Reaction of 2-perfluoroalkanoylcyclohexane-1,3-diones and 3-chloro-2-perfluoroalkanoylcyclohex-2-ene-1-ones with amines

Article abstract of DOI:10.1134/S1070428009070033

Reactions of 2-perfluoroalkanoylcyclohexane-1,3-diones with primary and secondary amines involved acid cleavage of the substrate with formation of the corresponding 3-aminocyclohex-2-en-1-ones. Vinylogous nucleophilic substitution in 3-chloro-2-perfluoroa

Full text of DOI:10.1134/S1070428009070033

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 7, pp. 993–1001. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © T.S. Khlebnikova, V.G. Isakova, F.A. Lakhvich, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 7,
pp. 1007–1015.
Reaction of 2-Perfluoroalkanoylcyclohexane-1,3-diones
and 3-Chloro-2-perfluoroalkanoylcyclohex-2-ene-1-ones
with Amines
T. S. Khlebnikova, V. G. Isakova, 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 July 9, 2008
Abstract—Reactions of 2-perfluoroalkanoylcyclohexane-1,3-diones with primary and secondary amines
involved acid cleavage of the substrate with formation of the corresponding 3-aminocyclohex-2-en-1-ones.
Vinylogous nucleophilic substitution in 3-chloro-2-perfluoroalkanoylcyclohex-2-ene-1-ones with amines led to
the formation of 3-amino-2-perfluoroalkanoylcyclohex-2-ene-1-ones.
DOI: 10.1134/S1070428009070033
Recently synthesized 2-perfluoroalkanoylcyclohex-
ane-1,3-diones [1] are reactive compounds due to the
presence of three electrophilic centers (one exocyclic
and two endocyclic carbonyl groups), and they can be
used as starting compounds in the synthesis of a large
series of new biologically active polyfluoroalkyl-con-
taining carbo- and heterocyclic systems. 2-Perfluoro-
alkanoylcyclohexane-1,3-diones and the corresponding
methyl enol ethers are known to react with difunctional
nitrogen-containing nucleophiles such as phenylhydra-
zines to give regioisomeric 1-aryl-3-polyfluoroalkyl-
6,7-dihydro-1H-indazol-4(5H)-ones and 2-aryl-3-per-
fluoroalkyl-6,7-dihydro-2H-indazol-4(5H)-ones,
respectively [2]. There are no published data on reac-
tions of fluoroalkyl-containing cyclic β,β′-triketones
with nitrogen-centered mononucleophiles.
2-perfluoroalkanoylcyclohexane-1,3-diones exhibit
various kinds of biological activity, such as antiinflam-
matory, antiaggregation, gastroprotective, etc. [5]; they
are also used in agriculture as potent herbicides
(Sethoxydim, Tralkoxydim, etc.) [6]. Taking into ac-
count specific properties of fluorine atom, replacement
of hydrogen by fluorine could essentially affect phys-
ical, chemical, and biological properties of organic
compounds [7].
In the present work we examined reactions of
2-perfluoroalkanoylcyclohexane-1,3-diones and
3-chloro-2-perfluoroalkanoylcyclohex-2-en-1-ones
with primary (aniline, 4-fluoroaniline, benzylamine,
4-fluorobenzylamine) and secondary amines (pyrroli-
dine, piperidine) with a view to obtain new polyfluoro-
alkyl-containing enaminodiketones of the cyclohexane
series.
Vinylogous amides at the exocyclic carbonyl group
of nonfluorinated 2-acylcyclohexane-1,3-diones are
generally synthesized by condensation of these com-
pounds with amines [8]. However, like acyclic poly-
fluorinated β,β′‑tricarbonyl compounds [4], 2-per-
fluoroalkanoylcyclohexane-1,3-diones Ia–If in reac-
tions with primary and secondary amines even at room
temperature underwent acid cleavage to cyclohexane-
1,3-diones which were converted into enamino ketones
IIa–IIl (Scheme 1).
Reactions of both acyclic and alicyclic polyfluoro-
alkyl-containing β-dicarbonyl compounds with amines
have been studied in sufficient detail [3]. Their regio-
selectivity depends on the amine nature, the presence
or absence of fluoroalkyl substituents at the carbonyl
groups, and reaction conditions, so that they may in-
volve either one or both carbonyl groups. The main
side processes in these transformations are acid cleav-
age and salt formation. Acid cleavage was observed
exclusively for fluorine-containing acyclic β,β′-tri-
ketones [4].
Depending on the ring and side chain structure,
enamino derivatives of nonfluorinated analogs of
To obtain enamino derivatives IVa–IVr and Va–Vr
of 2-perfluoroalkanoylcyclohexane-1,3-diones it is
993

KHLEBNIKOVA et al.
994
Scheme 1.
O
R2R3NH
R1
R1
NR2R3
O
O
O
IIa–IIl
RF
R1
R1
O
O
O
O
Ia–If
R2R3NH
RF
RF
(COCl)2
R1
R1
R1
R1
IVa–IVr, Va–Vr
Cl
NR2R3
IIIa–IIIf
I, III, R1 = Me, RF = CF3 (a), C2F5 (b), C3F7 (c); R1 = H, RF = CF3 (d), C2F5 (e), C3F7 (f); II, R1 = Me, R2 = H, R3 = Ph (a),
4-FC6H4 (b), PhCH2 (c), 4-FC6H4CH2 (d); R2R3 = (CH2)4 (e), (CH2)5 (f); R1 = H, R2 = H, R3 = Ph (g), 4-FC6H4 (h), PhCH2 (i),
4-FC6H4CH2 (j); R2R3 = (CH2)4 (k), (CH2)5 (l); IV, V, R2 = H, R3 = Ph, RF = CF3 (a), C2F5 (b), C3F7 (c); R3 = 4-FC6H4, RF = CF3 (d),
C2F5 (e), C3F7 (f); R3 = PhCH2, RF = CF3 (g), C2F5 (h), C3F7 (i); R3 = 4-FC6H4CH2, RF = CF3 (j), C2F5 (k), C3F7 (l); R2R3 = (CH2)4,
RF = CF3 (m), C2F5 (n), C3F7 (o); R2R3 = (CH2)5, RF = CF3 (p), C2F5 (q), C3F7 (r); IV, R1 = Me; V, R1 = H.
necessary that nucleophilic attack be directed at the
trigonal C3 center, which may be achieved via initial
transformation of β,β′-triketones Ia–If into their enol
derivatives and treatment of the latter with amines. We
synthesized chlorovinyl diketones IIIa–IIIf by reac-
tion of β,β′-triketones Ia–If with excess oxalyl
chloride at room temperature. Unlike β,β′-triketones
having no fluorine atoms (the corresponding vinylo-
gous acid chlorides are formed in 3–5 h [9]), the
reactions with compounds Ia–If lasted 3–4 days, the
conversion of dimedone derivatives Ia–Ic was not
complete, and the yield of β-chlorovinyl diketones
IIIa–IIIc ranged from 60 to 68%. Presumably, the
reason is the presence of electron-withdrawing per-
fluoroalkanoyl substituent; the formation of chloro-
cyclohexenones IIIa–IIIc is also hampered due to
steric hindrances created by methyl groups in position
5 of the six-membered ring.
in the IR spectra a set of absorption bands in the
regions 1745–1750, 1680–1685, and 1615–1625 cm–1,
which belong to stretching vibrations of the uncon-
jugated exocyclic carbonyl group, conjugated endo-
cyclic carbonyl group, and double C=C bond, respec-
tively. The presence of a band at 1745–1750 cm–1
indicates that the exocyclic carbonyl group is forced
out from conjugation with the endocyclic C=C bond;
analogous pattern was observed previously for non-
fluorinated cyclic chlorovinyl diketones [9].
The IR spectra of 3-amino-2-perfluoroalkanoyl-
cyclohex-2-en-1-ones IVa–IVr and Va–Vr contained
absorption bands typical of endocyclic (1645–
1690 cm–1) and exocyclic carbonyl groups (1590–
1640 cm–1) and double C=C bond (1515–1585 cm–1).
The NH proton in compounds IV and V derived from
primary amines is involved in strong intramolecular
hydrogen bond with the exocyclic carbonyl group, and
1
Compounds IIIa–IIIf were treated with 2 equiv of
the corresponding amine, 1 equiv of which was con-
sumed for binding liberated hydrogen chloride. The
reactions were carried out in chloroform at room tem-
perature (reaction time 2–3 h), and the products were
3-amino-2-polyfluoroalkanoylcyclohex-2-en-1-ones
IVa–IVr and Va–Vr (yield 73–94%; Scheme 1). As
with fluorine-free analogs [8], the reaction was regio-
selective, and it followed vinylogous substitution
mechanism with formation of only one product.
its signal appeared in the H NMR spectra at δ 12.5–
13.0 (IVa–IVf, Va–Vf) or 11.4–11.9 ppm (IVg–IVk,
13
Vg–Vk). In the C NMR spectra of IVa–IVr and Va–
Vr signals from the endocyclic carbonyl carbon atom
and CH atom at the double bond were located at
δC 192.7–195.1 and 166.1–174.9 ppm, respectively.
The exocyclic carbonyl carbon atom in trifluoroacetyl
derivatives IVa, IVd, IVg, IVj, IVm, IVp, Va, Vd,
Vg, Vj, Vm, and Vp resonated as a quartet at
δC 178.1–183.9 ppm (2JCF = 35–36 Hz), while the cor-
responding signal in the spectra of pentafluoropro-
pionyl derivatives IVb, IVe, IVh, IVk, IVn, IVq, Vb,
Ve, Vh, Vk, Vn, and Vq and hexafluorobutanoyl
derivatives IVc, IVf, IVi, IVl, IVo, IVr, Vc, Vf, Vi,
The structure of compounds II–V was confirmed
by elemental analyses and IR, NMR, and mass spectra,
as well as by comparing with published data. Chloro-
vinyl diketones IIIa–IIIf characteristically displayed
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

REACTION OF 2-PERFLUOROALKANOYLCYCLOHEXANE-1,3-DIONES
995
trum, ν, cm–1: 1585, 1535, 1515. 1H NMR spectrum, δ,
ppm: 1.04 s (6H, CH3), 2.15 s (2H, CH2), 2.35 s (2H,
CH2), 5.32 s (1H, 2-H), 6.97 m (2H, Harom), 7.05 m
Vl, Vo, and Vr was a triplet at δC 180.6–189.9 ppm
(2JCF = 26– 28 Hz). The 19F NMR spectra of IVa, IVd,
IVg, IVj, IVm, IVp, Va, Vd, Vg, Vj, Vm, and Vp
contained a singlet at δF –72.5 to –73.5 ppm typical of
trifluoroacetyl group. Compounds IVb, IVe, IVh, IVk,
IVn, IVq, Vb, Ve, Vh, Vk, Vn, and Vq showed
fluorine signals at δF –79.1 to –80.3 (CF3) and –115.4
to –117.4 ppm (CF2), and signals from fluorine atoms
in hexafluorobutanoyl derivatives IVc, IVf, IVi, IVl,
IVo, IVr, Vc, Vf, Vi, Vl, Vo, and Vr were located at
δF –80.5 to –81.2 (CF3), –110.6 to –113.0 (CF2), and
–121.8 to –123.1 ppm (CF2).
13
(2H, Harom), 7.86 br.s (1H, NH). C NMR spectrum,
δC, ppm (JCF, Hz): 28.2, 29.7, 32.8, 43.0, 50.3, 97.2,
116.0 d (2J = 23), 126.2 d (3J = 8), 134.2 d (4J = 2),
19
160.3 d (1J = 246), 162.8, 198.1. F NMR spectrum:
δF –116.14 ppm.
3-(4-Fluorobenzylamino)-5,5-dimethylcyclohex-
2-en-1-one (IId). Yield 92%, mp. 142–145°C. IR spec-
1
trum, ν, cm–1: 1605, 1575. H NMR spectrum, δ, ppm
(J, Hz): 1.06 s (6H, CH3), 2.16 s (2H, CH2), 2.28 s
3
(2H, CH2), 4.24 d (2H, CH2, J = 4.3), 5.19 s (1H,
EXPERIMENTAL
2-H), 6.05 br.s (1H, NH), 7.01 m (2H, Harom), 7.23 m
(2H, Harom). 13C NMR spectrum, δC, ppm (JCF, Hz):
28.2, 29.7, 32.9, 43.3, 46.5, 49.4, 97.7, 115.8 d (2J =
22), 129.3 d (3J = 8), 132.3, 162.3 d (1J = 247), 164.3,
196.3. 19F NMR spectrum: δF –114.46 ppm.
The NMR spectra were recorded on a Bruker
Avance-500 spectrometer from solutions in CDCl3
13
using tetramethylsilane (1H, 500 MHz; C, 125 MHz)
and CCl3F (19F, 470 MHz) as internal references. The
IR spectra were measured on a UR-20 instrument from
samples prepared as KBr pellets (crystalline sub-
stances) or films (oily substances). The melting points
were determined on a Boetius melting point apparatus.
The progress of reactions and the purity of products
were monitored by TLC on Silufol UV-254 plates
using diethyl ether as eluent. Initial polyfluoroalkyl-
containing β,β′-triketones Ia–If were prepared accord-
ing to the procedure described in [1].
3-(4-Fluorophenylamino)cyclohex-2-en-1-one
(IIh). Yield 88%, mp 164–167°C. IR spectrum, ν,
1
cm–1: 1600, 1580. H NMR spectrum, δ, ppm (J, Hz):
3
3
1.99 quint (2H, CH2, J = 6.2), 2.32 t (2H, CH2, J =
3
6.2), 2.53 t (2H, CH2, J = 6.2), 5.37 s (1H, 2-H),
6.99 m (2H, Harom), 7.10 m (2H, Harom), 7.54 br.s (1H,
NH). 13C NMR spectrum, δC, ppm (JCF, Hz): 21.8,
29.4, 36.2, 98.7, 116.1 d (2J = 23), 126.3 d (3J = 8),
133.9, 160.4 d (1J = 246), 164.4, 198.4. 19F NMR spec-
trum: δF –115.92 ppm.
Reactions of 2-perfluoroalkanoylcyclohexane-
1,3-diones Ia–If with amines (general procedure).
Triketone Ia–If, 1 mmol, was dissolved in 20 ml of
chloroform, 1 mmol of the corresponding amine (ani-
line, 4-fluoroaniline, benzylamine, 4-fluorobenzyl-
amine, pyrrolidine, or piperidine) was added, and the
mixture was stirred for 7 h. The mixture was washed
with water and dried over magnesium sulfate, the
solvent was removed under reduced pressure, and the
residue was recrystallized from diethyl ether–hexane to
isolate individual enamino ketones IIa–IIl.
3-(4-Fluorobenzylamino)cyclohex-2-en-1-one
(IIj). Yield 90%, mp 114–117°C. IR spectrum, ν, cm–1:
1
1600, 1555. H NMR spectrum, δ, ppm (J, Hz):
3
3
1.96 quint (2H, CH2, J = 6.4), 2.28 t (2H, CH2, J =
3
3
6.4), 2.39 t (2H, CH2, J = 6.4), 4.19 d (2H, CH2, J =
5.1), 5.11 s (1H, 2-H), 5.59 br.s (1H, NH), 7.02 m (2H,
H
arom), 7.23 m (2H, Harom). 13C NMR spectrum, δC,
ppm (JCF, Hz): 22.0, 29.6, 36.4, 46.4, 97.3, 115.8 d
(2J = 22), 129.4 d (3J = 8), 132.6, 162.3 d (1J = 247),
164.5, 197.5. 19F NMR spectrum: δF –114.66 ppm.
3-Chloro-2-polyfluoroalkanoylcyclohex-2-en-
1-ones IIIa–IIIf (general procedure). A mixture of
1 mmol of compound Ia–If and 10 mmol of oxalyl
chloride was kept for 3–4 days at room temperature.
Excess oxalyl chloride was removed under reduced
pressure, the residue was dissolved in 15 ml of chloro-
form, the solution was washed with a saturated solu-
tion of sodium hydrogen carbonate and water and dried
over magnesium sulfate, and the solvent was removed
on a rotary evaporator.
5,5-Dimethyl-3-phenylaminocyclohex-2-en-1-one
(IIa) [10], 3-benzylamino-5,5-dimethylcyclohex-2-en-
1-one (IIc) [10], 5,5-dimethyl-3-(pyrrolidin-1-yl)cy-
clohex-2-en-1-one (IIe) [11], 5,5-dimethyl-3-piperi-
dinocyclohex-2-en-1-one (IIf) [12], 3-phenylamino-
cyclohex-2-en-1-one (IIg) [13], 3-benzylaminocyclo-
hex-2-en-1-one (IIi) [10], 3-(pyrrolidin-1-yl)cyclohex-
2-en-1-one (IIk) [14], and 3-piperidinocyclohex-2-en-
1-one (IIl) [15] were reported previously; their prop-
erties were consistent with published data.
3-(4-Fluorophenylamino)-5,5-dimethylcyclohex-
3-Chloro-5,5-dimethyl-2-trifluoroacetylcyclohex-
2-en-1-one (IIb). Yield 90%, mp 191–194°C. IR spec-
2-en-1-one (IIIa). Yield 60%, mp 67–70°C. IR spec-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

KHLEBNIKOVA et al.
996
1
2
trum, ν, cm–1: 1750, 1680, 1625. H NMR spectrum,
δ, ppm: 1.26 s (6H, CH3), 2.40 s (2H, CH2), 2.73 s
(2H, CH2). 13C NMR spectrum, δC, ppm (JCF, Hz):
27.8, 33.8, 48.3, 50.0, 114.8 q (1J = 291), 133.8,
157.2, 184.1 q (2J = 40), 193.4. 19F NMR spectrum:
δF –77.24 ppm (CF3).
(1J = 267), 117.5 q.t (1J = 288, J = 33), 135.2, 159.1,
187.1 t (2J = 31), 193.3. F NMR spectrum, δF, ppm:
–80.87 (CF3), –118.53 (CF2), –126.22 (CF2).
19
Reactions of chlorovinyl diketones IIIa–IIIf with
amines (general procedure). Compound IIIa–IIIf,
1 mmol, was dissolved in 15 ml of chloroform,
2 mmol of the corresponding amine was added, and the
mixture was stirred for 2–3 h, the progress of the
reaction being monitored by TLC. When the reaction
was complete, the mixture was washed with water and
dried over magnesium sulfate, the solvent was distilled
off under reduced pressure, and the residue was recrys-
tallized from diethyl ether–hexane. Compounds IVa–
IVr and Va–Vr were isolated as colorless crystalline
substances.
3-Chloro-5,5-dimethyl-2-(2,2,3,3,3-pentafluoro-
propanoyl)cyclohex-2-en-1-one (IIIb). Yield 63%,
colorless oily substance. IR spectrum, ν, cm–1: 1750,
1685, 1625. NMR spectrum H, δ, ppm : 1.16 s (6H,
2CH3), 2.40 s (2H, CH2), 2.73 s (2H, CH2). C NMR
1
13
spectrum, δC, ppm (JCF, Hz): 27.7, 33.7, 48.3, 50.0,
106.3 t.q (1J = 268, J = 38), 117.7 q.t (1J = 288, J =
2
2
34), 134.1, 157.1, 187.0 t (2J = 30), 193.34. F NMR
19
spectrum, δF, ppm: –81.59 (CF3), –121.41 (CF2).
3-Chloro-2-(2,2,3,3,4,4,4-heptafluorobutanoyl)-
5,5-dimethylcyclohex-2-en-1-one (IIIc). Yield 68%,
colorless oily substance. IR spectrum, ν, cm–1: 1750,
5,5-Dimethyl-2-trifluoroacetyl-3-phenylamino-
cyclohex-2-en-1-one (IVa). Yield 92%, mp 110–
113°C. IR spectrum, ν, cm–1: 1665, 1615, 1580.
1H NMR spectrum, δ, ppm: 1.04 s (6H, CH3), 2.39 s
(2H, CH2), 2.49 s (2H, CH2), 7.19 m (2H, Harom),
7.43 m (1H, Harom), 7.49 m (2H, Harom), 12.97 br.s
(1H, NH). 13C NMR spectrum, δC, ppm (JCF, Hz): 27.9,
31.5, 41.8, 51.5, 105.7, 117.3 q (1J = 287), 125.9,
128.6, 129.9, 135.8, 173.1, 180.4 q (2J = 36), 193.0.
19F NMR spectrum: δF –72.75 ppm (CF3). Found, %:
C 61.59; H 5.11; N 4.42. C16H16F3NO2. Calculated, %:
C 61.71; H 5.18; N 4.50.
1
1685, 1625. H NMR spectrum, δ, ppm: 1.16 s (6H,
13
CH3), 2.40 s (2H, CH2), 2.73 s (2H, CH2). C NMR
spectrum, δC, ppm (JCF, Hz): 27.8, 33.8, 48.5, 50.1,
2
107.9 t.t (1J = 269, J = 33), 108.7 t.m (1J = 267),
117.5 q.t (1J = 289, 2J = 33), 134.3, 157.2, 186.9 t (2J =
31), 193.4. 19F NMR spectrum, δF, ppm: –80.77 (CF3),
–118.45 (CF2), –126.16 (CF2).
3-Chloro-2-trifluoroacetylcyclohex-2-en-1-one
(IIId). Yield 97%, mp 83–86°C. IR spectrum, ν, cm–1:
1
1745, 1680, 1615. H NMR spectrum, δ, ppm (J, Hz):
5,5-Dimethyl-2-(2,2,3,3,3-pentafluoropropan-
oyl)-3-phenylaminocyclohex-2-en-1-one (IVb). Yield
89%, mp 126–129°C. IR spectrum, ν, cm–1: 1665,
3
3
2.18 quint (2H, CH2, J = 6.5), 2.55 t (2H, CH2, J =
3
13
6.5), 2.87 t (2H, CH2, J = 6.5). C NMR spectrum,
δC, ppm (JCF, Hz): 21.4, 34.5, 36.1, 114.8 q (1J = 291),
1
1595, 1565. H NMR spectrum, δ, ppm: 1.02 s (6H,
134.8, 159.0, 184.2 q (2J = 40), 193.3. F NMR spec-
19
CH3), 2.38 s (2H, CH2), 2.49 s (2H, CH2), 7.16 m (5H,
Harom), 12.83 br.s (1H, NH). 13C NMR spectrum, δC,
ppm (JCF, Hz): 28.0, 31.7, 41.9, 51.6, 107.0, 109.0 t.q
(1J = 271, 2J = 35), 119.1 q.t (1J = 288, 2J = 36), 126.0,
128.6, 129.9, 135.8, 172.7, 183.9 t (2J = 27), 193.0.
19F NMR spectrum, δF, ppm: –79.53 (CF3), –116.24
(2F, CF2). Found, %: C 56.61; H 4.86; N 3.93.
C17H16F5NO2. Calculated, %: C 56.49; H 4.77; N 3.88.
trum: δF –77.36 ppm (CF3).
3-Chloro-2-(2,2,3,3,3-pentafluoropropanoyl)-
cyclohex-2-en-1-one (IIIe). Yield 90%, colorless oily
substance. IR spectrum, ν, cm–1: 1745, 1685, 1620.
1H NMR spectrum, δ, ppm (J, Hz): 2.18 quint (2H,
3
3
CH2, J = 6.2), 2.55 t (2H, CH2, J = 6.2), 2.87 t (2H,
3
13
CH2, J = 6.2). C NMR spectrum, δC, ppm (JCF, Hz):
21.4, 34.6, 36.2, 106.3 t.q (1J = 268, 2J = 38), 117.9 q.t
2-(2,2,3,3,4,4,4-Heptafluorobutanoyl)-5,5-di-
methyl-3-phenylaminocyclohex-2-en-1-one (IVc).
Yield 88%, mp 56–59°C. IR spectrum, ν, cm–1: 1665,
(1J = 288, J = 34), 135.1, 159.0, 187.2 t (2J = 31),
2
193.3. 19F NMR spectrum, δF, ppm: –81.65 (CF3),
1
–121.47 (CF2).
1595, 1565. H NMR spectrum, δ, ppm: 1.03 s (6H,
3-Chloro-2-(2,2,3,3,4,4,4-heptafluorobutanoyl)-
cyclohex-2-en-1-one (IIIf). Yield 88%, colorless oily
substance. IR spectrum, ν, cm–1: 1745, 1680, 1615.
1H NMR spectrum, δ, ppm (J, Hz): 2.17 quint (2H,
CH3), 2.38 s (2H, CH2), 2.50 s (2H, CH2), 7.17 m (3H,
Harom), 7.48 m (2H, Harom), 12.68 br.s (1H, NH).
13C NMR spectrum, δC, ppm (JCF, Hz): 28.0, 31.8,
41.8, 51.4, 107.1, 109.9 t.m (1J = 269), 110.8 t.t (1J =
3
3
2
2
CH2, J = 6.1), 2.55 t (2H, CH2, J = 6.1), 2.87 t (2H,
269, J = 31), 118.1 q.t (1J = 288, J = 34), 126.0,
128.6, 129.9, 135.8, 172.3, 184.3 t (2J = 27), 193.1.
19F NMR spectrum, δF, ppm: –80.78 (CF3), –111.44
3
13
CH2, J = 6.1). C NMR spectrum, δC, ppm (JCF, Hz):
21.4, 34.8, 36.2, 107.9 t.t (1J = 269, 2J = 33), 108.6 t.m
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REACTION OF 2-PERFLUOROALKANOYLCYCLOHEXANE-1,3-DIONES
997
(CF2), –121.80 (CF2). Found, %: C 52.63; H 3.98;
N 3.47. C18H16F7NO2. Calculated, %: C 52.54; H 3.92;
N 3.41.
31.0, 40.6, 47.9, 51.2, 105.3, 117.4 q (1J = 288), 127.1,
128.5, 129.3, 135.0, 174.1, 179.7 q (2J = 36), 192.7.
19F NMR spectrum: δF –72.51 (CF3). Found, %:
C 62.66; H 5.54; N 4.25. C17H18F3NO2. Calculated, %:
C 62.76; H 5.58; N 4.31.
3-(4-Fluorophenylamino)-5,5-dimethyl-2-tri-
fluoroacetylcyclohex-2-en-1-one (IVd). Yield 90%,
mp 97–100°C. IR spectrum, ν, cm–1: 1680, 1610, 1570.
1H NMR spectrum, δ, ppm: 1.04 s (6H, CH3), 2.38 s
(2H, CH2), 2.44 s (2H, CH2), 7.18 m (4H, Harom),
12.85 br.s (1H, NH). 13C NMR spectrum, δC, ppm (JCF,
Hz): 27.9, 31.6, 41.8, 51.5, 105.9, 117.0 d (2J = 23),
117.3 q (1J = 288), 128.0 d (3J = 9), 131.9 d (4J = 2),
162.2 d (1J = 250), 173.4, 180.5 q (2J = 36), 193.0.
19F NMR spectrum, δF, ppm: –72.80 (CF3), –111.91
(1F). Found, %: C 58.21; H 4.54; N 4.19. C16H15F4NO2.
Calculated, %: C 58.36; H 4.59; N 4.25.
3-Benzylamino-5,5-dimethyl-2-(2,2,3,3,3-penta-
fluoropropanoyl)cyclohex-2-en-1-one (IVh). Yield
94%, mp 94–97°C. IR spectrum, ν, cm–1: 1665, 1590,
1
1565. H NMR spectrum, δ, ppm (J, Hz): 1.04 s (6H,
CH3), 2.30 s (2H, CH2), 2.54 s (2H, CH2), 4.60 d (2H,
CH2, 3J = 5.7), 7.26 m (3H, Harom), 7.33 m (2H, Harom),
11.71 br.s (1H, NH). 13C NMR spectrum, δC, ppm
(JCF, Hz): 28.2, 31.1, 40.6, 47.8, 51.1, 106.6, 109.1 t.q
(1J = 269, 2J = 35), 119.2 q.t (1J = 288, 2J = 36), 127.0,
128.5, 129.3, 135.0, 173.8, 183.2 t (2J = 27), 192.7.
19F NMR spectrum, δF, ppm: –79.55 (CF3), –116.15
(CF2). Found, %: C 57.71; H 4.89; N 4.80.
C18H18F5NO2. Calculated, %: C 57.60; H 4.83; N 3.73.
3-(4-Fluorophenylamino-5,5-dimethyl-2-
(2,2,3,3,3-pentafluoropropanoyl)cyclohex-2-en-1-
one (IVe). Yield 92%, mp 108–111°C. IR spectrum, ν,
1
cm–1: 1665, 1605, 1565. H NMR spectrum, δ, ppm:
3-Benzylamino-2-(2,2,3,3,4,4,4-heptafluoro-
butanoyl)-5,5-dimethylcyclohex-2-en-1-one (IVi).
Yield 88%, mp 72–75°C. IR spectrum, ν, cm–1: 1665,
1595, 1575. 1H NMR spectrum, δ, ppm (J, Hz): 1.05 s
(6H, CH3), 2.31 s (2H, CH2), 2.54 s (2H, CH2), 4.60 d
1.02 s (6H, CH3), 2.38 s (2H, CH2), 2.49 s (2H, CH2),
7.17 m (4H, Harom), 12.83 br.s (1H, NH). 13C NMR
spectrum, δC, ppm (JCF, Hz): 28.0, 31.7, 41.9, 51.5,
2
107.1, 109.0 t.q (1J = 271, J = 35), 117.0 d (2J = 23),
2
3
119.1 q.t (1J = 288, J = 36), 128.0 d (3J = 9), 131.8
(2H, CH2, J = 5.9), 7.26 m (3H, Harom), 7.41 m (2H,
(4J = 2), 162.2 d (1J = 250), 173.1, 184.0 t (2J = 28),
192.9. 19F NMR spectrum, δF, ppm: –79.58 (CF3),
–111.96 (F), –116.30 (CF2). Found, %: C 53.75;
H 4.14; N 3.61. C17H15F6NO2. Calculated, %: C 53.83;
H 3.99; N 3.69.
H
arom), 11.58 br.s (1H, NH). 13C NMR spectrum, δC,
ppm (JCF, Hz): 28.3, 31.2, 40.6, 47.8, 50.9, 106.8,
2
109.8 t.m (1J = 269), 110.8 t.t (1J = 269, J = 31),
2
118.1 q.t (1J = 288, J = 34), 127.0, 128.6, 129.4,
19
134.9, 173.3, 183.7 t (2J = 26), 192.7. F NMR spec-
trum, δF, ppm: –80.83 (CF3), –111.37 (CF2), –121.79
(CF2). Found, %: C 53.73; H 4.21; N 3.23.
C19H18F7NO2. Calculated, %: C 53.65; H 4.27; N 3.29.
3-(4-Fluorophenylamino)-2-(2,2,3,3,4,4,4-hepta-
fluorobutanoyl)-5,5-dimethylcyclohex-2-en-1-one
(IVf). Yield 87%, mp 51–54°C. IR spectrum, ν, cm–1:
1
1670, 1605, 1565. H NMR spectrum, δ, ppm: 1.03 s
3-(4-Fluorobenzylamino)-5,5-dimethyl-2-tri-
fluoroacetylcyclohex-2-en-1-one (IVj). Yield 93%,
mp 79–82°C. IR spectrum, ν, cm–1: 1665, 1605, 1580.
1H NMR spectrum, δ, ppm (J, Hz): 1.06 s (6H, CH3),
2.30 s (2H, CH2), 2.58 s (2H, CH2), 4.62 d (2H, CH2,
3J = 5.7), 7.09 m (2H, Harom), 7.27 m (2H, Harom),
11.84 br.s (1H, NH). 13C NMR spectrum, δC, ppm
(JCF, Hz): 28.2, 31.0, 40.6, 47.2, 51.2, 105.3, 116.3 d
(2J = 22), 117.4 q (1J = 288), 129.1 d (3J = 8), 130.8,
162.6 d (1J = 248), 174.0, 179.7 q (2J = 36), 192.7.
19F NMR spectrum, δF, ppm: –72.53 (CF3), –113.40
(F). Found, %: C 59.39; H 4.94; N 4.06. C17H17F4NO2.
Calculated, %: C 59.47; H 4.99; N 4.08.
(6H, CH3), 2.37 s (2H, CH2), 2.45 s (2H, CH2), 7.18 m
13
(4H, Harom), 12.57 br.s (1H, NH). C NMR spectrum,
δC, ppm (JCF, Hz): 28.0, 31.8, 41.8, 51.4, 107.2,
2
109.8 t.m (1J = 269), 110.8 t.t (1J = 269, J = 31),
117.0 d (2J = 23), 118.3 q.t (1J = 288, 2J = 34), 128.0 d
(3J = 9), 131.8 (4J = 2), 162.2 d (1J = 250), 172.6,
19
184.4 t (2J = 27), 193.0. F NMR spectrum, δF, ppm:
–80.80 (CF3), –111.52 (CF2), –111.93 (F), –121.86
(CF2). Found, %: C 50.46; H 3.59; N 3.31.
C18H15F8NO2. Calculated, %: C 50.36; H 3.52; N 3.26.
3-Benzylamino-5,5-dimethyl-2-trifluoroacetyl-
cyclohex-2-en-1-one (IVg). Yield 93%, mp 62–65°C.
1
IR spectrum, ν, cm–1: 1665, 1605, 1575. H NMR
3-(4-Fluorobenzylamino)-5,5-dimethyl-2-
(2,2,3,3,3-pentafluoropropanoyl)cyclohex-2-en-1-
one (IVk). Yield 80%, mp 87–90°C. IR spectrum, ν,
spectrum, δ, ppm (J, Hz): 1.04 s (6H, CH3), 2.30 s (2H,
3
CH2), 2.57 s (2H, CH2), 4.62 d (2H, CH2, J = 5.8),
1
7.27 m (2H, Harom), 7.37 m (3H, Harom), 11.88 br.s
cm–1: 1650, 1600, 1570. H NMR spectrum, δ, ppm
(1H, NH). 13C NMR spectrum, δC, ppm (JCF, Hz): 28.2,
(J, Hz): 1.05 s (6H, CH3), 2.31 s (2H, CH2), 2.55 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

KHLEBNIKOVA et al.
998
3
(2H, CH2), 4.59 d (2H, CH2, J = 5.7), 7.09 m
(2H, Harom), 7.24 m (2H, Harom), 11.66 br.s (1H, NH).
13C NMR spectrum, δC, ppm (JCF, Hz): 28.2, 31.1,
2-(2,2,3,3,4,4,4-Heptafluorobutanoyl)-5,5-di-
methyl-3-(pyrrolidin-1-yl)cyclohex-2-en-1-one
(IVo). Yield 79%, mp 87–90°C. IR spectrum, ν, cm–1:
1
40.6, 47.2, 51.1, 106.7, 109.1 t.q (1J = 271, J = 35),
2
1665, 1630, 1520. H NMR spectrum, δ, ppm (J, Hz):
116.4 d (2J = 22), 119.2 q.t (1J = 288, 2J = 36), 130.0 d
(3J = 8), 130.8 d (4J = 3), 162.7 d (1J = 248), 173.7,
1.09 s (6H, CH3), 2.01 m (4H, CH2), 2.28 s (2H, CH2),
2.54 s (2H, CH2), 2.81 m (2H, CH2), 3.64 m (2H,
CH2). 13C NMR spectrum, δC, ppm (JCF, Hz): 24.6,
25.9, 28.4, 31.1, 44.8, 50.9, 51.7, 55.7, 107.8, 109.5 t.t
(1J = 268, 2J = 31), 109.7 t.m (1J = 268), 118.0 q.t (1J =
288, 2J = 34), 166.2, 186.4 t (2J = 27), 194.7. 19F NMR
spectrum, δF, ppm: –81.22 (CF3), –110.58 (CF2),
–122.37 (CF2). Found, %: C 49.48; H 4.52; N 3.65.
C16H18F7NO2. Calculated, %: C 49.36; H 4.66; N 3.60.
183.2 t (2J = 27), 192.7. F NMR spectrum, δF, ppm:
19
–79.62 (CF3), –113.35 (F), –116.22 (CF2). Found, %:
C 54.90; H 4.29; N 3.51. C18H17F6NO2. Calculated, %:
C 54.97; H 4.36; N 3.56.
3-(4-Fluorobenzylamino)-2-(2,2,3,3,4,4,4-hepta-
fluorobutanoyl)-5,5-dimethylcyclohex-2-en-1-one
(IVl). Yield 83%, mp 65–68°C. IR spectrum, ν, cm–1:
1
5,5-Dimethyl-3-piperidino-2-trifluoroacetylcyclo-
1660, 1605, 1575. H NMR spectrum, δ, ppm (J, Hz):
hex-2-en-1-one (IVp). Yield 80%, mp 109–112°C. IR
1.07 s (6H, CH3), 2.33 s (2H, CH2), 2.54 s (2H, CH2),
1
spectrum, ν, cm–1: 1665, 1625, 1535. H NMR spec-
4.59 d (2H, CH2, 3J = 5.8), 7.10 m (2H, Harom), 7.25 m
13
trum, δ, ppm (J, Hz): 1.13 s (6H, CH3), 1.75 m (6H,
CH2), 2.28 s (2H, CH2), 2.53 s (2H, CH2) 3.36 m (4H,
CH2). 13C NMR spectrum, δC, ppm (JCF, Hz): 23.2,
26.2, 28.7, 31.5, 44.3, 50.5, 53.3, 106.4, 116.9 q (1J =
(2H, Harom), 11.54 br.s (1H, NH). C NMR spectrum,
δC, ppm (JCF, Hz): 28.3, 31.2, 40.6, 47.2, 50.9, 106.8,
109.8 t.m (1J = 269), 110.8 t.t (1J = 269, 2J = 31), 116.4
d (2J = 22), 118.1 q.t (1J = 288, 2J = 34), 128.9 d (3J =
8), 130.7 d (4J = 3), 162.7 d (1J = 248), 173.2, 183.8 t
19
290), 171.8, 179.9 q (2J = 35), 194.1. F NMR spec-
trum: δF –73.17 ppm (CF3). Found, %: C 59.25;
H 6.59; N 4.53. C15H20F3NO2. Calculated, %: C 59.40;
H 6.65; N 4.62.
(2J = 27), 192.7. F NMR spectrum, δF, ppm: –80.86
19
(CF3), –111.41 (CF2), –113.20 (F), –121.82 m (CF2).
Found, %: C 51.59; H 3.93; N 3.20. C19H17F8NO2.
Calculated, %: C 51.47; H 3.87; N 3.16.
5,5-Dimethyl-2-(2,2,3,3,3-pentafluoropropan-
oyl)-3-piperidinocyclohex-2-en-1-one (IVq). Yield
78%, mp 136–139°C. IR spectrum, ν, cm–1: 1655,
1615, 1515. 1H NMR spectrum, δ, ppm (J, Hz): 1.13 s
(6H, CH3), 1.74 m (6H, CH2), 2.30 s (2H, CH2), 2.52 s
5,5-Dimethyl-3-(pyrrolidin-1-yl)-2-trifluoroace-
tylcyclohex-2-en-1-one (IVm). Yield 83%, mp 151–
154°C. IR spectrum, ν, cm–1: 1690, 1620, 1525.
1H NMR spectrum, δ, ppm (J, Hz): 1.09 s (6H, CH3),
2.02 m (4H, CH2), 2.27 s (2H, CH2), 2.55 s (2H, CH2),
13
(2H, CH2), 3.37 m (4H, CH2). C NMR spectrum, δC,
ppm (JCF, Hz): 23.3, 26.3, 28.8, 31.4, 44.5, 50.5, 53.2,
107.4, 108.2 t.q (1J = 271, 2J = 35), 119.0 q.t (1J = 288,
2J = 36), 171.8, 182.7 t (2J = 27), 193.5. 19F NMR
spectrum, δF, ppm: –80.06 (CF3), –117.32 (CF2).
Found, %: C 54.28; H 5.65; N 3.89. C16H20F5NO2.
Calculated, %: C 54.39; H 5.71; N 3.96.
13
2.76 m (2H, CH2), 3.65 m (2H, CH2). C NMR spec-
trum, δC, ppm (JCF, Hz): 24.6, 25.9, 28.3, 31.1, 44.5,
50.8, 51.5, 55.8, 107.2, 116.3 q (1J = 290), 166.1,
183.9 q (2J = 35), 195.0. 19F NMR spectrum:
δF –73.73 ppm (CF3). Found, %: C 58.00; H 6.21;
N 4.78. C14H18F3NO2. Calculated, %: C 58.12; H 6.27;
N 4.84.
2-(2,2,3,3,4,4,4-Hexafluorobutanoyl)-5,5-dimeth-
yl-3-piperidinocyclohex-2-en-1-one (IVr). Yield
77%, mp 80–83°C. IR spectrum, ν, cm–1: 1670, 1625,
5,5-Dimethyl-2-(2,2,3,3,3-pentafluoropropan-
oyl)-3-(pyrrolidin-1-yl)cyclohex-2-en-1-one (IVn).
Yield 78%, mp 143–146°C. IR spectrum, ν, cm–1:
1
1520. H NMR spectrum, δ, ppm (J, Hz): 1.12 s (6H,
CH3), 1.73 m (6H, CH2), 2.28 s (2H, CH2), 2.51 s (2H,
13
1
CH2), 3.36 m (4H, CH2). C NMR spectrum, δC, ppm
1660, 1625, 1520. H NMR spectrum, δ, ppm (J, Hz):
(JCF, Hz): 23.3, 26.3, 28.8, 31.5, 44.5, 50.4, 53.1,
1.09 s (6H, CH3), 2.01 m (4H, CH2), 2.28 s (2H, CH2),
2.55 s (2H, CH2), 2.79 m (2H, CH2), 3.64 m (2H,
CH2). 13C NMR spectrum, δC, ppm (JCF, Hz): 24.6,
25.9, 28.3, 31.0, 44.9, 51.0, 51.7, 55.6, 107.7 t.q (1J =
2
107.4, 109.7 t.m (1J = 268), 109.9 t.t (1J = 270, J =
2
30), 118.0 q.t (1J = 288, J = 35), 171.5, 183.9 t (2J =
27), 193.4. 19F NMR spectrum, δF, ppm: –80.94 (CF3),
–113.02 (CF2), –123.11 (CF2). Found, %: C 50.73;
H 5.06; N 3.55. C17H20F7NO2. Calculated, %: C 50.62;
H 5.00; N 3.47.
269, J = 35), 108.0, 119.0 q.t (1J = 288, J = 36),
166.5, 185.9 t (2J = 27), 194.7. 19F NMR spectrum, δF,
ppm: –79.42 (CF3), –115.46 (CF2). Found, %: C 53.23;
H 5.39; N 4.20. C15H18F5NO2. Calculated, %: C 53.10;
H 5.35; N 4.13.
2
2
3-Phenylamino-2-trifluoroacetylcyclohex-2-en-1-
one (Va). Yield 87%, mp 125–128°C. IR spectrum, ν,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

REACTION OF 2-PERFLUOROALKANOYLCYCLOHEXANE-1,3-DIONES
999
1
cm–1: 1670, 1620, 1570. H NMR spectrum, δ, ppm
3-(4-Fluorophenylamino)-2-(2,2,3,3,3-penta-
fluoropropanoyl)cyclohex-2-en-1-one (Ve). Yield
85%, mp 123–126°C. IR spectrum, ν, cm–1: 1665,
3
(J, Hz): 1.92 quint (2H, CH2, J = 6.4), 2.47 t (2H,
3
3
CH2, J = 6.4), 2.63 t (2H, CH2, J = 6.4), 7.20 m
(2H, Harom), 7.40 m (1H, Harom), 7.47 m (2H, Harom),
12.85 br.s (1H, NH). 13C NMR spectrum, δC, ppm
(JCF, Hz): 20.1, 28.9, 37.8, 106.7, 117.3 q (1J = 288),
125.9, 128.6, 129.8, 135.9, 174.3, 180.8 q (2J = 36),
193.4. 19F NMR spectrum: δF –72.61 ppm (CF3).
Found, %: C 59.28; H 4.22; N 4.89. C14H12F3NO2.
Calculated, %: C 59.37; H 4.27; N 4.94.
1
1615, 1570. H NMR spectrum, δ, ppm (J, Hz):
3
3
1.95 quint (2H, CH2, J = 6.4), 2.50 t (2H, CH2, J =
3
6.4), 2.59 t (2H, CH2, J = 6.4), 7.18 m (4H, Harom),
12.64 br.s (1H, NH). 13C NMR spectrum, δC, ppm
(JCF, Hz): 20.1, 28.8, 37.7, 108.0, 108.9 t.q (1J = 271,
2J = 35), 116.9 d (2J = 23), 119.1 q.t (1J = 288, J =
2
36), 127.9 d (3J = 9), 131.8, 162.2 d (1J = 250), 174.3,
184.4 t (2J = 28), 193.2. F NMR spectrum, δF, ppm:
19
2-(2,2,3,3,3-Pentafluoropropanoyl)-3-phenyl-
aminocyclohex-2-en-1-one (Vb). Yield 88%, mp 109–
112°C. IR spectrum, ν, cm–1: 1665, 1600, 1565.
1H NMR spectrum, δ, ppm (J, Hz): 1.94 quint (2H,
–79.61 (CF3), –112.06 (F), –116.29 (CF2). Found, %:
C 51.17; H 3.11; N 3.92. C15H11F6NO2. Calculated, %:
C 51.29; H 3.16; N 3.99.
3
3
3-(4-Fluorophenylamino)-2-(2,2,3,3,4,4,4-hepta-
fluorobutanoyl)cyclohex-2-en-1-one (Vf). Yield 86%,
mp 56–59°C. IR spectrum, ν, cm–1: 1665, 1620, 1560.
1H NMR spectrum, δ, ppm (J, Hz): 1.95 quint (2H,
CH2, J = 6.3), 2.50 t (2H, CH2, J = 6.3), 2.63 t (2H,
CH2, 3J = 6.3), 7.20 m (2H, Harom), 7.44 m (3H, Harom),
12.75 br.s (1H, NH). 13C NMR spectrum, δC, ppm (JCF,
Hz): 20.2, 28.9, 37.8, 107.8, 109.0 t.q (1J = 271, J =
2
3
3
35), 119.1 q.t (1J = 288, J = 36), 125.9, 128.6, 129.8,
2
CH2, J = 6.3), 2.49 t (2H, CH2, J = 6.3), 2.59 t (2H,
3
135.8, 174.1, 184.2 t (2J = 27), 193.4. F NMR spec-
19
CH2, J = 6.3), 7.19 m (4H, Harom), 12.50 br.s (1H,
NH). 13C NMR spectrum, δC, ppm (JCF, Hz): 20.1,
28.7, 37.5, 108.1, 109.9 t.m (1J = 268), 110.7 t.t (1J =
trum, δF, ppm: –79.56 (CF3), –116.21 (CF2). Found, %:
C 54.17; H 3.70; N 4.26. C15H12F5NO2. Calculated, %:
C 54.06; H 3.63; N 4.20.
2
269, J = 31), 116.9 d (2J = 23), 118.2 q.t (1J = 288,
2J = 35), 128.0 d (3J = 9), 131.8 d (4J = 2), 162.2 d
(1J = 250), 174.0, 184.8 t (2J = 26), 193.4. F NMR
19
2-(2,2,3,3,4,4,4-Heptafluorobutanoyl)-3-phenyl-
aminocyclohex-2-en-1-one (Vc). Yield 89%, mp 98–
101°C. IR spectrum, ν, cm–1: 1670, 1605, 1570.
1H NMR spectrum, δ, ppm (J, Hz): 1.94 quint (2H,
spectrum, δF, ppm: –80.87 (CF3), –111.60 (CF2),
–112.18 (F), –121.99 (CF2). Found, %: C 47.75;
H 2.70; N 3.42. C16H11F8NO2. Calculated, %: C 47.89;
H 2.76; N 3.49.
3
3
CH2, J = 6.4), 2.49 t (2H, CH2, J = 6.4), 2.62 t (2H,
CH2, 3J = 6.4), 7.20 m (2H, Harom), 7.41 m (1H, Harom),
7.47 m (2H, Harom), 12.62 br.s (1H, NH). 13C NMR
spectrum, δC, ppm (JCF, Hz): 20.2, 28.8, 37.6, 108.0,
3-Benzylamino-2-trifluoroacetylcyclohex-2-en-1-
one (Vg). Yield 90%, mp 67–69°C. IR spectrum, ν,
1
cm–1: 1670, 1600, 1580. H NMR spectrum, δ, ppm
109.9 t.m (1J = 268), 110.7 t.t (1J = 269, J = 31),
2
3
(J, Hz): 1.97 quint (2H, CH2, J = 6.4), 2.42 t (2H,
118.1 q.t (1J = 288, J = 34), 125.9, 128.6, 129.9,
2
3
3
CH2, J = 6.4), 2.69 t (2H, CH2, J = 6.4), 4.61 d (2H,
CH2, 3J = 5.8), 7.27 m (2H, Harom), 7.38 m (3H, Harom),
11.80 br.s (1H, NH). 13C NMR spectrum, δC, ppm
(JCF, Hz): 19.5, 27.4, 37.4, 47.9, 106.3, 117.3 q (1J =
287), 127.2, 128.6, 129.4, 134.8, 175.0, 180.4 q (2J =
135.8, 173.7, 184.6 t (2J = 27), 193.5. F NMR spec-
19
trum, δF, ppm: –80.85 (CF3), –111.49 (CF2), –121.91
(CF2). Found, %: C 50.26; H 3.23; N 3.69.
C16H12F7NO2. Calculated, %: C 50.14; H 3.16; N 3.65.
19
36), 193.0. F NMR spectrum: δF –72.76 ppm (CF3).
3-(4-Fluorophenylamino)-2-trifluoroacetylcyclo-
Found, %: C 60.76; H 4.82; N 4.79. C15H14F3NO2. Cal-
culated, %: C 60.61; H 4.75; N 4.71.
hex-2-en-1-one (Vd). Yield 86%, mp 104–107°C. IR
1
spectrum, ν, cm–1: 1670, 1620, 1580. H NMR spec-
3
trum, δ, ppm (J, Hz): 1.94 quint (2H, CH2, J = 6.3),
3-Benzylamino-2-(2,2,3,3,3-pentafluoropropan-
oyl)cyclohex-2-en-1-one (Vh). Yield 89%, mp 70–
73°C. IR spectrum, ν, cm–1: 1660, 1595, 1575. 1H NMR
3
3
2.47 t (2H, CH2, J = 6.3), 2.60 t (2H, CH2, J = 6.3),
7.16 m (2H, Harom), 7.23 m (2H, Harom), 12.73 br.s (1H,
NH). 13C NMR spectrum, δC, ppm (JCF, Hz): 20.1,
28.8, 37.8, 106.8, 116.9 d (2J = 23), 117.3 q (1J = 288),
128.0 d (3J = 9), 132.0 d (4J = 3), 162.2 d (1J = 250),
174.7, 180.9 q (2J = 36), 193.3. 19F NMR spectrum, δF,
ppm: –72.66 (CF3), –112.35 (F). Found, %: C 55.70;
H 3.61; N 4.59. C14H11F4NO2. Calculated, %: C 55.82;
H 3.68; N 4.65.
3
spectrum, δ, ppm (J, Hz): 1.97 quint (2H, CH2, J =
3
3
6.4), 2.42 t (2H, CH2, J = 6.4), 2.67 t (2H, CH2, J =
3
6.4), 4.60 d (2H, CH2, J = 5.8), 7.26 m (2H, Harom),
7.37 m (3H, Harom), 11.60 br.s (1H, NH). 13C NMR
spectrum, δC, ppm (JCF, Hz): 19.5, 27.4, 37.3, 47.9,
107.6, 109.0 t.q (1J = 271, 2J = 35), 119.1 q.t (1J = 288,
2J = 36), 127.1, 128.6, 129.4, 134.9, 174.9, 183.8 t
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

KHLEBNIKOVA et al.
1000
19
3
3
(2J = 27), 193.2. F NMR spectrum, δF, ppm: –79.57
(CF3), –116.21 (CF2). Found, %: C 55.48; H 4.11;
N 4.10. C16H14F5NO2. Calculated, %: C 55.34; H 4.06;
N 4.03.
CH2, J = 6.4), 2.42 t (2H, CH2, J = 6.4), 2.68 t (2H,
3
3
CH2, J = 6.4), 4.59 d (2H, CH2, J = 5.7), 7.09 m
(2H, Harom), 7.26 m (2H, Harom), 11.43 br.s (1H, NH).
13C NMR spectrum, δC, ppm (JCF, Hz): 19.6, 27.3,
37.1, 47.2, 107.7, 109.9 t.m (1J = 269), 110.7 t.t (1J =
3-Benzylamino-2-(2,2,3,3,4,4,4-heptafluorobuta-
noyl)cyclohex-2-en-1-one (Vi). Yield 88%, mp 80–
83°C. IR spectrum, ν, cm–1: 1665, 1595, 1575. 1H NMR
spectrum, δ, ppm (J, Hz): 1.97 quint (2H, CH2, J =
6.4), 2.39 t (2H, CH2, J = 6.4), 2.67 t (2H, CH2, J =
2
269, J = 30), 116.4 d (2J = 22), 118.1 q.t (1J = 288,
2J = 35), 129.1 d (3J = 8), 130.7 d (4J = 3), 162.7 d
(1J = 248), 174.4, 184.4 t (2J = 26), 193.2. F NMR
19
3
3
3
spectrum, δF, ppm: –80.92 (CF3), –111.59 (CF2),
–113.31 (F), –121.96 (CF2). Found, %: C 49.31;
H 3.22; N 3.46. C17H13F8NO2. Calculated, %: C 49.17;
H 3.16; N 3.37.
3
6.4), 4.59 d (2H, CH2, J = 5.8), 7.25 m (2H, Harom),
7.37 m (3H, Harom), 11.46 br.s (1H, NH). 13C NMR
spectrum, δC, ppm (JCF, Hz): 19.6, 27.3, 37.1, 47.9,
107.6, 109.9 t.m (1J = 268), 110.7 t.t (1J = 269, J =
2
3-(Pyrrolidin-1-yl)-2-trifluoroacetylcyclohex-2-
en-1-one (Vm). Yield 80%, mp 103–105°C. IR spec-
trum, ν, cm–1: 1655, 1625, 1525. 1H NMR spectrum, δ,
31), 118.1 q.t (1J = 288, J = 34), 127.2, 128.6, 129.4,
2
134.9, 174.6, 184.2 t (2J = 26), 193.3. F NMR spec-
19
3
ppm (J, Hz): 1.95 quint (2H, CH2, J = 6.3), 2.04 m
trum, δF, ppm: –80.90 (CF3), –111.55 (CF2), –121.91
(CF2). Found, %: C 51.30; H 3.49; N 3.46.
C17H14F7NO2. Calculated, %: C 51.39; H 3.55; N 3.53.
(4H, CH2), 2.36 t (2H, CH2, 3J = 6.3), 2.73 t (2H, CH2,
3J = 6.3), 2.80 m (2H, CH2), 3.66 m (2H, CH2).
13C NMR spectrum, δC, ppm (JCF, Hz): 19.8, 24.6,
25.8, 31.3, 37.5, 51.4, 55.9, 108.0, 116.5 q (1J = 290),
167.9, 182.9 q (2J = 35), 195.1. 19F NMR spectrum:
δF –73.65 ppm (CF3). Found, %: C 55.31; H 5.47;
N 5.45. C12H14F3NO2. Calculated, %: C 55.17; H 5.40;
N 5.36.
3-(4-Fluorobenzylamino)-2-trifluoroacetylcyclo-
hex-2-en-1-one (Vj). Yield 92%, mp 133–135°C. IR
spectrum, ν, cm–1: 1660, 1620, 1585. H NMR spec-
1
3
trum, δ, ppm (J, Hz): 1.99 quint (2H, CH2, J = 6.4),
3
3
2.44 t (2H, CH2, J = 6.4), 2.69 t (2H, CH2, J = 6.4),
4.59 d (2H, CH2, 3J = 5.7), 7.10 m (2H, Harom), 7.26 m
13
2-(2,2,3,3,3-Pentafluoropropanoyl)-3-(pyrrolidin-
1-yl)cyclohex-2-en-1-one (Vn). Yield 79%, mp 102–
105°C. IR spectrum, ν, cm–1: 1650, 1625, 1515.
1H NMR spectrum, δ, ppm (J, Hz): 1.95 quint (2H,
CH2, 3J = 6.4), 2.02 m (4H, CH2), 2.37 t (2H, CH2, 3J =
(2H, Harom), 11.75 br.s (1H, NH). C NMR spectrum,
δC, ppm (JCF, Hz): 19.6, 27.4, 37.4, 47.3, 106.5, 116.4 d
(2J = 22), 117.3 q (1J = 287), 129.1 d (3J = 8), 130.6 d
(4J = 3), 162.7 d (1J = 248), 174.8, 180.7 q (2J = 36),
192.8. 19F NMR spectrum, δF, ppm: –72.76 (CF3),
–113.15 (F). Found, %: C 57.27; H 4.22; N 4.51.
C15H13F4NO2. Calculated, %: C 57.15; H 4.16; N 4.44.
3
6.4), 2.71 t (2H, CH2, J = 6.4), 2.81 m (2H, CH2),
3.64 m (2H, CH2). 13C NMR spectrum, δC, ppm (JCF,
Hz): 19.7, 24.6, 25.9, 31.6, 37.7, 51.5, 55.7, 108.8,
108.9 t.q (1J = 269, J = 35), 119.0 q.t (1J = 288, J =
36), 168.2, 185.1 t (2J = 28), 194.8. 19F NMR spec-
trum, δF, ppm: –79.12 (CF3), –115.37 (CF2). Found, %:
C 50.02; H 4.48; N 4.43. C13H14F5NO2. Calculated, %:
C 50.17; H 4.53; N 4.50.
2
2
3-(4-Fluorobenzylamino)-2-(2,2,3,3,3-penta-
fluoropropanoyl)cyclohex-2-en-1-one (Vk). Yield
93%, mp 69–72°C. IR spectrum, ν, cm–1: 1660, 1595,
1
1515. H NMR spectrum, δ, ppm (J, Hz): 1.99 quint
3
3
(2H, CH2, J = 6.4), 2.42 t (2H, CH2, J = 6.4), 2.68 t
(2H, CH2, 3J = 6.4), 4.59 d (2H, CH2, 3J = 5.7), 7.09 m
(2H, Harom), 7.26 m (2H, Harom), 11.55 br.s (1H, NH).
13C NMR spectrum, δC, ppm (JCF, Hz): 19.5, 27.4,
37.3, 47.2, 107.6, 108.9 t.q (1J = 271, 2J = 35), 116.4 d
(2J = 22), 119.1 q.t (1J = 288, 2J = 36), 129.1 d (3J = 8),
130.7 d (4J = 2), 162.7 d (1J = 250), 174.8, 183.9 t
2-(2,2,3,3,4,4,4-Heptafluorobutanoyl)-3-(pyrroli-
din-1-yl)cyclohex-2-en-1-one (Vo). Yield 77%,
mp 105–108°C. IR spectrum, ν, cm–1: 1655, 1610,
1
1535. H NMR spectrum, δ, ppm (J, Hz): 1.96 quint
3
(2H, CH2, J = 6.4), 2.02 m (4H, CH2), 2.38 t (2H,
CH2, 3J = 6.4), 2.72 t (2H, CH2, 3J = 6.4), 2.83 m (2H,
19
(2J = 27), 193.1. F NMR spectrum, δF, ppm: –79.63
13
CH2), 3.66 m (2H, CH2). C NMR spectrum, δC, ppm
(CF3), –113.30 (F), –116.26 (CF2). Found, %: C 52.49;
H 3.51; N 3.79. C16H13F6NO2. Calculated, %: C 52.61;
H 3.59; N 3.83.
(JCF, Hz): 19.8, 24.6, 25.9, 31.5, 37.5, 51.6, 55.8,
108.7, 109.7 t.m (1J = 269), 109.7 t.t (1J = 268, J =
2
31), 118.1 q.t (1J = 288, J = 35), 167.9, 185.9 t (2J =
2
27), 194.8. 19F NMR spectrum, δF, ppm: –81.18 (CF3),
–110.70 (CF2), –122.32 (CF2). Found, %: C 46.69;
H 3.98; N 3.96. C14H14F7NO2. Calculated, %: C 46.55;
H 3.91; N 3.88.
3-(4-Fluorobenzylamino)-2-(2,2,3,3,4,4,4-hepta-
fluorobutanoyl)cyclohex-2-en-1-one (Vl). Yield 90%,
mp 69–72°C. IR spectrum, ν, cm–1: 1665, 1580, 1515.
1H NMR spectrum, δ, ppm (J, Hz): 2.00 quint (2H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 7 2009

REACTION OF 2-PERFLUOROALKANOYLCYCLOHEXANE-1,3-DIONES
1001
vich, K.I., Filyakova, V.I., and Postovskii, I.Ya., Izv.
Akad. Nauk SSSR, Ser. Khim., 1981, p. 2346; Pashke-
vich, K.I. and Filyakova, V.I., Izv. Akad. Nauk SSSR,
Ser. Khim., 1984, p. 623; Pashkevich, K.I., Khomu-
tov, O.G., and Sevenard, D.V., Russ. J. Org. Chem.,
1998, vol. 34, p. 1727; Volochnyuk, D.M., Pushechni-
kov, A.O., Krotko, D.G., Sibgatulin, D.A., Kovalyo-
va, S.A., and Tolmachev, A.A., Synthesis, 2003, p. 1531;
Pashkevich, K.I., Khomutov, O.G., and Sevenard, D.V.,
Izv. Ross. Akad. Nauk, Ser. Khim., 1999, p. 562;
Mkrtchyan, E.G., Yanchevskii, D.S., Chizhov, D.L., and
Charushin, V.N., Izv. Ross. Akad. Nauk, Ser. Khim.,
2005, p. 2086.
3-Piperidino-2-trifluoroacetylcyclohex-2-en-1-
one (Vp). Yield 79%, mp 87–90°C. IR spectrum, ν,
1
cm–1: 1670, 1630, 1560. H NMR spectrum, δ, ppm
3
(J, Hz): 1.76 m (6H, CH2), 1.96 quint (2H, CH2, J =
3
3
6.3), 2.32 t (2H, CH2, J = 6.3), 2.73 t (2H, CH2, J =
13
6.3), 3.41 m (4H, CH2). C NMR spectrum, δC, ppm
(JCF, Hz): 19.0, 23.2, 26.0, 31.0, 37.0, 53.3, 106.8,
117.2 q (1J = 290), 173.2, 178.1 q (2J = 35), 194.5.
19F NMR spectrum: δ –73.05 ppm (CF3). Found, %:
C 56.60; H 5.79; N 5.01. C13H16F3NO2. Calculated, %:
C 56.72; H 5.86; N 5.09.
2-(2,2,3,3,3-Pentafluoropropanoyl)-3-piperidino-
cyclohex-2-en-1-one (Vq). Yield 76%, mp 104–
107°C. IR spectrum, ν, cm–1: 1645, 1625, 1520.
1H NMR spectrum, δ, ppm (J, Hz): 1.75 m (6H, CH2),
4. Saloutin, V.I., Burgart, Ya.V., and Chupakhin, O.N.,
Ftorsoderzhashchie trikarbonil’nye soedineniya (Fluor-
ine-Containing Tricarbonyl Compounds), Yekaterin-
burg: NISO Ural. Otd. Ross. Akad. Nauk, 2002, p. 164.
5. Kuz’mitskii, B.B., Malaeva, L.P., Khlebnikova, T.S.,
and Lakhvich, F.A., Farmakol. Toksikol., 1989, vol. 52,
p. 45; Kuz’mitskii, B.B., Ignat’eva, T.N., Khlebniko-
va, T.S., and Lakhvich, F.A., Vestsi Akad. Navuk BSSR,
Ser. Khim. Navuk, 1989, p. 65; Kuz’mitskii, B.B., Golu-
beva, M.B., Mizulo, N.A., Romanova, V.N., Khlebniko-
va, T.S., and Lakhvich, F.A., Vestsi Akad. Navuk BSSR,
Ser. Khim. Navuk, 1989, p. 82.
3
3
1.97 quint (2H, CH2, J = 6.4), 2.34 t (2H, CH2, J =
3
6.4), 2.72 t (2H, CH2, J = 6.4), 3.43 m (4H, CH2).
13C NMR spectrum, δC, ppm (JCF, Hz): 18.9, 23.2,
26.1, 31.1, 37.1, 53.2, 107.7, 108.5 t.q (1J = 272, J =
2
35), 119.0 q.t (1J = 288, J = 36), 173.1, 180.6 t (2J =
2
27), 193.9. 19F NMR spectrum, δF, ppm: –80.30 (CF3),
–117.39 (CF2). Found, %: C 51.57; H 4.90; N 4.24.
C14H16F5NO2. Calculated, %: C 51.70; H 4.96; N 4.31.
6. Mel’nikov, N.N., Novozhilov, K.V., and Belan, S.R.,
Pestitsidy i regulyatory rosta rastenii (spravochnik)
(Pesticides and Plant Growth Regulators. Reference
Book), Moscow: Khimiya, 1995.
7. Kirsch, P., Modern Fluoroorganic Chemistry: Synthesis,
Reactivity, Applications, Weinheim: Wiley, 2004.
2-(2,2,3,3,4,4,4-Heptafluorobutanoyl)-3-piperi-
dinocyclohex-2-en-1-one (Vr). Yield 73%, mp 85–
88°C. IR spectrum, ν, cm–1: 1660, 1615, 1535.
1H NMR spectrum, δ, ppm (J, Hz): 1.75 m (6H, CH2),
3
3
1.97 quint (2H, CH2, J = 6.4), 2.35 t (2H, CH2, J =
3
6.4), 2.72 t (2H, CH2, J = 6.4), 3.42 m (4H, CH2).
8. Rubinov, D.B., Rubinova, I.L., and Akhrem, A.A.,
13C NMR spectrum, δC, ppm (JCF, Hz): 19.1, 23.3,
26.0, 31.0, 36.9, 53.1, 107.8, 109.6 t.m (1J = 268),
Chem. Rev., 1999, vol. 99, p. 1047.
9. Akhrem, A.A., Moiseenkov, A.M., and Lakhvich, F.A.,
Izv. Akad. Nauk SSSR, Ser. Khim., 1971, p. 2786;
Tamura, Y., Wada, A., Sasho, M., and Kita, Y., Chem.
Pharm. Bull., 1983, vol. 31, p. 52; Lakhvich, F.A. and
Khlebnikova, T.S., Vestsi Akad. Navuk BSSR, Ser. Khim.
Navuk, 1989, p. 39.
2
2
110.2 t.t (1J = 270, J = 31), 118.0 q.t (1J = 289, J =
35), 172.8, 181.9 t (2J = 26), 193.9. 19F NMR spec-
trum, δF, ppm: –80.51 (CF3), –112.98 (CF2), –123.03
(CF2). Found, %: C 48.16; H 4.38; N 3.80.
C15H16F7NO2. Calculated, %: C 48.01; H 4.30; N 3.73.
10. Scott, K.R., Edafiogho, I.O., Richardson, E.L.,
Farrar, V.A., Moore, J.A., Tietz, E.I., Hinko, C.N.,
Chang, H., El-Assadi, A., and Nicholson, J.M., J. Med.
Chem., 1993, vol. 36, p. 1947.
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