Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2- benzodioxaphosphepin-5-one with phenanthrenequinone and dibenzoyl

Article abstract of DOI:10.1134/S1070428011100125

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2- benzodioxaphosphepin-5-one with 9,10-phenanthrenequinone and dibenzoyl gave hydrolytically unstable spirophosphoranes with five- and seven-membered rings, 2-phenyl-4,4-bis(trifluoromethyl)-

Full text of DOI:10.1134/S1070428011100125

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 10, pp. 1521–1526. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.F. Mironov, L.M. Burnaeva, Yu.Yu. Borisova, A.T. Gubaidullin, I.A. Litvinov, G.A. Ivkova, I.V. Konovalova, 2011, published in
Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 10, pp. 1494–1499.
Reactions of 2-Phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-
1,3,2-benzodioxaphosphepin-5-one with Phenanthrenequinone
and Dibenzoyl
V. F. Mironova, b, L. M. Burnaevab, Yu. Yu. Borisovab, A. T. Gubaidullina, I. A. Litvinova,
G. A. Ivkovab, and I. V. Konovalovab
a Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
e-mail: mironov@iopc.ru
b Privolzhsk (Kazan) Federal University, Kazan, Tatarstan, Russia
Received April 4, 2011
Abstract—Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one
with 9,10-phenanthrenequinone and dibenzoyl gave hydrolytically unstable spirophosphoranes with five- and
seven-membered rings, 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-
2,2′-phenanthro[9,10-d][1,3,2]dioxaphosphol]-5-one and 2,4′,5′-triphenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-
spiro[[1,3,2]benzodioxaphosphepine-2,2′-[1,3,2]dioxaphosphol]-5-one. The structure of the first of these was
proved by X-ray analysis.
DOI: 10.1134/S1070428011100125
Tervalent phosphorus derivatives are key precursors
of various organophosphorus compounds with differ-
ent coordination numbers of the phosphorus atom
[1–4]. This is related to accessibility of lone electron
pair on the phosphorus atom and thermodynamic
favorability for the formation of phosphoryl com-
pounds. Cyclic phosphorylated derivatives of salicylic
acid having a fairly reactive carbonyl group in the
β-position with respect to the phosphorus atom occupy
a specific place among P(III) compounds. They are
capable of being involved in cascade reactions with ac-
tivated carbonyl compounds, Schiff bases, and ylidene
derivatives of dicarbonyl compounds. In these reac-
tions, the carbonyl group can participate in one or
another step of the cascade process, leading to the
formation of 1,3,2-dioxa(oxaza)- and 1,4,2-dioxa-
(oxaza)phosphepines, 1,2-oxaphospholanes, and other
difficultly accessible compounds [5–12].
We recently showed that cyclic phosphorus(III)
derivatives having an activated carbonyl group in the
γ-position with respect to the phosphorus atom, e.g.,
2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-
benzodioxaphosphepin-5-one (I), also undergo cascade
transformations by the action of trichloroacetaldehyde
and hexafluoroacetone. As a result, cage-like propeller
phosphorane with a phosphorus–carbon bond (struc-
ture II) [13, 14] or spiran structure III is formed; in the
latter structure, the γ-carbonyl carbon atom becomes
a spiro atom [15] (Scheme 1).
Scheme 1.
O
P
Ph
8
7
Ph
*
O
O
*
P
O
Ph
1
P
R1
R1C(O)R2
X = H, Cl
CCl3CHO
X = Cl
O2
O
O
3
5
4
O
6
*
X
X
Cl
CF3
CF3
R2
O9
CCl3
O
10
*
O
F3C
CCl3
CF3
II
I
III
R1 = R2 = CF3; R1 = CCl3, R2 = H.
1521

MIRONOV et al.
1522
While developing the above approach, in the pres-
zodioxaphosphepine-2,2′-[1,3,2]dioxaphosphol]-5-one
(VII, δP –37.6 ppm).
ent work we performed reactions of benzodioxaphos-
phepine I with α-dicarbonyl compounds, 9,10-phenan-
threnequinone (IV) and dibenzoyl (V, benzil). It is
known that α-diketones react with common trialkyl
phosphites to produce 1,3,2-dioxaphospholes [16]; in
some cases, these compounds are unstable and are
readily converted into more stable four-coordinate
phosphorus compounds, the dioxaphosphole ring being
conserved [17] or opened [16]. The stability of λ5-di-
oxaphosphole structure increases in going from acyclic
phosphites to five-membered cyclic P(III) derivatives
[18]. Dialkoxy-λ3-phosphanyl isocyanates having
a carbonyl group in the β-position with respect to the
phosphorus atom reacted with diacetyl and dibenzoyl
either at both carbonyl groups to afford cycloaddition
products, 1,3,2-dioxaphospholes, or at the isocyanate
carbonyl group with formation of oxazaphospholanes
having P–C and P–O bonds in the ring [19]. Dibenzoyl
reacted with “salicyl” phosphites along two pathways,
yielding 1,3,2-dioxaphosphepine and spirocyclic pen-
taalkoxyphosphorane, and the latter underwent thermal
decomposition to phosphole derivative via elimination
of salicylic fragment [20].
The IR spectrum of phosphorane VI contained
an absorption band at 1699 cm–1 typical of stretching
vibrations of ketone carbonyl group, and two quartets
belonging to two nonequivalent trifluoromethyl groups
were present in its 19F NMR spectrum at δF –70.78 and
–72.05 ppm (4JFF = 9.2 Hz). Analogous pattern was
observed in the 19F NMR spectrum of VII (δF –70.81,
4
–72.0 ppm, JFF = 9.1 Hz). The carbonyl carbon atom
resonated in the 13C NMR spectrum of VI at
δC 188.88 ppm. Thus the carbonyl group in cyclic
phosphonite I does not participate in the reactions with
quinone IV and diketone V, presumably due to steric
hindrances in carbonyl compounds IV and V, which
prevent formation of phosphorane structure analogous
to that formed in the reaction with trichloroacetal-
dehyde [14].
Crystalline phosphorane VI was isolated by keep-
ing the reaction mixture at low temperature in an inert
atmosphere. Its structure was proved by X-ray analysis
(Fig. 1); the principal geometric parameters of mole-
cule VI are given in table. The phosphorus atom has
a trigonal bipyramid configuration with axial–equato-
rial orientation of the dioxaphosphole and dioxaphos-
phepine rings: the O1 and O11 atoms occupy axial posi-
tions, and the O4 and O6 atoms and the phenyl group
are equatorial. The seven-membered heteroring adopts
a distorted boat conformation with the planar [within
0.020(4) Å] C8C9C10O11 four-atom fragment; the P1,
O6, and C7 atoms deviate from that plane toward one
side by different distances, which defines boat con-
formation. The five-membered P5O1C2C3O4 ring is
planar, and it lies in the same plane with the phenan-
threne system. On the whole, structural parameters of
molecule VI are similar to those reported previously
for spirophosphoranes consisting of one five-mem-
bered ring and one seven-membered ring [21].
The reactions of compound I with 9,10-phenan-
threnequinone (IV) and dibenzoyl (V) occurred under
mild conditions (2 months at 20–25°C; Scheme 2).
Scheme 2.
27
14
34
26
28
O
35
15
16
13
12
33
32
25
24
29
2
O
O
O
I
10
11
1
17
18
9
8
5P
6O
30
CF3
7
O
4
3
19
20
O
23
22
31
F3C
21
IV
VI
Ph
Ph
O
O
O
Phosphorane VI displays a variety of intermolec-
ular interactions in the crystalline structure. π-Electron
interactions between the aromatic phenanthrene frag-
ments related to each other through a symmetry center
(2 – x, 1 – y, 1 – z) give rise to π-dimers, the distance
between the centroids of the phenanthrene rings being
3.57 Å (the shortest distance between their planes is
3.42 Å, and the dihedral angle is 0°). The same mole-
cules are also linked through pair C–H···F interactions
with the following parameters: H16 ···F302 2.48 Å,
∠C16H16F302 163° (Fig. 2). The other interactions
(C–H···O, C–F···π, and C–H···π) lead to the forma-
P
I
O
Ph
O
O
O
CF3
VII
F3C
V
According to the P–{1H} NMR data, the products
31
were spirophosphorane compounds, 2-phenyl-4,4-bis-
(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxa-
phosphepine-2,2′-phenanthro[9,10-d][1,3,2]dioxaphos-
phol]-5-one (VI, δP –31.9 ppm) and 2,4′,5′-triphenyl-
4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]ben-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011

REACTIONS OF 2-PHENYL-4,4-BIS(TRIFLUOROMETHYL)-4,5-DIHYDRO-...
1523
Selected bond lengths (d, Å) and bond (ω, deg) and dihedral angles (φ, deg) in the molecule of 2-phenyl-4,4-bis(trifluoro-
methyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-phenanthro[9,10-d][1,3,2]dioxaphosphol]-5-one (VI)
Bond
d, Å
Angle
ω, deg
Angle
φ, deg
P5–O1
P5–O6
P5–O11
P5–O4
P5–C24
O1–C2
O4–C3
O6–C7
O8–C8
O11–C10
C2–C3
C7–C8
C8–C9
C9–C10
C7–C31
1.626(3)
1.633(3)
1.669(3)
1.715(3)
1.802(4)
1.391(4)
1.358(5)
1.425(5)
1.201(5)
1.381(4)
1.352(5)
1.565(5)
1.477(6)
1.388(6)
1.543(6)
O1P5O6
O1P5O11
O6P5O11
O1P5O4
O6P5O4
O11P5O4
O1P5C24
O6P5C24
C2O1P5
C3O4P5
C7O6P5
C10O11P5
O6C7C8
O8C8C9
O8C8C7
125.0(2)
086.8(1)
092.6(1)
089.8(1)
084.1(1)
172.7(2)
119.2(2)
115.8(2)
114.7(2)
112.4(2)
133.4(2)
120.8(2)
116.5(3)
122.5(4)
115.6(4)
O11P5O6C7
O6P5O11C10
C24P5O11C10
P5O6C7C8
O6C7C8O8
O8C8C9C10
O8C8C9C32
C7C8C9C32
P5O11C10C9
0–21.1(3)
0–72.3(3)
–171.8(3)
0–66.3(5)
–162.4(4)
–147.7(5)
0–25.5(7)
–152.9(4)
0–81.4(4)
tion of a three-dimensional network in crystal; the cal-
culated packing index is fairly high (70.3%).
the phenanthrene fragment of VIII (as compared to
cyclic structure VI), as well as the absence of coupling
between the phosphorus atom and C7 (δC 82.59 ppm,
septet, 2JCF = 28.7 Hz), also indicated acyclic structure
of compound VIII. Hydrolytic stability of four-coor-
dinate phosphorus derivatives having a hydroxyphen-
Mild hydrolysis of phosphorane VI (CDCl3, atmos-
pheric moisture) involved opening of both dioxaphos-
phepine and dioxaphosphole rings and afforded 9-hy-
droxyphenanthren-10-yl 2-(3,3,3-trifluoro-2-hydroxy-
1-oxo-2-trifluoromethylpropyl)phenyl phenylphospho-
nate (VIII, δP 21.2 ppm; Scheme 3).
C32
C33
C34
O8
C9
C8
Scheme 3.
C35
27
28
F311
F301
F312
C10
O11
F302
O6
26
29
24
C7
34
35
C31
25
13
14
33
10
H2O
C30
P
O
O1
O
12
P5
15
C13
2
VI
C14
32
9
O
HO
C25
3
8
F313
C26
C2
16
F303
C27
17
18
C12
O
HO
23
22
C15
31
C24
30
C3
CF3
19
F3C
O4
C29
21
20
C16
C23
C17
C18
C19
VIII
C28
C22
Compound VIII showed in the 19F NMR spectrum
a singlet at δF –72.86 ppm due to two equivalent tri-
fluoromethyl groups. The phosphorus nucleus in VIII
C20
C21
resonated in the 31P NMR spectrum as a broadened
4
triplet of triplets at δP 21.3 ppm (3JPH = 14.5, JPH
=
Fig. 1. Structure of the molecule of 2-phenyl-4,4-bis(tri-
fluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphe-
pine-2,2′-phenanthro[9,10-d][1,3,2]dioxaphosphol]-5-one
(VI) according to the X-ray diffraction data.
4.5 Hz). The structure of VIII was confirmed by the
13
1
13C, C–{1H}, APT (13C, 1H), and H–1H COSY spec-
tra. Nonequivalence of carbon nuclei and protons in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011

MIRONOV et al.
1524
V = 1242.4(6) Å3; Z = 2; space group P-1; M 1204.8;
C30H17F6O5P; dcalc = 1.61 g/cm3; F(000) = 612. Total of
5376 reflection intensities were measured, 3141 of
which were characterized by I > 2σ. No reduction in
intensity of three control reflections was observed
during the data acquisition process. Absorption by
the crystal was taken into account empirically (μCu
=
17.86 cm–1). The data were acquired and processed
using an Alpha Station 200 PC (MolEN software) [25].
The structure was solved by the direct method using
SIR program [26] and was refined first in isotropic and
then in anisotropic approximation using SHELX97
software [27]. Hydrogen atoms were placed into cal-
culated positions which were refined according to the
riding model. All calculations were performed with the
aid of WinGX [28]. The final divergence factors were
R = 0.062 and wR2 = 0.153 (for 5076 independent re-
flections). Intermolecular contacts in crystal, including
hydrogen bonds, were analyzed using PLATON
program [29].
Fig. 2. A fragment of crystal packing of phosphorane VI
(view along the 0y axis). Only hydrogen atoms involved in
C–H···F interactions (dashed lines) are shown.
anthrene fragment was noted previously [21–24]; it
was attributed to formation of intramolecular hydrogen
bond between the hydroxy and phosphoryl groups.
The coordinates of atoms in structure VI and their
temperature parameters were deposited to the Cam-
bridge Crystallographic Data Center (http://www.ccdc.-
cam.ac.uk; entry no. CCDC 740323).
Thus the reaction of 2-phenyl-4,4-bis(trifluoro-
methyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-
one with 9,10-phenanthrenequinone and benzil does
not involve the carbonyl group in the former and yields
hydrolytically unstable spirophosphoranes with five-
and seven-membered rings.
2-Phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-
spiro[[1,3,2]benzodioxaphosphepine-2,2′-phenan-
thro[9,10-d][1,3,2]dioxaphosphol]-5-one (VI).
9,10-Phenanthrenequinone (IV), 1.87 g (0.009 mol),
was added at 20°C under dry argon to a mixture 3.54 g
(0.009 mol) of dioxaphosphepine I and 30 ml of
methylene chloride. The mixture was left to stand for
2 months at room temperature (20°C) and then kept for
24 h at 0°C. The crystalline product was filtered off
and dried under reduced pressure (12 mm). Yield 89%,
mp 140°C. IR spectrum, cm–1: 3378, 3076, 3033, 1969,
1946, 1913, 1884, 1827, 1794, 1699, 1669, 1617,
1604, 1584, 1519, 1479, 1454, 1411, 1377, 1338,
1230, 1164, 1116, 1061, 1031, 979, 959, 942, 876, 844,
822, 771, 750, 719, 686, 668, 655, 626, 609. 13C NMR
spectrum (CDCl3, 100.6 MHz), δC, ppm (hereinafter,
the multiplicity of the corresponding signal in the
13C–{1H} NMR spectrum is given in parentheses; for
atom numbering, see Schemes 2 and 3): 84.71 sept.d
(sept.d) (C7, 2JCF = 30.0, 2JCP = 12.0 Hz), 120.55 d.d (s)
EXPERIMENTAL
The IR spectra were recorded on a Specord M-80
spectrometer from samples dispersed in mineral oil
(between KBr plates) or pelleted with KBr. The NMR
spectra were measured on Varian Unity-300 (300 MHz
1
for H, 121.42 MHz for 31P, and 282.4 MHz for 19F),
1
Bruker Avance-600 (600 MHz for H, 150.9 MHz for
13C, and 243.0 MHz for 31P), and Bruker MSL-400
1
instruments [100.6 MHz; 13C, 13C–{1H})]. The H and
13C chemical shifts were determined relative to the cor-
responding solvent signals (CDCl3). The 31P chemical
shifts were measured relative to H3PO4 as external
19
reference, and the F chemical shifts were determined
relative to hexafluorobenzene as internal reference and
were then recalculated to CFCl3.
1
3
(C16, JCH = 162.2, JCH = 7.8 Hz), 120.72 q.d (q.d)
(C30F3, JCF = 296.2, JCP = 4.2 Hz), 120.98 q.d (q.d)
1
3
X-Ray analysis of compound VI. The X-ray
diffraction data were acquired on an Enraf–Nonius
CAD-4 diffractometer at 20°C (λCuKα, θmax < 74.35°).
Triclinic crystals with the following unit cell param-
eters (20°C): a = 9.191(2), b = 10.028(3), c =
14.280(4) Å; α = 88.51(2), β = 84.16(2), γ = 71.61(2)°;
(C31F3, JCF = 289.3, JCP = 10.2 Hz), 121.71 d.d.d (d)
1
3
3
3
(C9, JCP = 11.4, JCH = 7.8, 7.8 Hz), 123.14 d.d (s)
1
3
(C14, JCH = 157.4, JCH = 7.2 Hz), 123.51 d.d.d (d)
(C35, 1JCH = 164.6, 3JCH = 7.2, 3JCP = 6.6 Hz), 125.03 d.d
(s) (C33, JCH = 164.6, JCH = 9.0 Hz), 125.10 s (d.d)
1
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011

REACTIONS OF 2-PHENYL-4,4-BIS(TRIFLUOROMETHYL)-4,5-DIHYDRO-...
1525
1
3
1
3
(C13, JCH = 161.0, JCH = 8.4 Hz), 126.86 m (br.s)
(s) (C17)129.10 d.d.d (d) (C26, JCH = 160.9, JCP
=
(C12), 127.06 d.d (s) (C15, 1JCH = 161.6, 3JCH = 8.4 Hz),
15.5, 3JCH = 8.3 Hz), 129.52 m (s) (C18), 132.17 d.d.d.d
(d) (C25, 1JCH = 163.1, 2JCP = 10.5, 3JCH = 7.4, 7.4 Hz),
127.89 m (br.s) (C17), 128.21 d.d.d (d) (C26, JCH
=
1
162.2, JCP = 19.2, JCH = 7.2 Hz), 130.80 d.d (s) (C32,
132.36 br.d.d (s) (C32, JCH = 164.4, JCH = 8.1 Hz),
3
3
1
3
1JCH = 165.8, JCH = 8.4 Hz), 132.47 d.m (d) (C27,
133.66 d.t.d.d (br.s) (C27, JCH = 162.5, JCP = 2.9,
3
1
4
1JCH = 165.2, JCH = 7.2, JCP = 3.6 Hz), 133.16 d.t (d)
3JCH = 7.6, 2JCH = 1.4 Hz), 137.94 d.d.d (s) (C34, 1JCH
=
3
4
1
3
3
2
(C24, JPC = 238.5, JCH = 7.8 Hz), 133.62 d.d.d.d (d)
161.2, JCH = 9.2, JCH = 1.8 Hz), 140.75 br.d.d (br.d)
1
2
3
2
3
(C25, JCH = 165.2, JC2P = 10.8, JCH = 7.2, 7.2 Hz),
(C3, JCP = 2.3, JCH = 3.5–4.0 Hz), 162.22 m (br.s)
134.91 m (d) (C2, C3, JCP = 2.4 Hz), 136.09 d.d (s)
(C10, JCP = 2.0, JCH = 9.8, 7.8, JCH = 1.5 Hz),
194.10 br.d (s) (C8, 3JCH = 3.9 Hz). 19F NMR spectrum
(acetone-d6): δF –72.86 ppm, s. 31P NMR spectrum
2
3
2
1
3
(C34, JCH = 161.6, JCH = 9.0 Hz), 152.52 d.d.d (d)
(C10, 2JCP = 12.0, 3JCH = 8.4, 8.4 Hz), 188.88 d (s) (C8,
3JCH = 3.0 Hz). 19F NMR spectrum (CDCl3), δF, ppm:
–72.05 q (4JFF = 9.2 Hz), –70.78 q (4JFF = 9.2 Hz).
31P–{1H} NMR spectrum (CDCl3, 121.42 MHz):
δP –31.9 ppm (s). Found, %: C 59.63; H 2.94.
C30H17F6O5P. Calculated, %: C 59.80; H 2.82.
(acetone-d6, 243.0 MHz): δP 21.2 ppm, br.t.t (3JPH
=
4
15.2, JPH = 4.5 Hz). Found, %: C 59.67; H 3.11.
C30H17F6O5P. Calculated, %: C 59.80; H 2.82.
2,4′,5′-Triphenyl-4,4-bis(trifluoromethyl)-4,5-di-
hydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-
[1,3,2]dioxaphosphol]-5-one (VII). Dibenzoyl (V),
2.53 g (0.012 mol), was added at 20°C under argon to
a solution of 4.74 g (0.012 mol) of compound I in
30 ml of methylene chloride. The mixture was kept for
2 months at 20°C and then for 2 days at 0°C, and the
precipitate was filtered off and dried under reduced
pressure (12 mm). Yield 81%, mp 78–82°C. 31P–{1H}
NMR spectrum (CDCl3, 121.42 MHz): δP –36.9 ppm.
Spirophosphorane VI underwent hydrolysis on ex-
posure to atmospheric moisture under mild conditions
(when its solution in CDCl3 was kept at 20°C) to give
compound VIII which was isolated as fine colorless
crystals with mp 137°C. H NMR spectrum (acetone-
d6, 600 MHz), δ, ppm: 7.04 d.d.d (1H, 33-H, J32,33
1
3
=
3
4
8.3, J334,33 = 7.2, J35,33 = 1.2 Hz), 7.09 br.d.d.d (1H,
4
4
35-H, JHH = 8.4, JHH = 1.2, JHP = 0.5–0.6 Hz),
3
19F NMR spectrum (CDCl3), δF, ppm: –70.6 q (4JFF
=
7.52 m and 7.56 m (2H, 14-H, 15-H, J13, 14 = 8.1,
3J15,14 = 7.1, J16, 14 = 1.2, J16, 15 = 8.2, J14, 15 = 7.1,
4J13, 15 = 1.4 Hz), 7.54 m (2H, 26-H), 7.62 m (1H,
27-H), 7.64 d.d.d (1H, 34-H, 3J35,34 = 8.4, 3J33,34 = 7.2,
4J32,34 = 1.4–1.5 Hz), 7.68–7.70 m (2H, 20-H, 21-H,
AB part of ABMX spin system), 8.05 br.d.d (1H, 13-H,
4
3
3
9.1 Hz), –72.3 q (4JFF = 10.7 Hz). H NMR spectrum
(CDCl3, 300 MHz): δ 6.92–8.55 ppm, m. Found, %:
C 60.08; H 3.37. C30H19F6O5P. Calculated, %: C 59.60;
H 3.15.
1
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 10-03-00525).
3JHH = 8.1, JHH = 1.2 Hz), 8.08 br.d.d.m (2H, 25-H,
4
3JHP = 15.5, 3JHH = 8.2, 4JHH = 1.3 Hz), 8.41 br.d.d (1H,
3
4
32-H, JHH = 8.3, JHH = 1.4–1.5 Hz), 8.46 m (1H,
22-H), 8.68 br.d (1H, 16-H, 3JHH = 8.2 Hz), 8.73 m (1H,
19-H). 13C NMR spectrum (acetone-d6, 150.9 MHz),
REFERENCES
δC, ppm: 82.59 sept (sept) (C7, JCF = 28.7 Hz),
2
1. Corbridge, D.E.C., Phosphorus 2000: Chemistry, Bio-
chemistry & Technology, Amsterdam: Elsevier, 2000.
118.52 d.d (s) (C19, JCH = 162.9, JCH = 7.6 Hz),
1
3
119.84 br.d.d (s) (C9, 3JCH = 7.4, 5.5 Hz), 119.84 d.d (s)
2. The Chemistry of Organophosphorus Compounds,
1
(C16, JCH = 164.9–65.0, 3JCH = 8.0 Hz), 121.38 d.d (s)
Hartley, F.R., Ed., Chichester: Wiley, 1996, vol. 4.
1
3
(C22, JCH = 161.6, JCH = 7.4 Hz), 122.13 br.q (br.q)
3. Handbook of Organophosphorus Chemistry, Engel, R.,
(C30, C31, JFC = 289.3 Hz), 122.97 d.d (s) (C13, JCH
=
1
1
Ed., New York: Marcel Dekker, 1992.
157.5–158.0, JCH = 7.7 Hz), 122.97 d.d.d (d) (C35,
1JCH = 157.5–158.0 Hz, overlapped by the C13 signal),
3
4. Quin, L.D., A Guide to Organophosphorus Chemistry,
New York: Wiley, 2000.
123.52 d.d.d (s) (C20, JCH = 162.2, JCH = 5.1, JCH
=
=
=
=
=
=
1
3
2
5. Mironov, V.F., Burnaeva, L.M., Litvinov, I.A., Kotoro-
va, Yu.Yu., Dobrynin, A.B., Musin, R.Z., and Konova-
lova, I.V., Izv. Ross. Akad. Nauk, Ser. Khim., 2004,
p. 1640.
3.5 Hz), 125.10 d.d (s) (C15, JCH = 161.3, JCH
1
3
8.3 Hz), 126.94 m (s) (C23), 127.17 d.d (s) (C21, 1JCH
160.9, JCH = 7.4 Hz), 127.26 d.d (s) (C14, JCH
3
1
160.8, JCH = 8.4 Hz), 127.45 br.d.d (s) (C33, JCH
3
1
6. Gubaidullin, A.T., Mironov, V.F., Burnaeva, L.M., Litvi-
nov, I.A., Dobrynin, A.B., Goryunov, E.I., Ivkova, G.A.,
Konovalova, I.V., and Mastryukova, T.A., Russ. J. Gen.
Chem., 2004, vol. 74, p. 842.
160.5, JCH = 8.0 Hz), 127.75 br.d.t (d) (C24, JCP
3
1
189.0, 3JCH = 7.8 Hz), 127.82 m (s) (C12), 128.24 d.d.d
(d) (C2, 2JCP = 8.8, 3JCH = 4.7, 4JCH = 1.5 Hz), 128.38 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011

MIRONOV et al.
1526
7. Konovalova, I.V., Mironov, V.F., Ivkova, G.A., Zagi-
dullina, E.R., Gubaidullin, A.T., Litvinov, I.A., and Ku-
rykin, M.A., Russ. J. Gen. Chem., 2005, vol. 75, p. 549.
Patwardhan, A.V., Kugler, H.G., and Smith, C.P., Tetra-
hedron, 1968, vol. 24, p. 2275; Ogata, Y. and Yama-
shita, M., J. Am. Chem. Soc., 1970, vol. 92, p. 4670.
8. Kotorova, Yu.Yu., Gubaidullin, A.T., Mironov, V.F.,
Burnaeva, L.M., Dobrynin, A.B., Musin, R.Z., Litvi-
nov, I.A., and Konovalova, I.V., Russ. J. Gen. Chem.,
2006, vol. 76, p. 437.
17. Ramirez, F., Madan, O.P., and Smith, C.P., J. Am. Chem.
Soc., 1965, vol. 87, p. 670.
18. Ramirez, F., Patwardhan, A.V., Kugler, H.G., and
Smith, C.P., J. Am. Chem. Soc., 1967, vol. 89, p. 6276.
9. Mironov, V.F., Gubaidullin, A.T., Burnaeva, L.M., Lit-
vinov, I.A., Ivkova, G.A., Romanov, S.V., Zyabliko-
va, T.A., Konovalov, A.I., and Konovalova, I.V., Russ. J.
Gen. Chem., 2004, vol. 74, p. 32.
10. Mironov, V.F., Zagidullina, E.R., Dobrynin, A.B., Gu-
baidullin, A.T., Latypov, S.K., Musin, R.Z., Litvi-
nov, I.A., Balandina, A.A., and Konovalova, I.V.,
Arkivoc, 2004, part (xii), p. 95.
11. Burnaeva, L.M., Mironov, V.F., Borisova, Yu.Yu., Gu-
baidullin, A.T., Dobrynin, A.B., Litvinov, I.A., Ivko-
va, G.A., Amerkhanova, N.K., and Konovalova, I.V.,
Russ. J. Gen. Chem., 2008, vol. 78, p. 410.
12. Burnaeva, L.M., Mironov, V.F., Borisova, Yu.Yu., and
Konovalova, I.V., Russ. J. Org. Chem., 2009, vol. 45,
p. 1868.
13. Mironov, V.F., Kotorova, Yu.Yu., Burnaeva, L.M., Ba-
landina, A.A., Latypov, Sh.K., Dobrynin, A.B., Gubai-
dullin, A.T., Litvinov, I.A., Musin, R.Z., and Konova-
lova, I.V., Mendeleev Commun., 2009, vol. 19, p. 34.
14. Mironov, V.F., Borisova, Yu.Yu., Burnaeva, L.M., Gu-
baidullin, A.T., Dobrynin, A.B., Litvinov, I.A., Mu-
sin, R.Z., and Konovalova, I.V., Izv. Ross. Akad. Nauk,
Ser. Khim., 2010, p. 804.
15. Mironov, V.F., Borisova, Yu.Yu., Burnaeva, L.M.,
Krivolapov, D.B., Litvinov, I.A., Zverev, V.V., Mu-
sin, R.Z., and Konovalova, I.V., Mendeleev Commun.,
2010, vol. 20, p. 44.
16. Kukhtin, V.A., Dokl. Akad. Nauk SSSR, 1958, vol. 121,
p. 466; Kukhtin, V.A., Kirillova, K.M., and Shagidul-
lin, R.R., Zh. Obshch. Khim., 1962, vol. 32, p. 649;
Ramirez, F., Nagabhushanam, M., and Smith, C.P.,
Tetrahedron, 1968, vol. 24, p. 1785; Ramirez, F.,
19. Konovalova, I.V., Burnaeva, L.A., Kashtanova, N.M.,
and Pudovik, A.N., Zh. Obshch. Khim., 1982, vol. 52,
p. 1965.
20. Mironov, V.F., Burnaeva, L.A., Konovalova, I.V., Khlo-
pushina, G.A., Mavleev, R.A., Chernov, P.P., and Pudo-
vik, A.N., Russ. J. Gen. Chem., 1993, vol. 63, p. 17.
21. Muthiah, C., Said, M.A., Pülm, M., Herbst-Irmer, R.,
and Kumara Swamy, K.C., Polyhedron, 2000, vol. 19,
p. 63.
22. Gallucci, J.C. and Holmes, R.R., Inorg. Chem., 1980,
vol. 19, p. 3540; Tyryshkin, N.I. and Fuzhenkova, A.V.,
Russ. J. Gen. Chem., 1993, vol. 63, p. 557.
23. Said, M.A., Pülm, M., Herbst-Irmer, R., and Kumara
Swamy, K.C., J. Am. Chem. Soc., 1996, vol. 118,
p. 9841.
24. Kumara Swamy, K.C., Said, M.A., Kumaraswamy, S.,
Herbst-Irmer, R., and Pülm, M., Polyhedron, 1998,
vol. 17, p. 3643.
25. Straver, L.H. and Schierbeek, A.J., MolEN, Structure
Determination System, Program Description, Nonius
B.V., 1994, vol. 1.
26. Altomare, A., Cascarano, G., Giacovazzo, C., and
Viterbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47,
p. 744.
27. Sheldrick, G.M., SHELXL97. A Computer Program for
Crystal Structure Determination, Göttingen: Univ. of
Göttingen, 1997.
28. Farrugia, L.J., J. Appl. Crystallogr., 1999, vol. 32,
p. 837.
29. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
p. 34.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011