Czech J. Food Sci.

Vol. 29, 2011, No. 2: 87–102

Pigments of Higher Fungi: A Review

Jan VELÍŠEK and Karel CEJPEK

Department of Food Chemistry and Analysis, Faculty of Food and Biochemical Technology,
Institute of Chemical Technology in Prague, Prague, Czech Republic

Abstract

Velíšek J., Cejpek K. (2011): Pigments of higher fungi – a review. Czech J. Food Sci., 29: 87–102.

This review surveys the literature dealing with the structure of pigments produced by fungi of the phylum Basidiomycota
and also covers their significant colourless precursors that are arranged according to their biochemical origin to the
shikimate, polyketide and terpenoid derived compounds. The main groups of pigments and their leucoforms include
simple benzoquinones, terphenylquinones, pulvinic acids, and derived products, anthraquinones, terpenoid quinones,
benzotropolones, compounds of fatty acid origin and nitrogen-containing pigments (betalains and other alkaloids).
Out of three orders proposed, the concern is only focused on the orders Agaricales and Boletales and the taxonomic
groups (incertae sedis) Cantharellales, Hymenochaetales, Polyporales, Russulales, and Telephorales that cover most of
the so called higher fungi often referred to as mushrooms. Included are only the European species that have generated
scientific interest due to their attractive colours, taxonomic importance and distinct biological activity.

Keywords: higher fungi; Basidiomycota; mushroom pigments; mushroom colour; pigment precursors

Mushrooms inspired the cuisines of many cul-
tures (notably Chinese, Japanese and European)
for centuries and many species were used in folk
medicine for thousands of years. However, lit-
tle is known that mushrooms were a commonly
used textile dye before the invention of synthetic
dyes because of the vast range of vivid and rich
colours achievable (Mussak & Bechtold 2009).
The chromophores of mushroom dyes contain a
variety of fascinating organic compounds. Their
pigmentation may vary with the age and some
undergo distinctive colour changes on bruising;
therefore, the colours of mushrooms are one of
the essential features used in their identification.
Furthermore, the pigments of mushrooms may
protect the organism from UV damage and bacte-
rial attack or play a role as insect attractants.
Mushrooms do not contain the pigments that
dominate in higher plant colours. Chlorophylls and
anthocyanins are not present in fungi at all; betalains,
carotenoids and other terpenoids are widespread
only in some species of higher fungi. Many of the
pigments of higher fungi are quinones or similar
conjugated structures that are mostly classified ac-
cording to the perceived biosynthetic pathways, re-
flecting their structure, to pigments derived from (i)
the shikimate (chorismate) pathway, (ii) the acetate-
malonate (polyketide) pathway, (iii) the mevalonate
(terpenoid) pathway, and (iv) pigments containing
nitrogen. Several review articles covering the litera-
ture published from its inception during the latter
half of the 19th century to the end of 2009 have been
already published (Gill & Steglich 1987; Gill
1994, 1996, 1999, 2003; Hanson 2008a,b; Räisänen
2009; Zhou & Liu 2010).
The shikimate pathway provides a route to the
essential amino acids phenylalanine, tyrosine and
tryptophan via the central intermediates shikimic
and chorismic acids. Phenylalanine and tyrosine are
precursors for a wide range of compounds includ-

Partly supported by the Ministry of Education, Youth and Sports of the Czech Republic, Project No. MSM 6046137305.

87
Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.

ing arylpyruvic, cinnamic and benzoic acids that
represent the building blocks for many pigments of
higher fungi. Condensation of two arylpyruvic acid
yields red to brown terphenylquinones and related
orange to red grevillins. Diarylcyclopentenones,
responsible for the colour changes in some bruised
mushrooms, are formed by ring contractions of
terphenylquinones while oxidative cleavage of the
hydroxyquinone ring in terphenylquinones and
rearrangement of thus formed intermediates results
in a series of yellow and orange lactones known as
pulvinic (pulvic) acids. Their decarboxylation yields
the yellow pulvinones that can be oxidised and fur-
ther transformed to a number of structurally related
products. Reduction of cinnamic acids affords the
corresponding alcohols that are the building blocks
of benzotropolone pigments. Tyrosine, hydroxy-
lated to 3,4-dihydroxyphenylalanine (DOPA), is
the precursor of the red-violet betacyanins and the
orange-yellow betaxanthins. Both amino acids and
their transformation products can be converted via
quinones into the heterogeneous dark pigments
melanins by the enzymatic browning reactions
(oxidations and polymerisations). Tryptophan is
transformed to hydroxyanthranilic acids that be-
come the precursor of phenoxazines and other ni-
trogen-containing pigments. Benzoquinones can be
synthesised from very different starting substances
and via different biochemical pathways, e.g. using
benzoic acids produced in the shikimate pathway.
Terpenoid quinones are formed by combination of
the shikimate pathway with the mevalonate path-
way. The polyketide pathway yields either aromatic
ketides or fatty acids. For the aromatic ketides, the
growing chain stabilises by cyclization reactions
and partial reduction, whereas for fatty acids, the
carbonyl groups of the chain are reduced before
attachment of the next C2 group. Products of this
pathway include tetra-, hepta-, octa- and higher
ketides and compounds of fatty acid origin. Fungi
contain a range of pigments of octaketide origin
(e.g. anthraquinones) that are based on the anthra-
9,10-quinone skeleton with both rings substituted.
In many cases, anthraquinones are found in fungi
as the corresponding colourless reduced forms
(anthranol, anthrone, anthrahydroquinone, and
oxanthrone derivatives) that may occur in the form
of various glycosides. Many natural anthraquinones
are oligomers formed by coupling of two or more
anthraquinone molecules. These oligomers further
differ in the points through which monomers are
attached and may have more than one polymor-
phic form (Velíšek et al. 2007, 2008; Velíšek &
Cejpek 2008). Styrylpyrones are biosynthesised
by a combined shikimate and polyketide pathway,
which otherwise yields various terpenoids includ-
ing carotenoids.
Various pigments and other fungi constituents
show important biological activities (antioxidative,
free radical scavenging, anticarcinogenic, immu-
nomodulatory, antiviral, and antibacterial) that
have generated intensive research interest (Steg-
lich 1981; Calìa et al. 2003; Liu 2006; Medicinal
Mushrooms 2008; Schüffler & Anke 2009).
The taxonomy of the kingdom Fungi (the subking-
dom Dikarya) is in a state of constant flux; therefore,
the most recent 2007 classification adopted by a
coalition of mycologists was used (Thorna et al.
2007; MycoBank 2010). Out of seven phyla (divisions)
proposed, the concern of this review only deals with
the phylum Basidiomycota (“club fungi”)1 (subphy-
lum Agaricomycotina, class Agaromycetes, subclass
Agaromycetidae) that covers most of the so called “high-
er fungi” often referred to as “mushrooms”growing
in Europe. The referred pigments, not reviewed up
to now, are arranged according to the mushroom
orders. Many other pigments were identified in
fungi indigenous to Australasia.
1 Agaricales
The genera Agaricus L., Leucoagarius Locq. ex
Singer and Macrolepiota Singer of the Agaricaceae,
including the common mushroom A. bisporus (J.E.
Lange) Imbach (now cultivated in at least 70 coun-
tries around the world), contain the glutamic acid
derived hydrazine agaritine (1) that may be enzy-
matically oxidised at the C-4 hydroxymethyl group
to the corresponding formyl and carboxyl deriva-

1
The clade containing Ascomycota and Basidiomycota is classified as subkingdom Dikarya. The phylum Ascomycota
(“sac fungi”) covers some higher fungi (belonging to the subdivision Pezizomycotina, class Pezizomycetes, subclass
Penzizomycodidae, order Pezizales), such as the true morel (Morchella Dill. ex Pers., Morchellaceae), the false morel
(Gyromitra Fr., Discinaceae) and the truffle (Tuber P. Micheli ex F.H. Wigg., Tuberaceae). Their pigments have been stud-
ied only sporadically; the black pigments of the black truffle T. melanosporum are polymeric allomelanins of polyketide
origin (D e A ngelis et al. 1996).

88
 O O
H H
O N COOH N COOHN N
H N N N N N N
N COOH N H H
H N N H
N HO NH
HO NH2
H
2
H O
Czech HO
J. Food Sci. NH2 ȱ O Vol. 29, 2011, ȱ
ȱ No. 2: 87–102
1.ȱagaritineȱȱ 1.ȱagaritineȱȱ 2.ȱagariconeȱȱ ȱ 2.ȱagariconeȱ
1. agaritine 2. agaricone
O
HO HO O
O O O O OH
H HO H
N COOH
N O COOH N N OH
N N N N
N NCOOH
N
N
COOH
H H COOH H H H H
O HO NH2 N NH2 NHO2 O NH2
H NH
ȱ NH2 ȱ ȱ ȱ ȱ ȱ ȱ
NH
1.ȱagaritineȱȱ 1.ȱagaritineȱȱ 3.ȱJȬglutamylȬ4Ȭhydroxybenzeneȱ
2.ȱagariconeȱȱ ȱ 3.ȱJȬglutamylȬ4Ȭhydroxybenzeneȱ
2.ȱagariconeȱȱ 4.ȱ2ȬhydroxyȬ4ȬiminoȬȱ
4.ȱ2ȬhydroxyȬ4Ȭimino
3. γ-glutamyl-4-hydroxybenzene
ȱȱ 4. 2-hydroxy-4-iminocyclohexa-2,5-dienone
ȱȱȱȱcyclohexaȬ2,5Ȭdienoneȱȱ
O O
O
O
HO
O  OH OH COOH
-
-
COO O
HOOC COO
–
COOH
HOOCN COOH – COO O COO- +
N COO + + O
H O+ N N O
H +N
–
NH2 +NH2 COO + O N
N NH O
O –
N N NH N N COO
ȱ ȱ ȱ O ȱ
OH
O COOH
ȬglutamylȬ4Ȭhydroxybenzeneȱ
3.ȱJȬglutamylȬ4Ȭhydroxybenzeneȱ 4.ȱ2ȬhydroxyȬ4ȬiminoȬȱ
4.ȱ2ȬhydroxyȬ4ȬiminocyclohexaȬ2,5Ȭdienoneȱȱ
OH
ȱȱȱȱcyclohexaȬ2,5Ȭdienoneȱȱ
COOH N
HOOC COOH HOOC N COOH
HOOC N COOH H
HOOC N COOH HOOC - N COOH HOOC - N COOH
H HOOC N H COOH
HOOC COO H COO OH ȱ H ȱ
H
COO
-
+ O + +
O +
N 5.ȱmuscapurpurinȱ
N O N 8.6.ȱmuskaaurinȱIȱ
COO
- 7.ȱmuskaaurinȱI
5. Nmuscapurpurin N 6. muskaaurin I 7. muskaaurin II vulgaxanthin I
O O COOH
tives, which are hydrolysed H to 4-(hydroxymethyl)- OH and yellowCONH muscaflavin
2
N (12). Muscaurin I (6) and
CONH2 N COOH N COOH
phenylhydrazine and 4-carboxymethylbenzoic
N acid, muscaurin N II (7) are derived from unusual nonpro-
H COOH H
HO NH2 + COOHacids + +
respectively. 4-(Hydroxymethyl)phenylhydrazine
HOOC N COOH is tein
HOOC N amino - ibotenic
HOOCO acidNN
andCOOH
COO
-stizolobic acid,
N COO
-
HOOC
+
N COOH + + H N – COO H
oxidised to NtheH corresponding
COO– N
H
diazonium COO cation.
– respectively,
N COO and are the major agaric pigments.
ȱ ȱ ȱ ȱ
The metabolic fate of 1.agaritine agaritine has been linked Pigments named 2. agaricone muscaurins III–VII are mix-
5.ȱmuscapurpurinȱ O
with the carcinogenity of the6.ȱmuskaaurinȱIȱ
mushroom (Walton 7.ȱmuskaaurinȱIIȱ tures of pigments derived 8.ȱvulgaxanthinȱIȱ
from common proteno-
O
et al. 2001). HO The yellow pigment characteristic of genous amino acids. Muscaurin HOOC OH
N
III is a mixture
COOH HOOC
ofN COOH
CONH2 O HOOC N COOH H
the yellow-staining
HOOC N A.
COOH xanthodermus
HOOCCOOH N Genev.
COOH and of
HOOC vulgaxanthin
N H
COOH I (8), known as H(S)-glutamine-beta- H
COOH HOOC N COOH
some other AgaricusH species
N is caused H
by another xanthin, H
miraxanthin ȱȱ IIIH(9), known ȱȱ
as (S)-aspartic ȱȱ
H + +
+ NH
azaquinone metabolite agaricone
-
N COO (2) that forms Nby COO
2- acid-betaxanthin,
9.ȱmiraxanthinȱIIIȱ
-
and a betaxanthin
10.ȱvulgaxanthinȱIIȱ
NH derived from
11.ȱindicaxanthinȱ
COO
9.N miraxanthin III 10. vulgaxanthin II 11. indicaxanthin 12. muscaflavin
oxidation of the corresponding leucophenol in the 2-aminoadipic acid. Muscaurin IV is a mixture of
3. γ-glutamyl-4-hydroxybenzene
damaged tissue. The agaritine analogues derived vulgaxanthin 4. 2-hydroxy-4-iminocyclohexa-2,5-dienone
O
I and miraxanthin III. Muscaurin
CH3 COOH
from 4-aminophenol γ-glutamyl-4-hydroxybenzene V is a mixture of vulgaxanthin II (10), known as
COOH + COOH
(3) readily oxidise toHOOC
the corresponding quinone (S)-glutamic acid-betaxanthin,
O R indicaxanthin (11),
HOOC N COOH N COOH HOOC N– COOH – N N CH3
HOOC R + HOOC COO N O COOH
H
via γ-glutamyl-3,4-dihydroxybenzene. H N This quinone COOH known as (S)-proline-betaxanthin,
H O O and betaxan-
ȱȱ
–
ȱȱ ȱȱ + ++
COO + O
thins derived from valine O Vand O ȱleucine.
O 2HMuscaurinCOO VI
O +
decomposes to 2-hydroxy-4-iminocyclohexa-2,5- N O –
N N N N
9.ȱmiraxanthinȱIIIȱ 10.ȱvulgaxanthinȱIIȱ O O H3
dienone (4), which imparts a pink-red colour 11.ȱindicaxanthinȱ
to some is a mixture12.ȱmuscaflavinȱ
of vulgaxanthin
H3 C
HOOC
N COOH O
II and N indicaxanthin.
COOH
O H
agarics (e.g. to A. bisporus) (Hanson N
HOOC 2008a,b). COOH Muscaurin
OH VII is derived from histidine (Muso
H ȱ ȱ ȱ CH3 2- ȱȱ ȱ
CH3 2005).
The striking orange-red pigments of the cap of 1976; Li & Oberlies
COOH ȱ 13.ȱhygroaurinsȱ(Rȱ=ȱaminoȱacidȱresidue)ȱȱ
fly agaric Amanita muscaria (L.) Hook.
13. hygroaurins (Amanita COOH
(R = amino
HOOC acidN residue)
Fly agaric
HOOCand O Nmushrooms
14.COOH CH3 of the
Namavadin genus NHygrocybe
HOOC COOH
HOOC R N+ COOH
Pers., Amanitaceae) are a Hmixture N of the purple H (Fr.) P. Kumm.HO(Hygrophoraceae),
O
CH
e.g. HH. conica
O + 3
betacyanin muscapurpurin (5), orange betaxan- (Schaeff.) P.OKumm., V commonly
O 2H known as the witch’s OCH3
5. muscapurpurin CH36. muskaaurin OCH I 3 7. muskaaurin II 8. vulgaxanthin I
O O
thins muscaurins (muscaaurins) I–VII (6 and 7) hat, synthesise the yellow pigment muscaflavin (12), OH OH O O HO
O HO H3 CO OH H3 C O N
OH O OH OH O
HOOC N COOH OH
H3 CO CONH2 OH H CH3 O OH OH
ȱ ȱ ȱ ȱOH
ȱ
COOH OH ȱ O OH ȱ H3 CO OH C
ȱ 13.ȱhygroaurinsȱ(Rȱ=ȱaminoȱacidȱresidue)ȱȱH3 CO OH 14.ȱamavadinȱ
O OH RO
+ + – + – CH 3 CH 3
OH N O OH
COO– N COO N COO

CH3
15.ȱfallacinolȱ 16.ȱ(3R,3Rȇ,M)ȬflavomanninȬ6,6ȇȬdiȬOȬmeth
15. fallacinol 16. (3R,3R',M)-flavomannin-6,6'-di-O-methyl
OCH3 ether O 17. (3R)-atrochrysone, R = H
O HO OH OH O (3R)-torosachrysone, R = CH3
OH OH O
H3 CO
OH
HOOC N COOH HOOC
O OH N OH COOH HOOC N OHCOOH N
H H HOOC COOH OH
H H
H3 CO
CH3 RO
OH O OH CH 3
9. miraxanthin III 10. vulgaxanthin II 11. indicaxanthinȱ 12. muscaflavin ȱ
15.ȱfallacinolȱ 16.ȱ(3R,3Rȇ,M)ȬflavomanninȬ6,6ȇȬdiȬOȬmethylȱetherȱȱȱȱȱȱȱȱȱȱ17.ȱ(3R)Ȭatrochrysone,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ(3R)Ȭtorosachrysone,ȱRȱ=ȱCH
CH3
89 3ȱ
COOH
O N CH3
R +
N O O
O +
O V O 2H
O O
 O O

HOOC N COOH
HOOC NHOOCCOOH
N COOH
HOOC NHOOCCOOH
N COOH
HOOC NHOOCCOOHN COOH
HOOC N COOH
H H H H H H H H
Vol. 29, ȱȱ
2011, No. 2: 87–102
ȱȱ ȱȱ ȱȱ ȱȱ ȱȱ ȱ Czech
ȱ J. Food Sci.
9.ȱmiraxanthinȱIIIȱ 10.ȱvulgaxanthinȱIIȱ
9.ȱmiraxanthinȱIIIȱ 11.ȱindicaxanthinȱ
10.ȱvulgaxanthinȱIIȱ 12.ȱmuscaflavinȱ
11.ȱindicaxanthinȱ 12.ȱmuscaflavinȱ
O
H
N COOH N 2-
N N CH3 CH3 2-
N
H COOH COOH H
HO NH2 O
+ NO O3
CH N CH3
R R +
N N O O O O+
V O OO 2H O +
1. agaritine 2. agaricone
O V O 2H
O O O O
H3 C N O HO
3C N O
HO HOOC N COOH
HOOC N COOH
O H H CH3 OH CH3
ȱ ȱ ȱ ȱ ȱ ȱ COOH ȱȱ ȱ ȱȱ ȱ ȱ ȱ
N
ȱ ȱ 13.ȱhygroaurinsȱ(Rȱ=ȱaminoȱacidȱresidue)ȱȱ
H 13.ȱhygroaurinsȱ(Rȱ=ȱaminoȱacidȱresidue)ȱȱ 14.ȱamavadinȱ 14.ȱamavadinȱ
NH2
NH
derived from dihydroazepine, and store it in the cup C. citrinus J.E. Lange ex P.D. Orton and C. croceus
CH3 CH3
3.skin. Analogously to betalamic acid involved
γ-glutamyl-4-hydroxybenzene OCH3 in 4.the (Schaeff.)
OCH 3 Gray, while in Australian fungi it forms as
2-hydroxy-4-iminocyclohexa-2,5-dienone
O O OH OH O OH OH O
formation of betalains, HO muscaflavin HO can spontane- a mixture of (3R,3R', M)-OH (16)OH and O(3R,3R', P)-atropoi-
OH OH O
H3 CO H3 CO COOH
ously condense OH with amino acids, OH under the forma- somers. The green (3R)-atrochrysone (17) occurs in
O OH OH O- OH OH OH -
COO OH
tion
HOOCof aldimine bonds, yielding yellow COOhygroaurins O
C. atrovirens Kalchbr. and C. odoratusOH (M.M.Moser) OH
- H3 CO H3 CO +
(13) (Muso 1976; Li
COO & Oberlies +2005).O M.M.Moser,
CH3 RO
(3S)-torosachrysone-8-O-methyl
CH + RO - ether
+ O
N COOCH 3
3 CH 3
OH O O OH OH N O OH N N N
The unusually high concentration of vanadium in C. fulmineus ȱ (Fr.) ȱFr., C. citrinus J.E.ȱ Lange ex ȱ
O COOH
in some Amanita
15.ȱfallacinolȱ species is ascribed to the forma- P.D. Orton, C. splendens R. Henry, T. equestre (L.) P.
16.ȱ(3R,3Rȇ,M)ȬflavomanninȬ6,6ȇȬdiȬOȬmethylȱetherȱȱȱȱȱȱȱȱȱȱ17.ȱ(3R)Ȭatrochrysone,ȱRȱ=ȱHȱ
15.ȱfallacinolȱ 16.ȱ(3R,3Rȇ,M)ȬflavomanninȬ6,6ȇȬdiȬOȬmethylȱetherȱȱȱȱȱȱȱȱȱȱ17.ȱ(3R)Ȭatrochrysone,ȱRȱ=ȱHȱ
OH
tion of amavadin (14), a pale blue complex (1:2) Kumm. and ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ(3R)Ȭtorosachrysone,ȱRȱ=ȱCH
the Sulphur Knight T. sulphureum 3ȱ (Bull.)
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ(3R)Ȭtorosachrysone,ȱRȱ=ȱCH 3ȱ
4+
of vanadium V with (2S,2´S)-N-hydroxyimino- HOOC
P. Kumm.
N COOH
(Gill & Steglich 1987; Gill 1994). A
HOOC N COOH HOOC N COOH HOOC N COOH
2,2'-dipropionic H acid, isolated originally H from number H of anthraquinone pigments H formally derived
A. muscaria (Bayer & Kneifel 1972). from torosachrysone and atrochrysone by coupling
The5. genus Cortinarius (Pers.)
muscapurpurin Gray (Cortina-
6. muskaaurin I (dimeric, trimeric
7. muskaaurin II and8.tetrameric
vulgaxanthin octaketides)
I have
riaceae) represents the largest genus of agarics, con- been described, mostly in Australian fungi belonging
taining about CONH1000
2 different species in Europe and to the genera Cortinarius, Dermocybe and, to a lesser
found worldwide together with COOH the closely related extent, Tricholoma (Gill & Morgan 2001).
genera+Dermocybe - (Fr.) Wünsche
+ (Cortinariaceae)
-
+
COO
The
- European members of the genus Cortinarius
N COO N COO N
and Tricholoma (Fr.) Staude (Tricholomataceae). A characteristically contain the xanthone dermoxan-
range of anthraquinones and biogenetically related thone (18) and O its methyl ester that were found in
metabolites has been found in these mushrooms the stem of the Surprise Webcap C. semisanguineus
principally due to the activity in the study of the (Fr.) Gill. These xanthones are responsible for the
HOOC N COOH HOOC N COOH HOOC N COOH N
Australian HOOCfluorescence
H Cortinarius/Dermocybe H species. The ma- H bright yellow H
COOH under UV light (Gill

jor dark orange pigment of the European toadstool 1999). The fruiting bodies of several Cortinarius
9.C. cinnabarinus
miraxanthin III Fr. is 10. fallacinol (6-O-methoxycitre-
vulgaxanthin II species, such
11. indicaxanthin 12. as the Violet Webcap C. violaceus
muscaflavin
orosein, 15) (Gill & Steglich 1987; Gill 1994). (L.) Gray, have a strikingly deep violet colour
Several species of the genera Cortinarius, Dermo- of the fruiting bodies, CH3 which 2- is ascribes to the
3+
COOH
cybe and Tricholoma, such as C. cinnamomeoluteus unique β-DOPA-Fe O
complex [Fe 3+L 2(H 2O 2)] – or
N CH3
P.D. Orton and T. equestre R (L.) +
N
P. Kumm. (trivially [Fe3+L4(H2O2)]2–,Owhere O L is the (3R)-β-DOPA anion
known as Man on Horseback), produce a bright ligand (19).OTheseV mushrooms +
O O 2 H concentrate iron
yellow dimeric anthraquinone flavomannin-6,6'- by as much as 100-fold O O over other Basidiomycota
di-O-methyl ether (16). This pigment is biosynthe- (Von NussbaumH3 C N et al. 1998).
O Unusually high con-
HOOC N COOH
H
sised by 7,7'-coupling of the corresponding green centrations of iron were also found in the Velvet CH 3

dihydroanthracenone (3R)-torosachrysone
13. hygroaurins (R = amino acid(17). In Bolete, Suillus
residue) variegatus (Sw.) Kuntze (Boletales)
14. amavadin
its homochiral form it also occurs in the European (Drbal et al. 1975; Kalač et al. 1989).
CH3
OCH3
O HO OH OH O
OH OH O
H3 CO
OH
O OH OH OH
OH
H3 CO
CH3 RO
OH O OH CH 3

15. fallacinol 16. (3R,3R',M)-flavomannin-6,6'-di-O-methyl ether 17. (3R)-atrochrysone, R = H

(3R)-torosachrysone, R = CH3

90
 Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102

HOOC
HOOC
HOOC OOO O OH
OH --–-- -
HOOC O
HOOC OH
OHOH O
OOO O OOO
OO O OOO O
O COOH
COOH
COOH
COOH
COOH
HHH H
H
RRRR R
--–-- - - NNN N COOH
N COOH
COOH
COOH
COOH
OOO O
O OOO
OO O COO
COO
COO
- -–-- -
COO
COO HHH H
H
COO
HH ++++
3CO OOO O
H ++ +
33CO
3H 3CO
H3 CO
CO O NH
NH
NH
333NH
NH HO
HO
HO
HOHO
NH 333 3
ȱȱȱȱ ȱ ȱȱȱȱ ȱ ȱȱȱȱ ȱ
18.ȱdermoxanthoneȱ
18.ȱdermoxanthoneȱ
18.ȱdermoxanthoneȱ
18.ȱdermoxanthoneȱ
18.ȱdermoxanthoneȱ 19.ȱΆȬDOPAȱanionȱ
19.ȱΆȬDOPAȱanionȱ
19.ȱΆȬDOPAȱanionȱ
19.ȱΆȬDOPAȱanionȱ
19.ȱΆȬDOPAȱanionȱ
19. β-DOPA anion 20.ȱscaurinȱA,ȱRȱ=ȱHȱ
20.ȱscaurinȱA,ȱRȱ=ȱHȱ
20.ȱscaurinȱA,ȱRȱ=ȱHȱ
20.ȱscaurinȱA,ȱRȱ=ȱHȱ
20.ȱscaurinȱA,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
OH
OH
OH
OH OOO O
O
OH OH
OH
OH
OHOH
HO
HO
HO
HOHO

OOO O
OOO O O
O
RRRR R
OOO O
O
OOO O
O
NNN N
N HO
HO
HO
HOHO
HHH H
H OH
OH
OH
OHOH RRRR R OOO O
O
NNN N
N
OOO O
O
OOO O COOCH
COOCH
COOCH
COOCH
COOCH
33333 3 HO OOO O
O
O HO
HO
HOHO
ȱȱȱȱȱȱȱȱ ȱȱ ȱȱȱȱȱȱȱȱ ȱȱ ȱȱȱȱȱȱȱȱ ȱȱ ȱȱȱȱ ȱ
21.ȱcanthinȬ6Ȭoneȱ
21.ȱcanthinȬ6Ȭoneȱ
21.ȱcanthinȬ6Ȭoneȱ
21.ȱcanthinȬ6Ȭoneȱ
21.ȱcanthinȬ6Ȭoneȱ 22.ȱinfractinȱA,ȱRȱ=ȱHȱ
22.ȱinfractinȱA,ȱRȱ=ȱHȱ
22.ȱinfractinȱA,ȱRȱ=ȱHȱ
22.ȱinfractinȱA,ȱRȱ=ȱHȱ
22.ȱinfractinȱA,ȱRȱ=ȱHȱ 23.ȱaurantricholoneȱ
23.ȱaurantricholoneȱ
23.ȱaurantricholoneȱ
23.ȱaurantricholoneȱ
23.ȱaurantricholoneȱ 24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
ȱȱȱȱ ȱ ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ
ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ ȱȱȱȱ ȱ
ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ
ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ
ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ ȱȱȱȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ

RRR
Scaurins (20) are the polyene pigments with RR Rand Pholiota (Fr.) P. Kumm., where they have a
bound glutamic OH acid
OH
OH
OH OHthat were isolated from the considerable taxonomic significance (GillNO 1994).
NO
NO
NO2NO
2222 2
fruiting bodies of C. scaurus (Fr.) Fr. (Gill OH
OH
1998,
OOO O
Hispidin is biosynthesised by two different
COOH
COOH
COOH
COOHCOOH mecha-
OHOH OHO
2003).
RRRR R Alkaloids containing HO
HO
HO
HO HO
the canthin-6-one nisms using the activated 4-hydroxy-6-methylpy- HHHH H
NNN N
HOOC
HOOCHOOC OO
HOOC O OOO O OOO O
O - -- - RRR R OOO O
O N
O O OH OH
OH OH
skeleton are produced by some other C. species. rone (a condensation product of three
O OO O O OO O R O O
O O N NNactivated
NCOOH
NCOOH Cl
COOH
COOH Cl
ClClCl
HHH
HHHH
H H OH
The R RR R O OH
HOHOHOHOparent compound canthin-6-one
HO HO
HO
HO
HOHO - -- - (21) occurs- -- - acetates) and the activated O OOO O3,4-dihydroxybenzoic
NN
O OO O
N N COOH COOH
COOH
COOH
OH
OH OH
ȱȱȱOO
ȱ Oȱ ȱȱȱȱ ȱ ȱȱȱȱȱ
ȱȱȱȱȱ
ȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱȱ ȱȱȱ
derivative ȱ ȱ
O OO OO COO COO
COO COO HH HH
in the bitter-tasting C. infractus (Pers.) Fr. together + ++ +
acid or from phenylalanine via a cinnamyl
H3H H 33H
CO 3 CO
CO
CO OO OO
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH NHNH
NH NH
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ 27.ȱdihydroxerulin,ȱRȱ=ȱCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH
HOHO
HO HO
27.ȱdihydroxerulin,ȱRȱ=ȱCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH 2ȬCH
222ȬCH
2ȬCH
ȬCH2ȬCH 2ȬCH
222ȬCH 2ȬCH2ȬCH
ȬCH 3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
333ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
with the β-carboline derivatives ȱ ȱȱ infractin33ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
A and
33ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
ȱ ȱȱ that is combined with either acetate or malonate
33ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
33ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
ȱ ȱȱ
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH 33ȱȱ ȱ
3 3ȱ 3ȱ
3
B (22) (Gill 1996).
18. dermoxanthone
18.ȱdermoxanthoneȱ 19. β-DOPA anion
19.ȱΆȬDOPAȱanionȱ
through the polyketide
20. scaurin A, R = H
20.ȱscaurinȱA,ȱRȱ=ȱHȱ
pathway. The related open
18.ȱdermoxanthoneȱ
18.ȱdermoxanthoneȱ 19.ȱΆȬDOPAȱanionȱ
19.ȱΆȬDOPAȱanionȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ 20.ȱscaurinȱA,ȱRȱ=ȱHȱ
20.ȱscaurinȱA,ȱRȱ=ȱHȱ
The benzotropolone derivative aurantricholone chain β-keto ester scaurin
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ(26,B,R =
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ R = COOCH OH 3
) was isolated
(23),
NH
NH NH
isolated from the bright orange-red
NH
NHNH
NH22NH
caps some years ago as the Brick Cap H. sublateritium
NH222NH
22 2 222 2
of Tricholoma aurantium (Schaeff.) Ricken, COOH
is OH (Schaeff.)
OH
OH OH OO OO
HOOC
HOOC
HOOC
HOOCOHOH
OH
HOOC
Quél. pigment. The yellow pigment
OH
COOH
COOH
COOH
COOH COOH
COOH
COOH COOH
COOH
closely related to the naphthalenoid pulvinic acid hispolon is the hydrolytic and decarboxylation HO HO
HO HO
OOO O
badione NNN NA occurring in the
N
O Boletales mushrooms NNNN N product NNof NN N the open chain β-ketoHHester HH
NNNN
H N (26) (Gill
OOO O
O OO O O OO OO OOO O
(see Chapter 2). RItRR Roccurs naturally as a metal 1994). It also occurs in mushrooms of the Hy- O
HHHH H NH
NHNH
NH NH HHH H
H
OO OO
chelate; theNH predominant
NH
NH
NH NH HN
counter ion is calcium
OO O O NH
NH
NH
NH menochaetaceae
NH HN HN
HN
HNHN
family, e.g. in several Inonotus
HN
HN
HN HN NNN N
N NNNN N X
XXX X NNNN N O
OOO O
OOOO O
(Klostermeyer et al. 2000). NN NNMinor pigments are OH P.
OH
OH OH
Karst.,NNNN HOOnnia
N HO
HO
HO OOO O P. Karsten and Phellinus Quél.
O
OOO O
O H H
H H OO OO O R RR R OO OO
the yellow RRRR R (Lee & Yun 2006)
N N aurantricholides A COOHand B (24). ȱȱspecies.
COOH
COOHCOOH
COOH
NN ȱȱȱȱ
ȱȱȱȱ
ȱȱȱȱ
ȱȱȱȱȱȱȱȱ ȱȱȱȱȱȱȱ
ȱȱȱȱ ȱ ȱȱȱ
ȱȱȱ ȱȱȱȱ ȱ ȱȱȱȱȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱ OO
ȱ
OȱOȱȱ ȱ
The yellow-brown styrylpyrone pigments
COOCHCOOCH
COOCH
COOCH bis- Orange-yellow polyenes of fatty acid origin,
29.ȱmycearubinȱAȱ
29.ȱmycearubinȱAȱ
29.ȱmycearubinȱAȱ
29.ȱmycearubinȱAȱ
29.ȱmycearubinȱAȱ
OO OO 30.ȱmycearubinȱBȱ
30.ȱmycearubinȱBȱ
30.ȱmycearubinȱBȱ
30.ȱmycearubinȱBȱ
30.ȱmycearubinȱBȱ 3 33 3 31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
HO HO
HO O O
O O
ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
HO
noryangonin and
ȱȱ ȱȱȱȱ hispidin (25) are widespread ȱȱ ȱȱȱȱ dihydroxerulin, xerulin ȱȱ ȱȱȱȱ and xerulinic acid (27), ȱ ȱȱ
ȱȱȱȱ ȱ ȱȱȱȱ ȱ ȱȱȱȱ ȱ ȱȱȱȱ ȱ ȱȱȱȱ ȱ ȱȱȱȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH 333ȱ3ȱ3ȱȱ 3ȱ ȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱȱhaematopodinȱB,ȱXȱ=ȱNH ȱ ȱȱ ȱ ȱ ȱ
among
21.ȱcanthinȬ6Ȭoneȱ
21.ȱcanthinȬ6Ȭoneȱfungi of the Strophariaceae
21. canthin-6-one
21.ȱcanthinȬ6Ȭoneȱ 22. infractin A,family,
22.ȱinfractinȱA,ȱRȱ=ȱHȱ
22.ȱinfractinȱA,ȱRȱ=ȱHȱ
22.ȱinfractinȱA,ȱRȱ=ȱHȱ R = H genera 23.are
23.ȱaurantricholoneȱ the pigments of Oudemansiella
aurantricholone
23.ȱaurantricholoneȱ
23.ȱaurantricholoneȱ 24. aurantricholide
24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ melanotricha
A, R = OH
ȱ Gymnopilus
ȱȱ P. Karst., ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ
Hypholomainfractin B,(Fr.)
ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ
ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ R = OH P. Kumm. ȱ ȱȱ (Dörfelt)
ȱ ȱȱ M.M. H Moser O OOO (Oudemansiella
O aurantricholide B,
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
HH C
Speg.,
R=H
H33C
3H 3C
3CH
C3 C
HH
H3H 3C
33C3C
C3 C
H
R RR R
OOOO O OOO O OH
OOO O
O O OH
OH
OHOH
OH
OH
OHOH HH OOOO O
H3H 3C
33C3C
H
C3 C NO 2NO
NO
NO 22 2
OOO O
O
COOHCOOH
COOH
COOH
OH
OH
OH OHOO OO
RRRR R OOOO O OOOO O OH
OH
OH HHHH
R RR R HO
HOHO
HO OHOH
OOO O
O OOO O
O O OO
OO OO O
R RR R OO
OO O N
ON
OO ONNN
N
NN ClCl
ClCl
OOOO O OOO O
O HHHH
HO
HO
HOHO HO
HO
HO
HOHO OO
OO O O O
O
OOO O O OH
OH
OHOH
HO
HO
HOHO
ȱ ȱȱ ȱ ȱȱ ȱȱȱȱȱ
ȱȱȱȱȱ
ȱȱȱȱȱ ȱ ȱȱ
OH
OH
OH
OHOH
25. bisnoryangonin,OOO O
R=H
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH 26. hispolon, R = CH 3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ 27. dihydroxerulin, R = CH
3 27.ȱdihydroxerulin,ȱRȱ=ȱCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH 2ȬCH
22ȬCH2-CH
ȬCH 2ȬCH 2-CH
22ȬCH
ȬCH 28. stephanosporin
3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
33ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
3
CH
O OH
OH OH
OH OH CH
CH
CH333CH
33 3
R RR R hispidin, R = OH HO
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
Rȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCHxerulin,
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
HO
HO
HOHO R = CH=CH-CH
3ȱ 33ȱȱ 3 OOOO O
ȱȱȱȱ ȱ ȱȱȱȱȱȱȱȱ ȱ ȱȱȱȱȱȱȱȱ ȱ
xerulinic acid, R = CH=CH- COOH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ 34.ȱleucomentinȬ2ȱȱ
34.ȱleucomentinȬ2ȱȱ
34.ȱleucomentinȬ2ȱȱ
34.ȱleucomentinȬ2ȱȱ
34.ȱleucomentinȬ2ȱȱ 35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
NH NH
NH2NH
22 2
NH NH
NH2NH
22 2
HOOC
HOOC
HOOC
HOOC
91
COOH
COOH
COOH
COOH COOH
COOH
COOH
COOH

OO
OO NN
NN NN
NN HH
HN
N H
NN
NN
NN
OO
OO OO
OO
HH
HH NH
NH
NHNH HH
HH
NH
NH
NHNH
 R RR R HO HO HOHO
O OO O OO O
O O OO O N NN N
R RR R N NN N Cl ClCl Cl
H HH H
HO HOHO
HO HO HOHO
HO O OO O O OO O OH OH OHOH
ȱ ȱȱ ȱ ȱ ȱȱ ȱ ȱȱȱȱȱ ȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱȱ ȱ ȱȱ ȱ
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH 27.ȱdihydroxerulin,ȱRȱ=ȱCH
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ 2ȬCH2ȬCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH 2ȬCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ 2ȬCHȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
2ȬCH
23ȬCH 2ȬCH 3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
Vol. 29, 2011, No. 2: 87–102
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH 3ȱ 3ȱ3ȱ 3ȱ
Czech J. Food Sci.
HOOC
HOOC
HOOC O O OH OH - - -
O OH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
O OO O O O O OO COOH
COOH
COOH
H HH
R RR
- NH
NH-2O- NH N NN COOH
COOH
COOH
ONH
- - -
NH2 NH
NH
2 NH
2 2 O OO O2 2 2 COO
COO
COO H HH
+ + +
H3H 3H
CO 3 CO
CO O OO NH
NH NH HO
HO
HOHOOC
HOOCHOOC
HOOC
COOHCOOHCOOH COOHCOOH
COOH3 3
3COOH
COOH ȱ ȱȱ ȱ ȱȱ ȱ ȱȱ
O OO O
18.ȱdermoxanthoneȱ
18.ȱdermoxanthoneȱ N19.ȱΆȬDOPAȱanionȱ
NN N
19.ȱΆȬDOPAȱanionȱ N H N HH
NN N 20.ȱscaurinȱA,ȱRȱ=ȱHȱ
20.ȱscaurinȱA,ȱRȱ=ȱHȱ
20.ȱscaurinȱA,ȱRȱ=ȱHȱ NNH N
N NN N 18.ȱdermoxanthoneȱ 19.ȱΆȬDOPAȱanionȱ
O OO O O OO O
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱscaurinȱB,ȱRȱ=ȱOHȱ
H HH H NH NH NHNH H HH H
NH NH
NH NH HN NH NHNH
NH HN HN HNHN
HN HNHN N NN N N NN N OH OH
OHO OO X XX X N NON N OO O
O OO O N OH
N NOH OOH
NO O O
O OO O HOHOHO
O OO O COOHCOOH
COOH
COOH R RR R
ȱȱȱȱ ȱȱȱȱȱȱȱȱȱȱȱȱ ȱ ȱȱȱ ȱ ȱȱȱȱȱȱȱȱ ȱȱȱ ȱ ȱȱȱȱȱȱȱȱȱȱ
ȱ ȱ ȱȱȱȱȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱ ȱ ȱȱ ȱ
O OO
O OOȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
29.ȱmycearubinȱAȱ
29.ȱmycearubinȱAȱ
29.ȱmycearubinȱAȱ
29.ȱmycearubinȱAȱ 30.ȱmycearubinȱBȱ
30.ȱmycearubinȱBȱ
30.ȱmycearubinȱBȱ
R R R 30.ȱmycearubinȱBȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
ȱ ȱ ȱ ȱȱ ȱ ȱ ȱȱ ȱ ȱ ȱȱ ȱ ȱ ȱȱ ȱ ȱ ȱȱ ȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH 3ȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH
O OO 3ȱ3ȱ 3ȱȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH ȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱ ȱ ȱ ȱ
O OO
N NN HO
HOHO
Physalacriaceae) that act as inhibitors of choles- of the OHOH OH
mushroom O OO O
H HH H3 C Hdecomposing
3HC
3CH3 C R under
RR the
O Oinfluence
O
N NN
terol biosynthesis (Kuhnt et al. 1990). H3 C H3HC3 CH3 C of air and light (Hopmann & Steglich 2006). O OO
COOCH
COOCH
The carrot O OO truffle, StephanosporaCOOCH caroticolor
3 3 3 O
OO O HOHO HO O OO
ȱȱ ȱȱ ȱȱ O OO O ȱȱ ȱȱ ȱȱ O ȱȱ OȱȱOȱȱ O
O OO O
OH OH OHOH ȱ ȱȱ
(Berk.) Pat. (Stephanospora H3 C Pat.,
H3HC3 C
H3 CStephanospo-
21.ȱcanthinȬ6Ȭoneȱ
21.ȱcanthinȬ6Ȭoneȱ
21.ȱcanthinȬ6Ȭoneȱ 22.ȱinfractinȱA,ȱRȱ=ȱHȱ
22.ȱinfractinȱA,ȱRȱ=ȱHȱ 23.ȱaurantricholoneȱ O
23.ȱaurantricholoneȱ 24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
raceae), contains in its 22.ȱinfractinȱA,ȱRȱ=ȱHȱ
subterranean tuber-like 23.ȱaurantricholoneȱ 2 Boletales OO24.ȱaurantricholideȱA,ȱRȱ=ȱOHȱ
O
ȱ ȱȱ ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ
ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱ
ȱȱinfractinȱB,ȱRȱ=ȱOHȱȱO O O O ȱ ȱ ȱ ȱ ȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱaurantricholideȱB,ȱRȱ=ȱHȱ
fruiting O
bodies
OO O
the R pigmentRR R stephanosporin O
(28).
O OO OH O OHOH
OH
OO O O OO O
This unusual hydrazine derivative is biosynthesised O OO O R RRMushrooms of the order Boletales are charac-
O OO O
using 2-chloro-4-nitrophenol as the building block. terised by a diversity HO HO HOHOof colours O OOmainlyO derived
OHOH OH
Both compounds occur naturally as their potas- from terphenylquinones and pulvinic acids. Ter- NONO 2NO
2 2
OH OH OHOH
COOH
COOH
COOH
sium salts O and
OO Oare responsible for the bright OHorange
OHOHOHOHO
OH OH OO phenylquinones, exemplified by polyporic CH 3 CH CH 3acid
3 CH 3
R RR R R R R HO HO HOHO O OO OH HH
colour of the mushroom ȱ O OOȱ ȱO(LangȱOOHOHO HOet al. 2001). (33) ȱ ȱ and ȱ ȱ ȱatromentin
ȱ ȱ (33), are
O OO mainly ȱ
produced
N Nȱ N ȱ ȱ ȱȱ ȱ
by
R RR N NN Cl ClCl
The pyrroloquinone alkaloids 34.ȱleucomentinȬ2ȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ isolated from My- wood-rotting higher
34.ȱleucomentinȬ2ȱȱ
34.ȱleucomentinȬ2ȱȱ
34.ȱleucomentinȬ2ȱȱ fungi of the orderOPolyporales
35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ O O
H HH
OH OH OH
HOHO HO HOHO HO OO O
cena (Pers.) Roussel (Mycenaceae)
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ ȱ ȱȱ species include ȱ growing ȱȱ on various deciduous trees ȱȱȱȱȱ but in other
ȱȱȱȱȱȱȱȱȱȱ ȱ ȱȱ
the25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
red pigments mycearubin A (29),
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH
25.ȱbisnoryangonin,ȱRȱ=ȱHȱȱȱȱȱȱȱȱ26.ȱhispolon,ȱRȱ=ȱCH mycearubin B higher fungi,
27.ȱdihydroxerulin,ȱRȱ=ȱCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH
27.ȱdihydroxerulin,ȱRȱ=ȱCH
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
3ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
such as in
2ȬCH
the
2ȬCH
2ȬCH 2ȬCH
Boletales
2ȬCH
2ȬCH
fungi, they
3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
3ȱȱȱȱȱȱȱȱȱȱ28.ȱstephanosporinȱ
(30) and related compounds from the fruiting bod- only appear sporadically.
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH
ȱȱȱȱȱȱhispidin,ȱRȱ=ȱOHȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulin,ȱRȱ=ȱCH=CHȬCH 3ȱ 3ȱ 3ȱHowever, atromentin
iesȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
ofȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
M. rosea (Schumach.) Gramberg (Peters & is their key intermediate for many conversions
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱxerulinicȱacid,ȱRȱ=ȱCH=CHȬCOOHȱ
Spiteller 2007a) and the Bleeding Fairy Helmet leading to more highly hydroxylated terphenyl-
NHNH2NH
M. haematopus
NHNH 2NH2 2 (Pers.) P. Kumm. The blue san- quinones, hydroxypulvinic acids, cyclopentenones
2 2

guinones ACOOH and B (31) were isolated from M. san- COOH COOHCOOH and related HOOC
HOOC
HOOC compounds. In the intact fruit bodies,
COOH
COOH
guinolenta (Alb. & Schwein.) O OO
P. Kumm. (Peters N NN
atromentin Noccurs NN
in the form of its H NHH
colourless
NN
N NN
& Spiteller 2007b) andO Ored O haematopodins from precursors leucomentins. O OO
the fragile reddish-brown stems of M. haematopus Leucoderivative
H HH ofNH
NH atromentin
NH esterified with H HH
NHNH NH HNHN HN
(Hopmann O OO
& Steglich
NHNH NH
HNHN 2006;
HN Peters
N N N et al.
N NN2008). (2Z,4S,5S)-4,5-epoxyhex-2-enoic XX acid
X from N NNthe O OO
N NN O OO
These alkaloids O OO are exemplified by theCOOH minor pigment O OO lignicolous R RR
fungi Tapinella atrotomentosa (Batsch)
COOH
COOH
haematopodin (32), aȱȱȱȱbreakdown ȱȱȱȱȱȱȱȱ product of the labile Šutara ȱ (Tapinella
ȱ ȱȱȱ
ȱ ȱȱȱ ȱȱȱ ȱ ȱ ȱ ȱȱȱȱȱȱȱȱȱ
E.-J. Gilbert, ȱȱȱȱȱȱȱȱȱ
ȱȱȱȱȱȱȱȱȱ
Tapinellaceae) spo-ȱ ȱ ȱ
red29.ȱmycearubinȱAȱ
haematopodin
29.ȱmycearubinȱAȱ
29.ȱmycearubinȱAȱ B (32), which is30.ȱmycearubinȱBȱ
the main pigment rophore
30.ȱmycearubinȱBȱ
30.ȱmycearubinȱBȱ is leucomentin-2 (34)
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ
31.ȱsanguinoneȱA,ȱRȱ=ȱHȱȱ (Gill & Steglich
ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
ȱȱȱȱȱȱȱȱȱȱȱȱ32.ȱhaematopodin,ȱXȱ=ȱOȱ
ȱ ȱȱ ȱ ȱȱ ȱ ȱȱ ȱ ȱȱ ȱ ȱȱ ȱ ȱȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH
1987; Gill 1994; Liu 2006;3ȱHanson
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱsanguinoneȱB,ȱRȱ=ȱCH 3ȱ 3ȱ ȱȱhaematopodinȱB,ȱXȱ=ȱNH
2008b). This
ȱȱhaematopodinȱB,ȱXȱ=ȱNH
ȱȱhaematopodinȱB,ȱXȱ=ȱNH ȱ ȱ ȱ

O OO
C3HC3 C
H3H
C3HC3 C
H3H
O OO O OO OH
OHOH
O OO
C3HC3 C
H3H O OO
O OO

R RR O OO O OO OH
OHOH
O OO O OO O OO
O OO O OO
HO
HOHO O OO

OH
OHOH
O OO OH
OHOH 3CH
CHCH 3 3
R RR HO
HOHO O OO
ȱ ȱȱ ȱ ȱȱ ȱ ȱ ȱ ȱȱ ȱ ȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ
33.ȱpolyporicȱacid,ȱRȱ=ȱHȱȱ 34.ȱleucomentinȬ2ȱȱ
34.ȱleucomentinȬ2ȱȱ
34.ȱleucomentinȬ2ȱȱ 35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ
35.ȱflavomentinȱAȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱatromentin,ȱRȱ=ȱOHȱ

92
Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102

OH OH
O O OH OH OH OH
O O OH OH OH OH
O O O O
HO HO
O O O O
O O O O O O
HO HO
O O
O O O O
HO HO HO HO
CH 3 CH 3 R R OH OH
ȱ ȱ ȱ ȱ ȱ ȱ ȱ ȱ
36.ȱspiromentinȱAȱȱ
36.ȱspiromentinȱAȱȱ 37.ȱcycloleucomelone,ȱRȱ=ȱHȱ
37.ȱcycloleucomelone,ȱRȱ=ȱHȱ ȱ ȱ ȱȱȱȱȱȱ38.ȱthelephoricȱacidȱȱ
ȱȱȱȱȱȱ38.ȱthelephoricȱacidȱȱ
ȱȱȱȱȱȱȱcyclovariegatin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱȱcyclovariegatin,ȱRȱ=ȱOHȱ

compound and leucomentin-3, R

2
R -4, -5 and -6 were
2
quinone ring has been O oxidized
-
O
- and opened. The
- -
found in a number of O OOH other
OH
OH OH
fungi.OH Mushrooms
OH of unsubstituted O OO
O
parent
O
O
compound,
O O pulvinic acid,
the genus R
1 Tapinella
R
1 also produce small amounts of only
R Roccurs in the form of its methyl ester named
3 3
orange-yellow flavomentins A-D R and R violet spiro- vulpinic acid. Xerocomic and variegatic acids play
O O O O
mentins HO A-D HO (spiromentins E-J, derivatives of ben- the HO
HO most important role being responsible for
O O O O
zene-1,2,4,5-tetraol, are colourless)ȱ derived ȱ ȱ
from
ȱ
the blue colours acquired inȱ manyȱ
boletes after
atromentin. The flavomentins
39.ȱatromenticȱacid,ȱR
39.ȱatromenticȱacid,ȱR 1ȱ=ȱR12ȱ=ȱR23ȱ=ȱR constitute
ȱ=ȱHȱȱ 3ȱ=ȱHȱȱ diesters their fruiting bodies are injured, which results in
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ40.ȱchinonmethidȱanionȱofȱxerocomicȱacid,ȱRȱ=ȱHȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ40.ȱchinonmethidȱanionȱofȱxerocomicȱacid,ȱRȱ=ȱHȱ
andȱȱȱȱȱȱxerocomicȱacid,ȱR
monoesters of atromentin
1ȱ=ȱH,ȱR
ȱȱȱȱȱȱxerocomicȱacid,ȱR with
2ȱ=ȱOH,ȱR
1ȱ=ȱH,ȱR (2Z,4S,5S)-4,5-
2ȱ=ȱOH,ȱR 3ȱ=ȱHȱ 3ȱ=ȱHȱ the oxidation of these acids to the corresponding
ȱȱȱȱȱȱchinonmethidȱanionȱofȱvariegaticȱacid,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱchinonmethidȱanionȱofȱvariegaticȱacid,ȱRȱ=ȱOHȱ
epoxyhex-2-enoic
ȱȱȱȱȱȱgomphidicȱacid,ȱR and (2Z,4E)-hexa-2,4-dienoic
ȱȱȱȱȱȱgomphidicȱacid,ȱR1ȱ=ȱH,ȱR
1 ȱ=ȱR ȱ=ȱOHȱ
ȱ=ȱH,ȱR ȱ=ȱR ȱ=ȱOHȱ
2 3
2 3 blue chinonmethid anions (40). Pulvinic acids are
ȱȱȱȱȱȱisoxerocomicȱacid,ȱR
acids. ȱȱȱȱȱȱisoxerocomicȱacid,ȱR
The spiromentins 1ȱ=ȱOH,ȱR
1ȱ=ȱOH,ȱR
possess 2ȱ=ȱR23ȱ=ȱR
ȱ=ȱHȱ3ȱ=ȱHȱspiro
a unique especially widespread in mushrooms belonging to
ȱȱȱȱȱȱvariegaticȱacid,ȱR
structure in which a1ȱ=ȱOH,ȱR
ȱȱȱȱȱȱvariegaticȱacid,ȱR 1ȱ=ȱOH,ȱR 2ȱ=ȱOH,ȱR
2ȱ=ȱOH,ȱR
4,5-dihydroxybenzo-1,2- 3ȱ=ȱHȱ3ȱ=ȱHȱ
the Gomphidiaceae and Suillaceae families, to the
quinone is linked to a lactone acetal unit (Besl genera 3 3 Gomphidius
2 2
Fr. and
OH OH
Suillus Gary. The yellow
R R R R
et al. 1989). Flavomentin A (35) and spiromentin O pigment O gomphidic HO HO
acid (39) was found for the first
OH OH
A (36) exemplify these OH OH metabolites. time in the1 Slimy Spike-cap G. glutinosus (Schaeff.
1
HO HO R R O OO
Simple oxidation products of terphenylquinones O O
ex Fr.) Fr. (Knight & Pattenden 1976).
O
under the preservation O O of the central HO HO quinone OH OH
The yellow-brown cap
O and
O stem of the Larch
HO HO R
4
R
4
O O
ring include cycloleucomelone (37)
O O
ȱ ȱ
and cyclova- Bolete Suillus grevillei (Klotzsch) Sing.ȱ contain
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
O O
ȱ
at
riegatin (37), which is the precursor of the violet least 11 yellow, orange and red pigments derived
41.ȱ3ȇ,4ȇ,4Ȭtrihydroxypulvinoneȱ
41.ȱ3ȇ,4ȇ,4Ȭtrihydroxypulvinoneȱ OH 42.ȱgrevillinȱAȱ
42.ȱgrevillinȱAȱ ȱ ȱ ȱ ȱ 43.ȱgomphilactoneȱ
43.ȱgomphilactoneȱ
thelephoric acid (38). O Cycloleucomelone occurs from decarboxylated pulvinic acids, of which 3',4',4-
ȱȱ ȱȱ ȱȱȱgrevillinȱBȱ ȱȱȱgrevillinȱBȱ OH OH
in the fruiting bodies O of Boletopsis leucomelaena trihydroxypulvinone OH (41) is the major pigmentOH
ȱȱ ȱȱ ȱȱȱgrevillinȱCȱ ȱȱȱgrevillinȱCȱO O
(Pers.) Fayod (Boletopsis Henn., Suillaceae) (Jägers ȱȱȱgrevillinȱDȱ
(Besl
ȱȱȱgrevillinȱDȱ
& Bresinsky 1997). Cyclovariegatin (37)
HO
et al. 1987) and is accompanied O by a series of is also partly responsible for its colour O (Edwards
colourless HO
analogues O containing five, four and O O & Gill O 1973). O
O O
three acetyl residues. O Cyclovariegatin occurs O in
O
O
O
O
In the pathway leading to atromentin,
O O O
instead of
this mushroom as the colourless peracetate HO HO
HO HOof the two C-C bonds only one HO C-CHO bond may be formed.
CH 3 R OH O grevil-
O
leucoform (Edwards & Gill 1973). TheO resulting
O lactonisation then yields
The major pigments of the order Boletales
36. spiromentin A
are lins (42). Grevillins A, B, C38.
37. cycloleucomelone,O R =OH
and D are a group of
thelephoricOacidO
the yellow pulvinic acids (39) that are formed
HO O
HO cyclovariegatin, Ocharacteristic
HO HO R = OH
orange to red
HO HO 2H-pyran-2,5(6H)dione
O O
HO HO
through lactone O formation,
O after
OH OH the terphenyl- O O pigments that occur only inOtheOfruiting body of
OH OH HOOCHOOC HOOCHOOC HOOCHOOC HOOCHOOC
O O
2 –
R OH OH O OH OH
R R –
O OH OH O O O
O O OH O
HO HO R1 O O
3 R
OH OH R OH OH OH OH
O ȱȱȱ ȱȱȱ ȱȱȱO ȱȱȱ ȱ ȱ
HO HO
O O ȱȱȱȱȱȱȱȱȱȱȱ46.ȱnorbadioneȱAȱ
44.ȱxerocomorubin,ȱRȱ=ȱHȱȱ
44.ȱxerocomorubin,ȱRȱ=ȱHȱȱ ȱ45.ȱbadioneȱAȱ
ȱ45.ȱbadioneȱAȱȱ ȱ ȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱ46.ȱnorbadioneȱAȱ
ȱȱȱȱȱȱvariegatorubin,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱvariegatorubin,ȱRȱ=ȱOHȱ
39. atromentic acid, R1 = R2 = R3 = H 40. chinonmethid anion of xerocomic acid, R = H
xerocomic acid, R1 = H, R2 = OH, R3 = H chinonmethid anion of variegatic acid, R = OH
gomphidic acid, R1 = H, R2 = R3 = OH
isoxerocomic acid, R1 = OH, R2 = R3 = H
variegatic acid, R1 = OH, R2 = OH, R3 = H

R
3
R
2
OH
OH
O HO 93
OH
1
HO R O O
O
O HO OH O
HO R
4
O
O O
Vol. 29, 2011, No. 2: 87–102 Czech J. Food Sci.

R
3
R
2
OH
O HO
OH
OH
1
HO R O O
O
O HO OH O
HO OH 4
O O R O
OH O OH
ȱ ȱȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱ ȱ
O OH OH
41.ȱ3ȇ,4ȇ,4Ȭtrihydroxypulvinoneȱ O
42.ȱgrevillinȱA,ȱR1ȱ=ȱR3ȱ=ȱR4ȱ=ȱH,ȱR2ȱ=ȱOHȱ O
43.ȱgomphilactoneȱ
ȱȱ HO
ȱȱȱgrevillinȱB,ȱȱR1ȱ=ȱR3ȱ=ȱH,ȱR2ȱ=ȱR4ȱ=ȱOHȱ
O O
O ȱȱ ȱȱȱgrevillinȱC,ȱȱR
O
1ȱ=ȱR2ȱ=ȱR4ȱ=ȱOH,ȱR3ȱ=ȱHȱ
O
HO
O ȱȱȱgrevillinȱD,ȱȱR1ȱ=ȱR3ȱ=ȱR4ȱ=ȱOH,ȱR2ȱ=ȱHȱ
O O
HO
mushrooms
 belonging to the genus Suillus Gray. Norbadione A (46)HOis the dominating compound
CH 3 R OH
S. grevillei (Klotzsch) Sing. and ȱ S. luteus (L. ex Fr.) in the dying ȱ ȱ mushroom Pisolithus arrhizus (Scop.) ȱ
S.36.ȱspiromentinȱAȱȱ
F. (Slippery Jack) contain grevillins A, B and C,
37.ȱcycloleucomelone,ȱRȱ=ȱHȱ Rauschert (Pisolithus
ȱ Alb. & Schwein, Scleroder-
ȱȱȱȱȱȱ38.ȱthelephoricȱacidȱȱ
S. granulatus (L. ex Fr.) O. Kuntze ȱȱȱȱȱȱȱcyclovariegatin,ȱRȱ=ȱOHȱ
(Weeping Bolete) mataceae) where it occurs in amount of over 25%
contains grevillins B, C and D, of which the major of the dry weight of the fungus. Badione A (45) and
pigment is grevillin D (Besl 2 et al. 1974). several similar compounds - are minor components
R O
The colourless,
O OHbut easily oxidisable 1,2,4-tri- (Winner O
et- al. 2004).
O
OH O
OH O
hydroxybenzene
1
and its derivatives commonly Oxidative coupling of two molecules of xerocomic
occurR in mushrooms belonging R
3 to the Gomphi- Racid (39) yields bright yellow sclerocitrin (47) oc-
diaceae family and O to the genus Suillus Gray. The curring in the O fruiting bodies of the common Earth
HO HO
oxidation products of 1,2,4-trihydroxybenzene Ball Scleroderma
O O citrinum Pers. (Scleroderma Pers.,
include the red gomphilactone ȱ ȱ
(43) and the cor- Sclerodermataceae) together ȱ with norbadione A
39.ȱatromenticȱacid,ȱR1ȱ=ȱR2ȱ=ȱR3ȱ=ȱHȱȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ40.ȱchinonmethidȱanionȱofȱxerocomicȱacid,ȱRȱ=ȱHȱ
responding biphenyls. Variegatorubin (44) and (46) as the main pigments, which are accompa-
ȱȱȱȱȱȱxerocomicȱacid,ȱR1ȱ=ȱH,ȱR2ȱ=ȱOH,ȱR3ȱ=ȱHȱ ȱȱȱȱȱȱchinonmethidȱanionȱofȱvariegaticȱacid,ȱRȱ=ȱOHȱ
xerocomorubin (44) exemplify
ȱȱȱȱȱȱgomphidicȱacid,ȱR1ȱ=ȱH,ȱR2ȱ=ȱR3ȱ=ȱOHȱ
the red pigments nied by xerocomic acid (39) and badione A (45)
formed from pulvinic acids
ȱȱȱȱȱȱisoxerocomicȱacid,ȱR 1ȱ=ȱOH,ȱR by 2the
ȱ=ȱR3second
ȱ=ȱHȱ lactone (Winner et al. 2004).
ring production (Besl & Bresinsky
ȱȱȱȱȱȱvariegaticȱacid,ȱR ȱ=ȱOH,ȱR ȱ=ȱOH,ȱR ȱ=ȱHȱ
1 2 3 1997). Sclerocitrin is the main pigment of the lemon-
High concentrations of radionuclides occurring in yellow coloured stalk base of the Peppery Bolete
the fruiting bodies of the Bay Bolete Boletus badius R Chalciporus
3
R
2
piperatus OH(Bull.) Bataille (Chalciporus
O HO
(Fr.) Fr. (Boletus Fr.,OHBoletaceae) after the nuclear reac- Bataille, Boletaceae). It is accompanied by the sec-
OH
1
torHO accident at Chernobyl have been ascribed to the ond yellow R pigment chalcitrinO(48), O
norbadione A
complexation of 137Cs by the so called HOnaphthalenoid O (46),
OH variegatic acid (39) and variegatorubin (44)
O O
pulvinic
HO acids that occur
O
as their potassium R
4
salts inO (Winner et al. 2004). O
the cap skin of this toadstool. Theȱ main compounds ȱȱȱȱȱȱȱȱȱ
The decarboxylation ȱ
products of pulvinic acids,
are badione A (45) and norbadione A (46)
41.ȱ3ȇ,4ȇ,4Ȭtrihydroxypulvinoneȱ that are 2,5-diarylcyclopentenones,
42.ȱgrevillinȱAȱ ȱ ȱ appear in fungi almost as
43.ȱgomphilactoneȱ
responsible for the chocolate brown ȱȱ ȱȱȱgrevillinȱBȱ
and golden frequently as terphenylquinones. Typical examples
yellow colours of cap skin of this bolete ȱȱ ȱȱȱgrevillinȱCȱ
and related are chamonixin (49), involutin (49) and the more
bolete species (Aumann et al. 1989). ȱȱȱgrevillinȱDȱ highly oxidised gyrocyanin (50) and gyroporin (50).
O
O O
O O
HO HO
O O

O O
HO O HO O
HO HO
O OH O O
OH HOOC HOOC HOOC HOOC
O
R OH OH
O
HO O

OH OH OH
ȱȱȱ ȱȱȱ ȱ
44.ȱxerocomorubin,ȱRȱ=ȱHȱȱ ȱ45.ȱbadioneȱAȱ ȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱ46.ȱnorbadioneȱAȱ
ȱȱȱȱȱȱvariegatorubin,ȱRȱ=ȱOHȱ

94
Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102

O
COOH OH
OH O
O
H
O HO HO
O H
H H
O
H O
O HO O
O HO

O HOOC HOOC
O
OH
OH
COOH

HO OH
ȱȱ ȱȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ47.ȱsclerocitrinȱȱ ȱ ȱ 48.ȱchalcitrinȱȱ

They occur e.g. in severalHOfamilies OHof Boletales, in the that

HO occurs O in S. granulatus (L. ex O Fr.) O.O Kuntze.
R
genera Chamonixia Rolland (Boletaceae), Gyrodon Its oxidationR products are responsible for the caps’
Opat. (Paxillaceae), Gyroporus Quél. (Gyroporaceae), brown colour. Prenylated benzoquinones, corre-
HO OH HO OH HO O
Leccinum Gray (Boletaceae), O Melanogaster Corda spondingO to 1,2,4-trihydroxybenzeneO-(mentioned
ȱ ȱ ȱ
(Melanogasteraceae), Paxillus Fr. (Paxillaceae) and above), mostly appear as meroterpenoids named
several other 49.ȱchamonixin,ȱRȱ=ȱHȱ
families and genera. The pigments are ȱȱ50.ȱgyrocyanin,ȱRȱ=ȱHȱȱ
boviquinones. Boviquinone-3 ȱ 51.ȱblueȱanionȱofȱgyrocyaninȱ
(2,5-dihydroxy-
ȱȱȱȱȱȱȱinvolutin,ȱRȱ=ȱOHȱȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱgyroporin,ȱRȱ=ȱOHȱ
responsible for the conspicuous deep brown and 3-farnesyl-1,4-benzoquinone) is biosynthesised
bright blue colour reactions OH observed when the by Chroogogompus rutilus (Schaeff.) O.K. Mill.,
fruiting bodies of mushrooms OH are bruised. Involutin Chroogomphus (Singer) O.K . Mill. (Gomphi-
occurs in P. involutus (Batsch ex Fr.) Fr. (chamonixin diaceae), bovinoquinone-4 O
(2,5-dihydroxy-3-gera-
O
CH3
is a minor compound); chamonixin is a constituent nylgeranyl-1,4-benzoquinone, COOH 53) is an example
OH
of
COOH OH O
OH in Suillus bovinus
in C. caespitosa H3 CRolland
O and gyrocyanin
CH3 CHin3 G. cya-
O
CH3 prenylated
CH3 OH benzoquinones O found
O H
O HO of the (L.) Roussel. H HO (Mühlbauer et al. 1998). The red
nescens (Bull. exOFr.) Quél. The colour changes
OHO HO
latter mushroom are associated with the Hrelated me- pigment O ȱ
tridentoquinone (54) is the main
H pigment
O H
H 52.ȱsuillinȱ of S. tridenticus O H
(Bres.) Singer, which is related
tabolite of gyrocyanin, which is oxidised to the blue H O H
H O
O to the linear boviquinone-4
HO O(53) from S. bovinus
anion (51) (Feling O et al. 2001; Hanson
O
O 2008b). HO HO O
O HO
The prenylated compounds occur only O
rarely (L.) Roussel. In the mushroom, tridentoquinone
HOOC
H3 C O CH 3 CH HOOC
HOOC CH 3 CH3 CH 3 CH 3
in Boletales Obeing biosynthesised HOOC O from 3,4-dihy-
3
OH
is accompanied
O
by several compounds H3 C of similar
OH O H O
droxybenzoic acidCH (Besl
3 & Bresinsky
OH OH1997). HThe structureOH
OH (Lang et al. 2008). Mushrooms CH 3
of the OH
3C
aromatic ring often COOHbears an additional farnesyl
COOH genus Rhizopogon Fr. (i.e. Rhizopogon pumilionum
C O (Ade) Bataille), closelyOH related to the genus
or geranylgeranyl side-chain HO HO derived fromH3the OH HO Suil-
HO
terpenoid pathway. SuillinO(52) is an CH3exampleȱȱ of lusO Gray, contain
CH3 rhizopogone
ȱȱ (55) as the main
O CH 3
ȱ ȱ ȱ ȱ
acetylated and prenylated 1,2,4-trihydroxybenzene
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ47.ȱsclerocitrinȱȱ ȱ 47. sclerocitrin
ȱ pigment (Lang et al. 2009).
48.ȱchalcitrinȱȱ 48. chalcitrin
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ53.ȱboviquinoneȬ4ȱȱ 54.ȱtridentoquinoneȱ 55.ȱrhizopogoneȱ
HO OH HO O O O
HO OH HO RO O O
R R
R
HO OH HO OH HO O
HO OH HO OH HO O -
O O O O - O
O O O
H ȱ ȱ ȱ
H3 COOC N 49. chamonixin,ȱȱ50.ȱgyrocyanin,ȱRȱ=ȱHȱȱ
R=H 50. CH
gyrocyanin,
3 R = H 51. blue anion of gyrocya
49.ȱchamonixin,ȱRȱ=ȱHȱ H ȱ 51.ȱblueȱanionȱofȱgyrocyaninȱ
involutin, R = OH CH3 gyroporin, R = OH
ȱȱȱȱȱȱȱinvolutin,ȱRȱ=ȱOHȱȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱgyroporin,ȱRȱ=ȱOHȱ ȱ
OH
56.ȱmelanocrocinȱ
OH
OH
OH
O
CH3
CH3 H3 C
H3 C CH 3 CH 3 CH 3
H3 C O CH3 CH3 CH3 CH3
H3 C O CH3 CH3 CH3 CH3
O
O CH CH 3 H3 C CH3
52. suillinȱ
3
CH 3
O 52.ȱsuillinȱ ȱ
57.ȱcanthaxanthinȱ 95
H3 C CH 3 CH 3 CH3
H3 C CH 3 CH 3 CH 3 CH 3 CH3 H3 C CH 3 H3 C
CH
CH 3
O O 3
O
O O H O
CH3 H
CH3 OH H3 C OH CH 3 O
OH H3 C OH CH 3 OH

HC
 CH3

H3 C O CH3 CH3 CH3 CH3

O
Vol. 29, 2011, No. 2: 87–102 ȱ Czech J. Food Sci.
O
52.ȱsuillinȱ
COOH O
OH
COOHOH O
O OH
OH H O
O HOO HO
H3 C CH 3 CH 3 CH 3 CH3 H3 C H
CH CH 3
O HO HO 3
O O O O H
H H
CH3 OH O OH CH 3 O H HOH
H H3 C H H
O O
O H HO O
O H3 C HO
O O
HO O
HO O HO HO
O
O HOOC O CH3 HOOC
O CH3 O CH 3
ȱ O OOH HOOC ȱ HOOC ȱ
O OH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ53.ȱboviquinoneȬ4ȱȱ OH 54.ȱtridentoquinoneȱ 55.ȱrhizopogoneȱ
OH
COOH
COOH
Melanocrocin (56) is aHOunique brilliant yellow OH
Karst., the polyporeOH with a red-brown fruiting
HO
polyene pigment, with bound phenylalanine, iso- body (Bu’Lock et al. 1962), where it is accompa-
47. sclerocitrin 48. chalcitrin
lated from the
H
Osubterranean fungus
47. Melanogaster
sclerocitrin
O
nied by bisnoryangonin (25), hypholomin B (58)
48. chalcitrin
broomeianus
H3 COOC N that resemble truffles
HO (Aulinger
OH and
CH3 the yellow
HO pigment
O hispolon (26, R = OCH 3) O
et al. 2001).H HO OH R
CH3 (Ali et al. 1996).
HO These
O
R pigments also occur O in O
R
ȱ
several mushrooms R of the Hymenochaetaceae
HO OH HO OH HO O
56.ȱmelanocrocinȱ
HO O OH family,
HO e.g. in Inonotus
O P. Karst.,
OH Onnia
HO P. KarstenO
-
O
3 Cantharellales O -
and Phellinus Quél. O species and in the genus Hy- O
49. chamonixin, R = H O 50. gyrocyanin, R = H 51. blue anion of gyrocyani
pholoma (Fr.) P. Kumm. of the Strophariaceae
49. chamonixin,
involutin, R R= =OH
H H3 C 50. gyrocyanin,
gyroporin, RR==OHH 51. blue anion of gyrocyani
Carotenoids
H3 C CH 3 are3 not widespread
CH CH 3 in higher fungi as family (Agaricales). Inoscavin A, reported to be
involutin, R = OH gyroporin, R = OH
they are in plants; nevertheless,OH they were isolated a free radical scavenger, isolated from the fruit-
from several yellow pigmentedOH Cantharellus
OH
CH CHJuss. H3 C ing
CH3bodies of the mushroom P. xeranticus (Berk.)
3 3
CH 3
(Cantharellaceae) species. The Golden OH Chanterelle Pegler (Phellinus, Hymenochaetaceae) has been
O CH3
C. cibarius Fr. pigment mixture was found to consist assigned ȱ the fusedCH3 styrylpyrone structure (59),
mainly of β-carotene57.ȱcanthaxanthinȱ
and also
H3 C present
O wereCH lycopene,
3 CH3 whichCH relates
3 inoscavin
CH3 A closely to hispidin (25)
H3 C O CH3 CH3 CH3 CH3
α-carotene and two other carotenes, O
probably the and thence to hypholomin B (58).
γ- and δ-isomers or the xanthophyl O canthaxanthin52. suillin
(57) that was found in the pink to red-orange 52.Cin-
suillin
nabar Chanterelle C. cinnabarinus (Schwein.) Sch- 5 Polyporales
wein. as the main pigment (Haxo 1950; Hanson
2008b). H3 C CH 3 CH 3 CH 3 CH3 CH 3 C
H3 C CH 3O CH 3
Species withinCH O
the
CH3
order Polyporales areH3sapro-
C
H 3 H3 C CH 3O C
CH3 O OH
trophic
H3 C
and
H
most
O of them wood-rotters. The Poly-
OH CH 3 O OH
CH3 OH poraceae are a family of such wood-decay fungiCH
OH that
H3 C 3 OH
4 Hymenochaetales HO contain
H3 C Opigments mostly derived from polyporic
HO
H3 C O
HO O CH3 acids and terphenylquinones.
O CH3 The dark red poly- HO O
Styrylpyrone hispidin (25) was originally O isolated
CH3 poric acid (33), O CH3
the parent compound of numerous O
as the main constituent of the 53. plant
boviquinone-4
pathogen terphenylquinones 54. tridentoquinone and related compounds, is the 55. rhizopog
53. boviquinone-4 54. tridentoquinone 55. rhizopog
the Chaga Fungus Inonotus hispidus (Bull.) P. major component of Hapalopilus nidulans (Fr.)

O O
HO O
H3 COOC HN CH3
H3 COOC H
N CH3 CH3
H
CH3
56. melanocrocin
56. melanocrocin

O
H3 C O
H3 C CH 3 CH 3 CH 3 H3 C
H3 C CH 3 CH 3 CH 3

CH3 CH 3 H3 C CH3
CH 3 CH3 CH 3 H3 C CH3
O CH 3
O
57. canthaxanthin
57. canthaxanthin

96
Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102

O
CH3

O O
O
HO
O O O
HO HO
O O
HO HO
OH OH
OH OH
58. hypholomin B 59. inoscavin A

P. Karst. (Hapalopilus P. Karst.) amounting up The striking

OH O yellowish or orange-coloured fruit-
OH
to 43% of its dry weight. Betulinans A (60) and B ing HO bodies of the wood-rottingOH edible mushroom
O O
(61) are two simple terphenylquinones recently Laetiporus sulphurous (Bull.) Murrill (Laetiporus O O
H CO O
found in the 3plant pathogen Lenzites betulina (L.) Murrill), HO belonging to the Fomitopsidaceae family,
Fr. (Lenzites Fr.) (Lee etOCH al. 1996; Gill 1999). The OCH3
contains non-isoprenoid polyene known as laetiporicN NH2
3
labile 2,3,4-trihydroxycinnamylO alcohol is the O build- acid A (predominantly occurring as the 7-cis-isomer,
COOH
HO OH
ing block of the purpurogallin (benzotropolone) 66) and 2-dehydro-3-deoxylaetiporic acid A (67)
derivative fomentariol
60. betulinan A (62) produced 61. by the plant
betulinan B as the 62.main pigments (Davoli et al.
fomentariol 63.2005).
cinnabarinic acid
pathogen, the Tinder Fungus, Fomes fomentarius
O
(L.) Fr. of the genus Fomes (Fr.) Fr. (Polyporaceae)
OCH3
OH HO
(Steglich & Zechlin 1978). 6 Russulales
OH
Pigments with a phenoxazine O chromophore
O
widely occur in lichens and to O
a smaller extent Apart from carotenoids, only a few lower ter-
H3 CO
in higher fungi of the Polyporaceae family. The R penoids areO coloured compounds. The colour of
OCH3
cinnabar red pigment HO of the wood-rotting fungus HO
the injured flesh as well as of the latex of several
Pycnoporus cinnabarinus (Jacq.) P. Karst. (Pycnopo- Lactarius Pers. (Russulaceae) species own to their
rus P. Karst.) is 2-amino-3H-phenoxazin-3-one-
64. corticin A colour changes
65. xylerythrin, R=H to sesquiterpenoids. The young
1,9-dicarboxylic acid named cinnabaric acid (63). peniophorin, fruiting body R = OHof L. deliciosus (L. ex Fr.) S. F. Gray
It is biosynthesized from 3-hydroxyanthranilic acid is first carrot-coloured, but slowly turns green
H3 C O
units formed as the tryptophan transformation on aging. The young L. deterrimus Gröger fruit-
products (Gripenberg 1958a). ing body CH is 3pale peach coloured and becomes
The cobalt Crust Fungus Terana caerulea (Lam.) apricot coloured with a greyish green shades on
Kuntze (Terana Adans.) of the Phanerochaetaceae aging. On cutting, L. deterrimus yields saffron or
family contains O
HOOC corticins A (64), B and C as the orange coloured latex. These colour changes are
colourless quinhydrones OH that are oxidized to the due to sesquiterpenoids CH3 derived from azulene. The
indigo-blue pigmentOin hymenal surface (Briggs compounds responsible O for these colour changes
66. laetiporic acid A O
et al. 1976). HOThe saprophytic fungus Phanerochaete in L. deliciosus are the blue lactarazulene, i.e.
O O O
sanguine
HO (Fr.) Pouzar (Phanerochaete P. Karst.) con-HO H1,4-dimethyl-7-(1-methylethenyl)azulene
3C O (68), and
O O
tains xylerythrin-type pigments (65). Their struc- lipophilic red-violet lactaroviolin, i.e. 4-methyl-
HO HO
tures suggest a biosynthesis from threeOH molecules of 7-(1-methylethenyl)azulene-1-carbaldehyde
CH3 OH (68).
arylpyruvic acids. The wood infected OH by this fungus is However, neither lactarazulene
OH nor lactaroviolin
ȱȱ
then coloured dark red by its mycelium (Gripenberg occurs as such. The orange colourȱ of the fungus
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ58.ȱhypholominȱBȱȱ
1965; Gripenberg & Martikkala ȱ 1970). ȱ ȱ ȱȱȱȱȱ59.ȱinoscavinȱAȱ
is due to the labile and easily oxidizable dihy-
OH O
OH
HOOC HO OH
O O
H3 CO O O O
67. 2-dehydro-3-deoxylaetiporic acid
HO A

OCH OCH3 H3 C N NH2

H3 C3 H3 C
O O COOH
HO OH
ȱ ȱ ȱ ȱ
ȱȱȱȱ60.ȱbetulinanȱAȱȱ ȱȱȱȱȱȱ61.ȱbetulinanȱBȱ ȱȱȱȱȱȱȱȱ62.ȱfomentariolȱȱ ȱ ȱȱ63.ȱcinnabarinicȱacidȱ
CH 2 CH 3
R RO CH2 O
H3 C H3 C O H3 C
OCH3
OH HO 97
68. lactarazulene,
O
R = CH3OH 69. dihydroazulen-1-ol (R = H) 70. 1,3,5,7(11),9-pentaenyl-14-guaianal
lactaroviolin, R = CH=O O
H3 CO O
R
O
OCH3
 O OH
O O
OH
H3 CO HO
O OO O
O OH
O HO O
H3 CO O R O
H3 CO O
O OCH3 HO OCH3 OCH3 NO NH2
HO HO COOH
O O CH3 HO ȱN OH ȱ NH2
Vol. 29, 2011,OCH
No.3 2: 87–102 OCH3
ȱ ȱ Czech ȱ J. Food Sci.
COOH
O O O ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ64.ȱcorticinȱAȱȱ
HO O ȱ ȱ OH 65.ȱxylerythrin,ȱRȱ=ȱHȱ
HO ȱȱȱȱ60.ȱbetulinanȱAȱȱ
ȱ ȱȱȱȱȱȱ61.ȱbetulinanȱBȱ
ȱ O ȱȱȱȱȱȱȱȱ62.ȱfomentariolȱȱ
ȱ ȱ ȱȱ63.ȱcinnabarinicȱacidȱ
ȱ
ȱ ȱO ȱ ȱ ȱ ȱȱȱȱȱȱpeniophorin,ȱRȱ=ȱOHȱ
O O
ȱȱȱȱ60.ȱbetulinanȱAȱȱ
HO ȱȱȱȱȱȱ61.ȱbetulinanȱBȱ ȱȱȱȱȱȱȱȱ62.ȱfomentariolȱȱ
HO ȱO ȱȱ63.ȱcinnabarinicȱacidȱ
O OCH3 O H3 C O
OH HO
HO OHO
OCH3 OH
OH O OH HO OH CH3
O OH
O OHOH ȱȱO ȱ
H3 CO R
O
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ58.ȱhypholominȱBȱȱ ȱ O
O OCH3ȱ ȱ
HOOC
ȱȱȱȱȱ59.ȱinoscavinȱAȱ
H3 CO HO R
O HO
OCH3 ȱ OH O OH ȱ ȱ
HO HO OH
O
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ64.ȱcorticinȱAȱȱ
ȱ O ȱ ȱ 65.ȱxylerythrin,ȱRȱ=ȱHȱ
OH HOȱ
66.ȱlaetiporicȱacidȱAȱ
ȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ64.ȱcorticinȱAȱȱ
H CO ȱ ȱ Oȱ
ȱ ȱ ȱ
65.ȱxylerythrin,ȱRȱ=ȱHȱ ȱȱȱȱȱȱpeniophorin,ȱRȱ=ȱOHȱ O O
3
HO H3 C O
ȱ ȱ ȱ ȱ ȱ ȱȱȱȱȱȱpeniophorin,ȱRȱ=ȱOHȱ H3 C O
OCH3 OCH3 N NH2

O H3 C O COOH CH3
O HO OH
CH3
ȱ ȱ ȱ ȱ
CH3
ȱȱȱȱ60.ȱbetulinanȱAȱȱ ȱȱȱȱȱȱ61.ȱbetulinanȱBȱ ȱȱȱȱȱȱȱȱ62.ȱfomentariolȱȱ ȱ ȱȱ63.ȱcinnabarinicȱacidȱ
HOOC
O
OCH
OH3
HOOC OH HO ȱ
OH OH HOOC
O 66.ȱlaetiporicȱacidȱAȱ
ȱ ȱ
O
66.ȱlaetiporicȱacidȱAȱ
O 67.ȱ2ȬdehydroȬ3ȬdeoxylaetiporicȱacidȱAȱ
HC O
H3 CO R 3
O
OCH3 HC O HC H3 C
droazulen-1-ol HO (69, R=H) or to their stearates, 3
HO uvidin A 3
and B (71) CH3 illustrate the broad variety of
ȱ ȱ
69, R = CO[CH 2] 16CH 3. Recently, three other redCH compounds found in L. uvidus (Fr.) Fr. Drimane
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ64.ȱcorticinȱAȱȱ
azulene pigments haveȱ been isolated ȱ 65.ȱxylerythrin,ȱRȱ=ȱHȱ 3
from the sesquiterpenoids like drimenol (72) and uvidins
ȱ
fruiting ȱ
bodies ȱ L. deliciosus
of ȱ ȱbeing 7-acetyl-4-
ȱȱȱȱȱȱpeniophorin,ȱRȱ=ȱOHȱ have CH
R so far been 2found only RO in L. uvidus,CHwhich 2

methylazulene-1-carbaldehyde, 7-(1,2-dihydroxy-H3 C hasO a white3 latex rapidly H C turning H3 C on expo-

violet
ȱ ȱ ȱ ȱ ȱȱȱȱȱȱȱȱ
1-methylethyl)-4-methylazulene-1-carbaldehyde sure to the air.
HOOC 68.ȱlactarazulene,ȱRȱ=ȱCH3ȱ ȱȱȱȱȱȱȱȱȱ69.ȱdihydroazulenȬ1Ȭolȱ(Rȱ=ȱH)ȱ 70.ȱ
and 7-acetyl-4-methylazulene-1-carboxylic acid Intact
CH3 fruiting bodies ȱ of Lactarius fuliginosus
ȱȱȱȱȱȱlactaroviolin,ȱRȱ=ȱCH=Oȱ
HOOC
(Xang et al. 2006; Zhou & Liu 2010). The red ȱ(Krapf ) Fr. and L. picinus Fr. contain the isoprenoid
67.ȱ2ȬdehydroȬ3ȬdeoxylaetiporicȱacidȱAȱ
pigment 1,3,5,7(11),9-pentaenyl-14-guaianal (70) quinol stearate of 4-methoxy-2-(3-methylbut-2-
67.ȱ2ȬdehydroȬ3ȬdeoxylaetiporicȱacidȱAȱ
H3 C(Paulet) Fr., the li- H3 C
was HOOC found in L. sanguifluus enyl)phenol (73). The pink-red stain and acrid H3 C
OH
pophilicH3 Cpigment 1-hydroxymethyl-4-methyl- H3 C taste that develops when the toadstool is bruised
ȱ H3 C
7-(1-methylethenyl)azulene stearate; 68, R = are due to its hydrolysis followed by oxidation to
66.ȱlaetiporicȱacidȱAȱ
CH 2OCO[CH 2] 16CH 3, is RresponsibleCH 2 the bril- ROa variety ofCH
for red benzofurans and chromenes (De CH 3
2 O
liant blue colour CH of the Indigo Milk H3 C Cap L. indigo H3 C O Bernardi H3 C et al. 1992). CH 3 H3 C
R 2 RO ȱ ȱ CH2 ȱ Oȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ ȱ
(Schwein.) Fr.
H3 C
(native to America and H3 C
Asia and The pale green aminobenzoquinone blennione
H3 C
also reported from68.ȱlactarazulene,ȱRȱ=ȱCH
ȱ ȱ
southern France) (Harmon 3ȱ ȱȱȱȱȱȱȱȱȱȱ69.ȱdihydroazulenȬ1Ȭolȱ(Rȱ=ȱH)ȱ
ȱ
CH3(74) occursȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ
in the fruit bodies 70.ȱ1,3,5,7(11),9ȬpentaenylȬ14Ȭguaianalȱ
of the ȱ common
et al. 1980; Ayer & 3ȱBrowne ȱȱȱȱȱȱlactaroviolin,ȱRȱ=ȱCH=Oȱ
1981; Koul et al. toadstool, the Slimy Milkcap Lactarius blen-
68.ȱlactarazulene,ȱRȱ=ȱCH ȱȱȱȱȱȱȱȱȱ69.ȱdihydroazulenȬ1Ȭolȱ(Rȱ=ȱH)ȱ 70.ȱ1,3,5,7(11),9ȬpentaenylȬ14Ȭguaianalȱ
1985; De Rosa & De Stefano 1987).
ȱȱȱȱȱȱlactaroviolin,ȱRȱ=ȱCH=Oȱ nius (Fr.) Fr. It is probably biosynthesized using
The milky juice of L. scrobiculatus (Scop.) Fr. 3,6-dihydroxyanthranilic acid units (Spiteller &
turns rapidly from white to yellow. A range of Steglich 2002). Biosynthetically closely related to
lactarane
HOOC and secolactarane sesquiterpenoids, bennione is the red pigment lilacinone (75), which
analogues of the above azulenes, have been iso- isȱ responsible for the violet colour of Lactarius
lated (Bosetti 67.ȱ2ȬdehydroȬ3ȬdeoxylaetiporicȱacidȱAȱ
et al. 1989). The structures of lilacinus (Lasch) Fr. (Spiteller et al. 2003).
H3 C H3 C H3 C

CH 2 CH 3
R RO CH2 O
H3 C H3 C H3 C
ȱ ȱ ȱ ȱ ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ ȱ
68.ȱlactarazulene,ȱRȱ=ȱCH3ȱ 69.ȱdihydroazulenȬ1Ȭolȱ(Rȱ=ȱH)ȱ
ȱȱȱȱȱȱȱȱȱ 70.ȱ1,3,5,7(11),9ȬpentaenylȬ14Ȭguaianalȱ
ȱȱȱȱȱȱlactaroviolin,ȱRȱ=ȱCH=Oȱ

98
 Czech J. Food Sci. Vol. 29, 2011, No. 2: 87–102

OH OH
OH OH OCH3
OCH3
H3 C H3 C
H3 C CH3 H3 C CH3
CH3 CH3
O
O CH 3
R CH 3
R H H
H C CH
H H OH CH3
H3 C CH33 O 3O H C CH3 OH CH3
ȱ ȱ ȱ ȱ ȱ ȱ ȱ ȱ ȱ
H3 C CH33
ȱ ȱ
71.ȱuvidinȱA,ȱRȱ=ȱHȱ ȱ
71.ȱuvidinȱA,ȱRȱ=ȱHȱ ȱ ȱȱ72.ȱdrimenolȱȱ
ȱȱ72.ȱdrimenolȱȱ ȱ ȱ ȱ 73.ȱ4ȬmethoxyȬ2Ȭ(3ȬmethylbutȬ2Ȭenyl)phenolȱ
73.ȱ4ȬmethoxyȬ2Ȭ(3ȬmethylbutȬ2Ȭenyl)phenolȱ
ȱȱȱȱȱȱuvidinȱB,ȱRȱ=ȱOHȱ
ȱȱȱȱȱȱuvidinȱB,ȱRȱ=ȱOHȱ

O HO
O HO
H2 N OH N
OCH 3 O N
OCH 3 OH
O H2 N OH OH OH OCH3 OH
OCH3
OCH3 OCH3
H N COOH
H2 N H32C COOH H3 CH3 C H3 C
CH3 HOOC CH3 CH3 N CH3
HOOC N NH2 N
O H NH2 N
HOOC NH2 HO
O O CH 3
HOOC NH2 O O CH 3
R R O O COOH
H OH O H H O O COOH H O OH
OH O ȱ O OH
H3 C CH3 O
ȱ ȱȱ
C 3CH3 O
H3 CH3CH
ȱ ȱ ȱȱ ȱ ȱ ȱ OH ȱ ȱ 3
H3 C CH CH3
ȱ
ȱ CH3 OHȱ
ȱ ȱ ȱ
ȱȱȱȱȱȱȱȱȱȱ74.ȱblennioneȱ
ȱȱȱȱȱȱȱȱȱȱ74.ȱblennioneȱ 75.ȱlilacinoneȱ
75.ȱlilacinoneȱ ȱ ȱ ȱ ȱ ȱ ȱ ȱȱȱȱȱȱȱȱ76.ȱnecataroneȱ
ȱȱȱȱȱȱȱȱ76.ȱnecataroneȱ
71.ȱuvidinȱA,ȱRȱ=ȱHȱ ȱ ȱȱ72.ȱdrimenolȱȱ
71.ȱuvidinȱA,ȱRȱ=ȱHȱ ȱ ȱ ȱ 73.ȱ4ȬmethoxyȬ2Ȭ(3ȬmethylbutȬ2Ȭenyl)phenolȱ
ȱȱ72.ȱdrimenolȱȱ ȱ 73.ȱ4ȬmethoxyȬ2Ȭ(3ȬmethylbutȬ2Ȭenyl)
ȱȱȱȱȱȱuvidinȱB,ȱRȱ=ȱOHȱ
2 ȱȱȱȱȱȱuvidinȱB,ȱRȱ=ȱOHȱ
1
2 R 1 R
R R
OH N N OH its de-
An alkaloidal N pigmentNnecatarone (76),O batrellaceae), which O
OCHincluded
3 HO e.g. the purple pig- HO
H3 C 1 2
hydrodimer OCH 3(77,
O CH3R = R = OH) prevailing H C
H32 N OCHCH in aged ment OH grifolinone B (80), the redOHketone N albatrellin
3 O3 OCH3 H2 N OCH3
fruiting
H2 N
N
bodiesN O andCOOH the 10-deoxydehydrodimer
N HN2 N COOH (81) and a variety of relatedCH compounds of the
3
(77,
R R 1 =H H, R 2 = OH) are the principal HOOC
H pigments N mushroom HOOC
NH 2 A. confluens N (Alb. &N Schwein.)NH2 Kotl. N
H C CH O OH HO O H OH H CH
ofHOOCthe
3 3 OO
green-brown OHNH HOflesh Oand H cap
C
HOOC CHskin of
O Lacta- O& Pouzar (Yang et
O al. 2008). 3
ȱ 2ȱ 3 3
ȱ ȱ NHO 2 ȱ O ȱ O ȱ
ȱ et COOH O O COOH
rius turpis OH (Weinm.)
O Fr. (Fugmann OHal.O1984, The Orange Tooth Hydnellum Oaurantiacum
OH
71.ȱuvidinȱA,ȱRȱ=ȱHȱ ȱ ȱ
ȱȱȱȱ77.ȱnecataroneȱdehydrodimerȱ ȱȱ72.ȱdrimenolȱȱ ȱ ȱȱ ȱ ȱ
73.ȱ4ȬmethoxyȬ2Ȭ(3ȬmethylbutȬ2Ȭenyl)phenolȱ ȱȱ ȱ
Klamann
ȱȱȱȱ77.ȱnecataroneȱdehydrodimerȱ
ȱȱȱȱȱȱuvidinȱB,ȱRȱ=ȱOHȱ
et al. 1989). (Batsch) P. Karst. (Hydnellum P. Karst., Peniophora-
ȱȱȱȱȱȱȱȱȱȱ74.ȱblennioneȱ 75.ȱlilacinoneȱ ȱ
ȱȱȱȱȱȱȱȱȱȱ74.ȱblennioneȱ ȱ ȱ 75.ȱlilacinoneȱ
ȱȱȱȱȱȱȱȱ76.ȱnecataroneȱ
Ochroleucins are the OCHmain pigments of the fruit- ceae) colour is derived OH from theȱterphenylquinone ȱ ȱ ȱȱȱȱȱȱȱȱ76.ȱnec
OCH3 3 OH
ingR 2bodies of the Common YellowR2Russula, 1 O Russula atromentin. The 3,6-dibenzoylatromentin,
HO named
O R CH 2 R1 O
O
N
ochroleuca OCH 3NOPers. and R.NOH O viscida
OH H Kudrna
CH2 N2 (Russula
N
OHaurantiacin,
N OCH3
was first isolated as a dark red pig-
Pers.,
H2 N Russulaceae).
H2 C
COOHThe labile yellow ochroleucin
H CH 3
CH 3 ment H2 C
from this mushroom and subsequently CH2
from
H OCH CH2
A H(78)
2C is rapidly OCH3 transformed
3
HOOC
to the stable N red H2various
H
C NHHydnellum
2 O
O species (Gripenberg
N 1956;
N CH O N NO N CH 3 O
OAurantiacin CH3
HOOC
ochroleucin CH 3 B NHO
3 (79) 2 (Sontag et al. 2006). O Gripenberg 1958b).
O O CH3 is accompanied
ȱ O CH 3 ȱ
OH O ȱ O COOH Oȱ OH
DimericO meroterpenoidOH HO ȱ O pigments have O been
OH HO with
O the corresponding
ȱ ȱ leucoform dihydroauran-
ȱ
78.ȱochroleucinȱAȱ
78.ȱochroleucinȱAȱ 79.ȱochroleucinȱBȱ
79.ȱochroleucinȱBȱ
reported from
ȱȱȱȱȱȱȱȱȱȱ74.ȱblennioneȱ
the Albatrellus Gray ȱ species (Al-
75.ȱlilacinoneȱ ȱ
tiacin and
ȱ
thelephoric
ȱ ȱ
acid.
ȱȱȱȱȱȱȱȱ76.ȱnecataroneȱ
O
ȱȱȱȱ77.ȱnecataroneȱdehydrodimerȱ O
O ȱȱȱȱ77.ȱnecataroneȱdehydrodimerȱ O
2 H3 C OH 1 H3 C OH
R H3 C OH R HC OH
OCH3 OCH 3 OH3 OH
N N CH3
O CH3 O CH 3
O O CH 3
O CH 2 O CH 2 O O
OH
O CH3 CH 3 CHOH O CH3 CH3 O CH 3
CHCH3 CH 3 CH3 CHCH CH
HC O 3 O CH 3
H3 C N 3 CH 3 N 3 OHCH OH H3 C
H3 C
CH 3
3 OH 3 O
CH 3 H CH 3CH 3 OH
H2 C CH 3 H2 C 3 H H2 C CH3 O 3 H2 C CH2 CH2
OCH3 OCH 3 O
O
CH 3 O OH HO O
CH3
O CH 3 O O CH 3 CH3 O O CH3
HO ȱ ȱ CH3 ȱ HO ȱ CH3 ȱ
HO CH3 ȱȱ HO CH3 ȱ
78.ȱochroleucinȱAȱ ȱȱ 79.ȱochroleucinȱBȱ 79.ȱochroleucinȱBȱ ȱ
ȱȱȱȱ77.ȱnecataroneȱdehydrodimerȱ 78.ȱochroleucinȱAȱ
80.ȱgrifolinoneȱBȱ
80.ȱgrifolinoneȱBȱ 81.ȱalbatrellinȱ
81.ȱalbatrellinȱ
OCH3 O O OH O O
OH H3 C H3 C H C OH H C OH H C H C OH
H3 C O OH 3 3 O H3 CO 3 O OH
3
O OCH OH O
OH H3 C H3 C 2 N N CH3 O O HO3 C OH
N CH
CH3 HC N CH 3
O O CH3 O CH33 O 3 CH 3
O O O + H3OC O O CH 3 O
OH O O CH + 3 H C O CH CHO +
H2 C N CHH C 3 3 2 + CH
OCH3 O CH3 N CH 3 CH3 CH3O 3 2 CH3 O CH 3 O CH3 CH3 CH N O CH33O
CH 3 CH3
H3 C HO O CH 3 OHH3 C- O O OH
-
CH 3H3 C OH HO CH3 OH H3 CN - O3 O- OH CH3 OH
HOCH 3 CH O O OH CH 3 HO O O CH3 O O CH OH
CH 3 CH3
3
ȱ 3 ȱ
HO OH HO OH
HO OH
78.ȱochroleucinȱAȱ HO
79.ȱochroleucinȱBȱ OH
HO CH3 ȱ ȱ ȱ ȱ ȱ ȱ
HO CH3 HO CH HO CH
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ82.ȱsarcoviolinȱ΅ȱȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ82.ȱsarcoviolinȱ΅ȱȱ ȱȱ 83.ȱsarcodoninȱ΅ȱ
ȱȱ
83.ȱsarcodoninȱ΅ȱ
3
ȱ
O O
ȱ H3 C 80.ȱgrifolinoneȱBȱ
OH 80.ȱgrifolinoneȱBȱ H C 81.ȱalbatrellinȱ 81.ȱalbatrellinȱ
ȱ 3 OH

ȱ ȱ O H3 C CH3 H3 C H3 C CH 3
O OH O O OH O O OH H3 C
O
H3 C
CH3 N CH 3 CH3 H3 C N
O
CH3 HC O
N3 O CH3CH 3
99 O H3 C
O CH3 O CH33 CH
H3 C CH 3 H3 C
O O OOH + O O O + H3 C O CH3O CHOH
3 O + H3 C O O CH 3 O +
CH 3 CH3 CH3 CH3 CH3
N N N N
- - - -
HO O OHOOH HOO O OH O OHOOH O O
HO CH3 HO CH3
HO OH ȱȱ ȱ
 O CH3 CH 3 CH3
H3 C CH 3 OH
CH 3
HO CH3
Vol. 29, 2011, No. 2: 87–102 ȱȱ
80.ȱgrifolinoneȱBȱ
H3 C
O OH
H3 C
N CH3
O O O +
N CH3
- -
HO O O OH
HO OH
ȱ ȱ
ȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱȱ82.ȱsarcoviolinȱ΅ȱȱ
ȱ 7 Thelephorales
ȱ Norlactarane and lactarane sesquiterpenes from Lacta-
The fruiting bodies of Sarcodon leucopus (Pers.)
Maas Geest. & Nannf. (Sarcodon Quél. ex P. Karst.,
Bankeraceae) contain a range of compounds related
to terphenylquinones. The main pigments are the
unusual nitrogenous violet terphenylquinols sar-
coviolins, exemplified by sarcoviolon α (82), which
are accompanied by their colourless precursors
sarcodonins (83) and structurally related com-
pounds (Geraci et al. 2000; Cali et al. 2004).
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Corresponding author:
Prof. Ing. Jan Velíšek, DrSc., Vysoká škola chemicko-technologická v Praze, Fakulta potravinářské a biochemické
technologie, Ústav chemie a analýzy potravin, Technická 5, 166 28 Praha 6, Česká republika
tel.: + 420 220 443 175, e-mail: jan.velisek@vscht.cz
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Recieved for publication December 29, 2010
Accepted after corrections January 15, 2011