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Chemical studies of marine invertebrates. VIII africanol, an unusual sesquiterpene from Lemnalia africana (Coelenterata, Octocorallia, Alcyonacea).
Lettera
Tat&e&on
Per-n
Noa. 9, PP 747 - 750, 1974.
Printed
Reee.
in
Great Britain.
Chemical studies of marine invertebrates. VIII.(‘) Africanol, an unusual sesquiterpene from Lem~Zia
ufricaw
(Coelenterata, Octocorallia, Alcyonacea). B.TlJRSCH,
J.C.SRAEKMAN:
D.DALOZE,
P.FRITZ,
A.KELECOM,
R.KARLSSON and D.LOSMAN. Collectif
da Bio-Qcologie
Faculte
das
Universite
(Received
presence
reported. have
of
During
found
report
the
[May,
18981.
the
occurrenca
such
compounds
and the This
in
to
structure
africanol,
of
[31 . extract
afforded,
(11
(ClSH2S0
in
closely
related
source
of
of
were
collected
animals
submitted
to
a yield
molecular
wera
ion
0.3
at
m/e
invertebrates,
the
extracted
m.p.
been we to
Lenmutia africaim
of
Leti,
methylene
column
province chloride
chromatography.
a crystalline
: 58-60°
yet
We wish
island
with
weight],
:
not
and diterpenes.
silicagel
222
marine
from
(21,
documented
these
around
% [dry
well
has
isolated
repetitive of
is
Alcyonarians
sesqui-
a sesquiterpene
1974)
21 Jmw
Gorgonians
screening
Sun-dried
with
J
the
be a rich
of L. africana
Indonesia
procedure
de Bruxelles
terpenoids
chemical
many species
resulting
africanal
of
a systematical
Specimens
of Maluku,
Libre
in UK 3 January 1974; accepted for publication
Whilst the
Sciences
;
:
compound
(oldie,
: + 59.5O 3
i
cc = 0.4741
The which
’
had to
Charge
UV [CH30Hl IR
spectrum
be tertiary
de Recherches
:
end absorptionl. indicated
since
it
the could
presence not
of
an hydroxyl
be acetylated
du F.N.R.S.
747
under
group
(vOH at
usual
conditions.
3500
cm-l1
No. 9
740
Moreover, 2.2
ppm.
It
and
1.10
ppm.
protons
This
spectrum.
The
presence
44.72
i
42.52
and
between
of
50.81
four
Is
of
appearing
(doublet
r 45.37 three
r 53.85
CH (20.84
0.88
the
absence
any
signal at
of
sp2 carbon
ppml,
and 56.15
five
1.00
A two
a cyclopropane
-1 cm
3080
below
0.95,
ppm 3 J = 7 Hzl.
at of
and 61.49 ; 26.79
of
presence
by a band
shows the
devoid
as 3H singlets
at
ppm suggested
only
is
In
the
atoms
IR but
:
CHg c31.71
ppml and three
also 36.44
C (-10.22
.
thus
a tricyclic
carbocyclic
sesquiterpeneskeleton
africanol
substantiated
not
ppml,
(51
group
and 0.75
CH3 (45.11
ppml
the
a low yield
0.1
of
groups,
methyl
was further
and 53.14
58.58
correlate
methyl
l3 C NMR spectrum
African01 to
tertiary
and one secondary
assumption
[41
1H NMR spectrum
three
absorption
group.
the
shows
the
ring
have
unsaturated
monohydroxylated
system
failed.
of
Under
hydrocarbons
africanol
a variety
(uide
ir~j?rul
sesquiterpene. with
of or
one of
conditions complex
All
the
already
africanol mixtures
our
attempts
known affords
of
either
untractable
products. The compound was thus which
led
to
orthorhombic The
unit
cell
structure system, contains
[I] space
-
relative
group
twelve
submitted
to
single
configuration.
p ZIZIZl
molecules
I
with
[61 .
crystal
X-ray
diffraction
The compound crystallises
a = 29.47
i,
b = 18.09
i
analysis in
the
and c = 9.71
i.
,
;
749
No. 9
When pyridinal formed
is submitted
or to acid treatment
from which
is isolated three
africanol
a fraction
-C-CHS
at 0.66,
of the cyclopropanic
protons
chromatography
on silicagel
to structure
obtained
hydrocarbons African01
the formation
0.66
columns
mixture
(1)
isomer-k
representative
be visualized
group
NMR
(CC141:
by repetitive
All these
data
probable
strongly data
that the two remaining
products
of africanol.
of a new type of tricyclic
as shown
is
hydrocarbons
the spectroscopic
dehydration
in
at 1.66 ppm and two
be separated
From
it is highly
possible
mixture
no uoHband;
:
10 % AgNOS.
hydrocarbon.
of isomers,
a complex
IR
one CH6-C=C
with
(POClS or SOClz
C15H_04 unsaturated
end absorptioni
:
impregneted
are the two other
could
acid),
0.1 and 0.6 ppml could
unsaturated
is the first
of which
three
and 0.91 ppmi
between
conditions
or hydrochloric
(LIV (CH60Hl
II for this
on the original
unsaturated
biological
containing
f71. One of these groups
point
(formic
to dehydration
sesquiterpene
hereunder.
-
The chemical
structure
of other
significance
is currently
under
alcyonarian investigation
terpenoids
as well
as their
in our laboratory.
750
No. 9
REFERENCES
cl1 Part VII.
J.Org.Chem.
[21 a. P.J.SCHEUER
"Chemistry
b. A.J.WEINHEIMER, Transactions University
(31 This
of the Drugs
is a part
(51 22.63
COC13,
MHz,
[fil A full
values
COC13,
paper
This work
Dr. D.ZIMMERMANN of the animal.
for the
Vol.
1973.
from the sea" p. 135
Marine
Technology
work will
we gratefully
appear
Society
of Sciences
C NMR spectrum
sources"
;
in
(19711.
XXIX,
alcyonarians
effected
acknowledge.
TMS. from
internal
CDC13.
shortly.
is also present
under
from marine
of Indonesian
in ppm are upfield
has been effected
13
J
derived
collection
internal
values
Institute
"Orugs
Nat. Products
in ppm from
of hydrocarbons
the Indonesian
products
contribution
positive
Ed. AC. Press
(19671.
of Org.
on the X-ray
[71 The same mixture
We thank
whose
products"
the Sea Symposium
of the comprehensive
by Mr. J.PIERRET, [41 60 MHz,
from
of natural
in the Chem.
natural
and L.S.CIERESZKO
Island
"Chemistry
(19701.
of marine
F.J.SCHMITZ
of Rhode
c. E.PREMUZIC Progress
-35, 2565
in the animal.
NATO Special
Research
Grant
[LIP11 for its support.
and Or. J.VERSEVELDT
ES-003.
We thank
also
for the identification
Tat&e&on
Per-n
Noa. 9, PP 747 - 750, 1974.
Printed
Reee.
in
Great Britain.
Chemical studies of marine invertebrates. VIII.(‘) Africanol, an unusual sesquiterpene from Lem~Zia
ufricaw
(Coelenterata, Octocorallia, Alcyonacea). B.TlJRSCH,
J.C.SRAEKMAN:
D.DALOZE,
P.FRITZ,
A.KELECOM,
R.KARLSSON and D.LOSMAN. Collectif
da Bio-Qcologie
Faculte
das
Universite
(Received
presence
reported. have
of
During
found
report
the
[May,
18981.
the
occurrenca
such
compounds
and the This
in
to
structure
africanol,
of
[31 . extract
afforded,
(11
(ClSH2S0
in
closely
related
source
of
of
were
collected
animals
submitted
to
a yield
molecular
wera
ion
0.3
at
m/e
invertebrates,
the
extracted
m.p.
been we to
Lenmutia africaim
of
Leti,
methylene
column
province chloride
chromatography.
a crystalline
: 58-60°
yet
We wish
island
with
weight],
:
not
and diterpenes.
silicagel
222
marine
from
(21,
documented
these
around
% [dry
well
has
isolated
repetitive of
is
Alcyonarians
sesqui-
a sesquiterpene
1974)
21 Jmw
Gorgonians
screening
Sun-dried
with
J
the
be a rich
of L. africana
Indonesia
procedure
de Bruxelles
terpenoids
chemical
many species
resulting
africanal
of
a systematical
Specimens
of Maluku,
Libre
in UK 3 January 1974; accepted for publication
Whilst the
Sciences
;
:
compound
(oldie,
: + 59.5O 3
i
cc = 0.4741
The which
’
had to
Charge
UV [CH30Hl IR
spectrum
be tertiary
de Recherches
:
end absorptionl. indicated
since
it
the could
presence not
of
an hydroxyl
be acetylated
du F.N.R.S.
747
under
group
(vOH at
usual
conditions.
3500
cm-l1
No. 9
740
Moreover, 2.2
ppm.
It
and
1.10
ppm.
protons
This
spectrum.
The
presence
44.72
i
42.52
and
between
of
50.81
four
Is
of
appearing
(doublet
r 45.37 three
r 53.85
CH (20.84
0.88
the
absence
any
signal at
of
sp2 carbon
ppml,
and 56.15
five
1.00
A two
a cyclopropane
-1 cm
3080
below
0.95,
ppm 3 J = 7 Hzl.
at of
and 61.49 ; 26.79
of
presence
by a band
shows the
devoid
as 3H singlets
at
ppm suggested
only
is
In
the
atoms
IR but
:
CHg c31.71
ppml and three
also 36.44
C (-10.22
.
thus
a tricyclic
carbocyclic
sesquiterpeneskeleton
africanol
substantiated
not
ppml,
(51
group
and 0.75
CH3 (45.11
ppml
the
a low yield
0.1
of
groups,
methyl
was further
and 53.14
58.58
correlate
methyl
l3 C NMR spectrum
African01 to
tertiary
and one secondary
assumption
[41
1H NMR spectrum
three
absorption
group.
the
shows
the
ring
have
unsaturated
monohydroxylated
system
failed.
of
Under
hydrocarbons
africanol
a variety
(uide
ir~j?rul
sesquiterpene. with
of or
one of
conditions complex
All
the
already
africanol mixtures
our
attempts
known affords
of
either
untractable
products. The compound was thus which
led
to
orthorhombic The
unit
cell
structure system, contains
[I] space
-
relative
group
twelve
submitted
to
single
configuration.
p ZIZIZl
molecules
I
with
[61 .
crystal
X-ray
diffraction
The compound crystallises
a = 29.47
i,
b = 18.09
i
analysis in
the
and c = 9.71
i.
,
;
749
No. 9
When pyridinal formed
is submitted
or to acid treatment
from which
is isolated three
africanol
a fraction
-C-CHS
at 0.66,
of the cyclopropanic
protons
chromatography
on silicagel
to structure
obtained
hydrocarbons African01
the formation
0.66
columns
mixture
(1)
isomer-k
representative
be visualized
group
NMR
(CC141:
by repetitive
All these
data
probable
strongly data
that the two remaining
products
of africanol.
of a new type of tricyclic
as shown
is
hydrocarbons
the spectroscopic
dehydration
in
at 1.66 ppm and two
be separated
From
it is highly
possible
mixture
no uoHband;
:
10 % AgNOS.
hydrocarbon.
of isomers,
a complex
IR
one CH6-C=C
with
(POClS or SOClz
C15H_04 unsaturated
end absorptioni
:
impregneted
are the two other
could
acid),
0.1 and 0.6 ppml could
unsaturated
is the first
of which
three
and 0.91 ppmi
between
conditions
or hydrochloric
(LIV (CH60Hl
II for this
on the original
unsaturated
biological
containing
f71. One of these groups
point
(formic
to dehydration
sesquiterpene
hereunder.
-
The chemical
structure
of other
significance
is currently
under
alcyonarian investigation
terpenoids
as well
as their
in our laboratory.
750
No. 9
REFERENCES
cl1 Part VII.
J.Org.Chem.
[21 a. P.J.SCHEUER
"Chemistry
b. A.J.WEINHEIMER, Transactions University
(31 This
of the Drugs
is a part
(51 22.63
COC13,
MHz,
[fil A full
values
COC13,
paper
This work
Dr. D.ZIMMERMANN of the animal.
for the
Vol.
1973.
from the sea" p. 135
Marine
Technology
work will
we gratefully
appear
Society
of Sciences
C NMR spectrum
sources"
;
in
(19711.
XXIX,
alcyonarians
effected
acknowledge.
TMS. from
internal
CDC13.
shortly.
is also present
under
from marine
of Indonesian
in ppm are upfield
has been effected
13
J
derived
collection
internal
values
Institute
"Orugs
Nat. Products
in ppm from
of hydrocarbons
the Indonesian
products
contribution
positive
Ed. AC. Press
(19671.
of Org.
on the X-ray
[71 The same mixture
We thank
whose
products"
the Sea Symposium
of the comprehensive
by Mr. J.PIERRET, [41 60 MHz,
from
of natural
in the Chem.
natural
and L.S.CIERESZKO
Island
"Chemistry
(19701.
of marine
F.J.SCHMITZ
of Rhode
c. E.PREMUZIC Progress
-35, 2565
in the animal.
NATO Special
Research
Grant
[LIP11 for its support.
and Or. J.VERSEVELDT
ES-003.
We thank
also
for the identification