Keto–Enol Equilibria in the Solid State
1
δ = 5.6 ppm, (d, 1 H, JH,F = 50.1 Hz). Likewise, the solid- series corroborate the presence of a single chemical species.
state IR of compound 3b, which can only exist as the di- Taken together, these facts are consistent with a chelated
ketone, displays two C=O bands at 1732 and 1761 cm–1.
A more detailed Raman spectroscopic study was under-
cis-enol structure (enol A) for β-diketone 1a, see Table 1.
taken on 4,4,4-trifluoro-1-phenyl-1,3-butanedione (1a) to Solution State Studies: NMR/Raman
ascertain whether multiple chemical species were present in
the solid-state and neat liquid. The results are shown in
Figure 3, where frame a depicts Raman spectra collected
from 1a as the sample underwent a solidǞliquid transition
from 20–84 °C and frame b shows a Hilbert–Noda synchro-
nous two-dimensional (2-D) correlation spectrum.
Spectroscopy
To assess whether the keto–enol and enol–enol equilibria
for β-diketones 1a–d and 2a–e were modulated in the solu-
tion state, 0.20 m solutions of compounds 1a–d were pre-
pared in sealed NMR tubes and H NMR (CDCl3 or [D6]-
DMSO) and Raman spectra (CDCl3 or CH3CN or [D6]-
1
The solidǞliquid phase transition study of 1a involved
a series of spectra collected at each temperature. The sample
temperature was held constant for a minimum of ten min-
utes between the incremental temperature increases. These
spectra showed no change over time or the temperature
range of the study. In Figure 3, frame a, the observation of
a lone, well-defined enolic C=O band at 1598 cm–1 in the
solid state (1602 cm–1 as a neat liquid) coupled with the
absence of bands above 1650 cm–1 suggests the presence of
enol form A which apparently does not undergo any ap-
preciable tautomerization during phase transition. If 1a
were a mixture of enol tautomers in the solid state or neat
liquid, one would anticipate that the C=O band would be
shifted to higher wavenumber and be somewhat broader in
appearance than the sharp C=O band observed.
DMSO) collected. Compounds 2a–e and 3b were examined
by H NMR in CDCl3. The results are recorded in Table 4.
1
The data in Table 4 reflect three distinct trends. For β-
diketones which are not fluorinated in the 2-position (1a–
d), a preference for cis-enol form A is indicated by the pre-
1
dominance of a H NMR resonance at δ(enol-H1) = 6.4–
6.9 ppm ([D6]DMSO), and Raman bands for enol A at
ν(enol) = 1590–1620 cm–1 ([D6]DMSO, CH3CN). The ob-
˜
servation that δH3 (enol-H3) moves to a lower chemical shift
in [D6]DMSO relative to that of CDCl3 suggests that polar,
aprotic solvents may disrupt the intramolecular H-bonding
of the chelated cis-enol form, see Figure 4.
Two-dimensional (2-D) correlation spectroscopy was
used to study which vibrational features were more suscep-
tible to change during the phase transition from solid to
liquid state.[15] The 2-D spectrum of 1a shows a strong, di-
rect correlation between the C=O band and the C–C–O
bend at 1230 cm–1, while being somewhat weakly correlated
to the C–F stretches at 1169, 1181 and 1353 cm–1 and the
C–H out-of-plane bend at 990 cm–1. This indicates possible
torsional adjustment of the molecule during the phase tran-
Figure 4. Disuption of cis-enol chelation.
Furthermore, and in accord with previous results,[1] the
sition, but the lack of complexity in the 2-D spectrum and 1-aryl-2-fluoro β-diketones 2a–e demonstrate only the di-
1
the absence of any new vibrational features in the Raman keto form, as evidenced by H NMR resonances: δ(H2) =
Table 4. Solution state diketone equilibria constants.
Method
NMR
KKǞE(A)
KEǞE
% Hydrate
δ / ppm
δ / ppm
[ ]: δH3 in [D6]DMSO
[ ]: δH1 in [D6]DMSO
( ): δH2 in [D6]DMSO
{ }: δH2 in CDCl3
(bǞa)
[D6]DMSO
(600 h)
{ }: δH3 in CDCl3
ν / cm–1
˜
Raman
ν / cm–1
[ ]: in [D6]DMSO
( ): in CH3CN
˜
[ ]: in [D6]DMSO
1a
1b
1c
1d
NMR
Raman
NMR
Raman
NMR
Raman
NMR
Raman
NMR
NMR
NMR
NMR
NMR
NMR
39.0
[6.8], (4.8)
not detected
[6.9]
not detected
[6.4]
not detected
[6.6], (4.2)
[1703]
(5.6), {5.7}
(5.5), {5.6}
(5.5), {5.6}
(5.4), {5.5}
(5.6), {5.7}
not detected
ϾϾ 1
ϾϾ 1
ϾϾ 1
ϾϾ 1
ϾϾ 1
ϾϾ 1
ϾϾ 1
ϾϾ 1
not detected
not detected
not detected
not detected
not detected
not detected
[14.2], {15.2}
[1594], (1599)
[10.8], {11.0}
(1608)
[14.1], {14.7}
(1613)
[16.3], (16.1)
[1603], (1620)
not detected
not detected
not detected
not detected
not detected
not detected
41
50
46
29
ϾϾ 1
ϾϾ 1
ϾϾ 1
ϾϾ 1
ϾϾ 1
2.2
Ͼ 1
2a
2b
2c
2d
2e
3b
ϽϽ 1
ϽϽ 1
ϽϽ 1
ϽϽ 1
ϽϽ 1
ϽϽ 1
45
60
52
35
41
70
Eur. J. Org. Chem. 2011, 936–941
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
939