Reaction of 5-oxo-2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2- benzodioxaphosphepine with chloral. the synthesis and spatial structure of 5-carbaphosphatrane containing a four-membered ring

Article abstract of DOI:10.1007/s11172-010-0167-3

Phosphorylation of 2-hydroxyphenyl 2,2,2-trifluoro-1-hydroxy-1- (trifluoromethyl)ethyl ketone with dichloro(phenyl)phosphine gave 5-oxo-2-phenyl-4,4-bis(trifluoromethyl)-4,5-di-hydro-1,3,2- benzodioxaphosphepine. Heating of the latter initiated an intramo

Full text of DOI:10.1007/s11172-010-0167-3

Russian Chemical Bulletin, International Edition, Vol. 59, No. 4, pp. 820—827, April, 2010
820
Reaction of 5ꢀoxoꢀ2ꢀphenylꢀ4,4ꢀbis(trifluoromethyl)ꢀ4,5ꢀdihydroꢀ1,3,2ꢀ
benzodioxaphosphepine with chloral. The synthesis and spatial structure
of 5ꢀcarbaphosphatrane containing a fourꢀmembered ring
V. F. Mironov,a,b Yu. Yu. Borisova,b L. M. Burnaeva,b A. T. Gubaidullin,a A. B. Dobrynin,a I. A. Litvinov,a
R. Z. Musin,a and I. V. Konovalovab
aA. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Eꢀmail: mironov@iopc.knc.ru
bV. I. Ul´yanovꢀLenin Kazan State University,
18 ul. Kremlevskaya, 420008 Kazan, Russian Federation.
Fax: +7 (843) 231 5416. Eꢀmail: liliya.burnaeva@ksu.ru
Phosphorylation of 2ꢀhydroxyphenyl 2,2,2ꢀtrifluoroꢀ1ꢀhydroxyꢀ1ꢀ(trifluoromethyl)ethyl
ketone with dichloro(phenyl)phosphine gave 5ꢀoxoꢀ2ꢀphenylꢀ4,4ꢀbis(trifluoromethyl)ꢀ4,5ꢀdiꢀ
hydroꢀ1,3,2ꢀbenzodioxaphosphepine. Heating of the latter initiated an intramolecular interacꢀ
tion of the P atom with the carbonyl group. Hydrolysis of the intermediate product yielded
3ꢀhydroxyꢀ2ꢀoxoꢀ2ꢀphenylꢀ3ꢀ[2,2,2ꢀtrifluoroꢀ1ꢀhydroxyꢀ1ꢀ(trifluoromethyl)ethyl]ꢀ2,3ꢀdiꢀ
5
hydroꢀ1,2λ ꢀbenzo[d]oxaphosphole. The reaction was highly stereoselective (PRCS/PSCR).
The reaction of the starting phosphepine with chloral proceeded highly stereoselectively
(PRCSCS/PSCRCR) to give a 5ꢀcarbaphosphatrane derivative containing a fourꢀmembered ring,
namely, 1ꢀphenylꢀ3ꢀtrichloromethylꢀ10,10ꢀbis(trifluoromethyl)ꢀ6,7ꢀbenzoꢀ2,4,8,9ꢀtetraoxaꢀ
5
1λ ꢀphosphatricyclo[3.3.2.01,5]decene. The trigonal bipyramid of the 5ꢀcarbaphosphatrane deꢀ
rivative is made up of the equatorial O atoms and the apical C atoms.
Key words: dioxaphosphepine, chloral, phosphorane, carbaphosphatrane, benzophosphole,
trigonal bipyramid, apicophilicity, oxaphosphetane, stereoselectivity.
Phosphoranes (compounds with a pentacoordinated
phosphorus atom) are intermediates in phosphorylation
and dephosphorylation of important natural hydroxyꢀconꢀ
taining compounds. That is why their synthesis, reactiviꢀ
ties, and configurational stabilities are under intensive
study.1—12 The benzodioxaphosphole fragment stabilizes
the pentacoordinated state of phosphorus most efficientꢀ
ly.5 Taking this into account, we have proposed a new
approach to the preparation of phosphoranes that involves
reactions of activated carbonyl compounds with benzoꢀ
dioxaphospholes containing the tricoordinated P atom and
a carbonyl or imino group in the γꢀ or δꢀposition relative
to the P atom in the endocyclic substituent. This approach
allowed highly regioꢀ and stereoselective synthesis of unꢀ
usual frameworkꢀtype phosphoranes with several chiral
centers.13—17
baseꢀcatalyzed phosphorylation of hydroxy ketone 1 (see
Ref. 18) with dichloro(phenyl)phosphine gave sevenꢀ
membered Pꢀheterocycle 2, which contains the nucleoꢀ
philic P atom along with the carbonyl group activated by
the electronꢀwithdrawing gemꢀbis(trifluoromethyl) fragꢀ
ment. Structure 2 was identified by 1H, 19F, and 31P NMR
and IR spectroscopy. The 31P{1H} NMR spectrum shows
a characteristic quartet of quartets at δP 173.1. The trifluꢀ
oromethyl groups are nonequivalent: their 19F NMR sigꢀ
nals appear as two multiplets at δF –73.5 and –74.0.
Benzophosphepinone 2 is fairly stable in an inert atꢀ
mosphere; however, it is oxidized with atmospheric oxyꢀ
gen to σ5λ4ꢀphosphepine (3) (δP 14.9). The IR spectrum
of compound 3 shows an band absorption at 1288 cm–1
(P=O). The trifluoromethyl groups remain nonequivalent:
their 19F NMR signals appear as two quartets at δF –73.57
and –74.13 (4JF,F = 9.2 Hz).
Results and Discussion
When heated or kept in CH2Cl2 (20 °C) for a long
period of time, benzophosphepinone 2 undergoes an inꢀ
tramolecular transformation leading to a compound with
a chemical shift δP of 60.4. One could assume that the
product is tricyclic spiro compound 4 resulting from an
In the present work, we continued to develop this apꢀ
proach by using PIII derivatives with the endocyclic
γꢀcarbonyl group as objects of investigations. For instance,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 804—810, April, 2010.
1066ꢀ5285/10/5904ꢀ0820 © 2010 Springer Science+Business Media, Inc.

Synthesis and structure of 5ꢀcarbaphosphatrane
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
821
Scheme 1
...
attack of the P atom on the C atom of the endocyclic
carbonyl group (intermediate zwitterion A, Scheme 1).
However, the compound isolated from the reaction mixꢀ
ture intensely absorbs in the range characteristic of hydroxy
groups (3074, 2798 cm–1). According to 31P, 13C{1H},
of these bonds are as follows: d(H(40) O(2´)), 1.66(5) Å,
...
...
d(O(4) O(2´)), 2.599(3) Å, angle O(4)—H(40) O(2´),
175(5)° (the symmetry operation code is x, 1/2 – y, 1/2 + z)
...
...
and d(H(3) F(5″)), 2.32(4) Å, d(O(3) F(3″)), 3.112 (2) Å,
...
angle O(3)—H(3) F(5″), 150(4)° (x, 1/2 – y, –1/2 + z).
1
13C, and H NMR and IR spectra, the product is diol 5.
The hydrogen bond between the H(4) atom of the fused
benzene fragment and the O(3) atom of the hydroxy group
unites adjacent chains related by a center of symmetry
along the axis 0b to form a supramolecular bilayer strucꢀ
ture (Fig. 3). The parameters of the hydrogen bond
C(4)—H(4) O(3´´´) (1 – x, 1 – y, –z) are d(H(4) O(3´´´ )),
2.58 Å, d(C(4) O(3´´´)), 3.521(4) Å, and angle
C(4)—H(4) O(3´´´), 169°. The bilayers are parallel to the
crystallographic plane 0bc. Their external sides bear the
phenyl fragments so that these bilayers are held togethꢀ
er in the crystal only by van der Waals and probably
π—π interactions. The interplanar spacings between the
fused benzene rings of adjacent (related by a center of
symmetry) molecules are 3.744 Å and those between the
Its molecular formula was confirmed by mass spectra and
elemental analysis data.
Diol 5 contains two chiral centers; however, this comꢀ
pound forms only one diastereomer, which suggests the
high stereoselectivity of both the intramolecular cyclizaꢀ
tion (because of the rigid cyclic structure of the starting
regent 2) and the hydrolysis of intermediate oxirane 4.
The relative configurations of the chiral centers of strucꢀ
ture 5 were determined by Xꢀray diffraction. The crystal
structure 5 is shown in Fig. 1; its selected geometrical
parameters are given in Table 1. The phospholane ring has
an envelope conformation; the P(2) atom deviates from
the plane O(1)C(7a)C(3a)C(3) by 0.56 Å. The phenyl subꢀ
stituent at the P atom is in the equatorial position, while
the phosphoryl group is axial.
...
...
...
...
F(4)
F(3)
The observed conformation of the molecule is stabiꢀ
lized by intramolecular hydrogen bonds. The hydroxy
group at the C(3) atom is linked with the phosphoryl group
by the most significant Hꢀbond with the following paramꢀ
F(2)
C(15)
F(1)
O(3)
F(5)
C(16)
C(14)
...
F(6)
eters: d(O(3)—H(3)), 0.88(3) Å, d(H(3) O(2)), 2.28(4)
C(5)
C(3a)
C(3)
...
...
Å, d(O(3) O(2)), 2.802(3) Å, angle O(3)—H(3) O(2),
118(4)°. Intermolecular interactions in the crystal strucꢀ
ture 5 include both classic hydrogen bonds and the bonds
C(4)
O(4)
O(2)
P(2)
C(8)
C(9)
C(7a)
C(6)
...
...
...
C—H F, C—H O, and O—H F. The classic hydrogen
bond O(4)—H(40) O(2´) unites molecules into a chain
C(10)
...
C(11)
O(1)
C(7)
C(13)
aligned with the crystallographic axis 0c; the hydrogen
C(12)
...
bond O(3)—H(3) F(5″) involving the fluorine atom form
chains along the same direction (Fig. 2). The parameters
Fig. 1. Crystal structure of phosphole 5.

822
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
Mironov et al.
Table 1. Selected bond lengths (d), bond angles (ω), and torsion angles (θ) in structure 5
Parameter
Value
Parameter
Bond angle
Value
Parameter
Bond angle
Value
Bond length
d/Å
ω/deg
ω/deg
P(2)—O(2)
P(2)—O(1)
P(2)—C(8)
P(2)—C(3)
O(4)—C(14)
O(1)—C(7A)
O(3)—C(3)
C(3A)—C(7A)
C(3A)—C(3)
C(14)—C(3)
1.482(2)
1.613(2)
1.780(2)
1.899(2)
1.390(3)
1.405(3)
1.412(3)
1.390(3)
1.535(3)
1.553(3)
O(2)—P(2)—O(1)
O(2)—P(2)—C(8)
O(1)—P(2)—C(8)
O(2)—P(2)—C(3)
O(1)—P(2)—C(3)
C(8)—P(2)—C(3)
C(7A)—O(1)—P(2)
C(4)—C(3A)—C(3)
C(7A)—C(3A)—C(3)
O(3)—C(3)—C(3A)
O(3)—C(3)—C(14)
115.3(1)
111.3(1)
103.6(1)
103.4(1)
96.5(1)
126.4(1)
108.3(1)
126.9(2)
114.0(2)
113.3(2)
108.4(2)
C(3A)—C(3)—C(14)
O(3)—C(3)—P(2)
C(3A)—C(3)—P(2)
C(14)—C(3)—P(2)
113.9(2)
110.3(2)
96.7(2)
114.1(2)
Torsion angle
θ/deg
O(1)—P(2)—C(8)—C(9)
138.8(2)
–37.9(2)
O(1)—P(2)—C(8)—C(13)
O(4)—C(14)—C(3)—O(3) –163.8(2)
O(4)—C(14)—C(3)—P(2) –40.5(2)
C(15)—C(14)—C(3)—P(2) –161.3(2)
planes of the phenyl substituents (related by another cenꢀ
ter of symmetry) is 3.337 Å.
with a simultaneous interaction of the P atom with the O
atom of chloral. The resulting zwitterion (B) undergoes
cyclization into carbaphosphatrane 6. During the reacꢀ
tion, two chiral centers are formed from two prochiral
carbonyl C atoms.
In the crystal of compound 5, fluorineꢀcontaining fragꢀ
ments of the molecules are localized as described earlier.19
In this case, these fragments virtually make up layers with
intermolecular (2.907(2)—3.126(2) Å) and intramolecuꢀ
Structure 6 was identified by NMR spectroscopy; its
molecular formula was confirmed by elemental analysis.
In the 1H NMR spectrum, a signal for the HC(3) proton
appears as a doublet at δ 5.77 (3JP,H = 7.3 Hz). The spatial
structure of compound 6 in the crystal is shown in Fig. 4
(Xꢀray diffraction data). Its selected geometrical parameꢀ
ters are given in Table 2. The coordination polyhedron of
the P atom is a slightly distorted trigonal bipyramid with
three equatorial O(2), O(8), and O(9) atoms (the sum of
the bond angles O—P—O is 359.3°); the configuration
of the chiral centers is P(1)RC(3)SC(5)S/P(1)SC(3)RC(5)R
(the configuration of the P atom was determined
from earlier cited24 data). The peculiarity of this structure
...
lar F F contacts (2.666(2)—2.828(2) Å). The packing
factor is 68.8.
A reaction of dioxaphosphepinone 2 with reactive chloꢀ
ral (Scheme 2) unexpectedly gives a 5ꢀcarbaphosphatrane
derivative, namely, 1ꢀphenylꢀ3ꢀtrichloromethylꢀ10,10ꢀ
bis(trifluoromethyl)ꢀ6,7ꢀbenzoꢀ2,4,8,9ꢀtetraoxaꢀ1λ5ꢀphosꢀ
phatricyclo[3.3.2.01,5]decene (6) (δP 4.6). This compound
is a first representative of carbaphosphatranes containing
a fourꢀmembered ring annulated with two fiveꢀmembered
rings along the P—C bond. Earlier,20—23 carbaphosphꢀ
atranes with fiveꢀ and sixꢀmembered rings annulated along
the P—C bond have been documented.
Apparently, the reaction involves an intramolecular
attack of the P atom on the endocyclic carbonyl group
a
O(1)
H(40)
C(4)
H(4)
O(4)
b
c
O(3)
0
F(5)
H(3)
P(2)
O(2)
Fig. 2. Fragment of an Hꢀbonded chain of phosphole molecules
5 in the crystal as viewed along the axis 0a. The hydrogen atoms
involved in hydrogen bonding are shown only (dashed lines).
Fig. 3. Supramolecular bilayer structure in the crystal of phosꢀ
phole 5 as viewed along the axis 0b. The hydrogen atoms involved
in hydrogen bonding are shown only (dashed lines).

Synthesis and structure of 5ꢀcarbaphosphatrane
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
823
Scheme 2
is the axial arrangement of the bonds P(1)—C(5) and
P(1)—C(15), which is in conflict with the apicophiliciꢀ
ty rule. The bond angle C(5)—P(1)—C(15) is 173.7(4)°.
The P—C bond lengths differ appreciably: the bridging
P(1)—C(5) bond of the tricyclic system (1.933(8) Å)
is strongly lengthened, while the exocyclic P(1)—C(15)
bond (1.811(9) Å) has a normal value. Apparently, this
is because the P(1)—C(5) bond is part of the strained
fourꢀmembered ring. The P—O bonds also differ in length:
P(1)—O(9) in the fourꢀmembered ring is the longest
bond (1.655(8) Å), P(1)—O(2) in the dioxaphospholane
ring is the shortest bond (1.563(7) Å), and P(1)—O(8)
in the oxaphospholane ring is the intermediate bond
(1.610(8) Å).
The oxaphosphetane, oxaphospholane, and dioxaꢀ
phospholane rings are planar within the experimental errors
(for the corresponding torsion angles, see Table 2); the
dihedral angles between their planes are about 60°, which
also provides evidence for the nearly ideal trigonalꢀbipyraꢀ
midal coordination of the P atom. Unfortunately, the qualꢀ
ity of the crystal of compound 6 prevents more detailed
discussion of the geometry of this molecule because of the
large error of its geometrical parameters.
In the absence of strong intermolecular interactions,
the molecular packing in the crystal of compound 6 mainꢀ
ly depends on van der Waals interactions. The distances
between the parallel benzene rings of adjacent molecules
(3.170 and 3.661 Å) correspond to weak interactions of
aromatic systems (Fig. 5). In the crystal, halogen—haloꢀ
...
gen areas are also localized. The interatomic F F disꢀ
Cl(1)
tances range from 2.99 to 3.33 Å for intermolecular conꢀ
Cl(2)
C(21)
F(1)
O(4)
F(2)
F(3)
Cl(3)
C(3)
C(22)
C(5)
O(2)
C(20)
C(15)
C(10)
C(23)
C(19)
P(1)
O(8)
O(9)
F(4)
C(6)
C(7)
C(18)
F(5)
C(11)
F(6)
C(12)
Fig. 4. Crystal structure of carbaphosphatrane 6.
C(16)
C(17)
C(13)
C(14)
Fig. 5. Chain of molecules 6 along the axis 0c.

824
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
Mironov et al.
Table 2. Selected bond lengths (d), bond angles (ω), and torsion angles (θ) in structure 6
Parameter
Value
Parameter
Bond angle
Value
Parameter
Bond angle
Value
Bond length
d/Å
ω/deg
ω/deg
C(3)—O(4)
C(3)—O(2)
C(5)—O(4)
C(5)—C(6)
C(5)—C(10)
C(5)—P(1)
C(6)—C(7)
C(7)—O(8)
C(10)—O(9)
C(15)—P(1)
O(2)—P(1)
O(8)—P(1)
O(9)—P(1)
1.42(1)
1.44(2)
1.42(2)
1.52(2)
1.56(1)
1.93(1)
1.38(2)
1.41(1)
1.47(1)
1.811(9)
1.56(1)
1.610(9)
1.655(6)
O(9)—P(1)—C(5)
C(15)—P(1)—C(5)
77.3(4)
173.7(4)
C(10)—C(5)—P(1)
C(7)—C(6)—C(5)
O(9)—C(10)—C(5)
C(3)—O(2)—P(1)
C(3)—O(4)—C(5)
C(7)—O(8)—P(1)
C(10)—O(9)—P(1)
O(2)—P(1)—O(8)
O(2)—P(1)—O(9)
O(8)—P(1)—O(9)
O(2)—P(1)—C(15)
O(8)—P(1)—C(15)
O(9)—P(1)—C(15)
O(2)—P(1)—C(5)
O(8)—P(1)—C(5)
86.4(6)
111.2(8)
95.9(6)
Torsion angle
θ/deg
120.8(7)
108.8(9)
116.1(7)
100.4(5)
121.9(5)
117.8(5)
118.5(5)
94.7(5)
92.0(4)
96.5(4)
87.3(6)
92.0(5)
O(2)—C(3)—O(4)—C(5)
P(1)—C(5)—O(4)—C(3)
C(3)—O(2)—P(1)—C(5)
–4(1)
3.1(8)
–0.7(7)
C(20)—C(15)—P(1)—O(9) –158.9(7)
O(4)—C(5)—P(1)—O(2)
C(6)—C(5)—P(1)—O(2)
C(10)—C(5)—P(1)—O(2)
O(4)—C(5)—P(1)—O(8)
C(6)—C(5)—P(1)—O(8)
C(10)—C(5)—P(1)—O(8)
O(4)—C(5)—P(1)—O(9)
C(6)—C(5)—P(1)—O(9)
–1.5(6)
119.7(8)
–119.2(8)
–123.4(7)
–2.2(9)
118.9(9)
117.8(7)
–121.0(9)
Bond angle
ω/deg
C(6)—C(5)—P(1)
104.3(8)
phosphine (2.74 g, 0.015 mol) in ether (20 mL) was added dropꢀ
wise under argon at –30 °C to a mixture of 2ꢀhydroxyphenyl
2,2,2ꢀtrifluoroꢀ1ꢀhydroxyꢀ1ꢀ(trifluoromethyl)ethyl ketone (1)
(4.41 g, 0.015 mol) and triethylamine (3.1 g, 0.031 mol) in ether
(75 mL). The reaction mixture was stirred for 1.5 h until it was
warmed to 20 °C and then kept for ~14 h. The precipitate
of triethylammonium chloride that formed was filtered off,
the filtrate was concentrated, and the residue was dried in vacuo
(20 °C, 0.1 Torr) to produce a fine crystalline solid. The yield
was 5.49 g (91%), m.p. 104—107 °C (decomp.). 19F NMR
tacts and from 2.57 to 2.71 Å for intramolecular ones. The
localization gives rise to islandꢀtype associates (the packꢀ
ing factor is 66.5).
Compound 6 undergoes slow hydrolysis in several pathꢀ
ways. One pathway leads to the formation of dioxaphosphꢀ
epine 7 resulting from cleavage of the P—C bond. Comꢀ
pound 7 was isolated by crystallization and characterized
by NMR and IR spectroscopy. The 31P{1H} NMR specꢀ
trum shows the corresponding singlet at δP 6.5. The
IR spectrum exhibits a wide band at 3280 cm–1 due to the
OH stretches.
To sum up, the use of PIII derivatives containing an
endocyclic carbonyl group in the γꢀposition relative to the
P atom in reactions with chloral allows the synthesis of
unusual framework phosphoranes. These are carbaphosꢀ
phatrane derivatives containing a fourꢀmembered cycle,
such as 1ꢀphenylꢀ3ꢀtrichloromethylꢀ10,10ꢀbis(trifluoroꢀ
methyl)ꢀ6,7ꢀbenzoꢀ2,4,8,9ꢀtetraoxaꢀ1λ5ꢀphosphatricycꢀ
lo[3.3.2.01,5]decene.
(CDCl3), δ: –73.57 (dq, CFA
,
4JPOCCF(A) = 20.5 Hz,
3
4JF(B)CCCF(A) = 9.2 Hz), –74.13 (dq, CFB
, =
4JF(A)CCCF(B)
3
= 9.2 Hz, JPOCCF(B) = 2.3 Hz). 31P{1H} NMR (121.42 MHz,
4
4
4
CDCl3), δ : 173.1 (qq, JPOCCF(A) = = 20.7 Hz, JPOCCF(B)
=
P
= 2.5 Hz). IR, ν/cm–1: 1684, 1600, 1444, 1288, 1164, 1128,
1064, 976, 896, 872, 776, 744, 712, 689.
Oxidation of compound 2 with oxygen was carried out by bubꢀ
bling dried oxygen through a solution of compound 2 in CH2Cl2
at 20 °C for 2 h. The solvent was removed and the residue was
crystallized from hexane to give 2,5ꢀdioxoꢀ2ꢀphenylꢀ4,4ꢀbisꢀ
5
(trifluoromethyl)ꢀ4,5ꢀdihydroꢀ1,3,2λ ꢀbenzodioxaphosphepine
(3). The yield was 89%, colorless crystalline precipitate, m.p.
82 °C. Found (%): C, 46.77; H, 2.41; P, 7.49. C16H9F6O4P.
Calculated (%): C, 46.83; H, 2.20; P, 7.56. 31P{1H} NMR
Experimental
1
(242.8 MHz, acetoneꢀd6), δ : 15.9. H NMR (600 MHz, aceꢀ
P
3
NMR spectra were recorded on Varian Unityꢀ300 (300 (1H),
121.42 (31P{1H}), and 282.4 MHz (19F)) and Bruker Avanceꢀ600
instruments (600 (1H), 242.8 (31P{1H}), and 150.9 MHz
(13C,13C{1H})). IR spectra were recorded on a Bruker Vectorꢀ22
FTIR spectrometer (KBr pellets or neat samples). Mass spectra
were measured on a TRACE MS Finnigan MAT instrument
(EI, 70 eV, direct inlet probe, ionization chamber temperature
200 °C). The evaporating tube was heated in a programmed
mode from 35 to 150 °C at a rate of 35 deg min–1. In the mass
spectra, the peaks of the ions containing the most commonly
encountered isotopes are included.
toneꢀd6), δ: 7.21 (d, H(9), JH(8)H(9) = 8.2 Hz); 7.54 (dd, H(7),
3
3JH(6)H(7) = 7.9 Hz, JH(8)H(7) = 7.7 Hz); 7.69 (br.ddd, H(12),
3JH(11)H(12) = 8.2—8.3 Hz, 3JH(13)H(12) = 7.5—7.6 Hz, 4JPH(12)
=
3
= 5.1 Hz); 7.84 (br.tm, H(13), JH(12)H(13) = 7.5—7.6 Hz,
5
4JH(11)H(13) = 2.2 Hz, JPH(13) = 1.2 Hz); 7.80 (br.dd, H(8),
3
3JH(7)H(8) = 7.7 Hz, JH(9)H(8) = 8.2 Hz); 7.90 (dd, H(6),
4
3JH(7)H(6) = 7.9 Hz, JH(8)H(6) = 1.7 Hz); 7.95 (br.ddd, H(11),
3JPH(11) = 14.5 Hz, 3JH(12)H(11) = 8.3 Hz, 4JH(13)H(11) = 2.2 Hz).
13C NMR (acetoneꢀd6), δ (hereafter, the shapes of the signals in
the 13C{1H} NMR spectrum are given in square brackets): 79.67
2
2
(septq [septq], C(4), JFCC(4) = 29.3 Hz, JPOC(4) = 7.2 Hz);
182.14 (br.s [s], C(5)), 123.98 (br.m [s], C(5a)); 128.37 (ddd [s],
C(6), 1JHC(6) = 165.1 Hz, 3JHC(8)CC(6) = 8.3 Hz, 2JHCC(6) = 2.5 Hz);
5ꢀOxoꢀ2ꢀphenylꢀ4,4ꢀbis(trifluoromethyl)ꢀ4,5ꢀdihydroꢀ1,3,2ꢀ
benzodioxaphosphepine (2). A solution of dichloro(phenyl)ꢀ

Synthesis and structure of 5ꢀcarbaphosphatrane
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
825
123.14 (dd [s], C(7), 1JHC(7) = 166.4 Hz, 3JHC(9)CC(7) = 7.7 Hz);
133.80 (ddd [s], C(8), 1JHC(8) = 164.8 Hz, 3JHC(6)CC(8) = 8.8 Hz,
2JHCC(8) = 1.7 Hz); 118.18 (ddddd [d], C(9), 1JHC(9) = 167.0 Hz,
1ꢀPhenylꢀ3ꢀtrichloromethylꢀ10,10ꢀbis(trifluoromethyl)ꢀ6,7ꢀ
5
benzoꢀ2,4,8,9ꢀtetraoxaꢀ1λ ꢀphosphatricyclo[3.3.2.01,5]decene
(6). A mixture of phosphonite 2 (2.76 g, 0.007 mol) and chloral
(2.07 g, 0.014 mol) in CH2Cl2 (20 mL) was kept under argon at
20 °C for two months. The solvent was removed in vacuo and
a residual yellow oil was dissolved in CH2Cl2—pentane (5 : 1)
and kept under argon for six days, while allowing slow evaporaꢀ
tion of the solvent. The yield of compound 6 was 1.78 g (47%),
colorless crystals, m.p. 119 °C. Found (%): C, 39.83; H, 2.03;
P, 5.66. C18H10Cl3F6O4P. Calculated (%): C, 39.89; H, 1.85;
P, 5.72. IR, ν/cm–1: 1614, 1592, 1476, 1462, 1441, 1355, 1323,
1293, 1223, 1168, 1127, 1109, 1069, 1041, 1018, 1003, 973, 935,
893, 867, 853, 839, 825, 794, 774, 764, 746, 728, 693, 645, 630.
3JPOCC(9) = 7.7 Hz, 3JHC(7)CC(9) = 7.7 Hz, 2JHC(8)C(9) = 1.2 Hz,
1
4JHC(6)CCC(9) = 1.2 Hz); 123.65 (br.dt [d], C(10), JPC(10)
=
3
= 196.8 Hz, JHC(12)CC(10) = 7.5 Hz); 128.55 (dddd [d], C(11),
C(15), JHC(11) = 164.9 Hz, JPCC(11) = 11.1 Hz, JHCCC(11)
1
2
3
=
3
= 7.7—7.8 Hz, JHCCC(11) = 7.7 Hz); 125.76 (dddd [d], C(12),
C(14), 1JHC(12) = 163.6 Hz, 3JPCCC(12) = 16.6 Hz, 3JHC(14)CC(12)
= 7.2 Hz, 2JHCC(12) = 1.7 Hz); 131.54 (br.dm [d], C(13), 1JHC(13)
=
=
= 159.8 Hz, 3JHC(11)CC(13) = 7.4—7.6 Hz, 4JPCCCC(13) = 2.8 Hz,
2JHC(12)C(13) = 2.5 Hz); 121.39 (q [q], CF3, JFC = 287.5 Hz);
1
121.26 (qd [qd], CF3, 1JFC = 288.0 Hz, 3JPOCC = 9.4 Hz).
3ꢀHydroxyꢀ2ꢀoxoꢀ2ꢀphenylꢀ3ꢀ[2,2,2ꢀtrifluoroꢀ1ꢀhydroxyꢀ1ꢀ
31P{1H} NMR (242.8 MHz, CDCl3), δ : 4.6 (s). 1H NMR
P
5
3
(trifluoromethyl)ethyl]ꢀ2,3ꢀdihydroꢀ1,2λ ꢀbenzo[d]oxaphosphole
(600 MHz, CDCl3), δ: 5.81 (d, H(3), JPH(3) = 7.1 Hz);
3
(5). Phosphonite 2 (2.38 g, 0.01 mol) was heated in a sealed tube
at 110 °C for 30 min. On cooling, the tube was opened and
CH2Cl2 (2 mL) was added. The resulting precipitate was filtered
off and recrystallized from acetone. The yield was 1.45 g (61%),
colorless crystals, m.p. 148—149 °C. Found (%): C, 46.71;
H, 2.91; P, 7.46. C16H11F6O4P. Calculated (%): C, 46.60;
H, 2.67; P, 7.52. MS, m/z (Irel (%)) (the peaks of the ions conꢀ
taining the most commonly encountered isotopes are cited): 412
7.05 (br.d, H(14), JH(13)H(14) = 7.8 Hz), 7.19 (br.dd, H(12),
3JH(11)H(12) = 8.1 Hz, 3JH(13)H(12) = 7.5 Hz); 7.38 (br.ddm, H(13),
3JH(14)H(13) = 7.8 Hz, 3JH(12)H(13) = 7.5 Hz, 4JH(11)H(13) = 1.4 Hz);
3
7.55 (br.d, H(11), JH(11)H(12) = 8.1 Hz); 7.50 (m, H(17));
3
7.56 (m, H(18)); 8.04 (br.ddm, H(16), JPCCH(16) = 16.0 Hz,
3JH(17)H(16) = 8.4 Hz, 4JH(18)H(16) = 1.2 Hz). 19F NMR (CDCl3),
δ: –72.81 (q, CF3, 4JFF = 10.7 Hz); –73.86 (q, CF3, 4JFF = 10.7 Hz).
13C NMR (CDCl3), δ: 101.92 (ddq [dq], C(3), 1JHC(3) = 190.6 Hz,
[M]+ (21.1), 395 [M – OH] (39.0), 394 [M – H2O]+ (52.3),
2JPOC(3) = 6.6 Hz, JFCCCOC(3) = 2.8 Hz); 88.62 (br.dd [d],
5
•
343 [M – CF3]+ (41.2), 326 [M – CF3 – OH]+ (10.0), 325
[M – CF3 – H2O]+ (19.6), 247 [M – (CF3)2CO + H]+ (31.2),
246 [M – (CF3)2CO]+ (44.2), 245 [M – (CF3)2CO – H]+ (52.3),
125 [PhPOH]+ (16.4), 124 [PhPO]+ (43.3), 121 [C6H4CO(OH)]+
(100.0), 92 [C6H4O]+ (54.4), 69 [CF3]+ (53.2). IR, ν/cm–1: 3521
s, 3074 vbr, vs, 2798, 1822, 1681, 1611, 1587, 1460, 1441, 1420,
1346, 1286 s, 1256 s, 1225 vs, 1199 s, 1155—1170 vs, 1117 s, 1083
s, 1048 s, 1027 m, 977 s, 957 m, 882 s, 869 sh, 847 m, 837 m, 801
C(5), 1JPC(5) = 109.9 Hz, 3JHC(11)CC(5) = 3.5 Hz); 125.10 (m [d],
2
2
C(6), JPCC(6) = 5.7 Hz); 153.83 (br.dddd [d], C(7), JPOC(7) =
3
3
= 8.8—9.0 Hz, JHC(11)CC(7) = 8.8—9.0 Hz, JHC(13)CC(7)
=
= 8.8—9.0 Hz, 2JHC(14)C(7) = 3.3 Hz); 80.49 (septd [septd], C(10),
2JFCC(10) = 30.6 Hz, JPCC(10) = 13.8 Hz); 127.75 (br.ddd [d],
2
C(11), 1JHC(11) = 162.7 Hz, 3JPCCC(11) = 18.2 Hz, 3JHC(13)CC(11)
=
1
= 8.6 Hz); 124.43 (dd [s], C(12), JHC(12) = 162.1 Hz,
3JHC(14)CC(12) = 7.8 Hz); 131.71 (ddd [s], C(13), JHC(13)
1
=
1
3
2
m, 760 s, 752 s, 736 m, 723 s, 712 s, 688 m, 668 m. H NMR
= 160.7 Hz, JHC(11)CC(13) = 8.6 Hz, JHCC(13) = 1.6—1.7 Hz);
(600 MHz, acetoneꢀd6), δ: 6.30 (br.s, OH); 7.14 (d, H(7),
112.96 (ddd [d], C(14), 1JHC(14) = 164.9 Hz, 3JPOCC(14) = 12.8 Hz,
3
1
3JH(6)H(7) = 8.1 Hz); 7.27 (dd, H(5), JH(4)H(5) = 7.7 Hz,
3JHC(12)CC(14) = 8.2—8.3 Hz); 135.25 (dt [d], C(15), JPC(15)
=
3
3
3JH(6)H(5) = 7.6 Hz); 7.50 (ddd, H(6), JH(7)H(6) = 8.1 Hz,
= 235.5 Hz, JHC(17),C(19)CC(15) = 7.8 Hz); 131.17 (br.dddd [d],
C(16), C(20), 1JHC(16),C(20) = 162.7 Hz, 2JPCC(16),C(20) = 11.0 Hz,
3JHC(18)CC(16) = 7.4 Hz, 3JHC(20)CC(16) = 7.4 Hz); 128.28 (ddd [d],
C(17), C(19), 1JHC(17),C(19) = 161.6 Hz, 3JPCCC(17),C(19) = 18.3 Hz,
3JHC(19)CC(17) = 7.5 Hz); 131.37 (dtd [d], C(18), 1JHC(18) = 160.2 Hz,
4
3JH(5)H(6) = 7.6 Hz, JH(4)H(6) = 1.2 Hz); 7.54 (br.ddd, H(10),
3JH(11)H(10) = 7.5 Hz, 3JH(9)H(10) = 7.4 Hz, 4JPCCCH(10) = 4.4 Hz);
3
7.67 (br.s, OH); 7.68 (br.td, H(11), JH(10)H(11) = 7.5 Hz,
4JH(9)H(11) = 1.3—1.4 Hz); 7.67 (br.dd, H(4), 3JH(5)H(4) = 7.7 Hz,
4JH(6)H(4) = 1.1—1.2 Hz); 8.01 (dd, H(9), 3JPH(9) = 12.8—12.9 Hz,
3JH(10)H(9) = 7.4 Hz). 31P{1H} NMR (124.42 MHz, CDCl3 + aceꢀ
3JHC(16),C(20)CC(18) = 7.5 Hz, JPCCCC(18) = 3.6 Hz); 97.57
4
2
3
(dd [d], C(21), JHC(3)C(21) = 11.4 Hz, JPOCC(21) = 3.5 Hz);
120.95 (qd [qd], C(22), 1JFC(22) = 285.1 Hz, 3JPOCC(22) = 12.8 Hz);
121.01 (qd [qd], C(23), 1JFC(23) = 285.1 Hz, 3JPOCC(23) = 8.0 Hz).
Phosphorane 6 (3.25 g, 0.006 mol) in contact with atmoꢀ
spheric moisture under mild conditions (air exposure in CDCl3
(7 mL) at 20 °C) underwent hydrolysis into 2ꢀoxoꢀ2ꢀphenylꢀ5ꢀ
(2,2,2ꢀtrichloroꢀ1ꢀhydroxyethoxy)ꢀ4,4ꢀbis(trifluoromethyl)ꢀ4,5ꢀ
toneꢀd6 (30%)), δ : 61.1. 19F NMR (acetoneꢀd6), δ: –68.33
P
(m, CF3); –68.51 (m, CF3). 13C NMR (acetoneꢀd6), δ: 84.79 (d [d],
1
2
C(3), JPC(3) = 93.4 Hz); 127.22 (m [d], C(3a), JPCC(3a)
=
1
= 14.9 Hz); 130.90 (br.dm [br.d], C(4), JHC(4) = 164.2 Hz,
3JPCCC(4) = 7.5 Hz); 125.50 (dd [s], C(5), JHC(5) = 162.5 Hz,
1
3JHC(7)CC(5) = 7.7 Hz); 133.64 (dd [s], C(6), 1JHC(6) = 162.0 Hz,
3JHC(4)CC(6) = 8.4 Hz); 116.03 (ddd [d], C(7), 1JHC(7) = 165.3 Hz,
5
dihydroꢀ1,3,2λ ꢀbenzodioxaphosphepine (7). Yield 1.61 g (48%),
3JHC(5)CC(7) = 7.8—8.0 Hz, JPOCC(7) = 6.6 Hz); 155.22 (br.dd
colorless crystals, m.p. 152 °C. Found (%): C, 38.49; H, 2.33;
P, 5.47. C18H12Cl3F6O5P. Calculated (%): C, 38.61; H, 2.14;
P, 5.54. 31P{1H} NMR (121.42 MHz, CDCl3 + DMSOꢀd6 (20%)),
3
3
3
[d], C(7a), JHC(4)CC(7a) = 9.1 Hz, JHC(6)CC(7a) = 9.1 Hz,
2JPOC(7a) = 1.4 Hz); 129.67 (dt [d], C(8), JPC(8) = 132.7 Hz,
1
3JHC(10)CC(8) = 8.6 Hz); 136.54 (dddd [d], C(9), 1JHC(9) = 165.3 Hz,
2JPCC(9) = 10.5 Hz, 3JHC(11)CC(9) = 7.7 Hz, 3JHC(13)CC(9) = 7.7 Hz);
δ : 6.5 (s). 1H NMR (600 MHz, CDCl3 + DMSOꢀd6 (20%)), δ:
P
3
5.27 (s, H(5)); 6.23 (s, H(16)); 6.82 (d, H(9), JH(8)H(9)
=
1
3
129.48 (br.ddd [d], C(10), JHC(10) = 161.3 Hz, JPCCC(10)
=
= 7.5 Hz); 7.33 (m, H(12)); 7.50 (m, H(11)); 7.54 (m, H(13));
= 14.9 Hz, 3JHC(12)CC(10) = 7.9—8.0 Hz); 135.12 (dm [d], C(11),
7.56 (br.dd, H(7), JH(8)H(7) = 7.7 Hz, JH(6)H(7) = 7.6 Hz);
7.67 (br.dd, H(8), 3JH(7)H(8) = 7.7 Hz, 3JH(9)H(8) = 7.5 Hz); 7.82
(br.dd, H(6), 3JH(7)H(6) = 7.6 Hz, 4JH(8)H(6) = 1.2—1.4 Hz); 8.63
(br.s, OH). 13C NMR (CDCl3 + DMSOꢀd6 (20%)), δ: 79.85
(septm [septd], C(4), 2JFCC(4) = 31.2 Hz, 2JPOC(4) = 7.5—8.5 Hz);
3
3
1JHC(11) = 158.5 Hz, JHC(9)CC(11) = 7.5 Hz, JPCCCC(11)
=
3
4
2
= 3.0 Hz); 82.46 (septd [septd], C(14), JFCC(14) = 27.7 Hz,
2JPCC(14) = 3.3 Hz); 124.38 (qd [qd], C(15), 1JFC(15) = 290.3 Hz,
3JPCCC(15) = 14.2 Hz); 124.79 (q [q], C(16), 1JFC(16) = 287.5 Hz,
3JPCCC(16) = 0 Hz).
1
67.83 (br.d [br.s], C(5), JHC(5) = 146.6 Hz); 125.44 (m [s],

826
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
Mironov et al.
1
C(5a)); 127.59 (br.dd [br.s], C(6), JHC(6) = 165.2 Hz,
3JHC(8)CC(6) = 7.5 Hz, 3JHC(5)CC(6) = 3.5—4.0 Hz); 124.19 (dd [s],
C(7), 1JHC(7) = 162.8 Hz, 3JHC(9)CC(7) = 7.8 Hz); 128.95 (dd [s],
C(8), 1JHC(8) = 162.8 Hz, 3JHC(6)CC(8) = 9.0 Hz); 117.96 (br.dm [d],
Singleꢀcrystal Xꢀray diffraction study of compounds 5 and 6
was performed at the Xꢀray Diffraction Division of the Collecꢀ
tive Use Center of the Spectroanalytical Center based on the
Diffraction Investigations Laboratory of the A. E. Arbuzov Instiꢀ
tute of Organic and Physical Chemistry (Kazan Research Cenꢀ
ter, Russian Academy of Sciences). The crystallographic paramꢀ
eters and the data collection and refinement statistics for strucꢀ
tures 5 and 6 are given in Table 3. The experiments were carried
out on a Nonius B.V. CADꢀ4 automatic fourꢀcircle diffractoꢀ
meter at –150 (5) and 20 °C (6) (graphite monochromator,
λ(CuꢀKα) radiation). The collected data were first processed
with the MolEN program25 on an AlphaStation 200 computer.
The intensities of three check reflections showed no decay durꢀ
ing the data collection; absorption correction was applied emꢀ
pirically. All structures were solved by the direct methods with
the SIR program26 and refined first isotropically and then anisoꢀ
tropically with the SHELXLꢀ97 (see Ref. 27) and WinGX proꢀ
grams.28 The H atoms of the hydroxy groups in structure 5 were
located from difference electronꢀdensity maps; the positions of
the other H atoms in both the structures were calculated from
stereochemical considerations and refined using appropriate
riding models. Intermolecular interactions were analyzed, and
figures were drawn, with the PLATON program.29
1
3
3
C(9), JHC(9) = 165.2 Hz, JHC(6)CC(8) = 8.4 Hz, JPOCC(9)
= 4.8 Hz); 145.23 (m [d], C(9a), JPOC(9a) = 9.0 Hz); 123.00
(dt [d], C(10), JPC(10) = 199.4 Hz, JHC(12)CC(10) = 7.8 Hz);
127.27 (dddd [d], C(11), C(15), 1JHC(11) = 164.6 Hz, 2JPCC(11)
= 10.2 Hz, JHC(11)CC(11) = 7.3 Hz, JHC(13)CC(11) = 7.3 Hz);
127.27 (dddd [d], C(12), 1JHC(12) = 163.4 Hz, 3JPCCC(12) = 16.8 Hz,
3JHC(12)CC(12) = 7.0 Hz, JHCC(12) = 1.6 Hz); 132.48 (br.dm
=
2
1
3
=
3
3
2
1
3
[br.d], C(13), JHC(13) = 161.0 Hz, JHC(11)CC(13) = 7.4 Hz,
4JPCCCC(13) = 3.5 Hz); 119.53 (qd [br.q], C(14), 1JFC(14) = 290.2 Hz,
3JHC(5)CC(14) = 3.0 Hz); 119.33 (qdd [qd], C(15), JFC(15)
=
1
= 289.6 Hz, 3JPOCC(15) = 10.2 Hz, 3JHC(5)CC(15) = 9.0 Hz); 98.62
1
3
(dd [s], C(16), JHC(16) = 172.4 Hz, JHC(5)OC(16) = 5.1 Hz);
97.78 (d [s], C(17), 2JHC(16)C(17) = 6.0 Hz).
Table 3. Crystallographic parameters and the data collection
statistics for structures 5 and 6
Parameter
5
6
The atomic coordinates and thermal parameters for strucꢀ
tures 5 and 6 have been deposited with the Cambridge Crystalloꢀ
graphic Data Center (http://www.ccdc.cam.ac.uk; CCDC Nos.
710 244 and 710 245, respectively).
Color
Colorless
Prisms
C16H11F6O4P C18H10Cl3F6O4P
412.22
Monoclinic
P21/c
Crystal shape
Molecular formula
Molecular weight
Crystal system
Space group
a/Å
b/Å
c/Å
α/deg
β/deg
541.58
Triclinic
P–1
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ00180a).
10.675(2)
12.242(2)
13.459(2)
—
110.18(1)
—
8.731(8)
10.04(2)
12.282(8)
93.52(2)
95.24(3)
103.54(3)
1039(2)
2
References
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γ/deg
3
V/Å
1650.9(5)
4
Z
dcalc/g cm–3
1.658
23.09
1.732
54.75
Absorbance, μ(Cu)/cm–1
Absorption correction
Radiation (λ/Å)
F(000)
Psiꢀscan
CuꢀKα (1.54184)
832
540
5283
Number of measured
reflections
Rint
Number of independent
reflections with I > 2σ(I)
Discrepancy factors
(I > 2σ(I))
3515
0.0546
3364
0.4918
3899
R
Rw
0.0678
0.1921
1.120
253
0.1219
0.2829
0.961
289
GOOF
Number of parameters
refined
Ranges of h, k, l indices
–13 ≤ h ≤ 12,
0 ≤ k ≤ 15,
0 ≤ l ≤ 16
–10 ≤ h ≤ 10,
–5 ≤ k ≤ 12,
–15 ≤ l ≤ 15
0.350/–0.322
Residual electron
0.442/–0.401
–3
density/e•Å
max/ρ
,
ρ
min

Synthesis and structure of 5ꢀcarbaphosphatrane
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 4, April, 2010
827
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Received December 10, 2008;
in revised form May 5, 2009