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Kansuinine B, a novel multi-oxygenated diterpene from euphorbia kansui liou.
Tetrahedron Lettera Ao.21
, pp 1703-1706,
1975.
Pergamon Preaa.
printed in Great Britain.
KANSUININE B, A NOVELWLTI-OXYGENATED DITERPENE FROMEUPHORBIA KANSUILIOU.
Daisuke Uemura, Chuji Katayama. Chemical Institute,
Etsuji Uno, Kyoyu Sasaki. and Yoshimasa Hirata
Faculty of Science,
Nagoya University,
Chikusa, Nagoya, Japan
Yuh-Pan Chen and Hong-Yen Hsu Brion Research Institute
of Taiwan, 116 Chung-Ching S.Rd., Sec.3,
(Received in Japan 15 March 1975; received UK for publication
In the course of a continuing
search for toxic
compounds, named kansuinine A and B. of kansuinine B (I), the first
structurally
We report herein the isolation
related
with kansuinine A1) .
Fractionation graphy (on silicic
of an ethanol extract, acid),
preparative
compound was published in 19744).
we obtained two novel and structural
These diterpenoids
guided by toxicity,
elucidation are
in high speed liquid
was made by column chromato-
thin layer chromatography, end high speed liquid The result
of the structural
study of the toxic
Kansuinine B was obtained by further purification
chromatography as a crystalline
Mass m/e 722.2489 (m* calcd.
by recycle
compound [C3BH42014; m.p. 160-
[alD23-+37 (c, 0.27 MeOH); IR(KBr) 3500, 1720 (broad absorption),
NMRFig.1;
11 April 1975)
activities.
chromatography (with MicroPak NH2 column) 3).
162”;
Taiwan
members of the rare jatrophone class 2) which have been shown to possess analgesic
and anti-writhing
operation
natural products,
Taipei,
1640, 1609, 1590 cm-‘;
722.2494)].
(21 R- H
(1) kansuinine B
(3)
1703
R- p-brwmbenxoate
Kansuinine Consequently,
the parent
information afforded
B has two acetate
about a diol
and purification the signal singlet.
attributed
kansuinine I948 (6,
B by periodic
CDC13) 1.89
converted
to
kansuinine
acid
(3H, s.
(1))
(5)
(2).
(3),
ring
[m.p. 9.56
the presence
of
by the group
compound (2) as a broad
action at C-20
the oxidation
240-242’; (lH,
of
Mass 720 (m+);
s, *CfiO)],
which was
From the nmr spectra
in pyridine.
possesses
an a-ketol
of the six
groups
of
shown below
and (3)
I
I
H
H
H
and (3))
at 6 4.0-4.1
since
the signal
at lower
field
was made clear.
From the above
under these results
formation (4)
afforded
of
of
(6 4.68) hemiketal
the structure the oxorane compound (6)
lattice
+ cl-I3 x 2, ;c=Q12
by X-ray
constants
R index
for
analysis
are a=10.57
B lacks
singlet,
this
the proton
was also 260-261’;
A, b=11.97 is
the signal
oxorane
ring,
but
of
of
one in compounds
during
of the a-ketol
of
instead
at C-8 in the nmr spectrum
occurred
0.07.
in the nmr spectra
than the corresponding formation
5) as shown
3527 reflections
in compound (2) because
of kansuinine
[m.p.
Iv)
?
in kansuinine
ring
11
established
But the epimerization conditions
I
as a broad
Kansuinine
respectively. group,
;
The final
and y=82.2’.
That the intramolecular
form was not observed
I1 and the
12
I
(3) was unambiguously group is
H
13 cc-c-c.-.
in compound (3) was present
B was observed
and (3).
CHH 131
at C-8 appeared
(2)
Keto aldehyde
and (5))
I
8=104.1°,
attached
Intramolecular
(4),
(2)
Furthermore,
H-8),
anhydride
from
B (1)
sodium bisulfite,
at 6 4.18
at the hydroxy
4.68
acetic
The space
Fig.3.
A, a=103.3O,
(2)
was obtained
(4)
with
with
group appeared
a keto..aldehyde
(III)
of,compound
compounds
of
methylene
br.s,
Kansuinine
reactions.
In the nmr spectrum
(6 5.02).
(lH,
We obtained
diterpene.
by treatment
which was esterified
‘a
‘7 *c-c-e
(111
The oxorane
(2)
afforded
followed
216-218O,
OR OH
The structure
kansuinine
a hydroxy
two protons
C-CO-CkI,),
ii-IA
the proton
of
oxygenated
chromatography.
m.p.
as shown in the nmr spectrum.
B were‘revealed.
- d2_ ;14
c=9.96
of
(3),
shift
a-l
in Fig.2.and
layer
groups
B by following
in pyridine
in pyridine.
a monoacetate
compounds
a3
(I)
thin
to two protons
chemical
a highly
of kansuinine
osmium tetroxide
chloride
from the
and two benzoate
C20H30010,
groups
And the p-bromobenzoate
judging
for
with
is
by preparative
of p-bromobenzoyl
these
alcohol
functional (2)
groups
the preparation
group -via
the ene-diol
9.
B was established observed
as shown in &
in the acidic
Mass 720 (m+);
media.
WMR(B, CDC13) 1.86
A,
no. 21
1705
-. ..~. 4
5
Fig. 1 ,
5
~
_-L-L IPPU
The nmr spectrum(100Mlz, C6D6)of kmsuinineB \
4-,
4
Fig. 3
Fig. 2
(4)R= H (5)R= k
..L.._. 2
(6)
(7)
1706
I?b.21
(3H, s, 4.50
C-CO:CH,),
(lH,
t,
3.55
(1H. d of q, J= 7,
J= 10 Hz, H-12),
4.73
(lH,
10 Hz, H-13),
br.s,
H-S),
The structure
was suggested
by the nmr spectrum
on the carbon
atoms bearing
oxygen
of protons
1765, 3.46
1725, (lH,
B (1) 1640,
at 6 3.69
(lH,
(lH,
s, &I$)]
compound (6).
atom constituting
at C-11 and C-12 appeared
of kansuinine
of
9.69
3.69
oxirane
and 6 4.50,
with HCl gas in MeOH gave compound (7)
1600,
d of q, J= 6,
1585 cm-‘;
to
conformations
and reactions
with
The s.ignal
ring
compound (6) with
3.57
periodic
of kansuinine
(lH,
HCl gas in MeOH. of two protons
disappeared,
and new signals
respectively.
Also,
[m.p.
IR(CHC13) 3500,
235-236’;
Mass 722 (m+); NMR(6, CDC13) 1.86
10 Hz, H-13),
was converted
d, J= 10 Hz, H-11),
(3H, br.s
treatment
6) , 0COCIf3),
d, J= 9 Hz:,. H-l])].
Furthermore,
compound (7)
in acetone-water.
The relationship
between
acid
B is under investigation.
REFERENCES 1)
D. Uemura, Y. Hirata,
2)
S.M. Kupchan,
3)
Y.P.
C.W. Singel,
Chen, and H.Y. Hsu, Tetrahedron M.J.
J. Amer. Chem. E., _--
z,
4476
We thank Dr. R.L.
Stevenson
Mats,
J.A.
Saenz Renauld,
Letters,
this
issue.
R.C. Haltiwanger,
and R.F.
Bryan
(1970).
(Varian
Aerograph,
Walnut Creek,
California)
for
helpful
discussions. 4)
D. Uemura, Y. Hirata,
5)
We prepared for
6)
This
several
Y.P.
Chen, and H.Y. Hsu, Tetrahedron
derivatives
for
X-ray
analysis,
but only
the purpose. signal
may be attributed
to the
acetoxyl
group
Letters,
at C-15.
this
2527,
2528
(1974).
compound was suitable
, pp 1703-1706,
1975.
Pergamon Preaa.
printed in Great Britain.
KANSUININE B, A NOVELWLTI-OXYGENATED DITERPENE FROMEUPHORBIA KANSUILIOU.
Daisuke Uemura, Chuji Katayama. Chemical Institute,
Etsuji Uno, Kyoyu Sasaki. and Yoshimasa Hirata
Faculty of Science,
Nagoya University,
Chikusa, Nagoya, Japan
Yuh-Pan Chen and Hong-Yen Hsu Brion Research Institute
of Taiwan, 116 Chung-Ching S.Rd., Sec.3,
(Received in Japan 15 March 1975; received UK for publication
In the course of a continuing
search for toxic
compounds, named kansuinine A and B. of kansuinine B (I), the first
structurally
We report herein the isolation
related
with kansuinine A1) .
Fractionation graphy (on silicic
of an ethanol extract, acid),
preparative
compound was published in 19744).
we obtained two novel and structural
These diterpenoids
guided by toxicity,
elucidation are
in high speed liquid
was made by column chromato-
thin layer chromatography, end high speed liquid The result
of the structural
study of the toxic
Kansuinine B was obtained by further purification
chromatography as a crystalline
Mass m/e 722.2489 (m* calcd.
by recycle
compound [C3BH42014; m.p. 160-
[alD23-+37 (c, 0.27 MeOH); IR(KBr) 3500, 1720 (broad absorption),
NMRFig.1;
11 April 1975)
activities.
chromatography (with MicroPak NH2 column) 3).
162”;
Taiwan
members of the rare jatrophone class 2) which have been shown to possess analgesic
and anti-writhing
operation
natural products,
Taipei,
1640, 1609, 1590 cm-‘;
722.2494)].
(21 R- H
(1) kansuinine B
(3)
1703
R- p-brwmbenxoate
Kansuinine Consequently,
the parent
information afforded
B has two acetate
about a diol
and purification the signal singlet.
attributed
kansuinine I948 (6,
B by periodic
CDC13) 1.89
converted
to
kansuinine
acid
(3H, s.
(1))
(5)
(2).
(3),
ring
[m.p. 9.56
the presence
of
by the group
compound (2) as a broad
action at C-20
the oxidation
240-242’; (lH,
of
Mass 720 (m+);
s, *CfiO)],
which was
From the nmr spectra
in pyridine.
possesses
an a-ketol
of the six
groups
of
shown below
and (3)
I
I
H
H
H
and (3))
at 6 4.0-4.1
since
the signal
at lower
field
was made clear.
From the above
under these results
formation (4)
afforded
of
of
(6 4.68) hemiketal
the structure the oxorane compound (6)
lattice
+ cl-I3 x 2, ;c=Q12
by X-ray
constants
R index
for
analysis
are a=10.57
B lacks
singlet,
this
the proton
was also 260-261’;
A, b=11.97 is
the signal
oxorane
ring,
but
of
of
one in compounds
during
of the a-ketol
of
instead
at C-8 in the nmr spectrum
occurred
0.07.
in the nmr spectra
than the corresponding formation
5) as shown
3527 reflections
in compound (2) because
of kansuinine
[m.p.
Iv)
?
in kansuinine
ring
11
established
But the epimerization conditions
I
as a broad
Kansuinine
respectively. group,
;
The final
and y=82.2’.
That the intramolecular
form was not observed
I1 and the
12
I
(3) was unambiguously group is
H
13 cc-c-c.-.
in compound (3) was present
B was observed
and (3).
CHH 131
at C-8 appeared
(2)
Keto aldehyde
and (5))
I
8=104.1°,
attached
Intramolecular
(4),
(2)
Furthermore,
H-8),
anhydride
from
B (1)
sodium bisulfite,
at 6 4.18
at the hydroxy
4.68
acetic
The space
Fig.3.
A, a=103.3O,
(2)
was obtained
(4)
with
with
group appeared
a keto..aldehyde
(III)
of,compound
compounds
of
methylene
br.s,
Kansuinine
reactions.
In the nmr spectrum
(6 5.02).
(lH,
We obtained
diterpene.
by treatment
which was esterified
‘a
‘7 *c-c-e
(111
The oxorane
(2)
afforded
followed
216-218O,
OR OH
The structure
kansuinine
a hydroxy
two protons
C-CO-CkI,),
ii-IA
the proton
of
oxygenated
chromatography.
m.p.
as shown in the nmr spectrum.
B were‘revealed.
- d2_ ;14
c=9.96
of
(3),
shift
a-l
in Fig.2.and
layer
groups
B by following
in pyridine
in pyridine.
a monoacetate
compounds
a3
(I)
thin
to two protons
chemical
a highly
of kansuinine
osmium tetroxide
chloride
from the
and two benzoate
C20H30010,
groups
And the p-bromobenzoate
judging
for
with
is
by preparative
of p-bromobenzoyl
these
alcohol
functional (2)
groups
the preparation
group -via
the ene-diol
9.
B was established observed
as shown in &
in the acidic
Mass 720 (m+);
media.
WMR(B, CDC13) 1.86
A,
no. 21
1705
-. ..~. 4
5
Fig. 1 ,
5
~
_-L-L IPPU
The nmr spectrum(100Mlz, C6D6)of kmsuinineB \
4-,
4
Fig. 3
Fig. 2
(4)R= H (5)R= k
..L.._. 2
(6)
(7)
1706
I?b.21
(3H, s, 4.50
C-CO:CH,),
(lH,
t,
3.55
(1H. d of q, J= 7,
J= 10 Hz, H-12),
4.73
(lH,
10 Hz, H-13),
br.s,
H-S),
The structure
was suggested
by the nmr spectrum
on the carbon
atoms bearing
oxygen
of protons
1765, 3.46
1725, (lH,
B (1) 1640,
at 6 3.69
(lH,
(lH,
s, &I$)]
compound (6).
atom constituting
at C-11 and C-12 appeared
of kansuinine
of
9.69
3.69
oxirane
and 6 4.50,
with HCl gas in MeOH gave compound (7)
1600,
d of q, J= 6,
1585 cm-‘;
to
conformations
and reactions
with
The s.ignal
ring
compound (6) with
3.57
periodic
of kansuinine
(lH,
HCl gas in MeOH. of two protons
disappeared,
and new signals
respectively.
Also,
[m.p.
IR(CHC13) 3500,
235-236’;
Mass 722 (m+); NMR(6, CDC13) 1.86
10 Hz, H-13),
was converted
d, J= 10 Hz, H-11),
(3H, br.s
treatment
6) , 0COCIf3),
d, J= 9 Hz:,. H-l])].
Furthermore,
compound (7)
in acetone-water.
The relationship
between
acid
B is under investigation.
REFERENCES 1)
D. Uemura, Y. Hirata,
2)
S.M. Kupchan,
3)
Y.P.
C.W. Singel,
Chen, and H.Y. Hsu, Tetrahedron M.J.
J. Amer. Chem. E., _--
z,
4476
We thank Dr. R.L.
Stevenson
Mats,
J.A.
Saenz Renauld,
Letters,
this
issue.
R.C. Haltiwanger,
and R.F.
Bryan
(1970).
(Varian
Aerograph,
Walnut Creek,
California)
for
helpful
discussions. 4)
D. Uemura, Y. Hirata,
5)
We prepared for
6)
This
several
Y.P.
Chen, and H.Y. Hsu, Tetrahedron
derivatives
for
X-ray
analysis,
but only
the purpose. signal
may be attributed
to the
acetoxyl
group
Letters,
at C-15.
this
2527,
2528
(1974).
compound was suitable