Reaction of 2-R-benzo[d]-1,3,2-oxazophosphorin-8-one with hexafluoroacetone. Synthesis and steric structure of 3-phenyl-9,9- bis(trifluoromethyl)-2-ethoxybenzo[d]-1,3,2-oxazaphosphepine-2,8-dione

Article abstract of DOI:10.1134/S1070363208030110

Reaction of hexafluoroacetone with 2-R-benzo[d]-1,3,2-oxazophosphorin-8- ones leads to the formation of seven-membered nitrogen-containing heterocycles, the derivatives of 3-phenyl-9,9-bis (trifluoromethyl)benzo[d]-1,3,2-oxaza- phosphepine-2,8-diones. Ste

Full text of DOI:10.1134/S1070363208030110

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 3, pp. 410–416. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © L.M. Burnaeva, V.F. Mironov, Yu.Yu. Borisova, A.T. Gubaidullin, A.B. Dobrynin, I.A. Litvinov, G.A. Ivkova, N.K. Amerkhanova,
I.V. Konovalova, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 3, pp. 425–431.
Reaction of 2-R-Benzo[d]-1,3,2-oxazophosphorin-8-one
with Hexafluoroacetone. Synthesis and Steric Structure
of 3-Phenyl-9,9-bis(trifluoromethyl)-2-ethoxybenzo[d]-1,3,2-
oxazaphosphepine-2,8-dione
L. M. Burnaevaa, V. F. Mironova,b, Yu. Yu. Borisovaa, A. T. Gubaidullinb, A. B. Dobryninb,
I. A. Litvinovb, G. A. Ivkovaa, N. K. Amerkhanovaa, and I. V. Konovalovaa
aKazan State University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
bArbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences, ul. Arbuzova
8, Kazan, 420088 Tatarstan, Russia
Received July 31, 2007
Abstract–Reaction of hexafluoroacetone with 2-R-benzo[d]-1,3,2-oxazophosphorin-8-ones leads to the
formation of seven-membered nitrogen-containing heterocycles, the derivatives of 3-phenyl-9,9-bis
(trifluoromethyl)benzo[d]-1,3,2-oxaza-phosphepine-2,8-diones. Steric structure of 2,3-diphenyl-9,9-bis
(trifluoromethyl)-benzo[d]-1,3,2-oxazaphosphepine-2,8-di-one was established by X-ray structural analysis.
By hydrolysis of the phosphepines a functionally substituted fluorinated ketone, 2-hydroxy-1-(2′-
phenylamino)phenyl-2-trifluoromethyl-3,3,3-trifluoro)propan-1-one, was obtained.
DOI: 10.1134/S1070363208030110
The attention paid to the synthesis and study of
chemical properties of Р(III)-phosphorylated deriv-
atives of hydroxycarboxylic acids originates from the
fact that these compounds are prepared from biolog-
ically active precursors like salicylic, mandelic and
other acids and therefore they are potentially capable
of possessing various biological activity. Another
circumstance that attracts attention is their unusual
reactivity due to the presence of very reactive Р(III)–
О–С(О) fragment that is easily attacked by both
nucleophiles and electrophiles. When the latter is a
compound with activated multiple bond (ketone,
aldehyde, imine, etc.), the reaction product is a six- or
seven-membered functionally substituted heterocycle
(dioxaphosphorinane, dioxaphosphepine, etc.), a Р-
analog of many biologically active compounds [1–6].
In extention of investigations in this area, in the
present work we first obtained Р(III)-derivatives
underlain by phenylanthranilic acid, 1,3,2-oxazophos-
phorin-8-ones (I, II), with the ring nitrogen atom
bound to phosphorus, and studied their reaction with
hexafluoroacetone. Synthesis of phosphorines I and II
was carried out along the known procedures (either by
reaction of phenylanthranylic acid with phenyldi-
chlorophosphine or by reaction of 3-phenyl-2-chloro-
benzo[d]-1,3,2-oxazophosphorin-8-one (III) with etha-
nol) [1, 3, 7]. In the 31Р-{1Н} NMR spectrum to these
compounds correspond typical low-field signals at δР
121.4 (I) and 119.9 (II) ppm.
Reaction of compounds I and II with hexa-
fluoroacetone was carried out under mild conditions
(ССl4, –50°C); it resulted in formation with a high
regioselectivity of 2-R-3-phenyl-9,9-bis(trifluoro-
methyl)-benzo[d]-1,3,2-oxa-zaphosphepine-2,8-di-
ones IV and V respectively. Obviously the reaction of
phosphorines I and II with hexafluoroacetone begins
as a nucleophilic attack of phosphorus atom on the
carbon atom of the carbonyl group to afford a bipolar
ion А which further undergoes rearrangement into ion
B. Further stabilization of ion B includes intra-
molecular nucleophilic substitution at sp2-hybridized
carbon atom resulting in the formation of 1,3,2-
oxazaphosphepine IV or V.
In the 31Р–{1H} NMR spectra (CH2Cl2) appear
signals at δР 12.9 (IV) and δР –6.3 ppm (V). In the IR
410

REACTION OF 2-R-BENZO[d]-1,3,2-OXAZOPHOSPHORIN-8-ONE
411
1
3
spectra characteristic adsorption bands are present (ν,
cm–1): 1712-1724 (С=О), 1594–1596 (СНarom), 1377
(CF), 1277–1284 (Р=О), 1032–1096 cm–1 (РОС). In
the 19F NMR spectra the CF3 groups give rise to
signals in the region of δF –69.42 to –76.90 ppm as two
constants with phosphorus nucleus, JРС 185.2, JРССС
2
4
16.0, JРСС 9.9–10.0, JРСССС 2.8 Hz. The signals of
compound IV are interpreted on the basis of АТР
experiments. Figure 1 shows fragments of 13С–{1Н}
NMR spectra and АТР.
4
quadruplets with the constant JFF 9.2–9.8 Hz. In the
The structure of phosphepine IV was also con-
firmed by X-ray structural analysis. Fig 2 shows
geometry of compound IV; Table 1 contains selected
geometric parameters of the molecule. The conforma-
tion of oxazaphosphepine heterocycle is a strongly di-
storted boat with planar fragment of four atoms,
N3С3aС7aС8, the residual atoms (P2, O1, C9) are
deviated from the plane to the same side by different
distances, –1.396(1), –1.837(2), and –1.053(3) Å res-
pectively. The carbonyl group С8=О8 is considerably
displaced from the plane of ortho-phenylene fragment
[torsion angle O8C8C7aC7 equals –41.9(4)°]. The nitro-
gen atom has planar-trigonal configuration, its lone
electron pair is practically orthogonal to the plane of the
ortho-phenylene fragment and has conformation more
favorable for conjugation with phenyl substituent at N3
atom [the torsion angle P2N3C16C17 is –139.6(3)°].
13С–{1H} NMR spectra of phosphepines IV and V the
following signals are observed that confirm presence
of a cyclic fragment: N3C3aC7aC8(O)C9O1P2: С8 (δС 190.3–
2
191.9), С3а (δС 140.7–142.7, JРNC 4.1-5.0), C7a (δС
133.0–134.9), С9 (δС 82.5–83.1 ppm, JFCC 29.8, JPOC
6.3–10.0 Hz). In the downfield region (140.8–
141.5 ppm) in the spectra of compounds IV and V
appears a doublet corresponding to sp2-hybridized
carbon atom С10 (2JРNC 4.4–5.5 Hz). The signals of
3
2
С
11–15 nuclei in phenyl substituent at the N atom appear
in the region of δС 126.1–129.6 ppm. The chemical
shifts of С4–7 nuclei are interpreted taking into account
a small difference in ortho- and para-effects of
shielding by N3 atom and deshielding by С=О
substituent and in keeping with the signal multiplicity.
The signals of carbon atoms in trifluoromethyl groups
appear at 119.72–120.10 ppm as typical quadruplets of
1
doublets with the constants JFF 289.1–289.7 and
In the phosphepine IV crystal the intermolecular
interactions of C–H…O type lead to formation of
centrosymmetrical Н-dimers. The parameters of С15–
H15…O2′ interactions (1/2 – x, 1/2 – y, 1 – z) are as
follows: H15…O2’ 2.47 Å, C15…O2′ 3.362(5) Å, φ(C15–
3JPOCC 5.8–14.8 Hz. In the 13С–{1Н} NMR spectrum
of compound IV the atoms С16–21 in the phenyl
substituent at the phosphorus atom resonate at 128.3–
133.3 ppm as doublets with typical spin–spin coupling
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 3 2008

412
BURNAEVA et al.
19
С18
18
17
O
16
13
4
2
N
3a
P
10
5
3
С12
С6
С11
С17
С19
12
11
1
O
С7
6
С5
С7a
8
7a
С10
CF3
7
9
С13
С4
O
CF3
С16
С3a
СF3
СF3
С10
С4
С13
С5
С6
С12
С7
С19
С17
С11
С18
142
138
134
130
126
122
118
δ, ppm
Fig. 1. Fragments of 13C–{1H} and ATP (150.6 MHz, CDCl3) NMR spectra of azaphosphepine IV.
parameters of interaction C18–H18…F5′ (1/2 + x, –1/2 –
y, 1/2 + z) are as follows: H18…F5′ 2.51 Å, C85…F5′
3.441(7) Å, φ(C18–H18…F5′) 175°.
H15…O2’) 160°. Owing to C–H…F interactions such
dimers are bound to form an infinite layer parallel to
the crystallographic plane (101) (Fig. 3) with
hydrophobic aromatic fragments located predo-
minantly on the outer sides of such layers. The
Analysis of intermolecular interactions showed a
significant number of intra- and intermolecular short
contacts of F–F type with fluorine–fluorine distances
in the range 2.84 to 3.09 Å. If we take the sum of van
der Waals radii plus 0.2 Å (to account for temperature
factor and errors at the determination of coordinates)
as a criterion of contact, then this system of contacts
leads to mutual binding of the fluorine-containing
fragments of the molecules and formation of three-
dimensional lattice (Fig. 4).
С14
С13
С10
С12
F1
F6
С9
С15
С22
С11
O2
O1
P2
F2
F5
С23
F3
F4
С8
N3
С17
С16
С3a
Hydrolysis of 1,3,2-oxazaphosphepines IV and V
with ethanol–water (1 : 1) mixture leads to functi-
onally substituted fluorinated ketone, 2-hydroxy-1-(2′-
phenylamino)phenyl-2-trifluoromethyl-3,3,3-trifluoro-
С18
С7a
С4
O8
С7
1
С5
С21
propan-1-one (VI). In its Н NMR spectrum (DMSO-
С6
С19
С20
d6) the amide and hydroxy group protons resonate in
the downfield region as singlets [δН 9.15 ppm (NH),
9.94 ppm (OH)]. The trifluoromethyl groups in 19F
NMR spectrum appear as singlet in the typical region
δF –74.51 ppm.
Fig. 2. Geometry of 2,8-dioxo-2,3-diphenyl-9,9-bis
(triflu-oromethyl)benzo[d]-1,3,2-oxazaphosphepine
IV in a crystal.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 3 2008

REACTION OF 2-R-BENZO[d]-1,3,2-OXAZOPHOSPHORIN-8-ONE
Selected bond lengths (d, Å), bond (φ, deg) and torsion (τ, deg) angles
413
Bond
d
Bond
d
Bond
d
C7a–C3а
C7a–C8
C3а–N3
1.389 (6)
1.473 (6)
1.424 (4)
C8–C9
C9–O1
C9–C22
1.561 (6)
1.406 (4)
1.548 (6)
C16–N3
N3–P2
O1–P2
1.449 (5)
1.652 (3)
1.608 (3)
C8–O8
Angle
1.206 (5)
C10–P2
Angle
1.780 (4)
O2–P2
Angle
1.451 (3)
φ
φ
φ
O8C8C7a
O8C8C9
C7aC8C9
O1C9C22
122.7 (4)
116.9 (4)
120.1 (3)
111.4 (3)
O1C9C8
113.7 (3)
121.9 (5)
116.8 (3)
119.2 (2)
O2P2O1
O2P2N3
O1P2N3
O2P2C10
115.8 (2)
113.6 (2)
101.5 (2)
114.5 (2)
C10C15C14
C7bN3C16
C7bN3P2
O1C9C23
101.7 (4)
C16N3P2
122.1 (3)
O1P2C10
99.8 (2)
C22C9C23
Angle
111.6 (4)
C9O1P2
Angle
129.3 (3)
N3P2C10
Angle
110.1 (2)
τ
τ
τ
O2P2O1C9
N3P2O1C9
–78.4
45.2
O2P2N3C16
O1P2C10C11
–23.92
–30.3
P2N3C16C17
C3aC16C21
138.6
122.3
C10P2O1C9
O1P2N3C3a
O2P2N3C3a
158.2
47.5
O2P2C10C11
P2O1C9C23
P2O1C9C8
–154.7
177.5
–67.2
P2N3C3aC7a
C16N3C3aC4
C7bC7aC8C9
–73.20
–55.8
52.3
172.5
C10P2N3C3a
O1P2N3C16
–57.5
P2O1C9C22
P2N3C16C21
58.5
C7C7aC8O8
O8C8C9O1
41.7
–148.9
–41.6
178.0
O2
F5
H15
H18
F5
H18
…
…
Fig. 3. Intermolecular C–H O and C–H F interactions (dot lines) in a crystal of compound IV (only the hydrogen atoms involved
in the interaction are shown).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 3 2008

414
BURNAEVA et al.
(a)
(b)
Fig. 4. Two projections on infinite lattice in the crystal of compound IV: (a) View along 0b axis, (b) View along 0с axis. The
fluorine-containing fragments are imaged in van der Waals radii, other atoms are not shown.
the solvent. The 31Р NMR spectra were measured
relatively to the external reference Н3РО4. The 19F
NMR spectra were recorded in СDCl3 with the internal
reference С6F6, and then chemical shifts were
recalculated to CFCl3.
2,3-Diphenylbenzo[d]-1,3,2-oxazophosphorin-8-
one (I). To a mixture of 0.22 mol of phenylanthra-
Thus the reaction of 2-R-3-phenylbenzo[d]-1,3,2-
nylic acid and 0.44 mol of triethylamine in ether (250
oxazophosphorin-8-ones II and III with hexafluoro-
ml) at –30°С was added dropwise with stirring a
acetone manifests specificity of the chemical pro-
solution of phenyldichlorophosphine (0.22 mol) in
perties of phosphorus heterocycles, namely, the easy
ether (30 ml). The reaction mixture was stirred till it
cleavage of the macroergic PO–C(O) bond and the
warmed to 20°С. Triethylammonim chloride preci-
ready formation of a new С–С bond. Like with the 2-
pitate was filtered off, and ether was removed by
R-benzo[d]-1,3,2-dioxaphosphorin-4-one derivatives,
distillation. The residue was dissolved in 15 ml of a
in this case the betaine А is unstable and undergoes
mixture of diethyl ether with pentane (1 : 1) and left
Р+–О–С– rearrangement. In the bipolar ion B the
for crystallization at 0°С. Compound I was then
nucleophilic substitution at the sp2-hybridized carbon
isolated as yellow crystals in 84% yield, mp 70–72°С.
atom occurs faster than addition of the second
31Р–{H} NMR spectrum (СН2Cl2): δР 121.4 ppm.
hexafluoroacetone molecule at the anionic center. It
Found, %: C 71.47; Н 4.38; P 9.72 С19H14NO2Р.
also should be noted that these reactions are
Calculated, %: C 71.35; Н 4.21; P 9.58.
regioselective, leading to the formation of 1,3,2-
oxazaphosphepines only; hydrolysis of the latter
allows a preparation of fluorinated hydroxyketons
hardly accessible by other methods.
3-Phenyl-2-ethoxybenzo[d]-1,3,2-oxazophospho-
rin-8-one (II). Along the procedure for the synthesis
of salicylphosphites from 0.09 mol of phenylan-
thranylic acid and 0.12 mol of РСl3 compound III was
prepared as a viscous liquid in 88% yield. 31Р–{1H}
NMR spectrum (СН2Cl2): δР 135.9 ppm. IR spec-trum,
cm–1: 1748, 1596, 1516, 1456, 1276, 1224, 1160, 1120,
1016, 892, 752, 696. To 0.08 mol of compound III in
150 ml of ether was added 1 : 1 mixture of ethyl
alcohol and triethylamine (0.08 mol each) in 20 ml of
ether at –20°С. The triethylammonium chloride
precipitate was filtered off, ether was removed by
distillation. The residue contained compound II as a
viscous liquid, yield 87%. 31Р–{1H} NMR spectrum
EXPERIMENTAL
The IR spectra were recorded on a Specord M-80
instrument from thin films or from suspensions of com-
pounds in mineral oil between KBr plates. The NMR spec-
tra were registered on a spectrometer Varian Unity-
300 (1Н, 300 MHz; 31Р, 121.42 MHz; 19F, 287.2 MHz).
The 13С, 13С−{1Н} and ATP NMR spectra were
obtained on a Bruker Avance-600 instrument (150.9
1
MHz). Chemical shifts Н and 13С were measured
relatively to the residual protons or carbon nuclei of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 3 2008

REACTION OF 2-R-BENZO[d]-1,3,2-OXAZOPHOSPHORIN-8-ONE
415
4
1
(toluene): dР 119.9 ppm. IR spectrum, cm–1: 1736,
1604, 1456, 1304, 1158, 1040, 876, 756, 696.
q (СF3, JFF 9.8). Н NMR spectrum (300 MHz,
3
3
CDCl3, δ ppm, J, Hz): 1.24 t.d (СН3, JPOCH 1.0, JНH
7.1), 4.25 m (ОСН2); the protons of phenyl rings
resonate as a multiplet at δ 6.94–7.52 ppm. 13С NMR
spectrum (СDСl3, δС ppm, J, Hz): 140.67 d (m) (С3a,
Reactions of compounds I and II with hexaflu-
oroacetone. To a solution of 1,3,2-oxazophosphorine
I or II (0.01 mol ) in 30–40 ml of CCl4 was condensed
hexafluoroacetone till the gain in weight corresponding
to 0.011 mol. The reaction mixture was allowed to
attain room temperature and left for 3 days. The
solvent was removed under a vacuum of 3 mm Hg, and
JPNC 4.1), 127.12 d (d.m) (С4, JHC 170.0, JPNC C
2
1
3
3а
4
3а
3.6), 134.95 s (d.d) (С5, 1JHC 164.2, 2JHC C 8.7), 127.32
5
4
s (d.d) (С6, JHC 164.2, JHCC 7.3), 130.31 s (d.m) (С7,
1
2
6
JHC 163.8), 133.04 s (m) (С7a), 190.29 s (d) (С8,
1
7
JHC CC 3.3), 83.11 sept.d (sept.d) (С9, 2JFCC 29.8, 2JPOC
3
7
9
6.3), 141.50 d (m) (С10, JPNC 5.5), 126.30 d (d.m)
2
14
benzo[d]-1,3,2-oxazaphosphepine IV or
V
was
(С11,15, JHC 160.8, JPNCC 3.1), 129.51 s (d.d) (С12,14
,
1
3
obtained in residue as a viscous liquid. 2,3-Diphenyl-
9,9-bis(tri-fluoromethyl)benzo[d]-1,3,2-oxazaphos-
phepine-2,8-dione IV can be crystallized gradually
from ether at 0°С as colorless crystals in 47% yield,
mp 153°С. IR spectrum, cm–1: 3067, 2924, 2854, 1712,
1594, 1451, 1277, 1141, 1066, 980, 886, 743, 691,
667, 566. The 31Р–{1Н} NMR spectrum (ССl4): δР
12.9 ppm. 19F NMR spectrum (СDCl3), dF, ppm, J, Hz:
JHC 162.3, JHC C 8.3), 126.70 s (d.t) (С13, JHC 161.9,
1
2
2
2
1
17
17
JHCC 7.3), 65.69 d (t.d.q) (С16, JHC 149.6, 2JPOC 6.3,
1
12
12
JHC C 4.4), 15.52 d (q.d.t) (С17, JHC 127.8, JPOC C
1
3
13
12
13
13
2
1
1
12 13
7.3, JHC C 2.9), 119.72 br.q.m (СF3, JFC 289.2, JPC
5.8). Found, %: s 49.43; Н 3.20; P 7.09.
С18H14F6NO3Р. Calculated, %: s 49.39; Н 3.16; Р 7.05.
Hydrolysis of compounds IV and V was carried out
in 30 ml of 1:1 acidified water–ethanol mixture at 90º
for 36 h. Then the reaction mixture was allowed to
attain room temperature, extracted with ether, the
extract was dried over MgSO4, and evaporated in a
vacuum of 12 mm Hg. The residue was 2-hydroxy-1-
(2'-phenylamino)phenyl-2-trifluoromethyl-3', 3', 3'-tri-
4
4
1
–69.42 q (СF3, JFF 9.2), –74.34 q (СF3, JFF 9.2). H
NMR spectrum (CDCl3), δ, ppm, J, Hz: 7.64 br.m
(Н17,21, JРH 13.8, JНН3 7.6–7.8), 7.60 m (Н7), 7.58
3
3
br.d.d. (Н5, JHH 7.5, JHH 7.5), 7.42–7.44 m (Н18,20
,
3
Н13, Н19), 7.27 br.d.d (Н12,14, JHH 7.7–8.0, JHН 8.0),
3
3
7.16 br.d.d. (Н6, JHН 7.5, JHН 7.5), 7.13 br.d (Н11,15
,
3
3
3JHН), 6.69 m (Н4). 13С NMR spectrum (hereinafter in
1
fluoropropan-1-one (V), a slightly yellowish oil. Н
parentheses is given the multiplicity of the signal in
NMR spectrum (DMSO-d6, δ, ppm): 9.94 s (NH), 9.15
br.s (ОН), 6.7–8.6 m (phenyl group protons). Found,
%: C 52.90; H 3.03. C16H11NO2F6. Calculated, %: C
52.58; H 2.75.
13С–{1Н} NMR spectrum) (СDСl3, δС ppm, J, Hz):
142.66 m (d) (С3a, JPNC 5.0), 128.95 d.d.d (d) (С4,
2
3а
1
1
3
3
5
4
6
4
4
JHC 161.9, JHC CC 8.3, JPNCC 2.8), 135.05 d.d (s) (С ,
JHC 164.0, JHC CC 8.7), 128.40 d.d (s) (С6, JHC
3
1
5
7
5
6
164.6, JHC CC 7.6), 130.23 d.d.d (s) (С7, JHC 164.6,
X-Ray structural analysis of compound IV was
carried out at the Division of Structural Investigations
of the Center of Joint Use of Scientific Instruments
based on the Laboratory of Diffraction Methods of the
Arbuzov Institute (IOPhKh) at Kazan Scientific Center
of the Russian Academy of Sciences. The experiment
was performed at 20°С on an automatic diffractometer
Enraf-Nonius CAD-4 with monochromated CuKα
irradiation (λ 1.54184Å, ω-scan, θ < 74.19°). The crys-
tals of C22H14F6NO3P are monoclinic, space group C2/c,
the cell parameters at 20°C are as follows: a 26.125(2)
Å, b 11.402(2) Å, c 19.603(3) Å, b 131.087(4)°, V
4401(1) Å3, Z 8, M 485.31, dcalc. 1.465 g/cm3, F(000)
1968. Intensities of 4527 reflexions were measured, of
them 3479 had I > 2s. No decrease in the intensity of
three control reflexions was observed during the
experiment. Extinction [μ(Cu) 18.07 cm–1] was taken
into account. The structure was solved by the direct
method using SIR program [8] and refined initially in
isotropic and then in anisotropic approximation using
3
1
4
6
7
3
2
3
JHC CC 6.6, JHC C 4.5), 134.88 br.d.d (s) (С7a, JHC CC
5
7
6
7
6
7a
5.4, 3JHC CC 5.4), 191.89 br.d (s) (С8, 3JHC CC 3.9–4.0),
4
7a
7
8
82.48 sept.d (sept.d) (С9, 2JHCC 29.8, JPOC 10), 140.84
2
9
9
m (d) (С10, JPNC 4.4), 126.07 br.d (d) (C11,15, JHC
2
1
16
161.6, JPNCC 2.8), 129.62 d.d (s) (C12,14, JHC 160.7,
3
1
3JHC
4JHC
8.0), 126.39 d.t (s) (C13, JHC 163.1,
1
12,14CC
18,20CCC
7.5), 128.30 d.t (d) (С16, 1JPC 185.2, JHCCC
19
3
7.9–8.0), 131.47 br.d.d.d.d (d) (С17,21, 1JHC 162.8, 2JPCC
3
3
17
21
17,21CC19
9.9–10.0, JHC CC 7.5–7.6, JHC
7.5–7.6), 128.82
d.d.d (d) (С18,20, 1JHC 163.4, 3J PCCC 16.0, 3J HC CC 8.1),
18,20
133.33 d. m (d) (С19, JHC 160.7, JHC
7.0–7.4,
1
3
13
12,14CC13
4
JPCCCC 2.8), 120.10 q (q) (СF3, 1JFC 289.1), 120.06 q.d
13
1
3
(q.d), (СF3, JFC 289.7, JPOCC 14.8). 3-Phenyl-9,9-bis-
(trifluoromethyl)-2-ethoxy-benzo[d]-1,3,2-azaphos-
phepin-2,8-dione (V), viscous liquid, yield 52%. IR
spectrum, ν, cm-1: 1724, 1598, 1492, 1452, 1284, 1140,
1032, 980, 888, 768, 700, 672. 31Р–{1Н} NMR
spectrum (ССl4): δР –6.3 ppm. 19F NMR spectrum
(СDCl3, δF ppm, J, Hz): –74.34 q (СF3, 4JFF 9.2), –76.90
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 3 2008

BURNAEVA et al.
416
Khlopushina, G.A. and Zyablikova, T.A., Zh. Obshch.
Khim., 1995, vol. 65, no. 12, p. 1986.
4. Mironov, V.F., Konovalova, I.V., and Burnaeva, L.M.,
Zh. Org. Khim., 1996, vol. 32, no. 3, p. 403.
5. Mironov, V.F., Burnaeva, L.M., Litvinov, I.A., Ko-
torova, Yu.Yu., Dobrynin, A.B., Musin, R.Z., and
Konovalova, I.V., Izv. Akad. Nauk, Ser. Khim., 2004,
no. 8, p. 1640.
SHELXL [9] and WinGX [10] programs. Coordinates
of hydrogen atoms were calculated on the basis of
stereochemical criteria and refined along the “rider”
model. The final values of divergence factors were R
0.0452, RW 0.1202 for 3479 independent reflexions
with F2 ≥ 4(F0). Preliminary the data obtained were
treated with MolEN [11] program. Analysis of
molecular and crystal structures and intermolecular
interactions was carried out with PLATON [12]
program. Atomic coordinates and their thermal
parameters for compound IV are deposited in the
Cambridge Data-base of X-ray Structural Data, No.
CCDC 651586.
6. Kotorova, Yu.Yu., Gubaidullin, A.T., Mironov, V.F., Bur-
naeva, L.M., Dobrynin, A.B., Musin, R.Z., Litvi-
nov, I.A., and Konovalova, I.V., Zh. Obshch. Khim.,
2006, vol. 76. no. 3, p. 459.
7. Kuliev, A.K., Moskva, V.V., Akhmetzade, D.A.,
Sakhnovskaya, T.A., and Zykova, T.A., Zh. Obshch.
Khim., 1984, vol. 54, no. 7, p. 1671.
ACKNOWLEDGMENTS
8. Altomare, A., Cascarano, G., Giacovazzo, C. and
Viterbo, D., Acta Crystallogr., A, 1991, vol. 47, no. 4,
p. 744.
9. Sheldrick, G.M., SHELXL97, a Computer Program for
Crystal Structure Determination, University Gottingen,
1997.
This work was financially supported by the Russian
Foundation for Basic Research (grant No. 05-03-
33008).
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 3 2008