Synthesis and structure of reaction products obtained from 1,2-epoxyperfluorobutane and bifunctional nucleophilic reagents

Article abstract of DOI:10.1134/S1070428009110219

1,2-Epoxyperfluorobutane readily reacts with bifunctional nucleophilic reagents to provide heterocyclic compounds with a pentafluoroethyl substituent. The reaction of this epoxide with thiourea and acetone thiosemicarbazone gave rise to 2-amino-5-pentaflu

Full text of DOI:10.1134/S1070428009110219

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 11, pp. 1700−1706. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © T.I. Filyakova, M.I. Kodess, P.A. Slepukhin, A.Ya. Zapevalov, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol.
45, No. 11, pp. 1706−1712.
Synthesis and Structure of Reaction Products Obtained
from 1,2-Epoxyperfluorobutane and Bifunctional
Nucleophilic Reagents
T. I. Filyakova, M. I. Kodess, P. A. Slepukhin, andA. Ya. Zapevalov
Postovsky Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences
Yekaterinburg, 620041Russia
e-mail: fc403@ios.uran.ru
Received January 21, 2009
Abstract—1,2-Epoxyperfluorobutane readily reacts with bifunctional nucleophilic reagents to provide heterocyclic
compounds with a pentafluoroethyl substituent. The reaction of this epoxide with thiourea and acetone
thiosemicarbazone gave rise to 2-amino-5-pentafluoroethyl-5-fluoro-4(5H)-thiazolinone and 2-iso-
propylidenehydrazono-5-pentafluoroethyl-5-fluoro-4-thiazolidinone respectively. The reaction of 1,2-
epoxyperfluorobutane with o-phenylenediamine and 2,3-diaminonaphthalene afforded in high yields 3-
pentafluoroethyl-2(1H)-quinoxalinone and 3-(pentafluoroethyl)benzo[g]-2(1H)-quinoxalinone. The molecular and
crystal structure of the obtained fluorine-containing heterocycles was established by XRD analysis.
DOI: 10.1134/S1070428009110219
The oxides of terminal fluoroolefins are highly reactive
compounds and important intermediates in the syntheses
of versatile polyfluorinated functional derivatives and
heterocyclic compounds endowed with a wide range of
biological activity and with useful technical properties [1–
6].
2,3-diaminonaphthalene and acetone thiosemicarbazone
whose reactions with terminal perfluorepoxides did not
appear in publications.
Like the perfluoroepoxypropane, oxirane I is
a preparatively accessible synthon [12, 13] that can be
utilized for the preparation of heterocyclic compounds
with a pentafluoroethyl substituent.
Perfluoroolefins oxides can be regarded as useful
building blocks for heterocyclic systems containing
fluorine atoms and perfuoroalkyl groups [6–11]. The most
thorough investigation was performed on reactions of
perfluoroepoxypropane that was an important semiproduct
in the fluoroorganic synthesis [1–3, 7–10]. The oxides of
higher terminal perfluoroolefins were poorly studied in
the heterocyclization reactions [7]. This fact to a large
extent originates from the ready isomerization of 1,2-
epoxyperfluoroalkanes under the action of nucleophilic
reagents with the formation of the derivatives of the
corresponding polyfluorinated acids [1, 2, 11].
We carried out the reaction of compound I with
thiourea in methanol that provided under mild conditions
2-amino- 5-pentafluoroethyl-5-fluoro-4(5H)-thiazolinone
(II) in a high yield.
1,2-Epoxyperfluorobutane (I) reacted in acetone with
acetone thiasemicarbazone gave in a good yield 2-iso-
propylidenehydrazono-5-pentafluoroethyl-5-fluoro-
thiazolidin-4-one (III). Compound III was isolated in the
individual state by column chromatography followed by
recrystallization from hexane. At the use in this reaction
of a proton-donor solvent (methanol) we obtained an
intractable mixture of products presumably due to side
processes of isomerization and polymerization. The
presence in the reaction mixture of the target compound
In extension of the studies in the field of perfluoro-
oxiranes and aiming at the synthesis of new fluorine-
containing heterocyclic compounds we studied the reac-
tions of the perfluoroepoxypropane homolog, 1,2-epoxy-
perfluorobutane (I), with a number of bifunctional
nucleophiles: thiourea, o-phenylenediamine, and also with
1
III was detected by H and 19F NMR spectra.
In order to obtain more complete information on the
structure of obtained compounds II and III we carried
1700

SYNTHESIS AND STRUCTURE OF REACTION PRODUCTS
1701
Scheme 1.
7
6
F3C CF2
O
5
S
4
F
Me2CO
S1 3 NH
NH2CNHN C(CH3)2
+
C2F5 CF CF2
2
O
N
I
9,10
8
N C(CH3)2
III
7
6
C2F5
F
O
F3C CF2
O
4
5
F
S1 N3
(NH2)2C=S
MeOH
S
N
2
NH
NH2
II
N C(CH3)2
A
1
out alongside the IR, H, 13C, 19F NMR spectral study
and elemental analysis also XRD analysis on their single
crystals. XRD data confirmed the formation of the
thiazolinone ring in the reaction of the terminal perfluoro-
oxiranes with thiourea (Scheme 1, Fig. 1) (No published
data existed on XRD studies of reaction products of
terminal perfluoroolefin oxides with dinucleophiles).
Fig. 2), but in the organic solvents it might be present in
a mixture with the tautomeric form A as indicated by the
broadened signals in the 13C NMR spectrum in the region
δ, ppm: 152.35 br.s (C2) and 164.39 br.d (C4). The
presence in the molecule of the C=N–N=C moiety with
a weak conjugation of the double bonds is unambiguously
manifested by the distribution of bond distances in this
fragment: C1=N2 1.260(3), N2–N3 1.420(3), N3=C6
1.276(3) . The prevalence of the imino-form in this case
may be due to its stabilization in the system of the
intermolecular hydrogen bonds (see the table).
Compound II in the crystal according to XRD data
exists in the amino-form (Fig. 1, protons are localized by
the direct method and refined independently).At the same
time the measured length of the exocyclic bond C1–N2
1.295(3) proved to be shorter that that of endocyclic
Formerly the reaction of perfluoroepoxypropane with
bonds C1–N1 1.312(3) and C2–N1 1.341(3) indicating
the strong delocalization of the electron density in the
system of the conjugated bonds. Yet the bond C2–O1
1.217(3) is close to a standard double bond and it is
not involved in the conjugatipon system. The ring is planar
with the deviation of atoms from the mean square plane
no more than 0.035 . About 20% of positions in the
crystal are occupied by the molecules of opposite con-
figuration (R/S), therefore the positions of S1, C3, and C4
atoms are disordered, and the position of atoms F1 and
F2 in the opposite configurations practically coincide.
Besides the molecules in the crystal are involved in the
system of intermolecular hydrogen bonds (see the table)
forming polymer “bands” with an interlayer distance of
ortho-disubstituted arenes afforded analogs of benzo-
~3.8
.
At the same time the XRD data showed that in the
Fig. 1. Molecular structure of thiazolinone II represented with
thermal ellipsoids of 50% probability.
crystal compound III exists as thiazolidinone (Scheme 1,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRYVol. 45 No. 11 2009

FILYAKOVA et al.
1702
Parameters of hydrogen bonds in crystals of compounds II–V
fused compounds [2, 8, 10], but the data on their structure
were in some events ambiguous. For instance, the product
of the reaction between the perfluoroepoxypropane and
o-phenylenediaminem was regarded as having either keto
[8] or enol form [2, 10].Analogous products were obtain-
ed in [14] from o-phenylenediamine and methyl esters
of perfluorinated α-ketoacids, and based on spectral data
(IR, 1H NMR spectra) they were assigned a structure of
an equilibrium mixture of keto and enol forms. In this
study a reaction was performed of epoxide I with the
o-phenylenediamine giving in a high yield heterocycliz-
ation product IV. The XRD analysis demonstrated that
in the crystal state 3-pentafluoroethyl-2(1H)-quinoxali-
none (IV) existed in the keto-form (Scheme 2, Fig. 3).
Therewith the length of the C–O bond is close to a standard
double bond, 1.236(3) , and the molecules are bound
into dimer by intermolecular hydrogen bonds involving
...
the N–H C=O moieties (see the table, Fig. 4). The
molecular packing is by layers, its interesting feature is
the presence of shortened π−π contacts between the
...
carbonyl groups of the neighboring layers σ O1 C1
[–x, 2 – σ, 1 – z] ~3.2 (Fig. 5).
Fig. 2. Molecular structure of thiazolidinone III represented
with thermal ellipsoids of 50% probability.
Fig. 3. Molecular structure of quinoxalinone IV represented
with thermal ellipsoids of 50% probability.
Fig. 4. Intermolecular hydrogen bonds in the crystal of
quinoxalinone IV.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

SYNTHESIS AND STRUCTURE OF REACTION PRODUCTS
1703
Fig. 6. Molecular structure of benzoquinoxalinone V.
compounds IV and V is practically within the error limits
of the measurements.
In the reaction mixture of epoxide I with o-phenyl-
enediamine alongside heterocycle IV a small amount of
Fig. 5. Intermolecular π−π contacts in the crystal of quinoxali-
noneIV.
1
benzimidazole VI was detected by H and 19F NMR
spectroscopy. The latter compound may result from the
competing isomerization reaction of the initial oxirane
(Scheme 3). The reaction mixture of epoxide I with 2,3-
diaminonaphthalene has a more complex compositiuon
and contains alongside the prevailing compound V
benzimidazole VII (signals of C3F7 group are present in
the 19F NMR spectrum) and other fluorine-containing
unidentified compounds, but their overall quantity is minor
(~10%).
Similarly 1,2-epoxyperfluorobutane (I) reacted with
2,3-diaminonaphthalene forming 3-(penta-fluoroethyl)-
benzo[g]-2(1H)-quinoxalinone (V) (Scheme 2). The
structure of compound V was proved by XRD analysis
PCA (Fig. 6). The fluorine atoms of the trifluoromethyl
group suffer strong thermal vibrations that are accounted
for in the model by the introduction of disordering of atoms
F1 and F3 by 2 positions with the occupancy factors 0.7
and 0.3 (the second component is not shown on Fig. 6).
Similar to compound IV in the crystal of substance V the
molecules are packed in layers, but the shortened π−π
contacts of carbonyl groups present in the packing of
quinoxalinone IV are lacking in crystals V. Apparently
the weakening of the π−π interaction compared to com-
pound IV results in the increase in the interlayer distance
to 3.4 . Yet in the packing the system is retained of
dimers bound by the hydrogen bonds (see the table), and
the difference in the hydrogen bonds parameters in
Compounds IV and V were isolated in the individual
state by crystallization from aqueous methanol, analytical
sample of quinoxalinone V was obtained by recrystalliz-
ation from a mixture ethyl acetate–hexane.
EXPERIMENTAL
1H, 13C, and 19F NMR spectra were registered on
a spectrometer Bruker DRX-400 (400, 100, and
Scheme 2.
Scheme 3.
NH2
9
10
5
4a
8a
N
CF2 CF3
6
4
NH2
Et2O
NH2
NH2
3
2
1
N
H
7
N
O
Nu
8
6
C3F7
C3F7
I
[C3F7CF=O]
I
IV
N
H
NH2
NH2
NH2
NH2
11
CF2
12
CF3
VI
5
4a
N
7
8
4
3
N
2
1
Et2O
9a
10a N
H
O
10
9
N
H
V
VII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

FILYAKOVA et al.
1704
376 MHz respectively), internal references TMS and
C6F6. The chemical shifts in the 19F NMR spectra are
reported with respect to CFCl3 and are considered as
positive in the growing field. The assignment of signals
in the 1H and 13C NMR spectra of compounds III and V
ether, filtered from insoluble impurities, the solvent was
removed, and the residue was recrystallized from aqueous
methanol. Yield 4.48 g (74%). Colorless crystals, mp 210–
212°C. IR spectrum, ν, cm–1: 3230 (NH), 1710 (C=O),
1
1650 (C=N). H NMR spectrum (acetone-d6), δ, ppm:
was confirmed by the data of 2D experiments 1H 1H
–
9.35 br.s (NH2). 13C NMR spectrum (acetone-d6), δ,
NOESY, 1H–13C HSQC and HMBC. IR spectra from
mulls of compounds in mineral oil were recorded on an IR
Fourier spectrometer Perkin Elmer Spectrum One.
Elemental analyses were performed using analyzer Perkin
Elmer PE 2400.
3
2
ppm: 177.22 d (C2, JCF 2.4 Hz), 177.00 d (C4, JCF
17.2 Hz), 119.19 q.t.d (C7, JCF 287.5, JCF 35.5, JCF
0.8 Hz), 111.95 d.d.q.d (C6, 1JCF 265.7, 260.7, 2JCF 38.0,
34.7 Hz), 107.04 d.d.d.q (C5, 1JCF 237.9, 2JCF 31.3, 27.86,
3JCF 0.7 Hz). 19F NMR spectrum (acetone-d6), δ, ppm:
1
2
3
78.49 d.d [3F, F7, J(F7,F5) 9.5, J(F7,F6A) 0.9 Hz],
4
3
XRD analysis of compounds II–V was carried out on
an automtic single-crystal diffractometer Xcalibur 3 with
CCD detector applying the standard procedure [MOK-
radiation, 295(2) K, graphite monochromator, ω-scan-
ning]. The correction for extinction was not done. The
structures were solved and refined applying software
SHELX-97 [16]. The structures were solved by the direct
method and refined in the full-matrix least-squares method
in the anisotropic approximation for all nonhydrogen
atoms. The hydrogen atoms were revealed from the
electron-density differences and they were included in
the refinement in the isotropic approximation in the rider
model. The hydrogen atoms involved into the hydrogen
bonds were solved by the direct method and were
included into the refining independently.
117.72 d.d.q [1F, F6A, 2J(F6A,F6B) 282.4, 3J(F6A,F5) 13.4,
3J(F6A,F7) 0.9], 121.36 d.d (1F, F6B, J(F6A,F6B) 282.4,
2
3J(F6B,F5) 15.4], 145.04 d.d.q (1F, F5, J(F5,F6B) 15.4,
3
3J(F5,F6A) 13.4, 4J(F5,F7) 9.5 Hz]. Found, %: C 23.84;
H 0.81; F 45.00; N 11.38; S 12.51. C5H2F6N2OS.
Calculated, %: C 23.81; H 0.79; F 45.24; N 11.11; S 12.70.
XRD analysis of compound II was carried out on
a crystal fragment (colorless prism) of the size
0.45×0.31×0.25 mm. C5H2F6N2OS, M 252.15, crystal
system triclinic, space group P-1, parameters of unit cell:
a 6.0783(6), b 6.7171(7), c 11.8302(12) , α 95.323(9),
β 93.955(8), γ 109.121(9) deg, V 451.85(8) 3, Z 2,
d
calc 1.853, μ 0.430 mm–1. Region of scanning 3.23 ≤ θ ≤
28.28, overall reflections number 2144 (Rint 0.0212),
reflections number with I > 2σ(I) 1150, the number of
The XRD data on compounds II–V are deposited into
the Cambridge Crystallographic Data Center under the
numbers CCDC 744889–744892 respectively. The free
access to these data is possible at the address
www.ccdc.cam. ac.uk/data_request/cif.
refined parameters 171. Final parameters of refinement:
R1 0.0488, wR2 0.1211 [for reflections with I > 2σ(I)],
R1 0.0922, wR2 0.1303 (for all reflections), quality factor
S 1.009. The residual peaks of maximum and minimum
3
Oxirane I was prepared by procedure [13], acetone
thiosemicarbazone, by method [15]. The ratio of the reac-
tion products was measured by comparison of the integral
intensity of the corresponding signals in the 19F NMR
spectra.
electron density 0.281 and –0.224 e/
.
2-Isopropylidenehydrazono-5-pentafluoroethyl-
5-fluoro-4-thiazolidinone (III). In a flask equipped with
a reflux cold finger condenser connected to a cooled trap
(–78°C), a gas-inlet tube, and a magnetic stirrer was
charged 1.32 g (10 mmol) of acetone thiosemicarbazone,
1.7 g (20 mmol) of NaHCO3, 30 ml of acetone, and at
stirring was passed through 2.38 g (11 mmol) of oxirane
I. The reaction mixture was stirred at room temperature
for 2 h, then the precipitate was filtered off, the filtrate
was poured into ice water, the separated precipitate was
filtered off and dried in air. The reaction product was
isolated by column chromatography (SiO2, eluent hexane–
acetone 2.5:1) followed by recrystallization from hexane.
Yield 2.2 g (72%). Colorless crystals, mp 98–99°C. IR
spectrum, ν, cm–1: 3102, 3165 (NH), 1747 (C=O), 1653
(C=N). 1H NMR spectrum (acetone-d6), δ, ppm: 11.9 br.s
The solvents used in the study were purified and dried
by standard procedures.
2-Amino-5-pentafluoroethyl-5-fluoro-4(5H)-
thiazolinone (II). In a flask equipped with a reflux cold
finger condenser connected to a cooled trap (–78°C),
a gas-inlet tube, and a magnetic stirrer was charged
3.96 g (52 mmol) of thiourea, 45 ml of methanol, and
5.18 g (24 mmol) of oxide I was passed into the reaction
mixture. The reaction mixture was stirred at room
temperature for 3 h, then poured into water (~200 ml),
the separated precipitate was filtered off, washed with
water, and dried in air. The dry product was dissolved in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

SYNTHESIS AND STRUCTURE OF REACTION PRODUCTS
1705
(NH), [2.10 s (3H), 2.08 s (3H), H9, H10]. 13C NMR
134.53 s (C5), 131.38 s (C8a), 131.13 s (C6/7), 125.14 s
(C7/6), 119.91 q.t (C10, 1JCF 286.5, 2JCF 35.5 Hz), 116.61 s
(C8), 112.28 t.q (C9, 1JCF 256.2, 2JCF 37.3 Hz). 19F NMR
spectrum (acetone-d6), δ, ppm: 81.26 t (3F, F10,
spectrum (acetone-d6), δ, ppm: 169.55 s (C8), 164.39 br.d
2
(C4, JCF 20 Hz), 152.35 br.s (C2), 119.08 q.t.d (C7,
2
3
1JCF 288.0, JCF 35.1, JCF 1.0 Hz), 111.83 d.d.q.d (C6,
1JCF 265.8, 261.9, 2JCF 38.2, 35.1 Hz), 99.49 d.d.d (C5,
3
3J 1.2 Hz), 116.36 q (2F, F9, J 1.2 Hz). Found, %:
2
1JCF 233.3, JCF 29.7, 27.9 Hz), 24.78 s, 18.86 s (C9,
C 45.48; H 1.63; F 35.94; N 10.63. C10H5F5N2O.
Calculated, %: C 45.46; H 1.90; F 35.99; N 10.61.
C10). 19F NMR spectrum (acetone-d6), δ, ppm: 78.98 d.d
[3F, F7, 4J(F7, F5) 9.6, 3J(F7, F6A) 0.8 Hz], 119.42 d.d.q
[1F, F6A, 2J(F6A, F6B) 283.1, 3J(F6A, F5) 14.9, 3J(F6A, F7)
0.8 Hz], 121.77 d.d [1F, F6B, 2J(F6A, F6B) 283.1, 3J(F6B,
F5) 15.9 Hz], 143.50 m (1F, F5). Found, %: C 31.34;
H 2.35; F 37.31; N 13.55; S 10.45. C8H7F6N3OS. Found,
%: C 31.27; H 2.28; F 31.27; N 13.68; S 10.42.
XRD analysis of compound IV was carried out on
a crystal fragment (colorless prism) of the size 0.49 ×
0.21 × 0.18 mm. C10H5F5N2O. M 264.16, crystal system
triclinic, space group P-1, unit cell parameters:
a 5.3300(9), b 8.6012(18), c 11.324(3) , α 86.349(18),
β 83.892(16), γ 85.230(15) deg, V 513.63(18) 3, Z 2,
d
calc 1.708, μ 0.174 mm–1. Region of scanning 3.07 ≤ θ ≤
XRD analysis of compound III was carried out on
a crystal fragment (colorless prism) of the size 0.52 ×
0.49 × 0.43 mm. C8H7F6N3OS. M 307.23, crystal system
triclinic, space group P-1, unit cell parameters:
28.27, overall reflections number 2402 (Rint 0.0174),
reflections number with I > 2σ(I) 1377, the number of
refined parameters 183. Final parameters of refinement:
R1 0.0345, wR2 0.0766 [for reflections with I > 2σ(I)], R1
0.0755, wR2 0.0839 (for all reflections), quality factor S
a 6.4645(7), b 9.6686(12), c 10.1911(16)
,
α 89.886(12), β 88.030(11), γ 73.907(11) deg,
V 611.63(14) 3, Z 2, dcalc 1.668, μ 0.336 mm–1. Region
of scanning 2.96 ≤ θ ≤ 28.30, overall reflections number
2959 (Rint 0.0141), reflections number with I > 2σ(I) 2013,
the number of refined parameters 176. Final parameters
of refinement: R1 0.0481, wR2 0.1561[for reflections with
I > 2σ(I)], R1 0.0682, wR2 0.1683 (for all reflections),
1.000. The residual peaks of maximum and minimum
3
electron density 0.190 and –0.195 e/
.
2-Heptafluoropropylbenzimidazole (IV). 19F NMR
spectrum coincides with the data in [17]. 1H NMR
spectrum (acetone-d6), δ, ppm: 6.35 m (2H), 6.28 m (2H)
(C4–7), AA'BB', Ar.
quality factor S 1.006. The residual peaks of maximum
3
and minimum electron density 0.372 and –0.394 e/
.
3-(Pentafluoroethyl)benzo[g]-2(1H)-quinoxali-
none (V). Under similar conditions through the mixture
of 1.44 g (9 mmol) of 2,3-diaminonaphthalene and 2.18 g
(26 mmol) of NaHCO3 in 35 ml of ethyl ether was bubbled
2.1 g (9.7 mmol) of oxirane I, the mixture was stirred at
room temperature for 6 h, then 10 ml of acetone was
added, the insoluble precipitate was filtered off. The
precipitate and the filtrate were separately worked up.
3-Pentafluoroethyl-2(1H)-quinoxalinone (IV). In
a flask equipped with a reflux cold finger condenser
connected to a cooled trap (–78°C), a gas-inlet tube, and
a magnetic stirrer was charged 1.52 g (14 mmol) of
O-phenylenediamine, 3.52 g of NaHCO3 (42 mmol), 35 ml
of ethyl ether and at stirring was passed through 3.2 g
(14.8 mmol) of oxirane I. The reaction mixture was stirred
at room temperature for 3 h, then 15 ml of acetone was
added, insoluble residue was filtered off. After removal
of solvents from the filtrate 3.2 g of yellow-brown residue
was obtained containing according to 19F NMR spectrum
quinoxalinone IV and benzimidazole VI in a ratio 93:7.
The product was dissolved in methanol, diluted with water,
the precipitate was filtered off, dried in air, and recrystal-
lized from aqueous methanol.Yield 2.88 g (78%). Colorless
crystals, mp 181–182°C. IR spectrum, ν, cm–1: 3340 (NH),
The precipitate was treated with water, insoluble part
was filtered off and dried in air, then recrystallized from
a mixture of ethyl acetate and hexane, 2:1, to obtain 0.78 g
of benzoquinoxalinone V, yellow needle crystals, mp 273–
274°C (subl.).
The residue obtained from the filtrate on removing
the solvents was dissolved in methanol, diluted with water,
the separated precipitate was filtered off, dried in air,
and recrystallized from aqueous methanol. We obtained
1.32 g of compound V.
1
1687 (C=O). H NMR spectrum (acetone-d6), δ, ppm:
11.83 br.s (1H, NH), 7.91 d.d (1H, H5, J 8.2, J 1.4 Hz),
7.74 d.d.d (1H, H7, J 8.4, J 7.1, J 1.4 Hz), 7.51 d.d (1H,
H8, J 8.4, J 1.2 Hz), 7.44 d.d.d (1H, H6, J 8.2, J 7.1,
J 1.2 Hz). 13C NMR spectrum (acetone-d6), δ, ppm:
152.52 s (C2), 145.72 t (C3, 2JCF 24.9 Hz), 134.56 s (C4a),
Overall yield 2.1 g (76%). IR spectrum, ν, cm–1: 3106,
1
3332 (NH), 1672 (C=O), 1630 (C=N). H NMR spec-
trum (DMSO-d6), δ, ppm: 12.91 br.s (1H, NH), 8.64 s
(1H, H5), 8.14 d (1H, H6, J 8.3 Hz), 8.02 d (1H, H9,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009

FILYAKOVA et al.
1706
J 8.4 Hz), 7.74 s (1H, H10), 7.66 d.d.d (1H, H8, J 8.4,
6.8, 1.4 Hz), 7.53 d.d.d (1H, H7, J 8.3, 6.8, 1.3 Hz). 13C
NMR spectrum (DMSO-d6), δ, ppm: 151.49 s (C2),
3. Eleuterio, H.S., J. Macromol. Sci.-Chem., 1972, vol. A6,
no. 6, p. 1027.
4. Ponomarenko, V.A., Krukovskii, S.P., andAlybina,A.Yu.,
Ftorsoderzhashchie geterotsepnye polimery (Fluorine-
containing Heterochain Polymers), Moscow: Nauka, 1973.
5. Novoe v tekhnologii soedinenii ftora (New in the
Technology of Fluorine Compounds), Isikava, N.,
Moscow: Mir, 1984.
6. Furin, G.G., Ftorsoderzhashchie geterotsiklicheskie
soedineniya. Sintez i primenenie (Fluorine-Containing
Heterocyclic Compounds. Synthesis and Application),
Novosibirsk: Nauka, 2001, p. 183.
2
145.18 m (C3, JCF 24.5 Hz), 134.95 s (C9a), 130.50 s
(C10a), 130.41 s (C5), 129.52 s (C4a), 129.47 s (C5a),
129.21 s (C8), 129.16 s (C6), 126.88 s (C9), 125.28 s,
(C7), 118.55 q.t (C12, 1JCF 287.8, 2JCF 35.5 Hz), 111.06 c
(C10), 110.98 t.q (C11, 1JCF 257.1, 2JCF 37.2 Hz). 19F NMR
spectrum (DMSO-d6), δ, ppm: 81.53 t (3F, F12, J 1.4 Hz),
116.48 br.s (2F, F11). Found, %: C 53.54; H 2.17; F 30.40;
N 8.98. C14H7F5N2O. Found, %: C 53.50; H 2.23;
F 30.25; N 8.92.
7. Knunyants, I.L., Shokhina, V.V., and Galakhov, I.V., Khim.
Geterotsikl. Soedin., 1966, vol. 6, p. 873.
XRD analysis of compound V was performed on
an orange needle crystal of the size 0.51 × 0.23 ×
0.09 mm. C14H7F5N2O. M 314.22, crystal system mono-
clinic, space group P21/n, unit cell parameters:
a 13.1743(15), b 5.1686(12), c 18.305(3) , α 90,
β 92.736(14), γ 90 deg, V 1245.0(5) 3, Z 4, dcalc 1.676,
μ 0.159 mm–1. Region of scanning 3.10 ≤ θ ≤ 26.37,
overall reflections number 2527 (Rint 0.0461), reflections
number with I > 2σ(I) 1080, the number of refined
parameters 221. Final parameters of refinement:
R1 0.0463, wR2 0.0923 [for reflections with I > 2σ(I)],
R1 0.1202, wR2 0.1017 (for all reflections), quality factor
8. Ishikava, N. and Sasaki, S., Bull. Chem. Soc. Jpn., 1977,
vol. 50, no. 8, p. 2164.
9. Cushman, M., Patel, H.P., Scheuring, J., and Bacher, A., J.
Org. Chem., 1992, vol. 57, p. 5630.
10. Nottke, J.E., US Patent 3928350, 1975; Ref. Zh. Khim., 1976,
16N248P.
11. Kvicala, J., Hovorkova, P., and Paleta, O., J. Fluor. Chem.,
2001, vol. 108, p. 1.
12. du Pont de Nemours, E.I. Co., UK Patent 904877, 1962;
Chem. Abstr., 1963, vol. 58, 12513b.
13. Filyakova, T.I., Zapevalov, A.Ya., and Kolenko, I.P.,
Inventor’s Certificate 666176; USSR Byull. Izobr., 1979,
no. 21.
14. Saloutin, V.I., Piterskikh, I.A., Pashkevich, K.I., and Kodess,
M.I., Izv. Akad. Nauk SSSR, Ser. Khim., 1983, p. 2586.
15. Mamedov, V.A., Valeeva, V.N., Antokhina, L.A.,
Nuretdinov, I.A., Izv. Akad. Naul SSSR, Ser. Khim., 1991,
p. 1422.
16. Sheldrick, G.M., Acta Cryst., 2008, vol.A64, p. 112.
17. Saloutina, L.V., Zapevalov, A.Ya., Saloutin, V.I., Ko-
dess, M.I., Kirichenko, V.E., Pervova, M.G., and Chupa-
khin, O.N., Zh. Org. Khim., 2006, vol. 42, p. 577.
S 1.002. The residual peaks of maximum and minimum
3
electron density 0.229 and –0.202 e/
.
REFERENCES
1. Tarrant, P., Allison, C.G., and Barthold, K.P., Fluor. Chem.
Rev., 1971, vol. 5, p. 77.
2. Millauer, H., Schwertfeger, and W., Siegemund, G., Angev.
Chem., 1985, vol. 97, p. 164.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 11 2009