MAGNETIC RESONANCE IN CHEMISTRY, VOL.

27, 11761183

Reference Data

' NMR of Lapachol and Some

C based on the results of a number of 1 D and
Related Naphthoquinones
BRIAN A. DAWSON (to whom correspon-
dence should be addressed), MICHEL
GIRARD, DARYL KINDACK, JULIE
FILLION and DENNIS V. C. AWANG
Bureau of Drug Research,
Health and Welfare Canada,
Tunney's Pasture,
Ottawa, Ontario,
Canada K1A OL2
13C N M R chemical shift assignments for
lapachol and nine related naphthoquinones
have been measured and interpreted. Data,
2D experiments performed at 9.4 T, correct
several previously reported assignments for
some of these compounds.
KEYWORDS 13C N M R Lapachol Naph-
thoquinones
INTRODUCTION
Recently we have been investigating the
naphthoquinone constituents of Tabebuia
spp. (Bignoneaceae) and have reported
HPLC and mass spectral methods for iden-
tifying them.I4 In this paper, we report the
I3C NMR data for these compounds, cor-
recting a number of previously reported
assignment^^-^ for some of them.
RESULTS AND DISCUSSION
The structures and numbering schemes for
the naphthoquinones studied are depicted in
Fig. 1 and the determined I3C chemical shift
assignments are presented in Table 1. For
eight of these compounds (HI),the chemical
shift assignments have been unambiguously
determined using a number of 1D and 2D
techniques. The assignments for the others
(for which only very small amounts were
available) were made by comparison with the
values for the known chemical shifts.

1 2

4 5 6

7 8 A

9 10
Figure 1. Structures and numbering scheme for the naphthoquinones.
8 1989 by John Wiley & Sons, Ltd.
 1177

Reference Data

Table 1. I3C chemical shifts (6) in ppm from TMS for the naphthoquinones
Carbon 1 2 3 4 5 8 7 0 0 1Q

1 181.61 181.92 179.16 172.10 181.31 179.86 179.70 180.63 173.93 173.50
2 152.67 156.30 151.88 150.72 151.25 154.53 178.39 174.38 152.86b NDfse
3 123.41 110.69 117.33 130.89 118.75 120.06 112.57 122.28 130.75 131.28
4 184.50 184.93 181.1 1 179.86 84.26 184.23 61.87 159.37 79.74 180.64
5 126.68 126.70 125.66 126.03 26.96 125.86 23.95 121.92 27.37" 127.01
6 134.75 135.27 133.52 132.88 34.80 133.74 33.66 135.21 34.31 133.81
7 132.77 133.13 132.77 133.17 32.95 132.82 30.50 129.67 34.446 133.93b
8 125.97 126.49 125.70 125.98 25.87 126.20 28.33 130.28 27.24' 126.91
9 129.37 129.40 130.97 131.88 29.39 131.10 29.98 128.56 32.63e 133.11
10 132.80 132.91 131.02 132.29 32.71 132.01 32.48 128.68 33.12e 134.44'
11 22.55 115.00 101.68 15.93 16.65 16.02 101.76 12.28 103.79
12 119.61 130.48 168.93 50.41 31.36 31.46 165.31 55.4gb 165.04"
13 133.73 79.79 27.82 33.39 78.04 79.15 27.79 187.48 63.88
14 25.69 27.98 20.16 22.15 26.43 26.62 20.61 26.77 21.50
15 17.83 27.98 20.16 22.15 26.43 26.62 20.61
"Too little material for 2D analysis; assignments by comparison with other compounds in table.
beAssignments may be interchanged.
' ND, peak not observed owing to insufficient signal-to-noise ratio.

The series of experiments used to arrive at
the shift assignments was basically the same
for seven of the naphthoquinones studied
(1-5, 7, 9, viz. high-resolution 'H and I3C
NMR spectra, 'H-'H COSY, and 13C-1H
COSY (short- and long-range) experiments.
For the other compound (6),it was necessary
to use a 13C-'3C COSY experiment in order
to make the carbon chemical shift assign-
ments.
I3C NMR chemical shift assignments have
been reported for a number of naphthoqui-
nones.'-* The results reported here are in
agreement with those of McDonald et al.' for
a-lapachone (6). However, all other sets of
data previously reported for the compounds
studied here contain some misassignments. In
fact, in one of these papers,' ten out of fifteen
of the assignments for lapachol have been
shown to be wrong.
EXPERIMENTAL
Materials
Lapachol (1) and 2-hydroxy-l,4naphthoqui-
none (2) were obtained from Aldrich
(Milwaukee, WI, USA). Compounds S S
were synthesized by published procedure^.^.^
Compounds 9 and 10 were isolated from T.
rosea bark. After identification by NMR and
MS, these compounds were synthesized;
chromium trioxide oxidation of 4 gave 9,
which was reduced with sodium borohydride
to give 10.
Spectra
Spectra were typically recorded for ca. 30 mg
of the naphthoquinone in 0.5 ml of CDCI, at
300 K on a Bruker AM400 spectrometer
equipped with an Aspect 3000 computer and
process controller, using DISNMR version
870101. The concentrations were different for
the INADEQUATE experiment for 6 (325
mg in 0.5 ml) and for 9 and 10 (< 1 mg in 0.5
ml). Standard microprograms from the
Bruker Software Library were employed.
The 'H-'H COSY experiments used
N-type phase cycling with a 45" mixing pulse.
The 'H-I3C COSY spectra were obtained
using a low decoupler power in the CW
mode (composite phase decoupling) with
polarization transfer from proton to 13C. The
FIDs for all 2D experiments were acquired
with sufficient data points and numbers of
evolution times to resolve all the proton and
carbon chemical shifts wherever possible. The
raw data were zero-filled in F , prior to FT,
and the sine-bell window function was
applied in both F, and F,. For long-range
'H-I3C coupling correlations, the delays
were chosen to emphasize values of ca. 7.5
Hz.
References
1. M. Girard, D. Kindack, B. A. Dawson,
J.-C. Ethier, D. V. C. Awang and A. H.
Gentry, J . Nat. Prod. 51, 1023 (1988).
2. D. V. C. Awang, D. Kindack and B. A.
Dawson, J. Chromatogr. 368, 439
(1986).
3. M. Girard, J.-C. Ethier, D. Kindack, B. A.
Dawson and D. V. C. Awang, J. Nat.
Prod. 50, 1149 (1987).
4. D. V. C. Awang, B. A. Dawson, J.-C.
Ether, A. H. Gentry, M. Girard and D.
Kindack, Rev. Latinoam. Quim., in press.
5. 1. A. McDonald, T. J . Simpson and A. F.
Sierakowski, Aust. J. Chem. 30, 1727
(1977).
6. L. David, J.-C. Gayet and H. Ves-
chambri, Agric. Biol. Chem. 49, 2693
(1985).
7. R. K. Goel, N. K. R. Pathak, M. Biswas,
B. Pandey and A. K. Sanyal, J . Pharm.
Pharmacol. 39,138 (1986).
8. S. L. Otten and J. P. Rosazza, J. Nat.
Prod. 44, 562 (1981).
Received 19 May 1989; accepted 18 July
1989