
represents a unique lichen metabolite, unlike all previ-
ously known natural tridepsides which contain only C 1
substituents and the structure skeleton as illustrated
in (25). Furthermore, from their h.p.l.c. behaviour,
the two remaining unidentiꢀed depsides present in the
Chromatography
Natural compounds were characterized by t.l.c. according
to the methods standardized for lichen products,6–9 and by
h.p.l.c. with retention index values (RI) calculated from benzoic
acid and solorinic acid controls.10 For t.l.c. standard RF values
were determined in three independent t.l.c. solvent systems:

New Depsides from Neofuscelia depsidella
1147
.
C5H11
C5H11
O
C
HO
OH
CO2H
OH
O
OH
dicyclohexylcarbodiimide
+
BnO
BnO
OH
C5H11
C5H11
(18)
(13)
(22)
+
C5H11
O
O
C
C5H11
C5H11
O
C
O
C
C5H11
C
O
O
O
O
Pd/C
H2
HO
OH
HO
OH
BnO
OH
HO
OBn
C5H11
C5H11
(26)
(27)
O
C
C5H11
C3H7
O
C
O
C
C5H11
C3H7
HO
O
O
O
CO2H
OH
dicyclohexylcarbodiimide
+
HO
OBn
MeO
OH
HO
OBn
MeO
C5H11
C5H11
(15)
(28)
(22)
Pd/C
H2
C3H7
O
C
O
C
C5H11
O
O
6
1
2
3
6'
5'
4'
3'
2''
5
4
1''
6''
1'
2'
3''
4''
5''
MeO
OH
HO
OH
C5H11
Scheme 1
(29)
(A) toluene/dioxan/acetic acid (180 : 45 : 5); (B) hexane/t-butyl
methyl ether/formic acid (140 : 7 : 18); (C) toluene/acetic acid
(170 : 30). For h.p.l.c. a Hewlett Packard 1050 system, a
Phenomenex Hypersil 5C18 column (250 by 4ꢀ6 mm) and a
diode array detector operating at 254 nm with a ꢀow rate of
1 ml/min were used. Two solvent systems were employed: 1%
aqueous orthophosphoric acid and methanol in the ratio 3 : 7
(L) and methanol (M). The run started with 100% L and was
raised to 58% M within 15 min, then to 100% M within a
further 15 min, followed by isocratic elution in 100% M for a
further 10 min.
3-Methoxy-5-propylphenol (12)
4-Hydroxy-2-methoxy-6-propylbenzoic acid (14) (120 mg)
was placed in a sublimation tube, heated at atmospheric pres-
sure at 90–100ꢀ for 15 min, and then sublimed under vacuum
(15 mmHg) at 100–120ꢀ. The crude sublimate was puriꢂed
by radial chromatography, with 5–10% ethyl acetate/light
petroleum as eluent, to give 3-methoxy-5-propylphenol (12)
(85 mg, 89%) as a colourless oil (Found: C, 68ꢀ9; H, 8ꢀ9%;
M+ꢁ, 166ꢀ0997. C10H14O2.0ꢀ5H2O requires C, 68ꢀ6; H, 8ꢀ6%;
C
10H14O2 requires M+ꢁ, 166ꢀ0994). 1H n.m.r. (CDCl3) ꢀ 0ꢀ93,
t, J 7ꢀ4 Hz, (CH2)2Me; 1ꢀ61, sextet, J 7ꢀ5 Hz, CH2CH2Me;
2ꢀ50, t, J 7ꢀ6 Hz, CH2C2H5; 3ꢀ77, s, OMe; 4ꢀ74, s, OH; 6ꢀ24,
t, J 2ꢀ2 Hz, 6ꢀ26, 6ꢀ33, 2 br s, H 2,4,6. Mass spectrum: m/z
166 (M, 10%), 138 (100).
Detection of New Depsides by Comparative Chromatography
and Mass Spectrometry
Synthesis of the Depsides
The lichen Neofuscelia depsidella Elix was collected on
exposed rocks in pasture, 0ꢀ5 km west of Glendu Bluꢁ, Lake
Wanaka, Otago, South Island, New Zealand, J.A. Elix 9842,
4 Jan. 1982 (WELT-holotype). Comparative t.l.c. and h.p.l.c.
indicated the presence of anziaic acid (2) [standard t.l.c. RF
values: (A) 0ꢀ40, (B) 0ꢀ55, (C) 0ꢀ33; standard h.p.l.c. RI
value: 0ꢀ50], decarboxydivaricatic acid (3), decarboxy-20-O-
methyldivaricatic acid (4), decarboxynorstenosporic acid (5),
decarboxynorimbricaric acid (6), decarboxystenosporic acid (7),
decarboxy-20-O-methylnorimbricaric acid (8), decarboxyanzi-
aic acid (9), decarboxyperlatolic acid (10), depsidellin A (23),
depsidellin B (27) and depsidellin C (29). This composi-
tion was also consistent with the observed mass spectrum of
the total lichen extract with prominent peaks at m/z 372
(C22H28O5), 358 (C21H26O5) and 344 (C20H24O5), and minor
peaks at m/z 564 (C33H40O8), 386 (C23H30O5) and 400
(C24H32O5).
The appropriate carboxylic acid, i.e. (15)–(18) (0ꢀ25 mmol),
and phenol, i.e. (11) or (13) (0ꢀ5 mmol) or (12) (0ꢀ25 mmol),
precursors were dried, dissolved in anhydrous toluene or a mix-
ture of anhydrous toluene and anhydrous ether, and stirred with
dicyclohexylcarbodiimide (0ꢀ25 mmol) at room temperature for
18 h–5 days. The dicyclohexylurea was removed by ꢂltration,
washed with toluene and the solvent evaporated under reduced
pressure. The residue obtained was puriꢂed by radial chro-
matography over silica gel, with 2ꢀ5–10% ethyl acetate/light
petroleum as eluent, and the ꢂnal product crystallized, where
appropriate, from ethyl acetate/light petroleum. When olivetol
(13) or divarinol (11) were used as the starting material two
major bands generally developed: the faster moving was the
depsidellin, and the slower the depside. Only one major band
was obtained when 3-methoxy-5-propylphenol (12) was used as
starting material.

1148
J. A. Elix and J. H. Wardlaw
3 0-Hydroxy-5 0-propylphenyl 2-Hydroxy-4-methoxy-6-
propylbenzoate (Decarboxydivaricatic Acid) (3)
2 br s, H 20,40,60; 11ꢀ50, s, 2-OH. Mass spectrum: m/z 372
(M, 10%), 194 (22), 193 (100), 124 (19). Standard t.l.c. RF
values: (A) 0ꢀ63, (B) 0ꢀ57, (C) 0ꢀ55. Standard h.p.l.c. RI
value: 0ꢀ51. The t.l.c., h.p.l.c. and ultraviolet properties of
synthetic decarboxystenosporic acid (7) were identical to those
of a major metabolite of N. depsidella.
The faster moving band yielded depsidellin A (23) (17 mg,
13%) as a colourless oil (Found: C, 69ꢀ9; H, 6ꢀ7. C33H40O8
requires C, 70ꢀ2; H, 7ꢀ1%). 1H n.m.r. (CDCl3) ꢀ 0ꢀ91, t, J
7ꢀ2 Hz, (CH2)4Me; 0ꢀ97, t, J 7ꢀ3 Hz, 2ꢁ(CH2)2Me; 1ꢀ30–
1ꢀ80, m, 2ꢁCH2Me, (CH2)3Me; 2ꢀ69, t, J 7ꢀ9 Hz, CH2C4H9;
2ꢀ98, t, J 7ꢀ7 Hz, 2ꢁCH2C2H5; 3ꢀ84, s, 2ꢁOMe; 6ꢀ38, 2 br d,
2ꢁH 3, 2ꢁH 5; 6ꢀ92, t, J 2ꢀ1 Hz, 6ꢀ96, 6ꢀ97, 2 br s, H 20,40,60;
11ꢀ44, s, 2ꢁ2-OH. Mass spectrum: m/z 564 (M, 0ꢀ7%), 194
(26), 193 (100), 124 (19). Standard t.l.c. RF values: (A) 0ꢀ77,
(B) 0ꢀ69, (C) 0ꢀ91. Standard h.p.l.c. RI value: 0ꢀ65. The
t.l.c., h.p.l.c. and ultraviolet properties of synthetic depsidellin
A (23) were identical to those of a submajor metabolite of N.
depsidella.
This compound was prepared by condensation of
2-hydroxy-4-methoxy-6-propylbenzoic acid (15) (70 mg,
0ꢀ333 mmol) and 5-propylbenzene-1,3-diol (11) (101ꢀ4 mg,
0ꢀ666 mmol) for 5 days. The slower moving band yielded
decarboxydivaricatic acid (3) (44ꢀ1 mg, 38%) as a colourless oil
(Found: C, 68ꢀ2; H, 6ꢀ8%; M+ꢁ, 344ꢀ1619. C20H24O5.0ꢀ5H2O
requires C, 68ꢀ0; H, 7ꢀ1%; C20H24O5 requires M+ꢁ, 344ꢀ1624).
1H n.m.r. (CDCl3) ꢀ 0ꢀ96, t, J 7ꢀ3 Hz, 2ꢁ(CH2)2Me; 1ꢀ50–
1ꢀ78, m, 2ꢁCH2CH2Me; 2ꢀ57, t, J 7ꢀ7 Hz, 50-CH2C2H5; 2ꢀ96,
t, J 7ꢀ7 Hz, 6-CH2C2H5; 3ꢀ83, s, OMe; 4ꢀ98, br s, 30-OH;
6ꢀ37, 6ꢀ38, 2d, J 2ꢀ4 Hz, H 3,5; 6ꢀ52, t, J 2ꢀ1 Hz, 6ꢀ58, 6ꢀ60,
2 br s, H 20,40,60; 11ꢀ49, s, 2-OH. Mass spectrum: m/z 344
(M, 6%), 194 (22), 193 (100), 192 (32), 166 (11), 165 (12),
164 (25), 163 (10), 153 (11), 152 (41), 149 (11), 138 (17),
137 (27), 136 (19), 135 (41), 125 (14), 124 (67), 123 (43),
121 (13), 108 (10), 107 (15), 105 (10). Standard t.l.c. RF
values: (A) 0ꢀ60, (B) 0ꢀ56, (C) 0ꢀ51. Standard h.p.l.c. RI
value: 0ꢀ45. The t.l.c., h.p.l.c. and ultraviolet properties of
synthetic decarboxydivaricatic acid (3) were identical to those
of a minor metabolite of N. depsidella.
3 0-Hydroxy-5 0-pentylphenyl 2-Hydroxy-4-methoxy-6-
pentylbenzoate (Decarboxyperlatolic Acid) (10)
The faster moving band yielded 5 0-propylbenzene-1 0,3 0-diyl
bis(2-hydroxy-4-methoxy-6-propylbenzoate) (depsidellin D) (24)
(22ꢀ6 mg, 13%) as colourless crystals, m.p. 87–89ꢀ (Found: C,
68ꢀ5; H, 6ꢀ9%; M+ꢁ, 536ꢀ2396. C31H36O8.0ꢀ5H2O requires
C, 68ꢀ2; H, 6ꢀ8%; C31H36O8 requires M+ꢁ, 536ꢀ2410). 1H
n.m.r. (CDCl3) ꢀ 0ꢀ98, 1ꢀ00, 2t, J 6ꢀ7, 6ꢀ9 Hz, 3ꢁ(CH2)2Me;
1ꢀ50–1ꢀ80, m, 3ꢁCH2Me; 2ꢀ68, t, J 7ꢀ7 Hz, 50-CH2C2H5;
2ꢀ98, t, J 7ꢀ7 Hz, 2ꢁ6-CH2C2H5; 3ꢀ84, s, 2ꢁOMe; 6ꢀ38, br s,
2ꢁH 3, 2ꢁH 5; 6ꢀ93, 6ꢀ97, 2 br s, H 20,40,60; 11ꢀ44, s, 2ꢁ2-OH.
Mass spectrum: m/z 536 (M, 0ꢀ7%), 194 (27), 193 (100), 192
(30), 165 (16), 152 (25), 137 (15), 135 (33), 124 (39), 123 (25),
121 (10), 107 (10).
This compound was prepared by condensation of
2-hydroxy-4-methoxy-6-pentylbenzoic acid (17) (71ꢀ5 mg, 0ꢀ30
mmol) and 5-pentylbenzene-1,3-diol(13) (108ꢀ1 mg, 0ꢀ60 mmol)
for 43 h. The slower moving band yielded decarboxyperlatolic
acid (10) (64ꢀ1 mg, 53%) as colourless crystals, m.p. 73–74ꢀ
(Found: C, 71ꢀ6; H, 8ꢀ3%; M+ꢁ, 400ꢀ2242. C24H32O5 requires
C, 72ꢀ0; H, 8ꢀ1%; M+ꢁ, 400ꢀ2250). 1H n.m.r. (CDCl3) ꢀ
0ꢀ86, 0ꢀ89, 2t, J 7ꢀ0, 6ꢀ7 Hz, (CH2)4Me; 1ꢀ26–1ꢀ74, m,
2ꢁCH2(CH2)3Me; 2ꢀ58, t, J 7ꢀ8 Hz, 50-CH2C4H9; 2ꢀ97, t, J
7ꢀ8 Hz, 6-CH2C4H9; 3ꢀ83, s, OMe; 4ꢀ88, br s, 30-OH; 6ꢀ37,
6ꢀ38, 2d, J 2ꢀ7 Hz, H 3,5; 6ꢀ50, t, J 2ꢀ2 Hz, 6ꢀ58, 6ꢀ60, 2
br s, H 20,40,60; 11ꢀ50, s, 2-OH. Mass spectrum: m/z 400 (M,
3%), 222 (19), 221 (100), 180 (18), 137 (14), 124 (73), 123
(20), 101 (14). Standard t.l.c. RF values: (A) 0ꢀ63, (B) 0ꢀ60,
(C) 0ꢀ56. Standard h.p.l.c. RI value: 0ꢀ55. The t.l.c. and
h.p.l.c. properties and the ultraviolet spectrum of synthetic
decarboxyperlatolic acid (10) were identical to those of a minor
metabolite of N. depsidella.
3 0-Methoxy-5 0-propylphenyl 2-Hydroxy-4-methoxy-6-
propylbenzoate (Decarboxy-2 0-O-methyldivaricatic Acid) (4)
This compound was prepared by condensation of the
benzoic acid (15) (50ꢀ6 mg, 0ꢀ241 mmol) and 3-methoxy-5-
propylphenol (12) (40 mg, 0ꢀ241 mmol) for 18ꢀ5 h. Decarboxy-
2 0-O-methyldivaricatic acid (4) (67ꢀ3 mg, 78%) was obtained
as a colourless oil (Found: C, 70ꢀ6; H, 7ꢀ0. C21H26O5 requires
C, 70ꢀ4; H, 7ꢀ3%). 1H n.m.r. (CDCl3) ꢀ 0ꢀ96, t, J 7ꢀ4 Hz,
2ꢁ(CH2)2Me; 1ꢀ60–1ꢀ78, m, 2ꢁCH2Me; 2ꢀ59, t, J 7ꢀ7 Hz,
50-CH2C2H5; 2ꢀ97, t, J 7ꢀ7 Hz, 6-CH2C2H5; 3ꢀ81, 3ꢀ83, 2s,
2ꢁOMe; 6ꢀ37, 6ꢀ38, 2d, J 2ꢀ6 Hz, H 3,5; 6ꢀ55, t, J 2ꢀ2 Hz,
6ꢀ60, 6ꢀ67, 2 br s, H 20,40,60; 11ꢀ52, s, 2-OH. Mass spectrum:
m/z 358 (M, 20%), 194 (36), 193 (100), 192 (13), 166 (17),
164 (11), 138 (23), 137 (17), 135 (13). Standard t.l.c. RF
values: (A) 0ꢀ74, (B) 0ꢀ73, (C) 0ꢀ88. Standard h.p.l.c. RI
value: 0ꢀ53. The t.l.c., h.p.l.c. and ultraviolet properties
of synthetic decarboxy-20-O-methyldivaricatic acid (4) were
identical to those of a major metabolite of N. depsidella.
3 0-Hydroxy-5 0-pentylphenyl 2,4-Dibenzyloxy-6-
propylbenzoate (19)
This compound was prepared by condensation of 2,4-
dibenzyloxy-6-propylbenzoic acid (16) (100 mg, 0ꢀ266 mmol)
and 5-pentylbenzene-1,3-diol (13) (95ꢀ8 mg, 0ꢀ531 mmol) for
72ꢀ5 h. The slower moving band yielded the depside (19)
(17 mg, 12%) as a colourless oil (Found: C, 74ꢀ0; H, 7ꢀ6%;
M+ꢁ, 538ꢀ2714. C35H38O5.1ꢀ5H2O requires C, 74ꢀ3; H, 7ꢀ3%;
C
35H38O5 requires M+ꢁ, 538ꢀ2719). 1H n.m.r. (CDCl3) ꢀ 0ꢀ88,
0ꢀ97, 2t, J 6ꢀ8, 7ꢀ4 Hz, (CH2)2Me, (CH2)4Me; 1ꢀ20–1ꢀ78,
m, CH2Me, (CH2)3Me; 2ꢀ48, 2ꢀ68, 2t, J 7ꢀ7 Hz, CH2C2H5,
CH2C4H9; 4ꢀ58, br s, 30-OH; 5ꢀ07, 5ꢀ08, 2s, OCH2; 6ꢀ21, br
s, H 3,5; 6ꢀ43, 6ꢀ49, 6ꢀ52, 3 br s, H 20,40,60; 7ꢀ36–7ꢀ52, m,
2ꢁPh. Mass spectrum: m/z 538 (M, 0ꢀ2%), 537 (0ꢀ3), 359
(85), 91 (100).
3 0-Hydroxy-5 0-pentylphenyl 2-Hydroxy-4-methoxy-6-
propylbenzoate (Decarboxystenosporic Acid) (7) and
5 0-Pentylbenzene-1 0,3 0-diyl Bis(2-hydroxy-4-methoxy-6-
propylbenzoate) (Depsidellin A) (23)
3 0-Hydroxy-5 0-propylphenyl 4-Benzyloxy-2-hydroxy-6-
pentylbenzoate (20)
These compounds were prepared by condensation of the
benzoic acid (15) (50ꢀ0 mg, 0ꢀ238 mmol) and 5-pentylbenzene-
1,3-diol (13) (85ꢀ7 mg, 0ꢀ476 mmol) for 5 days. The slower
moving band yielded decarboxystenosporic acid (7) (50ꢀ2 mg,
This compound was prepared by condensation of 4-benzyloxy-
2-hydroxy-6-pentylbenzoic acid (18) (141ꢀ5 mg, 0ꢀ45 mmol) and
5-propylbenzene-1,3-diol (11) (137 mg, 0ꢀ90 mmol) for 47 h.
The slower moving band yielded the depside (20) (117 mg,
58%) as colourless crystals, m.p. 96–97ꢀ (Found: C, 74ꢀ8;
H, 7ꢀ5%; M+ꢁ, 448ꢀ2248. C28H32O5 requires C, 75ꢀ0; H,
7ꢀ2%; M+ꢁ, 448ꢀ2250). 1H n.m.r. (CDCl3) ꢀ 0ꢀ86, 0ꢀ95,
2t, J 6ꢀ7, 7ꢀ3 Hz, (CH2)2Me, (CH2)4Me; 1ꢀ20–1ꢀ72, m,
CH2Me, (CH2)3Me; 2ꢀ57, t, J 7ꢀ6 Hz, CH2C2H5; 2ꢀ97, t, J
7ꢀ7 Hz, CH2C4H9; 4ꢀ88, vbr s, 30-OH; 5ꢀ09, s, OCH2; 6ꢀ45,
57%) as a colourless oil (Found: C, 66ꢀ7; H, 7ꢀ9%; M+ꢁ
,
372ꢀ1936.
C
22H28O5.1ꢀ5H2O requires C, 66ꢀ2; H, 7ꢀ8%;
C
22H28O5 requires M+ꢁ, 372ꢀ1937). 1H n.m.r. (CDCl3) ꢀ
0ꢀ89, 0ꢀ96, 2t, J 6ꢀ6, 7ꢀ4 Hz, (CH2)2Me, (CH2)4Me; 1ꢀ20–
1ꢀ74, m, CH2Me, (CH2)3Me; 2ꢀ58, t, J 7ꢀ7 Hz, CH2C4H9;
2ꢀ96, t, J 7ꢀ7 Hz, CH2C2H5; 3ꢀ83, s, OMe; 4ꢀ88, s, 30-OH;
6ꢀ37, 6ꢀ38, 2 br d, H 3,5; 6ꢀ51, t, J 2ꢀ0 Hz, 6ꢀ59, 6ꢀ60,

New Depsides from Neofuscelia depsidella
1149
br s, H 3,5; 6ꢀ51, 6ꢀ58, 6ꢀ59, 3 br s, H 20,40,60; 7ꢀ34–7ꢀ50, m,
Ph; 11ꢀ49, s, 2-OH. Mass spectrum: m/z 448 (M, 3%), 297
(100).
3 0-Hydroxy-5 0-pentylphenyl 2,4-Dihydroxy-6-
propylbenzoate (Decarboxynorstenosporic Acid) (5)
Hydrogenolysis of the depside (19) (14 mg) gave decar-
boxynorstenosporic acid (5) (9ꢀ1 mg, 98%) as colourless crys-
tals, m.p. 84–85ꢀ (Found: C, 70ꢀ7; H, 7ꢀ4%; M+ꢁ, 358ꢀ1791.
3 0-Methoxy-5 0-propylphenyl 4-Benzyloxy-2-hydroxy-6-
pentylbenzoate (21)
C
21H26O5 requires C, 70ꢀ4; H, 7ꢀ3%; C20H24O5 requires
This compound was prepared by condensation of the acid
(18) (47ꢀ7 mg, 0ꢀ152 mmol) and 3-methoxy-5-propylphenol (12)
(25ꢀ2 mg, 0ꢀ152 mmol) for 15 h. The major band yielded the
depside (21) (40ꢀ8 mg, 58%) as colourless crystals, m.p. 105–
106ꢀ (Found: C, 75ꢀ3; H, 7ꢀ2%; M+ꢁ, 462ꢀ2404. C29H34O5
requires C, 75ꢀ3; H, 7ꢀ4%; M+ꢁ, 462ꢀ2406). 1H n.m.r. (CDCl3)
ꢀ 0ꢀ87, 0ꢀ96, 2t, J 6ꢀ8, 7ꢀ3 Hz, (CH2)2Me, (CH2)4Me; 1ꢀ22–
1ꢀ74, m, CH2Me, (CH2)3Me; 2ꢀ59, t, J 7ꢀ7 Hz, CH2C2H5;
2ꢀ98, t, J 7ꢀ8 Hz, CH2C4H9; 3ꢀ81, s, OMe; 5ꢀ09, s, OCH2;
6ꢀ45, br s, H 3,5; 6ꢀ54, t, J 2ꢀ2 Hz, 6ꢀ59, 6ꢀ68, 2 br s,
H 20,40,60; 7ꢀ30–7ꢀ46, m, Ph; 11ꢀ51, s, 2-OH. Mass spectrum:
m/z 462 (M, 6%), 91 (100).
M+ꢁ, 358ꢀ1780). 1H n.m.r. (CDCl3) ꢀ 0ꢀ89, 0ꢀ95, 2t, J
6ꢀ7, 7ꢀ2 Hz, (CH2)2Me, (CH2)4Me; 1ꢀ20–1ꢀ74, m, CH2Me,
(CH2)3Me; 2ꢀ57, t, J 7ꢀ7 Hz, CH2C4H9; 2ꢀ95, t, J 8ꢀ2 Hz,
CH2C2H5; 5ꢀ20, 5ꢀ65, 2 br s, 4-OH, 30-OH; 6ꢀ31, 6ꢀ32, 2d, J
2ꢀ4 Hz, H 3,5; 6ꢀ50, t, J 2ꢀ0 Hz, 6ꢀ58, 6ꢀ60, 2 br s, H 20,40,
60; 11ꢀ48, 2-OH. Mass spectrum: m/z 358 (M, 8%), 180
(43), 179 (100), 178 (11), 138 (15), 137 (19), 125 (15), 124
(67), 123 (33). Standard t.l.c. RF values: (A) 0ꢀ45, (B) 0ꢀ45,
(C) 0ꢀ27. Standard h.p.l.c. RI value: 0ꢀ43. The t.l.c. and
h.p.l.c. behaviour and the ultraviolet spectrum of synthetic
decarboxynorstenosporic acid (5) were identical to those of a
minor metabolite of N. depsidella.
3 0-Hydroxy-5 0-pentylphenyl 4-Benzyloxy-2-hydroxy-6-
pentylbenzoate (22) and 5 0-Pentylbenzene-1 0,3 0-diyl
Bis(4-benzyloxy-2-hydroxy-6-pentylbenzoate) (26)
3 0-Hydroxy-5 0-propylphenyl 2,4-Dihydroxy-6-
pentylbenzoate (Decarboxynorimbricaric Acid) (6)
Hydrogenolysis of the depside (20) (56 mg) gave decar-
boxynorimbricaric acid (6) (41 mg, 92%) as colourless crystals,
m.p. 99–100ꢀ (Found: C, 70ꢀ2; H, 7ꢀ1%; M+ꢁ, 358ꢀ1780.
These compounds were prepared by condensation of the
acid (18) (189ꢀ5 mg, 0ꢀ6 mmol) and 5-pentylbenzene-1,3-diol
(13) (217ꢀ3 mg, 1ꢀ2 mmol) for 17 h. The slower moving band
yielded the depside (22) (171 mg, 60%) as colourless crystals,
m.p. 70–71ꢀ (Found: C, 75ꢀ6; H, 7ꢀ6%; M+ꢁ, 476ꢀ2560.
C
21H26O5 requires C, 70ꢀ4; H, 7ꢀ3%; M+ꢁ, 358ꢀ1780). 1H
n.m.r. (CDCl3) ꢀ 0ꢀ86, 0ꢀ95, 2t, J 6ꢀ9, 7ꢀ4 Hz, (CH2)2Me,
(CH2)4Me; 1ꢀ22–1ꢀ74, m, CH2Me, (CH2)3Me; 2ꢀ57, t, J
7ꢀ7 Hz, CH2C2H5; 2ꢀ96, t, J 7ꢀ8 Hz, CH2C4H9; 4ꢀ96, 5ꢀ37,
2 br s, 4-OH, 30-OH; 6ꢀ31, 6ꢀ32, 2d, J 2ꢀ5 Hz, H 3,5; 6ꢀ51,
t, J 2ꢀ0 Hz, 6ꢀ57, 6ꢀ60, 2 br s, H 20,40,60; 11ꢀ44, s, 2-OH.
Mass spectrum: m/z 358 (M, 9%), 208 (23), 207 (100), 163
(10), 152 (16), 151 (11), 150 (14), 137 (13), 124 (24), 123 (22),
122 (10). Standard t.l.c. RF values: (A) 0ꢀ46, (B) 0ꢀ53, (C)
0ꢀ29. Standard h.p.l.c. RI value: 0ꢀ42. The t.l.c., h.p.l.c. and
ultraviolet properties of synthetic (6) were identical to those
of a minor metabolite of N. depsidella.
C
30H36O5 requires C, 75ꢀ6; H, 7ꢀ6%; M+ꢁ, 476ꢀ2563). 1H
n.m.r. (CDCl3) ꢀ 0ꢀ86, 0ꢀ89, 2t, J 7ꢀ0, 6ꢀ8 Hz, (CH2)4Me;
1ꢀ22–1ꢀ72, m, 2ꢁ(CH2)3Me; 2ꢀ58, t, J 7ꢀ7 Hz, 50-CH2C4H9;
2ꢀ97, t, J 7ꢀ8 Hz, 6-CH2C4H9; 4ꢀ92, vbr s, 30-OH; 5ꢀ09,
s, OCH2; 6ꢀ45, br s, H 3,5; 6ꢀ50, 6ꢀ58, 6ꢀ60, 3t, J 2ꢀ1 Hz,
H 20,40,60; 7ꢀ32–7ꢀ48, m, Ph; 11ꢀ49, s, 2-OH. Mass spectrum:
m/z 476 (M, 4%), 297 (100).
The faster moving band yielded the diester (26) (51 mg,
11%) as colourless crystals, m.p. 84–85ꢀ (Found: C, 76ꢀ6; H,
7ꢀ0. C49H56O8 requires C, 76ꢀ1; H, 7ꢀ3%). 1H n.m.r. (CDCl3)
ꢀ 0ꢀ86, 0ꢀ91, 2t, J 6ꢀ9, 6ꢀ7 Hz, 3ꢁ(CH2)4Me; 1ꢀ26–1ꢀ78,
m, 3ꢁ(CH2)3Me; 2ꢀ68, t, J 7ꢀ7 Hz, 50-CH2C4H9; 2ꢀ99, t, J
7ꢀ7 Hz, 2ꢁ6-CH2C4H9; 5ꢀ09, s, 2ꢁOCH2; 6ꢀ46, br s, 2ꢁH 3,
2ꢁH 5; 6ꢀ92, t, J 2ꢀ1 Hz, 6ꢀ95, 6ꢀ96, 2 br s, H 20,40,60;
7ꢀ32–7ꢀ52, m, 2ꢁPh; 11ꢀ43, s, 2ꢁ2-OH. Mass spectrum: m/z
593 (0ꢀ3%), 297 (100).
3 0-Methoxy-5 0-propylphenyl 2,4-Dihydroxy-6-pentylbenzoate
(Decarboxy-2 0-O-methylnorimbricaric Acid) (8)
Hydrogenolysis of the depside (21) (37 mg) gave decarboxy-
2 0-O-methylnorimbricaric acid (8) (29ꢀ5 mg, 99%) as colourless,
rod-shaped crystals, m.p. 96–97ꢀ (Found: C, 70ꢀ8; H, 7ꢀ5%;
M+ꢁ, 372ꢀ1932. C22H28O5 requires C, 70ꢀ9; H, 7ꢀ6%; M+ꢁ
,
372ꢀ1937). 1H n.m.r. (CDCl3) ꢀ 0ꢀ86, 0ꢀ96, 2t, J 6ꢀ9, 7ꢀ3 Hz,
(CH2)2Me, (CH2)4Me; 1ꢀ24–1ꢀ74, m, CH2Me, (CH2)3Me;
2ꢀ59, t, J 7ꢀ6 Hz, CH2C2H5; 2ꢀ97, t, J 7ꢀ9 Hz, CH2C4H9;
3ꢀ81, s, OMe; 5ꢀ26, s, 4-OH; 6ꢀ31, 6ꢀ32, 2 br d, H 3,5; 6ꢀ54,
6ꢀ59, 6ꢀ68, 3 br s, H 20,40,60; 11ꢀ46, s, 2-OH. Mass spectrum:
m/z 372 (M, 15%), 208 (24), 207 (100), 166 (18), 151 (14), 150
(11), 138 (20), 137 (13), 123 (12). Standard t.l.c. RF values:
(A) 0ꢀ60, (B) 0ꢀ56, (C) 0ꢀ48. Standard h.p.l.c. RI value:
0ꢀ51. The t.l.c., h.p.l.c. and ultraviolet properties of synthetic
decarboxy-20-O-methylnorimbricaric acid (8) were identical to
those of a submajor metabolite of N. depsidella.
5 00-Pentylbenzene-1 00,3 00-diyl 1 00-(4-Benzyloxy-2-hydroxy-6-
pentylbenzoate) 3 00-(2 0-Hydroxy-4 0-methoxy-6 0-
propylbenzoate) (28)
This compound was prepared by condensation of the benzoic
acid (15) (41ꢀ8 mg, 0ꢀ2 mmol) and the phenol (22) (94ꢀ8 mg,
0ꢀ2 mmol) for 42 h. The major band yielded the diester
(28) (95 mg, 71%) as a colourless oil (Found: C, 72ꢀ4; H,
7ꢀ3%; M+ꢁ, 668ꢀ3342. C41H48O8.0ꢀ5H2O requires C, 72ꢀ7;
H, 7ꢀ3%;
C
41H48O8 requires M+ꢁ, 668ꢀ3349). 1H n.m.r.
(CDCl3) ꢀ 0ꢀ86, 0ꢀ91, 0ꢀ97, 3t, J 6ꢀ9, 6ꢀ7, 7ꢀ4 Hz, (CH2)2Me,
2ꢁ(CH2)4Me; 1ꢀ24–1ꢀ76, m, CH2Me, 2ꢁ(CH2)3Me; 2ꢀ69,
t, J 7ꢀ8 Hz, 500-CH2C4H9; 2ꢀ98, 2ꢀ99, 2t, J 7ꢀ6, 7ꢀ7 Hz,
CH2C2H5, 6-CH2C4H9; 3ꢀ84, s, OMe; 5ꢀ09, s, OCH2; 6ꢀ38,
6ꢀ46, 2s, H 3,5,30,50; 6ꢀ92, t, J 1ꢀ9 Hz, 6ꢀ96, br s, H 200,400,600;
7ꢀ30–7ꢀ48, m, Ph; 11ꢀ42, 11ꢀ44, 2s, 2-OH, 20-OH. Mass
spectrum: m/z 668 (M, 0ꢀ02%), 193 (100).
3 0-Hydroxy-5 0-pentylphenyl 2,4-Dihydroxy-6-pentylbenzoate
(Decarboxyanziaic Acid) (9)
Hydrogenolysis of the depside (22) (55 mg) gave the decar-
boxylated depside (9) (43ꢀ2 mg, 97%) as colourless crystals,
m.p. 102–104ꢀ (Found: C, 70ꢀ2; H, 8ꢀ0%; M+ꢁ, 386ꢀ2096.
C
23H30O5.0ꢀ5H2O requires C, 69ꢀ8; H, 7ꢀ9%; C23H30O5
Hydrogenolysis of the Protected Depsides and Depsidellins
requires M+ꢁ, 386ꢀ2093). 1H n.m.r. (CDCl3) ꢀ 0ꢀ86, 0ꢀ89, 2t,
J 6ꢀ9, 6ꢀ8 Hz, (CH2)4Me; 1ꢀ22–1ꢀ72, m, 2ꢁ(CH2)3Me; 2ꢀ58,
t, J 7ꢀ8 Hz, 50-CH2C4H9; 2ꢀ96, t, J 7ꢀ9 Hz, 6-CH2C4H9;
5ꢀ07, 5ꢀ49, 2 br s, 4-OH, 30-OH; 6ꢀ31, 6ꢀ32, 2d, J 3ꢀ0 Hz,
H 3,5; 6ꢀ50, t, J 2ꢀ1 Hz, 6ꢀ57, 6ꢀ60, 2 br s, H 20,40,60; 11ꢀ48,
2-OH. Mass spectrum: m/z 386 (M, 2%), 207 (46), 180 (30),
138 (11), 137 (12), 125 (10), 124 (100), 123 (28). Standard
A solution of the protected depside or depsidellin (0ꢀ1 mmol)
in ethyl acetate (10 ml) was stirred with palladium on carbon
(10%, 50 mg) at room temperature in a hydrogen atmosphere
for 16 h. After ꢂltration of the catalyst the solvent was evap-
orated to give the depside or depsidellin, which crystallized,
where appropriate, from ethyl acetate.

1150
J. A. Elix and J. H. Wardlaw
t.l.c. RF values: (A) 0ꢀ48, (B) 0ꢀ46, (C) 0ꢀ32. Standard
h.p.l.c. RI value: 0ꢀ48. The t.l.c. and h.p.l.c. behaviour and
the ultraviolet spectrum of synthetic decarboxyanziaic acid (9)
were identical to those of a major metabolite of N. depsidella.
20-OH. Mass spectrum: m/z 578 (M, 0ꢀ08%), 227 (13), 208
(13), 207 (43), 194 (22), 193 (100), 192 (18), 164 (14), 137
(10), 135 (18), 124 (20), 123 (14). Standard t.l.c. RF values:
(A) 0ꢀ59, (B) 0ꢀ49, (C) 0ꢀ53. Standard h.p.l.c. RI value:
0ꢀ63. The t.l.c., h.p.l.c. and ultraviolet properties of synthetic
depsidellin C (29) were identical to those of a major metabolite
of N. depsidella.
5 0-Pentylbenzene-1 0,3 0-diyl Bis(2,4-dihydroxy-6-
pentylbenzoate) (Depsidellin B) (27)
Hydrogenolysis of the diester (26) (46 mg) gave depsidellin B
(27) (30 mg, 85%) as colourless crystals, m.p. 114–115ꢀ (Found:
C, 70ꢀ4; H, 7ꢀ7%; M+ꢁ, 592ꢀ3022. C35H44O8 requires C, 70ꢀ9;
H, 7ꢀ5%; M+ꢁ, 592ꢀ3036). 1H n.m.r. (CDCl3) ꢀ 0ꢀ86, 0ꢀ90, 2t,
J 6ꢀ9 Hz, 3ꢁ(CH2)4Me; 1ꢀ24–1ꢀ72, m, 3ꢁ(CH2)3Me; 2ꢀ68,
t, J 7ꢀ8 Hz, 50-CH2C4H9; 2ꢀ98, t, J 7ꢀ8 Hz, 2ꢁ6-CH2C4H9;
5ꢀ52, br s, 2ꢁ4-OH; 6ꢀ32, s, 2ꢁH 3, 2ꢁH 5; 6ꢀ92, t, J 2ꢀ0 Hz,
6ꢀ95, 6ꢀ96, 2 br s, H 20,40,60; 11ꢀ41, s, 2-OH. Mass spectrum:
m/z 592 (M, 0ꢀ08%), 386 (12), 208 (24), 207 (100), 180 (18),
151 (10), 150 (14), 138 (10), 137 (14), 125 (10), 124 (45),
123 (22). Standard t.l.c. RF values: (A) 0ꢀ47, (B) 0ꢀ42, (C)
0ꢀ32. Standard h.p.l.c. RI value: 0ꢀ60. The t.l.c. and h.p.l.c.
behaviour and the ultraviolet spectrum of synthetic depsidellin
B (27) were identical to those of a major metabolite of N.
depsidella.
Acknowledgments
We thank the Australian Research Council for gen-
erous ꢀnancial support of this work, and Mrs Jenny
Rothschild for the high-resolution mass spectrometry
measurements.
References
1
Culberson, C. F., and Culberson, W. L., Syst. Bot., 1976,
1, 325.
Elix, J. A., Aust. J. Chem., 1974, 27, 1767.
Elix, J. A., Parker, J. L., Tearne, P. D., and Wardlaw, J.
H., Aust. J. Chem., 1985, 38, 1863.
Elix, J. A., Barclay, C. E., David, F., Griꢃn, F. K., Hill,
2
3
4
5 00-Pentylbenzene-1 00,3 00-diyl 1 00-(2-Hydroxy-4-methoxy-6-
propylbenzoate) 3 00-(2 0,4 0-Dihydroxy-6 0-pentylbenzoate)
(Depsidellin C) (29)
A. M., McConnell, D. B., and Wardlaw, J. H., Aust. J.
Chem., 1993, 46, 301.
Elix, J. A., and Wardlaw, J. H., Aust. J. Chem., 1986, 39,
227.
Culberson, C. F., J. Chromatogr., 1972, 72, 113.
Culberson, C. F., and Ammann, K., Herzogia, 1979, 5, 1.
Culberson, C. F., and Johnson, A., J. Chromatogr., 1982,
238, 483.
Elix, J. A., and Ernst-Russell, K. D., ‘A Catalogue of Stan-
5
Hydrogenolysis of the diester (28) (82 mg) gave a mixture,
which was puriꢂed by radial chromatography by using ethyl
acetate/light petroleum as eluent to yield depsidellin C (29)
(49 mg, 69%) as a colourless oil (Found: C, 69ꢀ2; H, 7ꢀ5%;
M+ꢁ, 578ꢀ2866. C34H42O8.0ꢀ5H2O requires C, 69ꢀ5; H, 7ꢀ4%;
6
7
8
9
C
34H42O8 requires M+ꢁ, 578ꢀ2879). 1H n.m.r. (CDCl3) ꢀ 0ꢀ87,
0ꢀ90, 0ꢀ97, 3t, J 7ꢀ1, 6ꢀ8, 7ꢀ4 Hz, (CH2)2Me, 2ꢁ(CH2)4Me;
1ꢀ28–1ꢀ78, m, CH2Me, 2ꢁ(CH2)3Me; 2ꢀ69, t, J 7ꢀ8 Hz, 500-
CH2C4H9; 2ꢀ98, t, J 7ꢀ7 Hz, CH2C2H5, 60-CH2C4H9; 3ꢀ84, s,
OMe; 5ꢀ22, br s, 40-OH; 6ꢀ32, 2 br d, 6ꢀ38, 2 br d, H 3,5,30,50;
6ꢀ91, 6ꢀ96, 2t, J 2ꢀ0 Hz, H 200,400,600; 11ꢀ37, 11ꢀ44, 2s, 2-OH,
dardized Thin Layer Chromatographic Data and Biosyn-
thetic Relationships for Lichen Substances’ 2nd Edn (Aus-
tralian National University: Canberra 1993).
Feige, G. B., Lumbsch, H. T., Huneck, S., and Elix, J. A.,
J. Chromatogr., 1993, 646, 417.
10