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A new diterpenoid related to eunicellin and cladiellin from a Muricella sp.
OO@-4039/00/0222-0079#02.00/0
Tetrahedron Letters Vol. 21, pp 879 - 880 @Pergamon Press Ltd. 1980. Printed in Great Britain
A NEW DITERPENOIDRELATEDTO EUNICELLINAND CLADIELLINFROMA MIJRICELLA Sp, Y, Kashman Department of Chemistry, Abstract: mceae)
Tel-Aviv University, Ramat Aviv,
The isolation and structyre elucidation of a new diterpenoid The H and 13C-NMRspectra are discussed. are reported.
Repeated silica-gel *(collected
column fractionation
of the petrol
near Dphira in the Gulf of Eilat,
a new compound, ophirin
(g;
m,p. 133-134”,
the Red Sea),
[a],-
2”,
analysed
of three 60 m.u. fragments from the very weak molecular 2E2[23%#
suggested
the presence
three carbonyl acetate trum”
of three acetate
(1730 and 1255 cm-‘)
absorptions
at 170.4s,
oxygen-bearing
carbons
From the latter
five
(90.2s,
in addition
to eight
lines
quartets
ing for 25 of the molecule’s
carbons or vinyl 5.38,
1.79,
methyls.
4.54 and 4.38) According
of five ional
groups:
to the spectral ophirin
a
H-13) and 5.38d(J-5.6Hz, NMR) suggested
the last
tricyclic.
(J-5.9Hz)
cladiellins7,
revealed
or a carbonyl
and a structure
the various
of this
no further
was undertaken to confirm
ophirin.
given below,
bearing
low field
protons
(9
type could be postulated. transformations
structure
in the basis 879
a
as 1. ,
of its
(6 5.66,
5.44,
2.66 and 2,Sl ppm” formula and the presence the following
funct-
XH-0-CHZ: e
to 2’”
The second double bond
indicated
at 5.66d(J-5.6Hz,
the presence
for the 3 acetates
(moiety z),
protons
con-
methyls on acetate
of moieties
(IR and “C-
and the molecule
at 6 4.54d
was there-
(J-1OHz) and 4.3abrd Further structural
are almost uncoupled among them-
the above structural
that ophirin
chemical
ophirin’s
can be explained
low-field
Combining all
it was probable
anlaysis
ether
by the two signals
45.lt.
was further
at 87.2 and 80.3 in the “C-NMR spectrum.
protons.
3 methines), available
since
also
36.0d.
of 3H
possessing
except
the acetate
21.3 and 18.3 account-
to the two coupled protons function,
in the spec-
Five other singlets
>C(OAcjCH3;
The l3 C- and ‘H-NMR spectra
as the two doublets
were not possible
of material
five
at 6 3.13,
to be a ditsrpenoid
oxygen to be part of a cyclic
or to other high-field
2 and additional tity
to either
three
and 120.6d)
43.2d,
of three acetates
and based mainly on the empirical
The ether moiety was supported
as well
conclusions selves
H-12) e
The absence of an hydroxyl
21.8,
3H each).
signals
in moiety b according
125.9s
at 48.4d,
22.0,
C b a at 6 5.44 and a methyl at 1.82 were attributed
was found to be incorporated
fore
The presence and 1.95s,
as three distinct data,
22.5,
could be assigned
was suggested
loss
342(12%) and
were revealed
to the carbon atoms bearing
-CH2CH=CCHJ;-CH(OAcjCH=CCHj; (CH3)2C(OAc)-;
A broad triplet
5 6 a.
2.00s
129.5d.
80.3d and 66.3d)
22,7,
The ‘H-NMR spectrum also
as well
methyl groups,
25,l.
26 carbon atoms4.
1.80 and 1.82)
Consecutive
in agreement with the suggested
double bonds [139,6s, 83.7s,
three belong
at 25.4,
dried Muricella
The IR spectrum’ while confirming 13 The C-NMRspectrum3 revealed
groups.
of the spectrum were located
firmed by the ‘H-NMR spectrum (6 2.01s. each (6 1..38, 1.55,
for C26H3g07’
ion at m/e 462 (402(24%),
and 167.5s
87.2d,
resonances,
groups ti The remaining resonance 30.9t
169.9s
of freeze
in up to 0.2% dry weight
showed no OH-band.
Furthermore two trisubstituted
groups I
and five
the presence
of acetates
from a horny-coral
ether extract afforded
Israel
was related
features
(moieties
to eunicellin6
a-
and the
In view of the very small quancould be carried The particular
crowded structure,
out,
and an x-ray
‘H-NMR,spectrum of thus having to main-
tain
a particular
conformation
in
solution.
The ‘H-NMRdata of 19,10 and the concluded H-13
5.66d
H-14
3 13s
H-l
2 66t
‘12,13
-5..6,
@1,1r90Q J1,2=10.J1,10=8.5
a. overlapping 13 C-NMRstudies
with H-4 and H-go.
6 90..2s
87 2d
83.7s
80.3d
2
18
9
c
3
dihedral
013,1$90”
of compound 1 suggested
J1,10=805
H-9
4.38brd
J8B,g=5”9
H-88
2,Sldd
Jaa,88
45.lt
10
(0):
2.43da
the following
66.,3d 48.4d 13
angles
H-10
8
11
36.0d
30.9t
1
4
14
190”
%i,9PgO” J8B,g=5.9
=13.5
assignments:
43.2d
@9,10
i5..4q E 25,lq iPr-Mes
l8..3q 16
Typ$gAc *~~‘6 Onhirin
Euniceliin.. Acknowiedgement: We are grateful coral
to Dr. Y, Loya and Mr. Y. Benayahu for collection
and to Ms. H. Ben-Yacov for technical
References
(l_) of the soft-
assistance.
and Notes,
1.
The base peak in the mass spectrum appears at m/e 174 (C12H140) and may represent
2.
membered ring fragment after loss of HOAc and 2H. -1 KBr L’max2940, 1730, 1530, 1375, 1255, 1135, 1070, 1025, 955, 935, 890, 860, 840 and 805 cm ,
3.
The (‘HI
NMR
spectra
were assigned 4.
The missing
in CDC13 solution
were recorded
instruments,
b-values
the ten
on a Bruker WH-90 (13C) and Bruker 27OMHz
are given in ppm from TMS; multiplicities
of the 13C- resonances
by SFORDexperiments
atom signal
vide infra)
(C-5,
may overlap
with one of the methyl groups in the
22-25 ppm region 5.
Extensive
6.
0. Kennard, D.G. Watson, La Riva dl Sanseverino,
double
Tetrahedron
irradiation
Letters,
experiments
8.
J. Clardy and J. Finer - to be published.
9.
Two other observable
10.
An LIS experiment using d27 -Eu(fod)3
11.
proton
protons
ibid
4643 (1977)..
are H-5 at 2.17m and H-5’ at 2,llm.
the cyclohexene
showed, according
ring with the following
to the methyl shifts, A6 order:
in UK 4 December 1979)
the complexation
H-lZand14,H-ZzrH-9,
and 6 13 C-NMRassignments were based on the chemical shifts and substituent 13 C-NMRspectra by SFORDexperiments. as correlations of the ‘H and
The
(Received
relationships.
R, Bosmans and C. Djerassi,
2879 (19681.
R. Kazalauskas,
to be over
the various
B. Tursch,
P.T, Murphy, R. J. Wells and P. Schonholzer,
7.
site
established
effects,
13
as well
Tetrahedron Letters Vol. 21, pp 879 - 880 @Pergamon Press Ltd. 1980. Printed in Great Britain
A NEW DITERPENOIDRELATEDTO EUNICELLINAND CLADIELLINFROMA MIJRICELLA Sp, Y, Kashman Department of Chemistry, Abstract: mceae)
Tel-Aviv University, Ramat Aviv,
The isolation and structyre elucidation of a new diterpenoid The H and 13C-NMRspectra are discussed. are reported.
Repeated silica-gel *(collected
column fractionation
of the petrol
near Dphira in the Gulf of Eilat,
a new compound, ophirin
(g;
m,p. 133-134”,
the Red Sea),
[a],-
2”,
analysed
of three 60 m.u. fragments from the very weak molecular 2E2[23%#
suggested
the presence
three carbonyl acetate trum”
of three acetate
(1730 and 1255 cm-‘)
absorptions
at 170.4s,
oxygen-bearing
carbons
From the latter
five
(90.2s,
in addition
to eight
lines
quartets
ing for 25 of the molecule’s
carbons or vinyl 5.38,
1.79,
methyls.
4.54 and 4.38) According
of five ional
groups:
to the spectral ophirin
a
H-13) and 5.38d(J-5.6Hz, NMR) suggested
the last
tricyclic.
(J-5.9Hz)
cladiellins7,
revealed
or a carbonyl
and a structure
the various
of this
no further
was undertaken to confirm
ophirin.
given below,
bearing
low field
protons
(9
type could be postulated. transformations
structure
in the basis 879
a
as 1. ,
of its
(6 5.66,
5.44,
2.66 and 2,Sl ppm” formula and the presence the following
funct-
XH-0-CHZ: e
to 2’”
The second double bond
indicated
at 5.66d(J-5.6Hz,
the presence
for the 3 acetates
(moiety z),
protons
con-
methyls on acetate
of moieties
(IR and “C-
and the molecule
at 6 4.54d
was there-
(J-1OHz) and 4.3abrd Further structural
are almost uncoupled among them-
the above structural
that ophirin
chemical
ophirin’s
can be explained
low-field
Combining all
it was probable
anlaysis
ether
by the two signals
45.lt.
was further
at 87.2 and 80.3 in the “C-NMR spectrum.
protons.
3 methines), available
since
also
36.0d.
of 3H
possessing
except
the acetate
21.3 and 18.3 account-
to the two coupled protons function,
in the spec-
Five other singlets
>C(OAcjCH3;
The l3 C- and ‘H-NMR spectra
as the two doublets
were not possible
of material
five
at 6 3.13,
to be a ditsrpenoid
oxygen to be part of a cyclic
or to other high-field
2 and additional tity
to either
three
and 120.6d)
43.2d,
of three acetates
and based mainly on the empirical
The ether moiety was supported
as well
conclusions selves
H-12) e
The absence of an hydroxyl
21.8,
3H each).
signals
in moiety b according
125.9s
at 48.4d,
22.0,
C b a at 6 5.44 and a methyl at 1.82 were attributed
was found to be incorporated
fore
The presence and 1.95s,
as three distinct data,
22.5,
could be assigned
was suggested
loss
342(12%) and
were revealed
to the carbon atoms bearing
-CH2CH=CCHJ;-CH(OAcjCH=CCHj; (CH3)2C(OAc)-;
A broad triplet
5 6 a.
2.00s
129.5d.
80.3d and 66.3d)
22,7,
The ‘H-NMR spectrum also
as well
methyl groups,
25,l.
26 carbon atoms4.
1.80 and 1.82)
Consecutive
in agreement with the suggested
double bonds [139,6s, 83.7s,
three belong
at 25.4,
dried Muricella
The IR spectrum’ while confirming 13 The C-NMRspectrum3 revealed
groups.
of the spectrum were located
firmed by the ‘H-NMR spectrum (6 2.01s. each (6 1..38, 1.55,
for C26H3g07’
ion at m/e 462 (402(24%),
and 167.5s
87.2d,
resonances,
groups ti The remaining resonance 30.9t
169.9s
of freeze
in up to 0.2% dry weight
showed no OH-band.
Furthermore two trisubstituted
groups I
and five
the presence
of acetates
from a horny-coral
ether extract afforded
Israel
was related
features
(moieties
to eunicellin6
a-
and the
In view of the very small quancould be carried The particular
crowded structure,
out,
and an x-ray
‘H-NMR,spectrum of thus having to main-
tain
a particular
conformation
in
solution.
The ‘H-NMRdata of 19,10 and the concluded H-13
5.66d
H-14
3 13s
H-l
2 66t
‘12,13
-5..6,
@1,1r90Q J1,2=10.J1,10=8.5
a. overlapping 13 C-NMRstudies
with H-4 and H-go.
6 90..2s
87 2d
83.7s
80.3d
2
18
9
c
3
dihedral
013,1$90”
of compound 1 suggested
J1,10=805
H-9
4.38brd
J8B,g=5”9
H-88
2,Sldd
Jaa,88
45.lt
10
(0):
2.43da
the following
66.,3d 48.4d 13
angles
H-10
8
11
36.0d
30.9t
1
4
14
190”
%i,9PgO” J8B,g=5.9
=13.5
assignments:
43.2d
@9,10
i5..4q E 25,lq iPr-Mes
l8..3q 16
Typ$gAc *~~‘6 Onhirin
Euniceliin.. Acknowiedgement: We are grateful coral
to Dr. Y, Loya and Mr. Y. Benayahu for collection
and to Ms. H. Ben-Yacov for technical
References
(l_) of the soft-
assistance.
and Notes,
1.
The base peak in the mass spectrum appears at m/e 174 (C12H140) and may represent
2.
membered ring fragment after loss of HOAc and 2H. -1 KBr L’max2940, 1730, 1530, 1375, 1255, 1135, 1070, 1025, 955, 935, 890, 860, 840 and 805 cm ,
3.
The (‘HI
NMR
spectra
were assigned 4.
The missing
in CDC13 solution
were recorded
instruments,
b-values
the ten
on a Bruker WH-90 (13C) and Bruker 27OMHz
are given in ppm from TMS; multiplicities
of the 13C- resonances
by SFORDexperiments
atom signal
vide infra)
(C-5,
may overlap
with one of the methyl groups in the
22-25 ppm region 5.
Extensive
6.
0. Kennard, D.G. Watson, La Riva dl Sanseverino,
double
Tetrahedron
irradiation
Letters,
experiments
8.
J. Clardy and J. Finer - to be published.
9.
Two other observable
10.
An LIS experiment using d27 -Eu(fod)3
11.
proton
protons
ibid
4643 (1977)..
are H-5 at 2.17m and H-5’ at 2,llm.
the cyclohexene
showed, according
ring with the following
to the methyl shifts, A6 order:
in UK 4 December 1979)
the complexation
H-lZand14,H-ZzrH-9,
and 6 13 C-NMRassignments were based on the chemical shifts and substituent 13 C-NMRspectra by SFORDexperiments. as correlations of the ‘H and
The
(Received
relationships.
R, Bosmans and C. Djerassi,
2879 (19681.
R. Kazalauskas,
to be over
the various
B. Tursch,
P.T, Murphy, R. J. Wells and P. Schonholzer,
7.
site
established
effects,
13
as well