Fluorinated 2-benzoylcyclohexane-1,3-diones and their vinylogous acyl chlorides in the reactions with primary and secondary amines

Article abstract of DOI:10.1134/S1070363211020137

The reaction of 5,5-dimethyl-2-[(3-fluoro- and 4-fluoro)benzoyl] cyclohexane-1,3-diones with primary and secondary amines affords their exocyclic enamine derivatives. Under similar conditions 5,5-dimethyl-2-(2-fluorobenzoyl)] cyclohexane-1,3-dione undergoes dehydrofluorination and intramolecular cyclization to give 3,3-dimethyl-2,3,4,9-tetrahydro-1H-xanthene-1,9-dione. The reaction of vinylogous substitution of the enol derivatives of the fluorinated 5,5-dimethyl-2-benzoylcyclohexane-1,3-diones (vinylogous acyl chlorides) with amines results in the formation of the endocyclic enaminoderivatives.

Full text of DOI:10.1134/S1070363211020137

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 2, pp. 361–368. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © T.S. Khlebnikova, V.G. Isakova, F.A. Lakhvich, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 2, pp. 261–268.
Fluorinated 2-Benzoylcyclohexane-1,3-diones
and Their Vinylogous Acyl Chlorides in the Reactions
with Primary and Secondary Amines
T. S. Khlebnikova, V. G. Isakova, and F. A. Lakhvich
Institute of Bioorganic Chemistry, Belarus National Academy of Sciences,
ul. Akademika Kuprevicha 5/2, Minsk, 22014 Belarus
e-mail: khlebnicova@iboch.bas-net.by
Received March 11, 2010
Abstract—The reaction of 5,5-dimethyl-2-[(3-fluoro- and 4-fluoro)benzoyl]cyclohexane-1,3-diones with
primary and secondary amines affords their exocyclic enaminе derivatives. Under similar conditions 5,5-
dimethyl-2-(2-fluorobenzoyl)]cyclohexane-1,3-dione undergoes dehydrofluorination and intramolecular
cyclization to give 3,3-dimethyl-2,3,4,9-tetrahydro-1Н-xanthene-1,9-dione. The reaction of vinylogous
substitution of the enol derivatives of the fluorinated 5,5-dimethyl-2-benzoylcyclohexane-1,3-diones
(vinylogous acyl chlorides) with amines results in the formation of the endocyclic enaminoderivatives.
DOI: 10.1134/S1070363211020137
The enaminoderivatives of 2-acylcycloalkane-1,3-
diones, depending on the structure of the cycle and the
side chain, possess different types of biological
activity, such as antibacterial, anti-inflammatory,
antiaggregant, antiischemic [1–4] and other types of
physiological activity; they are also known as effective
and ecologically safe plant protection agents [5, 6].
Recently fluorine compounds found wide application
in the production of drugs and pesticides [7–10]. The
introduction of fluorine atoms in the structure of
compounds substantially affects their physical and
chemical properties, reactivity, and biological activity.
The use of the readily available polycarbonyl “building
blocks” seems to be most effective for the design of
the fluorinated organic compounds.
The goal of the present work was to synthesize new
enaminoderivatives of 2-benzoylcyclohexane-1,3-diones
having fluorine atoms in the molecule.
The fluorinated 2-benzoylcyclohexane-1,3-diones
(Iа–Ic) existing in the enol form, as well as their
nonfluorinated analogs [13, 14], are rather strong
vinylogous acids, which may enter the reaction of
condensation with N-nucleophiles, including primary
and secondary amines. We have investigated the
reactions of 5,5-dimethyl-2-benzoylcyclohexane-1,3-
diones (Iа–Ic) having fluorine atoms in different
positions of the aromatic ring, with primary (aniline, 4-
fluoroaniline, benzylamine, 4-fluorobenzylamine) and
secondary (pyrrolidine, piperidine) amines.
The reaction of condensation was performed by
refluxing the equivalent amounts of the fluorinated 2-
benzoylcyclohexane-1,3-diones (Ib, Ic) and primary
(aniline, 4-fluoroaniline, benzylamine, 4-fluorobenzyl-
amine) or secondary (pyrrolidine, piperidine) amines
for 3 h in benzene. The amination at the carbonyl
group of the side acyl chain took place and the
corresponding exocyclic enaminoderivatives IIa–IIl
were formed in 80–98% yield. It should be noted that
in the case of 5,5-dimethyl-2-(2-fluorobenzoyl)
cyclohexane-1,3-dione (Iа) we failed to obtain the
corresponding enaminoderivatives, since under the
The recently synthesized fluorinated 2-benzoyl-
cyclohexane-1,3-diones [11] are promising polyfunc-
tional block-synthons for preparation of various carbo-
and heterocyclic structures containing fluorine atoms
in the aromatic ring, including the compounds with
high biological activity. The described chemical
transformations of the fluorinated 2-benzoylcyclo-
hexane-1,3-diones include their reactions as well as the
reactions of methyl ethers of the enol forms with N,N-
dinucleophiles with the formation of regioisomeric
indazolones [12].
361

362
KHLEBNIKOVA et al.
O
NR1R2
R1R2NH
O
X
IIа_IIl
X = 3'-F, 4'-F
O
O
O
O
R1R2NH
X = 2'-F
O
Iа_Ic
O
X
(COCl)2
III
O
O
O
O
R1R2NH
Cl
NR1R2
Vа_Vr
X
X
IVа_IVc
I, IV, X = 2'-F (a), 3'-F (b), 4'-F (c); II, V, R1 = H: R2 = C6H5, X = 3'-F (a); R2 = C6H5, X = 4'-F (b); R2 = 4-FC6H4, X = 3'-
F, (c); R2 = 4-FC6H4, X = 4'-F (d); R2 = C6H5CH2, X = 3'-F (e); R2 = C6H5CH2, X = 4'-F (f); R2 = 4-FC6H4CH2, X = 3'-F (g);
R2 = 4-FC6H4CH2, X = 4'-F (h); R1-R2 = (CH2)4: X = 3'-F (i); X = 4'-F (j); R1-R2 = (CH2)5: X = 3'-F (k); X = 4'-F (l); V,
R1 = H: R2 = C6H5, X = 2'-F (m); R2 = 4-FC6H4, X = 2'-F (n); R2 = C6H5CH2, X = 2'-F (o); R2 = 4-FC6H4CH2, X = 2'-F (p);
R1-R2 = (CH2)4, X = 2'-F (q); R1-R2 = (CH2)5, X = 2'-F (r).
reaction conditions the elimination of hydrogen fluoride
and the intramolecular cyclization occurred with the
formation of 3,3-dimethyl-2,3,4,9-tetrahydro-1Н-
xanthene-1,9-dione (III), identical to the one obtained
earlier [15, 16] by trying to perform the О–С-
isomerization of 3-benzoyloxy-2-cyclohexene-1-ones
having the fluorine atom in the ortho-position of the
benzene ring in the presence of aluminum chloride in
dichloroethane or in the presence of KCN and
triethylamine in methylene chloride in order to
synthesize the corresponding fluorinated 2-benzoylcyclo-
hexane-1,3-diones.
of the fluorinated 2-benzoylcyclohexane-1,3-diones
Iа–Ic with excess of oxalyl chloride at room
temperature, with primary (aniline, 4-fluoroaniline,
benzylamine, 4-fluorobenzylamine) and secondary
(pyrrolidine, piperidine) amines. Compounds IVа–IVc
were treated with two-fold excess of the amine for 2–
3 h in anhydrous chloroform at room temperature
(1 equivalent of amine bound the evolved hydrogen
chloride). The reaction proceeds regioselectively with
exclusive formation of the endocyclic enamino-
derivatives of 2-(fluorobenzoyl)cyclohexane-1,3-diones
(Vа–Vr) in 78–90% yield.
The reactions of the enol derivatives of 2-
acylcyclohexane-1,3-diones (vinylogous acyl chlorides
and methyl ethers) with N-nucleophiles are different
from the reactions of β,β'-triketones: they do not react
at the carbonyl group of the acyl moiety but rather
enter the reaction of vinylogous nucleophilic
substitution with the formation of the endocyclic
products [13]. These enol derivatives possess an
enhanced reactivity as compared with β,β'-triketones,
therefore the substitution takes place at room
temperature. We performed the reaction of
chlorovinyldiketones IVа–IVc prepared by treatment
The structure of all synthesized compounds was
1
proved by the data of elemental analysis, IR and Н,
13С, 19F NMR spectroscopy (see the table). IR spectra
of compounds IIа–IIl contain three characteristic
absorption bands corresponding to the double bond in
the region 1515–1560 cm–1 and conjugated carbonyl
1
groups at 1575–1615, 1640–1670 cm–1. In the Н
NMR spectra the signal of the proton of NH group in
enaminoderivatives IIа–IId and IIe–IIh linked by a
strong intramolecular hydrogen bond with the carbonyl
group resonates at δ 14.6–14.7 and 13.6 ppm,
respectively. The signal of the carbon atom at the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

FLUORINATED 2-BENZOYLCYCLOHEXANE-1,3-DIONES
IR and 1Н, 13С, 19F NMR spectra of compounds IIа–IIl and Vа–Vr
363
Comp.
no.
IR,
19F NMR, δ,
ppm
1Н NMR, δ, ppm (J, Hz)
13С NMR, δ, ppm (JC–F, Hz)
ν, cm–1
1670, 1.11 s (6Н, 2СН3), 2.34 s (2Н, СН2), 2.58 s (2Н, 28.4, 30.4, 52.4, 53.2, 108.3, 115.1 d (J 23), 116.0 d –112.49 m
1615, СН2), 6.80 m (3Н, Нarom), 6.89 m (1Н, Нarom), 7.00 (J 21), 123.5 d (J 2), 125.2, 126.8, 128.9, 130.0 d
1560 m (1Н, Нarom), 7.13 m (3Н, Нarom), 7.24 m (1Н, (J 8), 136.0 d (J 8), 136.8, 162.5 d (J 247), 167.6,
IIа
Нarom), 14.71 br.s (1Н, NH)
195.3, 200.5
1670, 1.12 s (6Н, 2СН3), 2.34 s (2Н, СН2), 2.57 s (2Н, 28.4, 30.3, 52.4, 53.4, 108.5, 115.6 d (J 22), 125.3, –111.32 m
1615, СН2), 6.77 m (2Н, Нarom), 6.97 m (2Н, Нarom), 7.09 126.6, 128.9, 129.9 d (J 8), 137.0, 162.9 d (J 250),
1560 m (3Н, Нarom), 7.15 m (2Н, Нarom), 14.68 br.s (1Н, NH) 168.3, 195.5, 200.5
IIb
IIc
1660, 1.11 s (6Н, 2СН3), 2.33 s (2Н, СН2), 2.58 s (2Н, 28.4, 30.4, 52.4, 53.2, 108.3, 115.0 d (J 23), 115.9 d –114.45 m,
1590, СН2), 6.79 m (2Н, Нarom), 6.85 m (3Н, Нarom), 7.01 (J 23), 116.1 d (J 21), 123.5 d (J 2), 127.0 (J 9), –112.23 m
1555 m (1Н, Нarom), 7.26 m (1Н, Нarom), 14.66 br.s (1Н, 130.1 d (J 8), 132.9 d (J 2), 135.8 d (J 8), 160.9 d
NH)
(J 248), 162.6 d (J 248), 167.9, 195.2, 200.7
1660, 1.11 s (6Н, 2СН3), 2.33 s (2Н, СН2), 2.57 s (2Н, 28.4, 30.3, 52.4, 53.3, 108.5, 115.6 d (J 22), 115.9 d –114.62 m,
1620, СН2), 6.75 m (2Н, Нarom), 6.85 m (2Н, Нarom), 6.98 (J 23), 127.0 d (J 9), 129.7, 129.8 d (J 8), 133.0 d –111.05 m
1555 m (2Н, Нarom), 7.07 m (2Н, Нarom), 14.64 br.s (1Н, (J 3), 160.8 d (J 248), 162.9 d (J 250), 169.5, 195.4,
IId
IIe
NH)
200.5
1660, 1.06 s (6Н, 2СН3), 2.25 s (2Н, СН2), 2.49 s (2Н, 28.4, 30.3, 48.3, 52.3, 52.9, 107.5, 113.5 d (J 23), –111.76 m
1570 СН2), 4.24 d (2Н, СН2, J 6.0), 6.85 m (1Н, Нarom), 115.9 d (J 21), 121.8, 127.2, 128.1, 129.0, 130.6 d
6.92 m (1Н, Нarom), 7.13 m (3Н, Нarom), 7.32 m (J 8), 136.0, 136.4 d (J 8), 162.8 d (J 248), 170.3,
(3Н, Нarom), 7.42 m (1Н, Нarom), 13.58 br.s (1Н, NH) 194.9, 200.1
1650, 1.05 s (6Н, 2СН3), 2.25 s (2Н, СН2), 2.48 s (2Н, 28.4, 30.3, 48.2, 52.3, 52.9, 107.8, 115.9 d (J 22), –111.84 m
1590, СН2), 4.25 d (2Н, СН2, J 6.0), 7.11 m (6Н, Нarom), 127.1, 128.0 d (J 7), 128.1, 129.0, 130.3 d (J 3),
IIf
1560 7.30 m (3Н, Нarom), 13.59 br.s (1Н, NH)
136.1, 162.8 d (J 249), 171.2, 195.2, 199.9
1660, 1.06 s (6Н, 2СН3), 2.25 s (2Н, СН2), 2.48 s (2Н, 28.4, 30.3, 47.6, 52.3, 52.9, 107.6, 113.5 d (J 23), –113.96 m,
1575, СН2), 4.21 d (2Н, СН2, J 5.9), 6.84 d (1Н, Нarom, 116.0 d (J 22), 121.7 (J 2), 128.3, 129.0 d (J 8), –111.62 m
1525 J 8.7), 6.90 d (1Н, Нarom, J 7.6), 7.02 m (2Н, 130.6 d (J 8), 131.8 d (J 3), 136.3 d (J 8), 162.4 d
IIg
Нarom), 7.09 m (2Н, Нarom), 7.14 m (1Н, Нarom), (J 247), 162.9 d (J 248), 170.2, 194.9, 200.2
7.42 m (1Н, Нarom), 13.55 br.s (1Н, NH)
1655, 1.06 s (6Н, 2СН3), 2.25 s (2Н, СН2), 2.48 s (2Н, 28.4, 30.3, 47.5, 52.3, 52.9, 107.9, 116.0 d (J 22), –114.15 m,
1585, СН2), 4.24 d (2Н, СН2, J 6.0), 7.01 m (2Н, Нarom), 128.1 d (J 8), 129.0 d (J 8), 130.2 d (J 4), 131.9 d –111.84 m
IIh
IIi
1560 7.10 m (6Н, Нarom), 13.56 br.s (1Н, NH)
(J 3), 162.4 d (J 247), 162.9 d (J 249), 171.2, 195.2,
200.1
1650, 1.07 s (6Н, 2СН3), 2.02 quint (2Н, СН2, J 6.8), 24.9, 25.1, 28.5, 30.9, 52.1, 53.8, 55.6, 111.4, 115.4 –112.32 m
1595, 2.08 quint (2Н, СН2, J 6.8), 2.28 s (4Н, СН2), 3.63 d (J 23), 117.2 d (J 21), 123.9 (J 2), 130.0 d (J 8),
1525 t (2Н, СН2, J 6.8), 3.80 t (2Н, СН2, J 6.8), 7.11 m 139.1 d (J 7), 162.4 d (J 248), 173.0, 192.9
(2Н, Нarom), 7.16 m (1Н, Нarom), 7.37 m (1Н, Нarom
)
1650, 1.07 s (6Н, 2СН3), 2.02 quint (2Н, СН2, J 6.6), 25.0, 25.1, 28.5, 30.9, 52.1, 53.9, 55.3, 111.6, 115.6 –109.47 m
1600, 2.08 quint (2Н, СН2, J 6.6), 2.28 s (4Н, СН2), 3.65 d (J 22), 130.5 d (J 9), 133.3 (J 3), 163.6 d (J 252),
1515 t (2Н, СН2, J 6.6), 3.81 t (2Н, СН2, J 6.6), 7.09 m 173.6, 192.8
IIj
(2Н, Нarom), 7.40 m (2Н, Нarom
)
1650, 1.08 s (6Н, 2СН3), 1.82 m (6Н, 3СН2), 2.30 s (4Н, 23.5, 27.0, 27.5, 28.6, 30.8, 52.2, 52.9, 57.3, 111.7, –112.24 m
1595, СН2), 3.50 m (2Н, СН2), 3.64 m (2Н, СН2), 7.09 116.1 d (J 23), 117.9 d (J 21), 124.8 (J 1), 130.1 d
1535 m (1Н, Нarom), 7.17 m (2Н, Нarom), 7.38 m (1Н, (J 8), 138.8 d (J 8), 162.5 d (J 248), 174.9, 193.3
IIk
Нarom
)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

364
KHLEBNIKOVA et al.
(Contd.)
Comp.
no.
IR,
19F NMR,
δ, ppm
1Н NMR, δ, ppm (J, Hz)
13С NMR, δ, ppm (JC–F, Hz)
ν, cm–1
1640, 1.08 s (6Н, 2СН3), 1.83 m (6Н, 3СН2), 2.29 s 23.5, 26.9, 27.5, 28.6, 30.8, 52.1, 52.8, 57.0, 111.7, –108.52 m
1595, (4Н, СН2), 3.53 m (2Н, СН2), 3.65 m (2Н, СН2), 115.8 d (J 22), 131.3 d (J 9), 132.6 (J 3), 164.3 d
IIl
1540 7.10 m (2Н, Нarom), 7.39 m (2Н, Нarom
)
(J 252), 175.5, 193.2
1650, 1.09 s (6Н, 2СН3), 2.33 s (2Н, СН2), 2.53 s (2Н, 28.2, 31.8, 41.5, 51.6, 108.2, 114.3 d (J 23), 116.9 d –113.93 m
1620, СН2), 7.10 m (1Н, Нarom), 7.20 m (4Н, Нarom), (J 21), 123.0 d (J 2), 126.0, 127.8, 129.2 d (J 8),
1570 7.35 m (2Н, Нarom), 7.46 m (2Н, Нarom), 13.01 br.s 129.7, 136.7, 144.8 d (J 7), 162.2 d (J 246), 170.1,
Vа
Vb
(1Н, NH)
194.3, 196.5
1645, 1.09 s (6Н, 2СН3), 2.34 s (2Н, СН2), 2.53 s (2Н, 28.2, 31.8, 41.5, 51.7, 108.3, 114.7 d (J 22), 126.0, –110.13 m
1600, СН2), 7.04 m (2Н, Нarom), 7.20 m (2Н, Нarom), 127.7, 129.7, 130.0 d (J 9), 136.8, 138.5 d (J 2), 164.1
1560 7.37 m (1Н, Нarom), 7.45 m (2Н, Нarom), 7.52 m d (J 250), 169.7, 194.4, 196.5
(2Н, Нarom), 12.90 br.s (1Н, NH)
1660, 1.08 s (6Н, 2СН3), 2.32 s (2Н, СН2), 2.48 s (2Н, 28.2, 31.8, 41.4, 51.5, 108.3, 114.3 d (J 23), 116.7 d –113.91 m,
1580, СН2), 7.09 m (1Н, Нarom), 7.18 m (6Н, Нarom), (J 23), 117.0 d (J 21), 123.1 d (J 2), 128.0 d (J 9), –113.30 m
Vc
Vd
Ve
Vf
1520 7.32 m (1Н, Нarom), 12.88 br.s (1Н, NH)
129.3 d (J 8), 132.7 d (J 2), 144.7 d (J 7), 161.8 d
(J 249), 162.3 d (J 246), 170.4, 194.3, 196.5
1645, 1.09 s (6Н, 2СН3), 2.33 s (2Н, СН2), 2.47 s (2Н, 28.2, 31.8, 41.4, 51.6, 108.4, 114.7 d (J 22), 116.7 d –113.41 m,
1610, СН2), 7.04 m (2Н, Нarom), 7.16 m (4Н, Нarom), (J 23), 128.0 d (J 9), 130.1 d (J 9), 132.8 d (J 2), 138.3 –109.90 m
1580, 7.51 m (2Н, Нarom), 12.78 br.s (1Н, NH)
d (J 3), 161.7 d (J 249), 164.1 d (J 250), 169.9, 194.3,
1520
196.5
1650, 1.11 s (6Н, 2СН3), 2.27 s (2Н, СН2), 2.55 s (2Н, 28.4, 31.1, 40.2, 47.4, 51.0, 107.7, 114.2 d (J 23), –114.07 m
1580 СН2), 4.60 d (2Н, СН2, J 5.9), 7.08 m (2Н, Нarom), 116.6 d (J 21), 122.9 d (J 1), 126.9, 128.2, 129.1,
7.18 m (1Н, Нarom), 7.31 m (4Н, Нarom), 7.40 m 129.2, 135.8, 145.1 d (J 7), 162.2 d (J 246), 171.6,
(2Н, Нarom), 11.90 br.s (1Н, NH)
193.7, 196.1
1630, 1.12 s (6Н, 2СН3), 2.28 s (2Н, СН2), 2.54 s (2Н, 28.5, 31.1 40.2, 47.4, 51.1, 107.7, 114.6 d (J 22), –110.56 m
1600, СН2), 4.59 d (2Н, СН2, J 5.9), 7.32 m (5Н, Нarom), 126.9, 128.2, 129.2, 129.9 d (J 9), 135.9, 138.8 d (J 2),
1575, 7.43 m (4Н, Нarom), 11.80 br.s (1Н, NH)
163.9 d (J 250), 171.3, 193.8, 196.2
1505
1650, 1.12 s (6Н, 2СН3), 2.28 (2Н, СН2), 2.54 s (2Н, 28.5, 31.2, 40.3, 46.7, 51.0, 107.8, 114.2 d (J 23), –114.04 m,
1585, СН2), 4.57 d (2Н, СН2, J 5.8), 7.08 m (4Н, Нarom), 116.2 d (J 22), 116.7 d (J 21), 122.9, 131.6 d (J 7), –113.78 m
1525 7.17 m (1Н, Нarom), 7.29 m (3Н, Нarom), 11.87 br.s 128.8 d (J 8), 129.2 d (J 7), 145.0 d (J 7), 162.2 d
Vg
Vh
Vi
(1Н, NH)
(J 246), 162.5 d (J 248), 171.4, 193.7, 196.3
1630, 1.12 s (6Н, 2СН3), 2.28 s (2Н, СН2), 2.53 s (2Н, 28.5, 31.1, 40.3, 46.7, 51.1, 107.8, 114.6 d (J 22), –110.42 m,
1600, СН2), 4.56 d (2Н, СН2, J 5.8), 7.01 m (2Н, Нarom), 116.2 d (J 22), 128.8 d (J 8), 129.9 d (J 9), 131.7 d –113.83 m
1570, 7.09 m (2Н, Нarom), 7.27 m (2Н, Нarom), 7.45 m (J 3), 138.7 d (J 2), 162.5 d (J 247), 164.0 d (J 250),
1515 (2Н, Нarom), 11.76 br.s (1Н, NH)
171.1, 193.8, 196.3
1650, 1.14 s (6Н, 2СН3), 1.88 m (4Н, 2СН2), 2.26 s 25.3, 28.6, 31.5, 44.1, 50.7, 60.7, 110.6, 115.6 d –108.20 m
1615, (2Н, СН2), 2.55 s (2Н, СН2), 3.21 m (4Н, 2СН2), (J 22), 118.5 d (J 22), 125.0, 129.6 d (J 8), 142.5 d
1530 7.14 m (1Н, Нarom), 7.35 m (1Н, Нarom), 7.52 m (J 6), 162.7 d (J 246), 163.2, 194.7, 196.5
(1Н, Нarom), 7.62 m (1Н, Нarom
)
1665, 1.14 s (6Н, 2СН3), 1.90 m (4Н, 2СН2), 2.26 s 25.2, 28.6, 29.7, 31.6, 44.1, 50.7, 110.7, 115.1 d –108.20 m
1600, (2Н, СН2), 2.54 s (2Н, СН2), 4.40 m (4Н, 2СН2), (J 22), 131.8 d (J 9), 136.5, 163.0, 165.0 d (J 252),
Vj
1540 7.05 m (2Н, Нarom), 7.86 m (2Н, Нarom
)
194.6, 196.3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

FLUORINATED 2-BENZOYLCYCLOHEXANE-1,3-DIONES
365
(Contd.)
Comp.
no.
IR,
19F NMR,
δ, ppm
1Н NMR, δ, ppm (J, Hz)
13С NMR, δ, ppm (JC–F, Hz)
ν, cm–1
1660, 1.18 s (6Н, 2СН3), 1.60 m (6Н, 3СН2), 2.27 s 23.7, 26.1, 28.8, 44.0, 50.2, 51.8, 60.7, 111.1, 115.4 d –113.38 m
1610, (2Н, СН2), 2.47 s (2Н, СН2), 3.17 m (4Н, СН2), (J 22), 118.9 d (J 22), 124.8 d (J 1), 129.8 d (J 8),
1540 7.16 m (1Н, Нarom), 7.37 m (1Н, Нarom), 7.50 m 141.9 d (J 6), 162.8 d (J 246), 166.8, 194.6, 196.8
Vk
(1Н, Нarom), 7.58 m (1Н, Нarom
)
1655, 1.18 s (6Н, 2СН3), 1.59 m (6Н, 3СН2), 2.27 s 23.7, 26.2, 28.9, 32.4, 44.0, 50.2, 51.7, 111.4, 115.3 d –107.53 m
1605, (2Н, СН2), 2.46 s (2Н, СН2), 3.17 m (4Н, СН2), (J 22), 131.6 d (J 9), 135.9, 164.2 d (J 253), 166.5,
Vl
1540 7.07 m (2Н, Нarom), 7.84 m (2Н, Нarom
)
194.6, 196.6
1645, 1.06 s (6Н, 2СН3), 2.31 s (2Н, СН2), 2.52 s (2Н, 28.1, 31.5, 41.5, 51.4, 109.6, 115.0 d (J 22), 124.1 d –115.91 m
1580 СН2), 7.00 m (1Н, Нarom), 7.21 m (3Н, Нarom), (J 2), 126.1, 127.8, 128.6 d (J 3), 129.7, 130.8 d (J 8),
7.38 m (3Н, Нarom), 7.47 m (2Н, Нarom), 13.57 br.s 131.9 d (J 16), 136.8, 158.7 d (J 247), 170.0, 192.4,
Vm
(1Н, NH)
194.3
1645, 1.06 s (6Н, 2СН3), 2.31 s (2Н, СН2), 2.46 s (2Н, 28.1, 31.5, 41.5, 51.3, 109.8, 115.0 d (J 22), 116.7 d –115.82 m,
1610, СН2), 7.00 m (1Н, Нarom), 7.18 m (5Н, Нarom), (J 23), 124.1 d (J 2), 128.0 d (J 8), 128.6 d (J 3), 130.9 –113.31 m
Vn
Vo
Vp
1570, 7.38 m (2Н, Нarom), 13.45 br.s (1Н, NH)
d (J 8), 131.7 d (J 16), 132.7 d (J 2), 158.7 d (J 247),
161.8 d (J 249), 170.2, 192.5, 194.3
1510
1640, 1.09 s (6Н, 2СН3), 2.27 s (2Н, СН2), 2.54 s (2Н, 28.3, 31.0, 40.3, 47.4, 50.8, 109.2, 115.0 d (J 22), –116.19 m
1575 СН2), 4.62 d (2Н, СН2, J 5.8), 6.98 m (1Н, Нarom), 124.0, 127.0, 128.2, 128.5 d (J 3), 129.2, 130.6 d (J 8),
7.16 m (1Н, Нarom), 7.34 m (5Н, Нarom), 7.41 m 132.1 d (J 16), 135.8, 158.6 d (J 247), 171.5, 192.0,
(2Н, Нarom), 12.42 br.s (1Н, NH)
193.9
1640, 1.09 s (6Н, 2СН3), 2.27 s (2Н, СН2), 2.53 s (2Н, 28.4, 31.0, 40.3, 46.7, 50.9, 109.3, 115.0 d (J 22), –113.86 m,
1580, СН2), 4.59 d (2Н, СН2, J 5.8), 6.97 m (1Н, Нarom), 116.2 d (J 22), 124.0 d (J 2), 128.5 d (J 3), 128.8 d –116.18 m
1520 7.10 m (2Н, Нarom), 7.16 m (1Н, Нarom.), 7.30 m (J 8), 130.7 d (J 8), 131.6 d (J 3), 132.0 d (J 16), 158.6
(2Н, Нarom.), 7.34 m (2Н, Нarom.), 12.39 br.s (1Н, d (J 247), 162.5 d (J 247), 171.3, 192.1, 193.9
NH)
1660, 1.10 s (6Н, 2СН3), 1.95 s (4Н, 2СН2), 2.23 s (2Н, 25.3, 28.5, 29.7, 30.9, 44.5, 51.0, 113.6, 115.5 d –114.81 m
1615, СН2), 2.56 s (2Н, СН2), 3.30 m (4Н, 2СН2), 6.98 (J 23), 124.1 d (J 2), 130.1, 130.6 d (J 12), 132.2 d
1525 m (1Н, Нarom), 7.19 m (1Н, Нarom), 7.38 m (1Н, (J 9), 160.5 d (J 251), 164.2, 190.5, 194.3
Vq
Vr
Нarom), 7.69 m (1Н, Нarom
)
1640, 1.14 s (6Н, 2СН3), 1.68 m (6Н, 3СН2), 2.24 s 23.7, 26.4, 28.8, 32.1, 44.4, 50.4, 52.5, 113.7, 115.5 d –115.49 m
1605, (2Н, СН2), 2.47 s (2Н, СН2), 3.26 m (4Н, СН2), (J 23), 124.2 d (J 2), 130.1, 130.2 d (J 13), 132.4 d
1510 6.99 m (1Н, Нarom), 7.20 m (1Н, Нarom), 7.41 m (J 9), 160.5 d (J 251), 168.2, 191.6, 194.5
(1Н, Нarom), 7.67 m (1Н, Нarom
)
fluorine atom in the 13С NMR spectrum of exocyclic
groups of the side chain, and the cycle. The signals of
the protons of the NH group linked by the intra-
molecular hydrogen bond with the carbonyl group, in
enaminodiketones IIа–IIl appears at
δ
162.4–
162.9 ppm (1JC–F 247–250 Hz).
1
the Н NMR spectra of enaminodiketones Vа–Vd,
The IR spectra of endocyclic enaminodiketones
Vа–Vr also contain three characteristic absorption
bands at 1505–1570, 1570–1620, and 1630–1665 cm–1,
corresponding to the double bond, conjugated carbonyl
Vm, Vn and Ve–Vh, Vo, Vp appear upfield from the
signals of the regioisomers IIа–IIl, at δ 12.8–13.6 and
11.8–12.4 ppm, respectively. It should be noted that
the signal of the carbon atom at the fluorine atom in
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366
KHLEBNIKOVA et al.
the 13С NMR spectrum of compounds Vа–Vr is
characterized by rather large range of chemical shifts
and the spin-spin coupling constants: δ 158.6–
165.0 ppm (1JC–F 246–253 Hz).
2-[Benzylamino(3-fluorophenyl)methylene]-5,5-
dimethylcyclohexane-1,3-dione (IIe). Yield 97%, mp
79–82°С. Found, %: C 75.12; H 6.35; N 4.01.
C22H22FNO2. Calculated, %: C 75.19; H 6.31; N 3.99.
2-[Benzylamino(4-fluorophenyl)methylene]-5,5-
dimethylcyclohexane-1,3-dione (IIе). Yield 90%, mp
155–158°С. Found, %: C 75.09; H 6.34; N 3.92.
C22H22FNO2. Calculated, %: C 75.19; H 6.31; N 3.99.
EXPERIMENTAL
NMR spectra were registered on a Bruker Avance-
500 spectrometer in CDCl3 using TMS as an internal
reference for Н (500 MHz) and 13С (125 MHz) and
1
5,5-Dimethyl-2-[(4-fluorobenzylamino)(3-fluoro-
phenyl)methylene]cyclohexane-1,3-dione (IIg). Yield
89%, mp 134–137°С. Found, %: C 71.61; H 5.77; N
3.85. C22H21F2NO2. Calculated, %: C 71.53; H 5.73; N
3.79.
CCl3F for 19F (470 MHz). IR spectra were recorded on
a UR-20 instrument in KBr. Melting points were
determined on a Boetius apparatus. IR and 1Н, 13С, 19F
NMR spectra of compounds IIа–IIl and Vа–Vr are
given in the table. Fluorinated 2-benzoylcyclohexane-
1,3-diones Iа–Ic were prepared according to [11]. The
reactions were followed and the purity of the products
controlled by thin layer chromatography on Silufol
UV–254 plates with ether as eluent. Preparative TLC
was performed on silica 60 HF254 plates (Aldrich).
5,5-Dimethyl-2-[(4-fluorobenzylamino)(4-fluoro-
phenyl)methylene]cyclohexane-1,3-dione (IIh). Yield
82%, mp 117–120°С. Found, %: C 71.48; H 5.70; N
3.74. C22H21F2NO2. Calculated, %: C 71.53; H 5.73; N
3.79.
5,5-Dimethyl-2-[(pyrrolidin-1-yl)(3-fluorophenyl)-
methylene]cyclohexane-1,3-dione (IIi). Yield 98%,
mp 139–143°С. Found, %: C 72.43; H 7.06; N 4.48.
C19H22FNO2. Calculated, %: C 72.36; H 7.03; N 4.44.
Condensation of 2-(fluorobenzoyl)cyclohexane-
1,3-diones Iа–Ic with amines. To the solution of
1 mmol of β,β'-triketone Iа–Ic in anhydrous benzene
(40 ml) 1 mmol of amine was added. The reaction
mixture was refluxed with separation of water for 3 h.
After removal of benzene on a rotary evaporator, from
the starting compounds Ib, Ic, enaminodiketones IIa–
IIl were isolated by preparative TLC on silica (ether–
hexane 2:1) as colorless crystals, and from compound
5,5-Dimethyl-2-[(pyrrolidin-1-yl)(4-fluorophenyl)-
methylene]cyclohexane-1,3-dione (IIj). Yield 95%,
mp 160–163°С. Found, %: C 72.41; H 7.07; N 4.49.
C19H22FNO2. Calculated, %: C 72.36; H 7.03; N 4.44.
1
Ia xanthene III was obtained. IR, Н, 13С, 19F NMR
5,5-Dimethyl-2-[(piperidin-1-yl)(3-fluorophenyl)-
methylene]cyclohexane-1,3-dione (IIk). Yield 98%,
mp 165–167°С. Found, %: C 72.84; H 7.30; N 4.21.
C20H24FNO2. Calculated, %: C 72.92; H 7.34; N 4.25.
spectra of compounds IIa–IIl are given in the table.
5,5-Dimethyl-2-[phenylamino(3-fluorophenyl)-
methylene]cyclohexane-1,3-dione (IIа). Yield 90%,
mp. 112–115°С. Found, %: C 74.87; H 6.03; N 4.21.
C21H20FNO2. Calculated, %: C 74.76; H 5.97; N 4.15.
5,5-Dimethyl-2-[(piperidin-1-yl)(4-fluorophenyl)-
methylene]cyclohexane-1,3-dione (IIl). Yield 80%,
mp 176–179°С. Found, %: C 72.99; H 7.38; N 4.30.
C20H24FNO2. Calculated, %: C 72.92; H 7.34; N 4.25.
5,5-Dimethyl-2-[phenylamino(4-fluorophenyl)-
methylene]cyclohexane-1,3-dione (IIb). Yield 85%,
mp 151–154°С. Found, %: C 74.82; H 6.02; N 4.22.
C21H20FNO2. Calculated, %: C 74.76; H 5.97; N 4.15.
3,3-Dimethyl-2,3,4,9-tetrahydro-1Н-xanthene-
1,9-dione (III). Yield 90%, mp 128–130°С. IR
1
spectrum, ν, cm–1: 1710, 1620. H NMR spectrum, δ,
5,5-Dimethyl-2-[(3-fluorophenyl)(4-fluorophenyl-
amino)methylene]cyclohexane-1,3-dione (IIc). Yield
90%, mp 99–103°С. Found, %: C 70.90; H 5.36; N
3.90. C21H19F2NO2. Calculated, %: C 70.97; H 5.39; N
3.94.
ppm: 1.18 s (6Н, 2СН3), 2.48 s (2Н, СН2), 2.88 s (2Н,
СН2), 7.41 m (2Н, Нarom), 7.67 m (1Н, Нarom), 8.24 m
(1Н, Нarom). 13С NMR spectrum, δ, ppm: 28.2, 31.8,
43.1, 52.4, 115.9, 117.7, 125.1, 125.9, 126.8, 133.9,
154.9, 173.6, 176.7, 194.0. Found, %: C 74.43; H 5.87.
C15H14O3. Calculated, %: C 74.36; H 5.82.
5,5-Dimethyl-2-[(4-fluorophenyl)(4-fluorophenyl-
amino)methylene]cyclohexane-1,3-dione (IId). Yield
87%, mp 150–153°С. Found, %: C 70.89; H 5.42; N
3.97. C21H19F2NO2. Calculated, %: C 70.97; H 5.39; N
3.94.
Synthesis of chlorovinyldiketones. To 1 mmol of
2-(fluorobenzoyl)cyclohexane-1,3-dione Iа–Ic 10 mmol
of oxalyl chloride was added. The reaction mixture
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FLUORINATED 2-BENZOYLCYCLOHEXANE-1,3-DIONES
367
was kept for 5 h at room temperature, excess oxalyl
chloride was removed under a reduced pressure, the
residue dissolved in 15 ml of chloroform, washed with
saturated solution of NaHCO3 (2×5 ml), water (2×
5 ml), dried over magnesium sulfate. After removal of
chloroform on a rotary evaporator the vinylogous acyl
chlorides IVа–IVc were obtained as colorless
crystalline compounds.
5,5-Dimethyl-3-(phenylamino)-2-(3-fluorobenzoyl)-
2-cyclohexen-1-one (Vа). Yield 79%, mp 106–109°С.
Found, %: C 74.83; H 6.01; N 4.20. C21H20NO2F.
Calculated, %: C 74.76; H 5.97; N 4.15.
5,5-Dimethyl-3-(phenylamino)-2-(4-fluorobenzoyl)-
2-cyclohexen-1-one (Vb). Yield 78%, mp 171–174°С.
Found, %: C 74.70; H 6.94; N 4.11. C21H20NO2F.
Calculated, %: C 74.76; H 5.97; N 4.15.
5,5-Dimethyl-2-(2-fluorobenzoyl)-3-chloro-2-cyclo-
hexene-1-one (IVа). Yield 95%, mp 53–57°С. IR spec-
trum, ν, cm–1: 1690, 1635, 1620. 1H NMR spectrum, δ,
ppm: 1.18 s (6Н, 2СН3), 2.41 s (2Н, СН2), 2.70 s (2Н,
СН2), 7.07 m (1Н, Нarom), 7.25 m (1Н, Нarom), 7.55 m
(1Н, Нarom), 7.98 m (1Н, Нarom). 13С NMR spectrum, δ,
ppm: 28.1, 33.5, 48.1, 50.6, 116.6 d (J 23 Hz), 124.7 d
(J 3 Hz), 130.9, 135.8 d (J 9 Hz), 139.3, 151.6 d (J 3
Hz), 162.3 d (J 257 Hz), 188.7, 194.4. 19F NMR, δ,
ppm: –111.93 m (1F).
5,5-Dimethyl-2-(3-fluorobenzoyl)-3-(4-fluoro-
phenylamino)-2-cyclohexen-1-one (Vc). Yield 77%,
mp 106–109°С. Found, %: C 71.05; H 5.43; N 3.99.
C21H19NO2F2. Calculated, %: C 70.97; H 5.39; N 3.94.
5,5-Dimethyl-2-(4-fluorobenzoyl)-3-(4-fluoro-
phenylamino)-2-cyclohexen-1-one (Vd). Yield 73%,
mp 136–139°С. Found, %: C 70.90; H 5.34; N 3.91.
C21H19NO2F2. Calculated, %: C 70.97; H 5.39; N 3.94.
3-(Benzylamino)-5,5-dimethyl-2-(3-fluorobenzoyl)-
2-cyclohexen-1-one (Ve). Yield 65%, mp 162–164°С.
Found, %: C 75.11; H 6.27; N 3.96. C22H22NO2F.
Calculated, %: C 75.19; H 6.31; N 3.99.
5,5-Dimethyl-2-(3-fluorobenzoyl)-3-chloro-2-
cyclohexene-1-one (IVb). Yield 98%, mp 67–70°С.
1
IR spectrum, ν, cm–1: 1700, 1635, 1595. H NMR
spectrum, δ, ppm: 1.23 s (6Н, 2СН3), 2.45 s (2Н,
СН2), 2.76 s (2Н, СН2), 7.30 m (1Н, Нarom), 7.46 m
(1Н, Нarom), 7.54 m (1Н, Нarom), 7.60 m (1Н, Нarom).
13С NMR, δ, ppm: 28.3, 33.8, 48.8, 50.6, 115.6 d
(J 23 Hz), 121.1 d (J 22 Hz), 125.0, 130.6 d (J 8 Hz),
137.1, 137.8 d (J 6 Hz), 153.4, 163.0 d (J 249 Hz),
191.5, 194.5. 19F NMR, δ, ppm: –111.82 m.
3-(Benzylamino)-5,5-dimethyl-2-(4-fluorobenzoyl)-
2-cyclohexen-1-one (Vf). Yield 67%, mp 155–158°С.
Found, %: C 75.10; H 6.26; N 3.94. C22H22NO2F.
Calculated, %: C 75.19; H 6.31; N 3.99.
5,5-Dimethyl-3-(4-fluorobenzylamino)-2-(3-fluoro-
benzoyl)-2-cyclohexen-1-one (Vg). Yield 75%, mp
188–191°С. Found, %: C 71.61; H 5.77; N 3.82.
C22H21NO2F2. Calculated, %: C 71.53; H 5.73; N 3.79.
5,5-Dimethyl-2-(4-fluorobenzoyl)-3-chloro-2-
cyclohexen-1-one (IVc). Yield 97%, mp 86–89°С. IR
spectrum, ν, cm–1: 1690, 1630, 1605. 1H NMR
spectrum, δ, ppm: 1.22 s (6Н, 2СН3), 2.44 s (2Н,
СН2), 2.76 s (2Н, СН2), 7.15 m (2Н, Нarom), 7.87 m
(2Н, Нarom). 13С NMR spectrum, δ, ppm: 28.3, 33.8,
48.17, 50.6, 116.1 d (J 22 Hz), 131.9 d (J 10 Hz),
132.2, 137.2, 153.1, 166.3 d (J 256 Hz), 191.1, 194.6.
19F NMR, δ, ppm: –103.48 m.
5,5-Dimethyl-3-(4-fluorobenzylamino)-2-(4-
fluorobenzoyl)-2-cyclohexen-1-one (Vh). Yield 75%,
mp 117–120°С. Found, %: C 71.62; H 5.78; N 3.84.
C22H21NO2F2. Calculated, %: C 71.53; H 5.73; N 3.79.
5,5-Dimethyl-3-(pyrrolidin-1-yl)-2-(3-fluoro-
benzoyl)-2-cyclohexen-1-one (Vi). Yield 90%, mp
184–187°С. Found, %: C 72.29; H 7.00; N 4.41.
C19H22NO2F. Calculated, %: C 72.36; H 7.03; N 4.44.
Reaction of vinylogous substitution in chloro-
vinyldiketones (IVа-IVc) with amines. To the
solution of 1 mmol of chlorovinyldiketone IIIа–IIIc in
15 ml of chloroform 2 mmol of amine was added. The
reaction mixture was stirred for 2–3 h (TLC control) at
room temperature, washed with water (2×5 ml), dried
over magnesium sulfate, solvent removed under
reduced pressure, the residue was crystallized from the
mixture ether-hexane. Endocyclic enaminodiketones
Vа–Vr were obtained as colorless crystals in 78–90%
yield. IR, 1Н, 13С, 19F NMR spectra of compounds Vа–Vr
are given in the table.
5,5-Dimethyl-3-(pyrrolidin-1-yl)-2-(4-fluoro-
benzoyl)-2-cyclohexen-1-one (Vj). Yield 88%, mp
175–177°С. Found, %: C 72.43; H 7.07; N 4.49.
C19H22NO2F. Calculated, %: C 72.36; H 7.03; N 4.44.
5,5-Dimethyl-3-(piperidin-1-yl)-2-(3-fluorobenzoyl)-
2-cyclohexen-1-one (Vk). Yield 88%, mp 155–158°С.
Found, %: C 72.84; H 7.30; N 4.21. C20H24NO2F.
Calculated, %: C 72.92; H 7.34; N 4.25.
5,5-Dimethyl-3-(piperidin-1-yl)-2-(4-fluorobenzoyl)-
2-cyclohexen-1-one (Vl). Yield 87%, mp 139–141°С.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

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KHLEBNIKOVA et al.
and Lakhvich, F.А., Vestsi Akad. Nauk BSSR. Ser.
Khim. Nauk, 1989, no. 5, p. 65.
Found, %: C 72.99; H 7.38; N 4.30. C20H24NO2F. Cal-
culated, %: C 72.92; H 7.34; N 4.25.
4. Kuzmitskii, B.B., Golubeva, M.B., Mizulo, N.A.,
Romanova, V.N., Khlebnikova, T.C., and Lakhvich, F.А.,
Vestsi Akad. Nauk BSSR. Ser. Khim. Nauk, 1989, no. 6,
p. 82.
5,5-Dimethyl-3-(phenylamino)-2-(2-fluorobenzoyl)-
2-cyclohexen-1-one (Vm). Yield 75%, mp 119–122°С.
Found, %: C 74.68; H 5.93; N 4.10. C21H20NO2F. Cal-
culated, %: C 74.76; H 5.97; N 4.15.
5. Belan, S.R., Grapov, A.F., and Mel’nikova, G.M.,
Novye pestitsidy. Spravochnik (New Perspective:
Handbook), Мoscow: Khimiya, 2001.
5,5-Dimethyl-2-(2-fluorobenzoyl)-3-(4-fluoro-
phenylamino)-2-cyclohexen-1-one (Vn). Yield 73%,
mp 127–129°С. Found, %: C 70.88; H 5.36; N 3.91.
C21H19NO2F2. Calculated, %: C 70.97; H 5.39; N 3.94.
6. Lakhvich, F.А., Rubinov, D.B., and Rubinova, I.L.,
Zemledelie i Zashchita Rastenii, 2006, vol. 47, no. 4,
p. 33.
5,5-Dimethyl-3-(benzylamino)-2-(2-fluorobenzoyl)-
2-cyclohexen-1-one (Vo). Yield 74%, mp 148–151°С.
Found, %: C 75.28; H 6.36; N 4.04. C22H22NO2F. Cal-
culated, %: C 75.19; H 6.31; N 3.99.
7. Kirsch, P., Modern Fluoroorganic Chemistry,
Weinheim: Wiley–VCH Verlag GmbH, 2004.
8. Jeschke, P., Chem. Bio. Chem., 2004, vol. 5, no. 7,
p. 571.
5,5-Dimethyl-2-(2-fluorobenzoyl)-3-(4-fluoro-
benzylamino)-2-cyclohexen-1-one (Vp). Yield 72%,
mp 140–143°С. Found, %: C 71.44; H 5.70; N 3.76.
C22H21NO2F2. Calculated, %: C 71.53; H 5.73; N 3.79.
9. Begue, J.-P. and Bonnet-Delpon, D., J. Fluorine Chem.,
2006, vol. 127, no. 8, p. 992.
10. Kirk, K.L., J. Fluorine Chem., 2006, vol. 127, no. 9,
p. 1013.
5,5-Dimethyl-3-(pyrrolidin-1-yl)-2-(2-fluoro-
benzoyl)-2-cyclohexen-1-one (Vq). Yield 70%, mp
156–157°С. Found, %: C 72.30; H 6.99; N 4.40.
C19H22NO2F. Calculated, %: C 72.36; H 7.03; N 4.44.
11. Khlebnikova, T.S., Isakova, V.G., Baranovskii, A.V.,
Lakhvich, F.A., and Lyakhov, A.S., Russ. J. Gen.
Chem., 2007, vol. 77, no. 10, p. 1724.
12. Khlebnikova, T.C., Isakova, V.G., and Lakhvich, F.А.,
Vestsi Akad. Nauk BSSR. Ser. Khim. Nauk, 2009, no. 3,
p. 79.
5,5-Dimethyl-3-(piperidin-1-yl)-2-(2-fluorobenzoyl)-
2-cyclohexen-1-one (Vr). Yield 73%, mp 123–125°С.
Found, %: C 73.01; H 7.39; N 4.31. C20H24NO2F.
Calculated, %: C 72.92; H 7.34; N 4.25.
13. Rubinov, D.B., Rubinova, I.L., and Akhrem, A.A.,
Chem. Rev., 1999, vol. 99, no. 4, p. 1047.
14. Borisov, E.V., Verenich, A.I., Govorova, А.А.,
Lyakhov, A.S., and Khlebnikova, T.S., Russ. Chem.
Bull., 2000, vol. 49, no. 6, p. 1068.
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