Regioselective reduction of 2-perfluoroalkanoylcyclohexane-1,3-diones and their enamino derivatives

Article abstract of DOI:10.1134/S1070363211040098

Ionic hydrogenation of 2-perfluoroalkanoylcyclohexane-1,3-diones and their endocyclic enamino derivatives containing a secondary amino group by the action of triethylsilane in trifluoroacetic acid in the presence of a catalytic amount of lithium perchlora

Full text of DOI:10.1134/S1070363211040098

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 4, pp. 672–679. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © T.S. Khlebnikova, V.G. Isakova, A.V. Baranovskii, F.A. Lakhvich, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81,
No. 4, pp. 579–586.
Regioselective Reduction of 2-Perfluoroalkanoylcyclohexane-
1,3-diones and Their Enamino Derivatives
T. S. Khlebnikova, V. G. Isakova, A. V. Baranovskii, and F. A. Lakhvich
Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus,
ul. Akademika Kuprevicha 5/2, Minsk, 220141 Belarus
e-mail: khlebnicova@iboch.bas-net.by
Received April 5, 2010
Abstract—Ionic hydrogenation of 2-perfluoroalkanoylcyclohexane-1,3-diones and their endocyclic enamino
derivatives containing a secondary amino group by the action of triethylsilane in trifluoroacetic acid in the
presence of a catalytic amount of lithium perchlorate involved regioselective reduction of the side-chain
carbonyl group to hydroxy with formation of the corresponding hydroxy diketones and hydroxy amino ketones,
respectively. Under analogous conditions endocyclic enamino derivatives possessing a tertiary amino group
underwent deacylation to give enamino ketones.
DOI: 10.1134/S1070363211040098
Due to the presence of polyfunctional β-tricarbonyl
group 2-perfluoroalkanoylcyclohexane-1,3-diones are
effective as building blocks in the synthesis of
polyfluoroalkyl-containing carbo- and heterocyclic
structures [1–3]. It is known that products of selective
reduction of carbonyl group in cyclic β,β′-triketones
and their derivatives are widely used in organic
synthesis, in particular in syntheses of naturally
occurring and related compounds [4, 5]. Catalytic
hydrogenation of non-fluorinated 2-acylcycloalkane-
1,3-diones is characterized by low selectivity; reduc-
tion products of both side-chain carbonyl group and
one endocyclic carbonyl group are formed [6]. On the
other hand, ionic hydrogenation conditions [7] ensured
regioselective reduction of the side-chain carbonyl
group to methylene group in both 2-acylcycloalkane-
1,3-diones and their endocyclic enamino derivatives
[8, 9], and this approach was followed in the synthesis
of prostaglandins and phytoprostanes [10–13]. Taking
into account specificity of fluorine, introduction of
fluorine atoms into molecules of the above compounds
could dramatically affect their physical, chemical, and
biological properties [14]. In continuation of our
studies on chemical modification of 2-perfluoro-
alkanoylcyclohexane-1,3-diones in the present work
we examined their reductive transformations and
analogous transformations of their endocyclic enamino
derivatives, as well as the effect of fluorine atoms on
the reaction direction and yield.
The behavior of 2-perfluoroalkanoylcyclohexane-
1,3-diones Ia–If and their enamino derivatives at the
endocyclic carbonyl group was examined under ionic
hydrogenation conditions. We found that triethylsilane
in trifluoroacetic acid in the presence of lithium
perchlorate selectively reduces the exocyclic (side-
chain perfluoroalkanoyl) carbonyl group to hydroxy
[15]. Ionic hydrogenation of 2-perfluoroalkanoyl-
cyclohexane-1,3-diones Ia–If was performed at room
temperature (reaction time 5 h), and the yields of hyd-
roxy diketones IIa–IIf thus obtained were 80–95%
(Scheme 1). Increase of the reaction time to 24 h and
more did not result in further reduction of compounds
IIa–IIf.
By treatment of 2-perfluoroalkanoylcyclohexane-
1,3-diones Ia–If with oxalyl chloride and subsequent
vinylogoous substitution in the resulting 3-chloro-2-
perfluoroalkanoylcyclohex-2-en-1-ones by the action
of primary and secondary amines we obtained in high
yield enamino diketones IIIa–IIIj, IVa–IVj, and Va–
Vf [3]. The behavior of secondary (IIIa–IIIj, IVa–
IVj) and tertiary (Va–Vf) enamino derivatives under
analogous ionic hydrogenation conditions was studied.
Compounds IIIa–IIIj and IVa–IVj containing a
secondary amino group were regioselectively reduced
to polyfluoroalkyl-substituted enamino hydroxy ketones
VIa–VIj and VIIa–VIIj, whereas enamino diketones
Va–Vf having a tertiary amino group underwent
672

REGIOSELECTIVE REDUCTION OF 2-PERFLUOROALKANOYLCYCLOHEXANE-...
673
Scheme 1.
OH OH
RF
O
OH
RF
Et3SiH/LiClO4
TFA
R1
R1
R1
R1
O
O
O
O
O
IIа−IIf
O
OH
RF
R1
R1
RF
NR2R3
R1
R1
O
O
IIIа−IIIj,
IVа−IVj
Iа−If
Et3SiH/LiClO4
TFA
(1) (COCl)2
(2) R2R3NH
RF
NR2R3
VIа−VIj, VIIа−VIIj
R1
R1
O
R1
R1
IIа−IIj, IVа−IVj, Vа−Vf
Vа−Vf
N
n
VIIIа−VIIId
I, II, R1 = H: RF = CF3 (а), C2F5 (b), C3F7 (c); R1 = Me: RF = CF3 (d), C2F5 (e), C3F7 (f); III, IV, VI, VII, R2 = H: R3 = Ph,
RF = CF3 (а), C2F5 (b), C3F7 (c); R3 = 4-FC6H4, RF = CF3 (d), C2F5 (e), C3F7 (f); R3 = C6H5CH2, RF = CF3 (g), C2F5 (h), C3F7
(i); R3 = 4-FC6H4CH2, RF = CF3 (j); III, VI, R1 = H; IV, VII, R1 = Me; V, R1 = H: RF = CF3, R2R3 = (CH2)4 (а); RF = C2F5,
R2R3 = (CH2)4 (b); RF = C3F7, R2R3 = (CH2)4 (c); R1 = Me: RF = CF3, R2R3 = (CH2)5 (d); RF = C2F5, R2R3 = (CH2)5 (e); RF =
C3F7, R2R3 = (CH2)5 (f); VIII, R1 = H: n = 1 (а), 2 (b); R1 = Me: n = 1 (c), 2 (d).
deacylation to enamino ketones VIIIa–VIIId. De-
acylation was also observed previously [9] in the
course of ionic hydrogenation of endocyclic enamino
derivatives of non-fluorinated β,β′-triketones [9].
–76.68 ppm (3JFH = 7 Hz), respectively. Compounds
IIb–IIf with a longer perfluoroalkyl chain were
characterized by a complex 19F NMR spectral pattern
due to magnetic nonequivalence of fluorine atoms in
the CF2 groups.
The structure of the newly synthesized compounds
was confirmed by their elemental analysis and IR and
1H, 13C, and 19F NMR spectra. Previously described
compounds were identified by comparison of their
spectral parameters with published data. The IR
spectra of hydroxy diketones IIa–IIf contained
absorption bands belonging to stretching vibrations of
the hydroxy group and conjugated carbonyl group and
double bond in the regions 3410–3440, 1605–1615,
and 1555–1585 cm–1, respectively. In the 13C NMR
spectra of trifluoromethyl derivatives IIa and IId, the
C–OH carbon atom appeared as a quartet at δC 67.7
and 67.4 ppm (2JCF = 32 Hz), and the corresponding
signal of pentafluoroethyl (IIb, IIe) and hexafluoro-
propyl derivatives (IIc, IIf) was a doublet of doublets
at δC 67.8 (JCF = 27, 23 Hz), 66.8 (JCF = 28, 23 Hz) and
66.8 (JCF = 29, 23 Hz), 66.5 ppm (JCF = 28, 22 Hz),
respectively. Hydroxy diketones IIa and IId displayed
in the 19F NMR spectra a signal from fluorine atoms in
the trfluoromethyl group at δF –76.86 (3JFH = 7 Hz) and
1
In the H NMR spectra of hydroxy diketones IIa–
IIf we observed neither enol nor hydroxy proton
signal, obviously because of fast exchange. Therefore,
additional proofs for the assumed structure of these
compounds were necessary. For this purpose, com-
pound IIb was subjected to exhaustive methylation
using a large excess of diazomethane. As a result, we
isolated 90% of dimethoxy derivative IX (Scheme 2).
Its formation seemed to be somewhat surprising taking
into account that diazomethane generally does not
alkylate alcoholic hydroxy groups in the absence of
Scheme 2.
OMe
F
OMe
F
F
2'
1'
3'
3
2
CH2N2
Et2O
4
5
IIb
1
F
F
O
6
IX
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 4 2011

674
KHLEBNIKOVA et al.
catalyst. Presumably, strong electron-withdrawing per-
fluoroalkyl group reduces the electron density on the
oxygen atom and enhances the reactivity of the OH
proton.
Thus, unlike fluorine-free cyclic β,β-triketones, the
reduction of 2-perfluoroacylcyclohexane-1,3-diones
Ia–If and their secondary endocyclic enamino deriva-
tives IIIa–IIIj and IVa–IVj under ionic hydrogenation
conditions selectively gives hydroxy diketones IIa–IIf
and hydroxy enamino ketones VIa–VIj and VIIa–
VIIj, respectively; the reaction direction may be
rationalized in terms of the effect of electron-
withdrawing perfluoroalkyl substituent.
The structure dimethoxy derivative IX was
examined by two-dimensional NMR spectroscopy.
Quaternary carbon atoms were identified by analysis
of their long-range couplings using HMBC technique.
Although perfluorinated C2′ and C3′ carbon atoms
displayed no cross peaks, they can be readily identified
by coupling with fluorine nuclei. The CF2 carbon atom
gave a triplet of quartets at δC 113.08 ppm (1J = 259,
2J = 36 Hz), and the CF3 signal was a quartet of triplets
at δC 118.99 ppm (1J = 287, 2J = 36 Hz). The carbonyl
carbon atom C1 (δC 198.30 ppm) displayed a strong
coupling with protons on C6 and less intense cross
peaks with protons on C4 and C5. The C3 carbon atom
(δC 180.72 ppm) showed strong cross peaks with
protons in the methoxy group attached thereto and
protons on C4 and a weak cross peak with protons on
C5. The C2 atom (δc 108.42 ppm) displayed couplings
with protons on C4 and C6. Due to coupling with
fluorine the C1′ atom gave a triplet at δC 71.68 ppm
(2J = 24 Hz) in the 13C NMR spectrum, and the HMBC
spectrum contained a weak cross peak with protons in
the methoxy group on C1′.
EXPERIMENTAL
The NMR spectra were recorded on a Bruker
Avance-500 spectrometer at 500 (1H), 125 (13C), and
470 MHz (19F) from solutions in CDCl3 unless
otherwise stated; the chemical shifts were determined
relative to tetramethylsilane (1H, 13C) or CCl3F (19F) as
internal reference. The IR spectra were measured in
KBr on a UR-20 spectrometer. The melting points
were determined on a Boetius melting point apparatus.
Initial 2-perfluoroalkanoylcyclohexane-1,3-diones Ia–
If were synthesized according to the procedure
reported in [16], and enamino derivatives IIIa–IIIj,
IVa–IVj, and Va–Vf were obtained as described in [3].
The progress of reactions and the purity of products
were monitored by TLC on Silufol UV-254 plates
using diethyl ether as eluent.
In the IR spectra of hydroxy enamino ketones VIa–
VIj and VIIa–VIIj we observed absorption bands
typical of hydroxy group and conjugated carbonyl
group and double bond in the regions 3290–3420,
1625–1690, and 1565–1585 cm–1, respectively. In the
1H NMR spectra of VIa–VIj and VIIa–VIIj, the NH
proton is involved in intramolecular hydrogen bond
with the OH group, and its signal appears in a weak
field, at δ 9.29–10.48 ppm. Trifluoromethyl derivatives
VIa, VId, VIg, VIj, VIIa, VIId, VIIg, and VIIj
displayed in the 13C NMR spectra a quartet at δC 66.0–
66.4 ppm (2JCF = 33 Hz) from the C–OH carbon atom,
and analogous signal of perfluoroethyl (VIb, VIe, VIh,
VIIb, VIIe, VIIh) and perfluoropropyl derivatives
(VIc, VIf, VIi, VIIc, VIIf, VIIi) was a doublet of
doublets at δC 64.7–65.4 ppm (JCF = 27–28, 22–23 Hz).
The 19F NMR spectra of VIa, VId, VIg, VIj, VIIa,
VIId, VIIg, and VIIj indicated spin–spin coupling
between fluorine atoms in the trifluoromethyl group
and proton on the tertiary carbon atom: the CF3 group
gave a doublet at δF –77.70–78.24 ppm (3JF–H 48 Hz).
The 19F NMR spectra of hydroxy enamino alcohols
with a longer perfluorinated side chain showed a
complex pattern.
Reduction of 2-perfluoroalkanoylcyclohexane-
1,3-diones Ia–If and their enamino derivatives IIIa–
IIIj, IVa–IVj, and Va–Vf (general procedure). Com-
pound Ia–If, IIIa–IIIj, IVa–IVj, or Va–Vf, 1 mmol,
was dissolved in 2 ml of trifluoroacetic acid, 2 ml of a
1% solution of lithium perchlorate in trifluoroacetic
acid and 4 mmol of triethylsilane were added, and the
mixture was stirred for 5 h at room temperature.
Trifluoroacetic acid was distilled off under reduced
pressure, the residue was washed with a small amount
of n-hexane (4×4 ml) and treated with chloroform, the
solution was filtered, and the solvent was removed to
isolate compounds IIa–IIf, VIa–VIj, VIIa–VIIj, and
VIIIa–VIIId. Hydroxy diketones IIa–IIf were
purified by recrystallization from acetone–hexane, and
hydroxy enamino ketones VIa–VIj and VIIa–VIIj
were recrystallized from diethyl ether–hexane.
The physical constants and spectral parameters of
5,5-dimethyl-2-(2,2,2-trifluoro-1-hydroxyethyl)cyclo-
hexane-1,3-dione (IId) [15], 5,5-dimethyl-2-(2,2,3,3,3-
pentafluoro-1-hydroxypropyl)cyclohexane-1,3-dione
(IIe) [15], 3-(pyrrolidin-1-yl)cyclohex-2-en-1-one
(VIIIa) [17], 3-piperidinocyclohex-2-en-1-one (VIIIb)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 4 2011

REGIOSELECTIVE REDUCTION OF 2-PERFLUOROALKANOYLCYCLOHEXANE-...
675
[18], 5,5-dimethyl-3-(pyrrolidin-1-yl)cyclohex-2-en-1-
one (VIIIc) [19], and 5,5-dimethyl-3-piperidino-
cyclohex-2-en-1-one (VIIId) [20] were consistent with
published data.
spectrum (pyridine-d5), δC, ppm: 27.7, 31.7, 47.4, 66.5
d.d (JCF = 28, 22 Hz), 105.6, 110.3 t.m (1J = 265 Hz),
2
116.8 t.t (1J = 259, J = 30 Hz), 118.5 q.t (1J = 288,
2J = 35 Hz), 189.1. 19F NMR spectrum (pyridine-d5),
δF, ppm: –81.1 s (3F, CF3), –118.2 d (1F, 2JFF = 277 Hz),
2-(2,2,2-Trifluoro-1-hydroxyethyl)cyclohexane-
1,3-dione (IIa). Yield 88%, mp 89–92°C. IR spectrum,
ν, cm–1: 3410, 1610, 1585. 1H NMR spectrum, δ, ppm:
2.00 q (2H, CH2, 3J = 6.5 Hz), 2.44 d. t (2H, CH2, 2J =
–125.1 d (1F, 2JFF = 290 Hz), –126.6 d.m (1F, 2JFF
279 Hz), –127.4 d.d (1F, JFF = 291, JFH = 6 Hz).
Found, %: C 42.51; H 3.84. C12H13F7O3. Calculated,
%: C 42.59; H 3.88.
=
2
3
3
2
3
17.9, J = 6.5 Hz), 2.50 d.t (2H, CH2, J = 17.4, J =
6.5 Hz), 5.47 m (1H, CHOH). 13C NMR spectrum
(pyridine-d5), δC, ppm: 21.0, 34.1, 67.7 q (2JCF = 32 Hz),
107.4, 127.0 q (1J = 285 Hz), 190.3. 19F NMR
3-Phenylamino-2-(2,2,2-trifluoro-1-hydroxyethyl)-
cyclohex-2-en-1-one (VIa). Yield 75%, mp 169–172°C.
1
IR spectrum, ν, cm–1: 3320, 1675, 1565. H NMR
spectrum (pyridine-d5): δF –77.86 ppm (3F, CF3, 3JFH
=
spectrum, δ, ppm: 1.90 m (2H, CH2), 2.58 m (4H,
CH2), 5.73 m (1H, CHOH), 7.16 m (2H, Harom), 7.36 m
(1H, Harom), 7.42 m (2H, Harom), 10.32 br.s (1H, NH).
13C NMR spectrum, δC, ppm: 20.6, 27.9, 32.5, 66.3 q
(2J = 33 Hz), 102.4, 125.4 q (1J = 283 Hz), 125.7,
128.4, 129.8, 136.1, 173.5, 193.3. 19F NMR spectrum:
7 Hz). Found, %: C 45.81; H 4.38. C8H9F3O3.
Cal=culated, %: C 45.72; H 4.32.
2-(2,2,3,3,3-Pentafluoro-1-hydroxypropyl)cyclo-
hexane-1,3-dione (IIb). Yield 92%, mp 93–96°C. IR
spectrum, ν, cm–1: 3425, 1605, 1555. 1H NMR
3
3
δF –78.01 ppm, d (3F, CF3, JFH = 5 Hz). Found, %: C
spectrum, δ, ppm: 2.00 q (2H, CH2, J = 6.3 Hz), 2.46
2
3
58.85; H 4.91; N 4.85. C14H14F3NO2. Calculated, %: C
58.95; H 4.95; N 4.91.
d.t (2H, CH2, J = 17.9, J = 6.3 Hz), 2.51 d.t (2H,
CH2, 2J = 17.7, 3J = 6.3 Hz), 5.56 m (1H, CHOH). 13C
NMR spectrum (pyridine-d5), δC, ppm: 21.1, 34.2, 67.8
2-(2,2,3,3,3-Pentafluoro-1-hydroxypropyl)-3-
phenylaminocyclohex-2-en-1-one (VIb). Yield 77%,
mp 92–95°C. IR spectrum, ν, cm–1: 3310, 1675, 1565.
1H NMR spectrum, δ, ppm: 1.89 m (2H, CH2), 2.59 m
(4H, CH2), 5.90 m (1H, CHOH), 7.57 m (2H, Harom),
7.39 m (3H, Harom), 10.48 br.s (1H, NH). 13C NMR
spectrum, δC, ppm: 20.4, 28.0, 32.3, 65.2 d.d (JCF = 28,
2
d.d (JCF = 27, 23 Hz), 106.8, 120.6 q.t (1J = 288, J =
2
36 Hz), 115.7 t.q (1J = 258, J = 34 Hz), 191.1. 19F
NMR spectrum (pyridine-d5), δF, ppm: –81.6 s (3F,
2
CF3), –121.4 d (1F, JFF = 268 Hz), –129.1 d.d (1F,
3
2JFF = 269, JFH = 22 Hz). Found, %: C 41.62; H 3.53.
C9H9F5O3. Calculated, %: C 41.55; H 3.49.
2
23 Hz), 102.2, 114.6 t.q (1J = 256, J = 35 Hz), 119.2
2-(2,2,3,3,4,4,4-Heptafluoro-1-hydroxybutyl)cyclo-
2
q.t (1J = 287, J = 36 Hz), 125.8, 128.6, 129.9, 136.0,
hexane-1,3-dione (IIc). Yield 95%, mp 72–75°C. IR
174.6, 193.0. 19F NMR spectrum, δF, ppm: –82.25 s
1
spectrum, ν, cm–1: 3435, 1605, 1555. H NMR spec-
2
3
(3F, CF3), –122.52 d.m (1F, JFF = 275 Hz), –127.65
trum, δ, ppm: 2.00 q (2H, CH2, J = 6.1 Hz), 2.45 d.t
d.d (1F, 2JFF = 275, 3JFH = 20 Hz). Found, %: C 53.81;
H 4.25; N 4.24. C15H14F5NO2. Calculated, %: C 53.74;
H 4.21; N 4.18.
2
3
(2H, CH2, J = 17.8, J = 6.1 Hz), 2.51 d.t (2H, CH2,
2J = 17.7, 3J = 6.1 Hz), 5.63 m (1H, CHOH). 13C NMR
spectrum (pyridine-d5), δC, ppm: 21.0, 34.1, 66.8 d.d
(JCF = 29, 22 Hz), 106.8, 110.6 t.m (1J = 266 Hz),
2-(2,2,3,3,4,4,4-Heptafluoro-1-hydroxybutyl)-3-
phenylaminocyclohex-2-en-1-one (VIc). Yield 79%,
mp 95–98°C. IR spectrum, ν, cm–1: 3300, 1675, 1570.
1H NMR spectrum, δ, ppm: 1.92 m (2H, CH2), 2.61 m
(4H, CH2), 5.98 m (1H, CHOH), 7.18 m (2H, Harom),
7.42 m (3H, Harom), 10.34 br.s (1H, NH). 13C NMR
spectrum, δC, ppm: 20.5, 28.1, 32.3, 65.3 d.d (JCF = 28,
23 Hz), 102.3, 109.5 t.m (1J = 266 Hz), 116.2 t.t (1J =
2
117.0 t.t (1J = 260, J = 29 Hz), 118.8 q.t (1J = 288,
2J = 34 Hz), 190.7. 19F NMR spectrum (pyridine-d5),
2
δF, ppm: –79.95 s (3F, CF3), –117.32 d.d (1F, JFF
=
3
2
276, JFH = 4 Hz), –123.28 d (1F, JFF = 289 Hz), –
2
2
125.47 d.m (1F, JFF = 276 Hz), –126.23 d (1F, JFF
=
290 Hz). Found, %: C 38.65; H 2.90. C10H9F7O3.
Calculated, %: C 38.72; H 2.92.
2
2
2-(2,2,3,3,4,4,4-Heptafluoro-1-hydroxybutyl)-5,5-
dimethylcyclohexane-1,3-dione (IIf). Yield 93%,
mp 102–105°C. IR spectrum, ν, cm–1: 3440, 1610,
255, J = 30 Hz), 118.0 q.t (1J = 288, J = 34 Hz),
125.8, 128.6, 129.9, 136.0, 174.6, 193.1. 19F NMR
spectrum, δF, ppm: –81.07 m (3F, CF3), –118.82 d.m
1
2
2
1565. H NMR spectrum (pyridine-d5), δ, ppm: 1.09 s
(1F, JFF = 282 Hz), –125.15 d.m (1F, JFF = 282 Hz),
(6H, CH3), 2.32 d (2H, CH2, 2J = 17.5 Hz), 2.36 d (2H,
–125.62 d.m (1F, JFF = 292 Hz), –127.45 d.d (1F,
2
2
3
CH2, J = 17.5 Hz), 5.62 m (1H, CHOH). 13C NMR
2JFF = 292, JFH = 11 Hz). Found, %: C 49.79; H 3.60;
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KHLEBNIKOVA et al.
N 3.58. C16H14F7NO2. Calculated, %: C 49.88; H 3.66;
N 3.64.
NMR spectrum, δ, ppm: 1.91 m (2H, CH2), 2.63 m
(4H, CH2), 4.60 d (2H, CH2, 3J = 5.9 Hz), 5.64 m (1H,
CHOH), 7.22 m (2H, Harom), 7.35 m (3H, Harom), 9.82
3-(4-Fluorophenylamino)-2-(2,2,2-trifluoro-1-
hydroxyethyl)cyclohex-2-en-1-one (VId). Yield 76%,
mp 134–137°C. IR spectrum, ν, cm–1: 3290, 1675,
3
br.t (1H, NH, J = 5.9 Hz). 13C NMR spectrum, δC,
ppm: 19.5, 26.6, 30.2, 48.6, 66.0 q (2J = 33 Hz), 101.7,
125.1 q (1J = 283 Hz), 127.1, 128.7, 129.4, 134.2,
176.9, 188.8. 19F NMR spectrum: δF –78.24 ppm, d
(3F, CF3, 3JFH = 6 Hz). Found, %: C 60.29; H 5.43; N
4.74. C15H16NO2F3. Calculated, %: C 60.20; H 5.39; N
4.68.
1
1570. H NMR spectrum, δ, ppm: 1.91 m (2H, CH2),
2.56 m (4H, CH2), 5.71 m (1H, CHOH), 7.14 m (4H,
H
arom), 10.27 br.s (1H, NH). 13C NMR spectrum, δC,
ppm: 20.5, 27.9, 32.4, 66.3 q (2J = 33 Hz), 102.9,
116.8 d (2J = 23 Hz), 125.4 q (1J = 284 Hz), 127.9 d
(3J = 9 Hz), 132.1, 162.2 d (1J = 250 Hz), 174.0, 193.6.
3-Benzylamino-2-(2,2,3,3,3-pentafluoro-1-hyd-
roxypropyl)cyclohex-2-en-1-one (VIh). Yield 80%,
mp 86–89°C. IR spectrum, ν, cm–1: 3300, 1675, 1575.
1H NMR spectrum, δ, ppm: 1.79 m (2H, CH2), 2.50 m
(4H, CH2), 4.49 m (2H, CH2), 5.74 m (1H, CHOH),
7.14 m (2H, Harom), 7.24 m (3H, Harom), 9.64 br.s (1H,
NH). 13C NMR spectrum, δC, ppm: 19.3, 26.6, 30.4,
48.35, 64.7 d.d (JCF = 28, 22 Hz), 101.3, 114.2 t.q (1J =
19F NMR spectrum, δF, ppm: –78.15 d (3F, CF3, 3JFH
=
4 Hz), –112.36 m (1F). Found, %: C 55.51; H 4.37; N
4.69. C14H13F4NO2. Calculated, %: C 55.45; H 4.32; N
4.62.
3-(4-Fluorophenylamino)-2-(2,2,3,3,3-pentafluoro-
1-hydroxypropyl)cyclohex-2-en-1-one (VIe). Yield
76%, mp 78–81°C. IR spectrum, ν, cm–1: 3290, 1675,
2
2
256, J = 36 Hz), 118.9 q.t (1J = 287, J = 36 Hz),
126.9, 128.4, 129.2, 134.3, 176.7, 189.3. 19F NMR
spectrum, δF, ppm: –82.30 s (3F, CF3), –122.55 d.m
1
1575, 1515. H NMR spectrum, δ, ppm: 1.81 m (2H,
CH2), 2.45 m (4H, CH2), 5.78 m (1H, CHOH), 7.02 m
(2H, Harom), 7.07 m (2H, Harom), 10.04 br.s (1H, NH).
13C NMR spectrum, δC, ppm: 20.3, 27.8, 32.8, 65.0 d.d
(1F, 2JFF = 275 Hz), –127.72 d.d (1F, 2JFF = 275, 3JFH
=
20 Hz). Found, %: C 55.11; H 4.66; N 4.05.
C16H16NO2F5. Calculated, %: C 55.02; H 4.62; N 4.01.
2
(JCF = 27, 22 Hz), 102.2, 114.5 t.q (1J = 257, J =
37 Hz), 116.62 d (2J = 23 Hz), 119.03 q.t (1J = 285,
2J = 35 Hz), 127.89 (3J = 9 Hz), 132.1, 162.0 d (1J =
249 Hz), 173.5, 194.0. 19F NMR spectrum, δF, ppm:
–82.26 s (3F, CF3), –112.55 m (1F), –122.65 d.m (1F,
3-Benzylamino-2-(2,2,3,3,4,4,4-heptafluoro-1-
hydroxybutyl)cyclohex-2-en-1-one (VIi). Yield 88%,
mp 135–138°C. IR spectrum, ν, cm–1: 3305, 1675,
1
2
3
2JFF = 275 Hz), –127.62 d.d (1F, JFF = 275, JFH
=
1575. H NMR spectrum, δ, ppm: 1.88 m (2H, CH2),
2
2.23 m (1H), 2.40 m (2H, CH2), 2.57 d.t (1H, J =
14 Hz). Found, %: C 50.91; H 3.65; N 3.91.
C15H13F6NO2. Calculated, %: C 51.00; H 3.71; N 3.96.
17.1, 3J = 5.0 Hz), 4.47 d.d (1H, 2J = 15.9, 3J = 6.1 Hz),
2
3
4.51 d.d (1H, J = 15.9, J = 6.1 Hz), 5.75 m (1H,
CHOH), 7.25 m (2H, Harom), 7.30 m (1H, Harom), 7.37
m (2H, Harom), 9.89 br.s (1H, NH). 13C NMR spectrum,
δC, ppm: 20.5, 26.5, 35.5, 47.14, 65.2 m, 101.4, 109.5
3-(4-Fluorophenylamino)-2-(2,2,3,3,4,4,4-hepta-
fluoro-1-hydroxybutyl)cyclohex-2-en-1-one (VIf).
Yield 77%, mp 89–92°C. IR spectrum, ν, cm–1: 3290,
1
2
t.m (1J = 266 Hz), 116.6 t.t (1J = 254, J = 25 Hz),
1675, 1570. H NMR spectrum, δ, ppm: 1.91 m (2H,
2
118.0 q.t (1J = 288, J = 34 Hz), 126.5, 127.8, 129.0,
CH2), 2.54 m (2H, CH2), 5.95 m (1H, CHOH), 7.15 m
(4H, Harom), 10.00 br.s (1H, NH). 13C NMR spectrum,
δC, ppm: 20.5, 28.0, 33.0, 65.4 d.d (JCF = 28, 23 Hz),
102.5, 109.5 t.m (1J = 266 Hz), 116.3 t.t (1J = 255, 2J =
137.1, 168.9 d (3J = 2 Hz), 194.9. 19F NMR spectrum,
δF, ppm: –81.07 t (3F, CF3, J = 10 Hz), –118.79 d.m
2
2
(1F, JFF = 282 Hz), –124.34 d.m (1F, JFF = 282 Hz),
2
30 Hz), 116.8 d (2J = 23 Hz), 118.1 q.t (1J = 288, J =
2
3
–125.42 d.d (1F, JFF = 291, JFH = 7 Hz), –127.22 d.d
34 Hz), 128.1 d (3J = 8 Hz), 132.4, 162.2 d (1J = 249 Hz),
173.9, 194.2. 19F NMR spectrum, δF, ppm: –81.40 m
(3F, CF3), –112.73 s (1F), –119.31 d.m (1F, 2JFF = 282 Hz),
2
3
(1F, JFF = 290, JFH = 9 Hz). Found, %: C 51.06; H
4.01; N 3.46. C17H16NO2F7. Calculated, %: C 51.14; H
4.04; N 3.51.
2
–125.17 d.m (1F, JFF = 278 Hz), –125.71 d.m (1F,
3-(4-Fluorobenzylamino)-2-(2,2,2-trifluoro-1-hyd-
2
3
2JFF = 286 Hz), –127.49 d.d (1F, JFF = 292, JFH = 11
roxyethyl)cyclohex-2-en-1-one (VIj). Yield 78%, mp
Hz). Found, %:
C 47.74; H 3.32; N 3.54.
1
92–95°C. IR spectrum, ν, cm–1: 3290, 1675, 1585. H
C16H13F8NO2. Calculated, %: C 47.65; H 3.25; N 3.47.
NMR spectrum, δ, ppm: 1.94 m (2H, CH2), 2.63 m
(4H, CH2), 4.59 d (2H, CH2, 3J = 4.7 Hz), 5.63 m (1H,
CHOH), 7.07 m (2H, Harom), 7.23 m (2H, Harom), 9.62
br.s (1H, NH). 13C NMR spectrum, δC, ppm: 19.6,
3-Benzylamino-2-(2,2,2-trifluoro-1-hydroxy-
ethyl)cyclohex-2-en-1-one (VIg). Yield 79%, mp 91–
1
94°C. IR spectrum, ν, cm–1: 3290, 1680, 1580. H
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677
2
26.6, 30.6, 47.8, 66.0 q (2J = 33 Hz), 101.7, 116.4 d
(2J = 22 Hz), 125.1 q (1J = 284 Hz), 129.0 d (3J = 8 Hz),
130.2 d (4J = 1 Hz), 162.7 d (1J = 248 Hz), 176.1,
189.74. 19F NMR spectrum, δF, ppm: –78.18 d (3F,
CF3, 3JFH = 5 Hz), –113.27 m (1F). Found, %: C 56.87;
H 4.81; N 4.47. C15H15NO2F4. Calculated, %: C 56.78;
H 4.77; N 4.41.
–125.30 d.m (1F, JFF = 280.3 Hz), –125.55 d.m (1F,
2JFF = 292 Hz), –127.42 d.d (1F, 2JFF = 292, 3JFH = 12 Hz).
Found, %: C 52.24; H 4.35; N 3.33. C18H18NO2F7.
Calculated, %: C 52.31; H 4.39; N 3.39.
3-(4-Fluorophenylamino)-5,5-dimethyl-2-(2,2,2-
trifluoro-1-hydroxyethyl)cyclohex-2-en-1-one (VIId).
Yield 75%, mp 98–101°C. IR spectrum, ν, cm–1: 3300,
1675, 1570. H NMR spectrum, δ, ppm: 0.98 s (3H,
CH3), 1.01 s (3H, CH3), 2.31 d (1H, J = 17.1 Hz),
2.35 d (1H, J = 17.1 Hz), 2.42 d (2H, CH2, J =
14.0 Hz), 5.69 m (1H, CHOH), 7.12 m (4H, Harom),
10.04 br.s (1H, NH). 13C NMR spectrum, δC, ppm:
26.9, 28.2, 32.3, 41.0, 46.7, 66.3 q (2J = 33 Hz),
101.54, 116.77 d (2J = 23 Hz), 125.5 q (1J = 284 Hz),
128.1 d (3J = 9 Hz), 132.4, 162.0 d (1J = 249 Hz),
171.1, 193.3. 19F NMR spectrum, δF, ppm: –77.96 d
(3F, CF3, JFH = 8 Hz), –112.70 m (1F). Found, %:
C 58.00; H 5.17; N 4.23. C16H17NO2F4. Calculated, %:
C 58.00; H 5.17; N 4.23.
1
5,5-Dimethyl-3-phenylamino-2-(2,2,2-trifluoro-1-
hydroxyethyl)cyclohex-2-en-1-one (VIIa). Yield
77%, mp 65–68°C. IR spectrum, ν, cm–1: 3280, 1675,
2
2
2
1
1565. H NMR spectrum, δ, ppm: 1.01 s (3H, CH3),
2
1.03 s (3H, CH3), 2.35 d (1H, J = 16.9 Hz), 2.43 s
2
(2H, CH2), 2.43 d (1H, J = 16.9 Hz), 5.72 m (1H,
CHOH), 7.14 m (2H, Harom), 7.36 m (1H, Harom), 7.43
m (2H, Harom), 9.92 br.s (1H, NH). 13C NMR spectrum,
δC, ppm: 27.2, 28.1, 32.4, 41.0, 47.1, 66.4 q (2J =
33 Hz), 101.5, 125.5 q (1J = 284 Hz), 126.0, 128.0,
129.7, 136.5, 169.8, 193.5. 19F NMR spectrum: δF
–77.70 ppm, d (3JFH = 7 Hz). Found, %: C 61.43; H
5.82; N 4.54. C16H18NO2F3. Calculated, %: C 61.34; H
5.79; N 4.47.
3
3-(4-Fluorophenylamino)-5,5-dimethyl-2-(2,2,3,3,3-
pentafluoro-1-hydroxypropyl)cyclohex-2-en-1-one
(VIIe). Yield 75%, mp 78–81°C. IR spectrum, ν, cm–1:
5,5-Dimethyl-2-(2,2,3,3,3-pentafluoro-1-hydroxy-
propyl)-3-phenylaminocyclohex-2-en-1-one (VIIb).
Yield 76%, mp 75–78°C. IR spectrum, ν, cm–1: 3290,
1
3305, 1675, 1570. H NMR spectrum, δ, ppm: 0.99
2
br.s (6H, CH3), 2.30 d (1H, J = 17.6 Hz), 2.35 d (1H,
1
1675, 1570, 1510. H NMR spectrum, δ, ppm: 1.01
2J = 17.6 Hz), 2.36 s (2H, CH2), 5.85 m (1H, CHOH),
7.11 m (4H, Harom), 9.84 br.s (1H, NH). 13C NMR
spectrum, δC, ppm: 26.8, 28.1, 32.1, 41.0, 47.1, 65.0
2
br.s (6H, CH3), 2.37 d (1H, J = 16.9 Hz), 2.43 s (2H,
CH2), 2.44 d (1H, 2J = 16.9 Hz), 5.90 m (1H, CHOH),
2
7.15 m (2H, Harom), 7.36 m (1H, Harom), 7.43 m (2H,
d.d (JCF = 28, 22 Hz), 101.4, 114.6 t.q (1J = 255, J =
H
arom), 10.18 br.s (1H, NH). 13C NMR spectrum, δC,
36 Hz), 116.6 d (2J = 23 Hz), 119.1 q.t (1J = 287,
2J = 36 Hz), 128.1 (3J = 8 Hz), 132.6, 161.8 d (1J =
249 Hz), 170.5, 193.9. 19F NMR spectrum, δF, ppm:
–82.26 s (3F, CF3), –113.16 m (1F), –121.95 d.m (1F,
2JFF = 273 Hz), –127.92 d.m (2JFF = 277 Hz). Found,
%: C 53.48; H 4.45; N 3.62. C17H17NO2F6. Calculated,
%: C 53.55; H 4.49; N 3.67.
ppm: 26.9, 27.9, 32.2, 41.0, 46.6, 65.1 d.d (JCF = 28,
2
23 Hz), 101.3, 114.6 t.q (1J = 255, J = 36 Hz), 119.1
2
q.t (1J = 287, J = 36 Hz), 125.9, 128.1, 129.7, 136.3,
171.3, 193.0. 19F NMR spectrum, δF, ppm: –82.21 s
2
(3F, CF3), –121.86 d.m (1F, JFF = 275 Hz), –127.95
d.d (1F, 2JFF = 275, 3JFH = 15 Hz). Found, %: C 56.11;
H 4.95; N 3.80. C17H18NO2F5. Calculated, %: C 56.20;
H 4.99; N 3.86.
3-(4-Fluorophenylamino)-2-(2,2,3,3,4,4,4-hepta-
fluoro-1-hydroxybutyl)-5,5-dimethylcyclohex-2-en-
1-one (VIIf). Yield 77%, mp 87–90°C. IR spectrum, ν,
2-(2,2,3,3,4,4,4-Heptafluoro-1-hydroxybutyl)-5,5-
dimethyl-3-phenylaminocyclohex-2-en-1-one (VIIc).
Yield 78%, mp 52–55°C. IR spectrum, ν, cm–1: 3305,
1675, 1565. 1H NMR spectrum, δ, ppm: 1.02 br.s (6H,
CH3), 2.41 m (4H, CH2), 6.00 m (1H, CHOH), 7.15 m
(2H, Harom), 7.39 m (3H, Harom), 10.38 br.s (1H, NH).
13C NMR spectrum, δC, ppm: 26.8, 27.9, 32.2, 41.0,
46.3, 65.2 d.d (JCF = 28, 23 Hz), 101.4, 109.4 t.m (1J =
cm–1: 3290, 1685, 1575. H NMR spectrum, δ, ppm:
1
2
1.00 s (3H, CH3), 1.01 s (3H, CH3), 2.30 d (1H, J =
16.9 Hz), 2.36 d (1H, 2J = 16.9 Hz), 2.38 s (2H, CH2),
5.94 m (1H, CHOH), 7.12 m (4H, Harom), 9.96 br.s
(1H, NH). 13C NMR spectrum, δC, ppm: 26.8, 28.1,
32.1, 41.0, 47.1, 65.2 d.d (JCF = 27, 23 Hz), 101.5,
109.4 t.m (1J = 266 Hz), 116.3 t.t (1J = 254, J =
2
266 Hz), 116.2 t.t (1J = 255, J = 31 Hz), 117.9 q.t
30 Hz), 116.6 d (J = 23 Hz), 117.9 q.t (1J = 288, J =
2
2
(1J = 288, J = 34 Hz), 125.9, 128.2, 129.7, 136.2,
34 Hz), 128.1 d (3J = 8 Hz), 132.6, 161.9 d (1J =
249 Hz), 170.7, 193.8. 19F NMR spectrum, δF, ppm:
–81.30 t (3F, CF3, J = 8), –113.12 s (1F), –118.63 d.m
2
172.0, 192.6. 19F NMR spectrum, δF, ppm: –81.28 t
2
(3F, CF3, J = 9.3), –118.57 d.m (1F, JFF = 282.3 Hz),
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KHLEBNIKOVA et al.
2
2
2
2
(1F, JFF = 283 Hz), –125.29 d.m (1F, JFF = 286 Hz),
d.m (1F, JFF = 291 Hz), –127.44 d.d (1F, JFF = 292,
3JFH = 11 Hz). Found, %: C 53.48; H 4.75; N 3.45.
C19H20NO2F7. Calculated, %: C 53.40; H 4.72; N 3.28.
2
–125.58 d.m (1F, JFF = 292 Hz), –127.44 d.d (1F,
2JFF = 292, JFH = 11 Hz). Found, %: C 50.20; H 3.99;
3
N 3.31. C18H17NO2F8. Calculated, %: C 50.12; H 3.97;
N 3.25.
3-(4-Fluorobenzylamino)-5,5-dimethyl-2-(2,2,2-
trifluoro-1-hydroxyethyl)cyclohex-2-en-1-one (VIIj).
Yield 76%, mp 84–87°C. IR spectrum, ν, cm–1: 3420,
3-Benzylamino-5,5-dimethyl-2-(2,2,2-trifluoro-1-
hydroxyethyl)cyclohex-2-en-1-one (VIIg). Yield
78%, mp 72–75°C. IR spectrum, ν, cm–1: 3420, 1675,
1
1690, 1625, 1575. H NMR spectrum, δ, ppm: 0.97 s
(3H, CH3), 1.04 s (3H, CH3), 2.42 s (2H, CH2), 2.47 d
(2H, CH2, 2J = 18.5 Hz), 4.57 d (2H, CH2, 3J = 5.6 Hz),
5.64 m (1H, CHOH), 7.06 m (2H, Harom), 7.23 m (2H,
1
1580. H NMR spectrum, δ, ppm: 0.96 s (3H, CH3),
2
1.05 s (3H, CH3), 2.48 d (1H, J = 17.2 Hz), 2.50 s
(2H, CH2), 2.54 d (1H, 2J = 17.2 Hz), 2.62 d (2H, CH2,
3J = 5.7 Hz), 5.67 m (1H, CHOH), 7.23 m (2H, Harom),
7.32 m (2H, Harom), 7.38 m (1H, Harom), 9.29 br.s (1H,
NH). 13C NMR spectrum, δC, ppm: 26.9, 28.7, 31.8,
39.9, 44.9, 48.2, 66.2 q (2J = 33 Hz), 100.6, 125.3 q
(1J = 284 Hz), 126.8, 128.5, 129.3, 134.9, 173.7,
189.7. 19F NMR spectrum, δF, ppm: –77.87 d (3F, CF3,
3JFH = 7 Hz). Found, %: C 62.30; H 6.11; N 4.22.
C17H20NO2F3. Calculated, %: C 62.38; H 6.16; N 4.28.
H
arom), 9.30 br.s (1H, NH). 13C NMR spectrum, δC,
ppm: 26.7, 28.2, 31.5, 39.2, 45.1, 47.4, 66.1 q (2J = 33 Hz),
100.6, 116.2 d (2J = 22 Hz), 125.4 q (1J = 284 Hz),
128.7 d (3J = 8 Hz), 131.1 d (3J = 2 Hz), 162.6 d (1J =
247 Hz), 173.6, 189.9. 19F NMR spectrum, δF, ppm:
3
–77.88 d (3F, CF3, JFH = 8 Hz), –113.72 m (1F).
Found, %: C 59.21; H 5.59; N 4.12. C17H19NO2F4.
Calculated, %: C 59.13; H 5.55; N 4.06.
Methylation of 2-(2,2,3,3,3-pentafluoro-1-hyd-
roxypropyl)cyclohexane-1,3-dione (IIb). A solution
of diazomethane in diethyl ether prepared as described
[21], 15 ml, was added dropwise under stirring over a
period of 30 min to a solution of 1 mmol of compound
IIb in 10 ml of diethyl ether cooled to 0°C. The
solvent was distilled off under reduced pressure, and
the residue was recrystallized from diethyl ether–
hexane to isolate 3-methoxy-2-(2,2,3,3,3-pentafluoro-
1-methoxypropyl)cyclohex-2-en-1-one (IX) as a color-
less crystalline substance. Yield 90%, mp 110–113°C.
3-Benzylamino-5,5-dimethyl-2-(2,2,3,3,3-penta-
fluoro-1-hydroxypropyl)cyclohex-2-en-1-one (VIIh).
Yield 82%, mp 79–82°C. IR spectrum, ν, cm–1: 3410,
1
1680, 1565. H NMR spectrum, δ, ppm: 0.95 s (3H,
2
CH3), 1.01 s (3H, CH3), 2.36 d (1H, J = 17.9 Hz),
2
2.40 d (1H, J = 17.9 Hz), 4.57 m (2H, CH2), 5.84 m
(1H, CHOH), 7.23 m (2H, Harom), 7.30 m (1H, Harom),
7.36 m (2H, Harom), 9.37 br.s (1H, NH). 13C NMR
spectrum, δC, ppm: 26.4, 28.5, 31.4, 39.7, 44.9, 47.9,
64.8 d.d (JCF = 28, 22 Hz), 100.3, 114.5 t.q (1J = 255,
2
1
2J = 36 Hz), 119.0 q.t (1J = 287, J = 36 Hz), 126.6,
IR spectrum, ν, cm–1: 1645, 1595. H NMR spectrum,
128.2, 129.1, 135.2, 174.2, 189.6. 19F NMR spectrum,
δ, ppm: 1.94 m (2H, 5-H), 2.31 d.d (2H, 6-H, J =
2
2
3
δF, ppm: –82.20 s (3F, CF32), –121.86 d.m (1F, JFF
=
17.7, J 5.7 Hz), 2.66 m (2H, 4-H), 3.25 s (3H, 1′-
275 Hz), –127.78 d.m (1F, JFF = 277 Hz). Found, %:
C 57.38; H 5.39; N 3.78. C18H20F5NO2. Calculated, %:
C 57.29; H 5.34; N 3.71.
OCH3), 3.83 s (3H, 3-OCH3), 5.05 m (1H, 1′-H). 13C
NMR spectrum, δC, ppm: 19.94 (C5), 25.53 (C4), 36.05
(C6), 56.19 (3-OCH3), 58.29 (1′-OCH3), 71.68 t (C1′,
2J = 24 Hz), 108.42 (C2), 113.08 t.q (C2′, 1J = 259, 2J =
3-Benzylamino-2-(2,2,3,3,4,4,4-heptafluoro-1-hyd-
roxybutyl)-5,5-dimethylcyclohex-2-en-1-one (VIIi).
Yield 79%, mp 116–119°C. IR spectrum, ν, cm–1:
1
2
36 Hz), 118.99 q.t (C3′, J = 287, J = 36 Hz), 180.72
(C3), 198.30 (C1). 19F NMR spectrum, δF, ppm: –83.58
s (3F, CF3), –121.36 d.m (1F, 1J = 267 Hz),
1
3415, 1670, 1575. H NMR spectrum, δ, ppm: 0.95 s
1
–124.80 d.d (1F, J = 274, 3JFH = 20 Hz). Found, %: C
(3H, CH3), 1.01 s (3H, CH3), 2.38 d (1H, 2J = 17.8 Hz),
2
45.76; H 4.50. C11H13F5O3. Calculated, %: C 45.84; H
4.55.
2.42 d (1H, J = 17.8 Hz), 2.44 s (2H, CH2), 4.57 m
(2H, CH2), 5.94 m (1H, CHOH), 7.23 m (2H, Harom),
7.30 m (1H, Harom), 7.36 m (2H, Harom), 9.50 br.s (1H,
NH). 13C NMR spectrum, δC, ppm: 26.4, 28.5, 31.5,
39.8, 44.8, 47.9, 65.0 d.d (JCF = 28, 22 Hz), 100.4,
109.3 t.m (1J = 266 Hz), 116.1 t.t (1J = 254, 2J = 30 Hz),
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2
117.8 q.t (1J = 288, J = 34 Hz), 126.6, 128.2, 129.1,
135.2, 174.4, 189.5. 19F NMR spectrum, δF, ppm:
2
–81.27 t (3F, CF3, J = 9 Hz), –118.60 d.m (1F, JFF
=
2
282 Hz), –125.12 d.m (1F, JFF = 277 Hz), –125.62
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