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Carbon-13 NMR spectra of juglone, naphthazarin and their derivatives
Tetrahedron Letters No. 8, pp 619 - 620, 1976.
CARBON-13
NMR
SPECTRA
Masaaki Shioncgi
Research
OF
JUGLONE,
Kobayashi,
Shionogi
(Received in Japan 27 December 1975;
of microbial Carbon-13
quinone NMR
syntheses
methyl
promises
are available
&,
and single-frequency
including
hydrogen
to compound,
of l&.0
0
for land
z.
phenone derivatives
L:
R = R’
2:
R=R’=,-,,
;t:
R =
$ $
R = OMe, R = OAc,
Iz:
R = R: = OH,
Z:
R = OMe,
8;
R = R’ = OMe,
2
R = OAc,
R”
=
(3,
vitamin signals
group,3
R = R’ = OAc,
x:
R = OMe,
Chemical-shift (12-14) w-
Osaka,
thus obtained.
553 Japan
R” = H R” = H
R” = H R” = H
619
studies
and studying
and acetylation juglone
(3,
with of 6
for 3 and 5
comparisons
moieties. bio-
SC data on peri-hydroxy-p-
by comparison
The additivity
R” = H
structures
techniques,
were extremely
R” = H
R’ = OAc,
Tsuji*
shifts. naphthazarin
were assigned by using ‘H-noise,3
reagent, 5 Yb(fod),,
H
R’ = OH,
_I&
DERIVATIVES
peri-hydroxy-p-naphthoquinone -
KS (3,
decoupling
R’ = R” = H R’ = R” = H R’ = OH,
Britain.
In the course of our chemical
13C chemical-shift
R”=& =
and Naoki
tool for determining
= H
R’
THEIR
Fukushima-ku,
encountered
The ‘%
for a carbonyl shift
SC data
= R”
7-g.
an NMR
Tori
values for the methylation
off-resonance3
bonding shift
and by employing
by an addition
OH,
a
Ltd.,
AND
have been reported.‘tz
if some fundamental with
Kazuo
Printed in &cat
received in UK for publication 15 January 1976)
to be a powerful
together
ethers and acetates
R
& Co.,
here SC data for I ,4-naphthoquinone
off-resonance,4
peri-OH
quinones
Terui,
we have frequently
of this kind of antibiotic,
We report
rules
antibiotics,2
spectroscopy3
naphthoquinones
their
occurring
NAPHTHAZARIN
Yoshihiro
Laboratory,
A number of naturally
Pergamon Press.
with useful,
of substituent
(6),
and
noise
known chemical-shift
C
values
from compound
and deuteriation
effect&
those of -o-hydroxyacetoTABLE
1 summarizes
chemical-shifts
(see
the
of
No. 8
620
TABLE
1.
‘%
Chemical
Shift
Data,
a 8c
1
184.6
184.9
190.0
184.0
184.0=
172.9
183.3
184.8
182.9
183.1
2
138.5
147.8
138.4
136.2
137.2
134.6
136.4
138.4
137.5
138.5
184.1 137.2
3
138.5
135.4
139.3
140.9
139.7
134.6
141 .7
138.4
140.6
138.5
139.5
4
184.6
184.3
183.9
185.0
183.5’
172.9
190.5
184.8
190.0
183.1
183.8
5
126.2
125.8’
118.9
118.3’
124.9
172.9
156.6b
153.7
160.2b
147.6
142.7
6 7
133.6 133.6
133.3 133.3
136.4 124.2
134.8 119.3c
134.7 129.6
134.6 134.6
126.8 123.6
120.5 120.5
126.2 133.3
130.9 130.9
131 .o 119.3
8
126.2
126.2’
161 .2
159.9
149.2
172.9
154.0
153.7
142.9
147.6
157.8
9
131.7
131 .9
114.8
120.3
123.3
fll.9
117.5’
120.9
121 .8
124.4
120.4
10
131.7
131.9
131 s
134.4
133.4
111.9
114.8=
120.9
114.8
124.4
124.5
56.9
57.0
QMe
16.3(2-Me)
56.6
CQMe
56.8
21 .o
-CC&
21 .o
169.2
a 15.087 internal
TMS) angle,
-0.4
169.4
Natural-abundance 13C FT NMR spectra were recorded on a Varian NV-14 MHz using about 0.2-0.5 mmol cm-3 solutions in CDCI, and a-mm spinning
flipping
.
are about +O.l 8”;
acquisition
FT measurement
conditions
time,
number of data points,
ppm was observed when &O
0.6
set;
21 .o
are as follows:
was added to the CDCI,
solution
.*
169.9
FT NMR spectrometer at tubes; errors of 6C (from
spectral
4820.
21 .o
169.2
width,
3923 Hz;
b An upfield
C These assignments
shift
pulse
of about
may be reversed
in each column. TABLE Subtituent a-OH 8-QMe
a-OAC
13C Substituent
2.
C-l
c-2
c-3
c-4
+5.4
-0.1
+0.8
-0.7
TABLE
Shifts,
C-5
AS in ppmf for l_
C-6
c-7
C-8
c-9
c-10
-7.3
+2.a
-9.4
+35 .o
-16.9
-0.2
+33.7
-11 .4
+2.7
+0.6
-2.3
+2.4
+0.4
-7.9=
+1 .2
-14.3=
(-6.0
-2.2
+l .6
+1 .l
-0.6=
-1 .6
-4.9c
-0.6’
-1 .3
+1 .2
-1 .lC
-1 .3
+1 .l
-4.0
+23 .O
-8.4
+1.7
(-6.0c
-1 .2
+0.4
-0.4=
+6.0
-1 .7
+5.4
-12.0
+8.5
+1.9)b
a Plus sign denotes a downfield C These values should
shifts _
Chemical
2) holds fairly
well
be noted that the shift Some applications
b
shift.
Values
in parentheses
be changed if the signal
assignments
complexed
of the present
preferentially
results
will
are the methylation
to the 4-CO
b-e published
+5.5
+2.5)b
or acetylation
are reversed.
except for &, where a delocalized-electronic
reagent
-1 .3
structure rather
is dominant.7
than the 1 -CO
It should
in 2.
later.
REFERENCES
(1) (2)
R.H.
“Naturally
Thomson,
C.-K. Laskin
Wat,
“Microbial
and H.A.
Occurring Quinones,”
Lechevalier,
CRC Press Inc.,
(4)
J.B. Stothers, “Carbon-13 E. Wenkert, A.O. Clause,
(5)
For a review,
(6)
F.W. Wehrli, J.C.S. Chem. Comm. S. Katagiri, M, Kuds and N. Fukuoka,
(3)
(7)
(Tokyo),
2nd Ed.,
Chem.
Sot.
Academic
of Microbiology.
III.
Press,
Rev.
2,
London (1971).
Microbial
Cleveland, Ohio (1973). ” Academic Press, New York
NMR Spectroscopy, D.W. Cochran and D. Doddrell,
see 8. C. Mayo,
” 2AO9 (1974).
Quinones,” in “Handbook
J. Amer. Chem. Sot.
Products,”
Ed. A.I.
(1972). g,
6879
(1969).
49 (1973).
663 (1975). “Abstracts of the 7th Symposium
on Structural
Organic
Chemistry
CARBON-13
NMR
SPECTRA
Masaaki Shioncgi
Research
OF
JUGLONE,
Kobayashi,
Shionogi
(Received in Japan 27 December 1975;
of microbial Carbon-13
quinone NMR
syntheses
methyl
promises
are available
&,
and single-frequency
including
hydrogen
to compound,
of l&.0
0
for land
z.
phenone derivatives
L:
R = R’
2:
R=R’=,-,,
;t:
R =
$ $
R = OMe, R = OAc,
Iz:
R = R: = OH,
Z:
R = OMe,
8;
R = R’ = OMe,
2
R = OAc,
R”
=
(3,
vitamin signals
group,3
R = R’ = OAc,
x:
R = OMe,
Chemical-shift (12-14) w-
Osaka,
thus obtained.
553 Japan
R” = H R” = H
R” = H R” = H
619
studies
and studying
and acetylation juglone
(3,
with of 6
for 3 and 5
comparisons
moieties. bio-
SC data on peri-hydroxy-p-
by comparison
The additivity
R” = H
structures
techniques,
were extremely
R” = H
R’ = OAc,
Tsuji*
shifts. naphthazarin
were assigned by using ‘H-noise,3
reagent, 5 Yb(fod),,
H
R’ = OH,
_I&
DERIVATIVES
peri-hydroxy-p-naphthoquinone -
KS (3,
decoupling
R’ = R” = H R’ = R” = H R’ = OH,
Britain.
In the course of our chemical
13C chemical-shift
R”=& =
and Naoki
tool for determining
= H
R’
THEIR
Fukushima-ku,
encountered
The ‘%
for a carbonyl shift
SC data
= R”
7-g.
an NMR
Tori
values for the methylation
off-resonance3
bonding shift
and by employing
by an addition
OH,
a
Ltd.,
AND
have been reported.‘tz
if some fundamental with
Kazuo
Printed in &cat
received in UK for publication 15 January 1976)
to be a powerful
together
ethers and acetates
R
& Co.,
here SC data for I ,4-naphthoquinone
off-resonance,4
peri-OH
quinones
Terui,
we have frequently
of this kind of antibiotic,
We report
rules
antibiotics,2
spectroscopy3
naphthoquinones
their
occurring
NAPHTHAZARIN
Yoshihiro
Laboratory,
A number of naturally
Pergamon Press.
with useful,
of substituent
(6),
and
noise
known chemical-shift
C
values
from compound
and deuteriation
effect&
those of -o-hydroxyacetoTABLE
1 summarizes
chemical-shifts
(see
the
of
No. 8
620
TABLE
1.
‘%
Chemical
Shift
Data,
a 8c
1
184.6
184.9
190.0
184.0
184.0=
172.9
183.3
184.8
182.9
183.1
2
138.5
147.8
138.4
136.2
137.2
134.6
136.4
138.4
137.5
138.5
184.1 137.2
3
138.5
135.4
139.3
140.9
139.7
134.6
141 .7
138.4
140.6
138.5
139.5
4
184.6
184.3
183.9
185.0
183.5’
172.9
190.5
184.8
190.0
183.1
183.8
5
126.2
125.8’
118.9
118.3’
124.9
172.9
156.6b
153.7
160.2b
147.6
142.7
6 7
133.6 133.6
133.3 133.3
136.4 124.2
134.8 119.3c
134.7 129.6
134.6 134.6
126.8 123.6
120.5 120.5
126.2 133.3
130.9 130.9
131 .o 119.3
8
126.2
126.2’
161 .2
159.9
149.2
172.9
154.0
153.7
142.9
147.6
157.8
9
131.7
131 .9
114.8
120.3
123.3
fll.9
117.5’
120.9
121 .8
124.4
120.4
10
131.7
131.9
131 s
134.4
133.4
111.9
114.8=
120.9
114.8
124.4
124.5
56.9
57.0
QMe
16.3(2-Me)
56.6
CQMe
56.8
21 .o
-CC&
21 .o
169.2
a 15.087 internal
TMS) angle,
-0.4
169.4
Natural-abundance 13C FT NMR spectra were recorded on a Varian NV-14 MHz using about 0.2-0.5 mmol cm-3 solutions in CDCI, and a-mm spinning
flipping
.
are about +O.l 8”;
acquisition
FT measurement
conditions
time,
number of data points,
ppm was observed when &O
0.6
set;
21 .o
are as follows:
was added to the CDCI,
solution
.*
169.9
FT NMR spectrometer at tubes; errors of 6C (from
spectral
4820.
21 .o
169.2
width,
3923 Hz;
b An upfield
C These assignments
shift
pulse
of about
may be reversed
in each column. TABLE Subtituent a-OH 8-QMe
a-OAC
13C Substituent
2.
C-l
c-2
c-3
c-4
+5.4
-0.1
+0.8
-0.7
TABLE
Shifts,
C-5
AS in ppmf for l_
C-6
c-7
C-8
c-9
c-10
-7.3
+2.a
-9.4
+35 .o
-16.9
-0.2
+33.7
-11 .4
+2.7
+0.6
-2.3
+2.4
+0.4
-7.9=
+1 .2
-14.3=
(-6.0
-2.2
+l .6
+1 .l
-0.6=
-1 .6
-4.9c
-0.6’
-1 .3
+1 .2
-1 .lC
-1 .3
+1 .l
-4.0
+23 .O
-8.4
+1.7
(-6.0c
-1 .2
+0.4
-0.4=
+6.0
-1 .7
+5.4
-12.0
+8.5
+1.9)b
a Plus sign denotes a downfield C These values should
shifts _
Chemical
2) holds fairly
well
be noted that the shift Some applications
b
shift.
Values
in parentheses
be changed if the signal
assignments
complexed
of the present
preferentially
results
will
are the methylation
to the 4-CO
b-e published
+5.5
+2.5)b
or acetylation
are reversed.
except for &, where a delocalized-electronic
reagent
-1 .3
structure rather
is dominant.7
than the 1 -CO
It should
in 2.
later.
REFERENCES
(1) (2)
R.H.
“Naturally
Thomson,
C.-K. Laskin
Wat,
“Microbial
and H.A.
Occurring Quinones,”
Lechevalier,
CRC Press Inc.,
(4)
J.B. Stothers, “Carbon-13 E. Wenkert, A.O. Clause,
(5)
For a review,
(6)
F.W. Wehrli, J.C.S. Chem. Comm. S. Katagiri, M, Kuds and N. Fukuoka,
(3)
(7)
(Tokyo),
2nd Ed.,
Chem.
Sot.
Academic
of Microbiology.
III.
Press,
Rev.
2,
London (1971).
Microbial
Cleveland, Ohio (1973). ” Academic Press, New York
NMR Spectroscopy, D.W. Cochran and D. Doddrell,
see 8. C. Mayo,
” 2AO9 (1974).
Quinones,” in “Handbook
J. Amer. Chem. Sot.
Products,”
Ed. A.I.
(1972). g,
6879
(1969).
49 (1973).
663 (1975). “Abstracts of the 7th Symposium
on Structural
Organic
Chemistry