Reactions of phenylenedioxytrihalophosphoranes with arylacetylenes (see abstract)

Article abstract of DOI:10.1023/A:1023349414864

As shown by NMR and IR spectroscopy and high-resolution mass spectrometry, the major products of the reaction of 2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2λ⁵-dioxaphosphole with phenylacetylene are a six-membered heterocyclic compound, 2-oxo-4-phenyl-2,5,6,7,8-pentachlorobenzo[e]-1,2λ⁵(2H)-oxaphosphorine, and the E and Z isomers of 2-(2,3,4,4,5-pentachlorocyclohexadienon-6-yl)-2-phenylvinylphosphonic dichloride. The molecular and supramolecular structure of the heterocycle and phosphorus-containing products of its hydrolysis were studied by single crystal X-ray diffraction.

Full text of DOI:10.1023/A:1023349414864

Russian Journal of General Chemistry, Vol. 72, No. 11, 2002, pp. 1764 1783. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 11, 2002,
pp. 1868 1888.
Original Russian Text Copyright
2002 by Mironov, Gubaidullin, Shtyrlina, Litvinov, Petrov, Konovalov, Dobrynin, Zyablikova, Musin, Morozov.
Reactions of Phenylenedioxytrihalophosphoranes
with Arylacetylenes: IV.1 Features of the Reaction
5
of 2,2,2,4,5,6,7-Heptachlorobenzo[d]-1,3,2 -dioxaphosphole
with Phenylacetylene. Molecular and Supramolecular Structure
of 2-Oxo-4-phenyl-2,5,6,7,8-pentachlorobenzo[e]-
5
1,2 (2H)-oxaphosphorine and Its Hydrolysis Products
V. F. Mironov, A. T. Gubaidullin, A. A. Shtyrlina, I. A. Litvinov, R. R. Petrov, A. I. Konovalov,
A. B. Dobrynin, T. A. Zyablikova, R. Z. Musin, and V. I. Morozov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received December 29, 2000
Abstract As shown by NMR and IR spectroscopy and high-resolution mass spectrometry, the major
products of the reaction of 2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2 5-dioxaphosphole with phenylacetylene
are a six-membered heterocyclic compound, 2-oxo-4-phenyl-2,5,6,7,8-pentachlorobenzo[e]-1,2 5(2H)-oxaphos-
phorine, and the E and Z isomers of 2-(2,3,4,4,5-pentachlorocyclohexadienon-6-yl)-2-phenylvinylphosphonic
dichloride. The molecular and supramolecular structure of the heterocycle and phosphorus-containing products
of its hydrolysis were studied by single crystal X-ray diffraction.
The reaction of PCl5 or aryltetrachlorophospho-
ranes with alkenes and alkynes is an important route
to unsaturated compounds containing a P C bond,
difficultly accessible by other routes [2, 3]. When
with the formation of benzo[e]-1,2(2H)-oxaphospho-
rines IV; the introduced halogen atom appears at the
p-position relative to endocyclic oxygen, and the
initially present halogen atom, at the p-position re-
lative to the carbon atom of the arising heteroring [9].
5
performed with 2,2,2-trichlorobenzo[d]-1,3,2 -dioxa-
phosphole I, this reaction unexpectedly yielded a
heterocyclic compound, benzo[e]-1,2(2H)-oxaphos-
phorine II [4 6], a phosphorus-containing analog of
coumarins. The reaction involves formation of the
phosphoryl group and P C bond, ipso substitution of
one of the oxygen atoms by carbon in the benzodioxa-
phospholane ring, which is usually very stable against
such transformations [7, 8], and selective introduction
of chlorine at the p-position relative to oxygen of the
phosphorine reteroring.
O
PCl3 + Ar C CH
X
O
III
O
Cl
O
X
P
HCl
Cl
Ar
IV
X = Cl, Br.
The reaction of dibormo-substituted phenylenedi-
O
Cl
O
O
O
P
PCl3 + Ar C CH
HCl
Cl
oxytrichlorophosphorane with phenylacetylene
yields, along with 2-oxo-6,7-dibromobenzo[e]-
1,2 (2H)-oxaphosphorine VI, also molecular chlo-
V
Ar
I
II
5
rine and product IVa of regioselective ipso substitu-
tion of chlorine for bromine [1].
Monohalo-substituted
phosphoranes III react with arylacetylenes similarly,
phenylenedioxytrichloro-
In this work (for preliminary communications, see
[10]), we performed the reaction of phenylacetylene
with 2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2 -dioxa-
5
1
For communication III, see [1].
1070-3632/02/7211-1764$27.00 2002 MAIK Nauka/Interperiodica

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
1765
15.2 ppm, d (2JPCH 25.6 Hz), typical of phospho-
nates. In the H NMR spectrum (CDCl3), the vinyl
O
O
1
Br
Br
PCl3 + Ph C CH
proton of the P CH=C moiety gives a downfield
doublet at 5.44 ppm, with the same coupling constant
2JPCH. The most convincing evidence of the cyclic
structure of VIII is offered by its 13C NMR spectrum
(Table 1). The spectrum is, on the whole, similar to
V
O
O
Br
Br
P
Cl
+ IVa
5
Cl2
that of 2-oxobenzo[e]-1,2 (2H)-oxaphosphorines
described previously [1, 6, 9], except that the C7 C10
signals are sowewhat shifted downfield owing to the
acceptor effect of the chlorine atoms. However, on
the whole, at complete substitution of chlorine atoms
for protons, the carbon signals of the benzophosphorine
core are shifted to different extents. For example, the
C7 nucleus appears to be less shielded than C5, whereas
in monochlorophosphorine II (Ar = Ph) and unsub-
Ph
VI
phosphole VII [11] containing chlorine atoms at the
o-positions to the oxygen atoms of the dioxaphos-
phole rings. We found that the presence of four chlo-
rine atoms in the phenyl moiety did not prevent for-
mation
of
2-oxo-2,5,6,7,8-pentachlorobenzo[e]-
5
stituted 2-bromo-2-oxo-4-phenylbenzo[e]-1,2 (2H)-
5
1,2 (2H)-oxaphosphorine VIII. The content of this
compound in the reaction mixture reached 40 45%.
Phosphorine VIII was isolated in 20 30% yield by
crystallization from CCl4 or CHCl3. In contrast to the
reactions of benzophospholes unsubstituted at the o-
positions, the reaction of VII with phenylacetylene
yielded as major products (55 60%) nonheterocyclic
compounds, a mixture of Z and E isomers of quinoid
vinylphosphonic dichlorides IXa and IXb.
oxaphosphorine [6] the pattern is opposite. The C5
nucleus in VIII is even more shielded than in II. The
spectrum contains two upfield doublets at
120.63
C
1
3
(C3, JPC 158.2 Hz) and 121.91 ppm (C5, JPOCC
5
18.7 Hz), and also a downfield doublet at 155.38 ppm
(C4, 2JPCC 0.8 Hz); the first two signals are additional-
ly split in doublets in the spectra taken without proton
decoupling. Such shifts are characteristic of the carbon
atoms of the C5 C4=C3 P(O) moiety. The value of
3
Cl
5
JPOCC is consistent with the realization of two coupl-
Cl
O
Cl
ing pathways (P C3 C4 C5 and P O C6 C5), which
is possible in cyclic structure VIII only. The signals
of C3 7 and C10 14 can be readily identified from their
splitting pattern due to coupling with protons and/or
phosphorus.
6
O
Cl
Cl
O
O
Cl
Cl
P
3
8
Ph C CH
Cl2
5 4
PCl3
9
10
11
Cl
12
13
Cl
16
15
VII
14
The structure of VIII was confirmed by single crys-
tal X-ray diffraction. Figure 1 shows the geometry of
VIII in the crystal, and the selected bond lengths,
bond angles, and torsion angles and the atomic coordi-
nates are listed in Tables 2 and 3. The heterocycle
VIII
8 7Cl
Cl
8 7Cl
Cl
6
O
6 O
Cl
Cl10
Cl
Cl10
O
9
9
Cl
Cl
5
5
contains two planar [within 0.0411(3) and 0.017(3)
]
P
3
4
4
3
fragments: C4C5C6O1 and P2C3C4C5. The P2 and C3
atoms deviated from the O1C6C5C4 plane to the same
side by 0.8543(0) and 0.368(3) , respectively. As for
the other plane, P2C3C4C5, there are also two atoms
deviating from this plane to the same side: O1 by
0.787(2) and C6 by 0.473(3) . The same direc-
tion of deviation of the two atoms from the plane
of the remaining four atoms defines the heteroring
conformation as an unsymmetrical (distorted) boat.
The two planar fragments form a dihedral angle of
18.7(3) . In the previously studied molecules of
+
+
Cl
Cl
Cl
Cl
16
15
14
11
12
13
16
15
14
11
12
P
O
13
IXa, Z
IXb, E
The structure of VIII was determined by H, 13C,
and 31P NMR spectroscopy and by high-resolution
mass spectrometry. The mass spectrum of VIII con-
tained a peak with m/z 412, corresponding to the
molecular ion of VIII, [MVIII]+ . The accurately meas-
ured mass of this ion, 411.8920, agrees with the cal-
culated mass of C14H635Cl5O2P, 411.8548. The iso-
topic pattern in the range m/z 412 419 is also consis-
tent with this composition. In the 31P NMR spectrum
1
5
2-hydroxy-2-oxobenzo[e]-1,2 (2H)-oxaphosphorines
[1, 6, 9], this angle is somewhat smaller (11 15 ).
The chlorine atom occupies the axial position, and
the phosphoryl group is in the equatorial position,
(CDCl3), phosphorine VIII gives a signal at
as follows from the deviations of Cl2 [2.5860(0)
]
P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1766
MIRONOV et al.
Table 1. 13C NMR data for VIII, IX, XIX, and XXIII (100.6 MHz, 40 C for solutions in CDCl3 and 50 C in other cases),
, ppm (J, Hz)
XXIII (acetone-d6
Atom
C3
VIII (CDCl3)
IXa, Z (CDCl3)a
IXb, E (CDCl3)a
XIX (DMF-d7)b
DMSO, 2: 1)c
120.63 d (d.d)
(158.2, PC3;
173.1, HC3)
120.23 d (d.d)
(163.4, PC3;
166.3, HC3)
152.87 d (m)
(3.8, PC3C4)
123.73 d (d.d)
(150.9, PC3;
167.6, HC3)
150.90 d (m)
(2.5, PC3C4)
119.93 d (d.d)
(190.0, PC3;
152.0, HC3)
129.82 d (d.d)
(172.0, PC3;
148.4, HC3)
C4
155.38 s (br.m)
(4.1, HC12C11C4;
3.9, HC3C4)
147.71 d (d.d.t)
(3.7, PC3C4;
143.95 d (d.d.t)
(3.0, PC3C4;
3.7 4.0, HC12C11C4;
3.7 4.0, HC3C4)
126.86 d (d.d)
(7.5, PCCC5;
10.5, HC3CC5)
149.72 s (s)
3.0 4.0, HC12C11C4;
3.0 4.0, HC3C4C5)
131.78 d (d.d)
(7.0, PCCC5;
12.0, HC3CC5)
153.13 s (s)
C5
121.91 d (d.d)
(18.7, PCCC5;
8.8, HC3CC5)
146.23 d (d)
132.79 d (d.d)
(8.4, PCCC5;
10.0, HC3CC5)
171.37 br.s
(br.s)
128.34 d (d.d)
(9.9, PCCC5;
6.6, HC3CC5)
171.36 br.s
(br.s)
C6
C7
C8
C9
(9.5, POC6)
124.75 d (d)
131.31 s (s)
131.31 s (s)
119.89 s (s)
130.52 s (s)
122.09 s (s)
121.50 s (s)
130.13 s (s)
124.33 s (s)
(7.4, POCC7)
136.25 d (d)
146.62 s (s)
79.71 s (s)
146.62 s (s)
79.71 s (s)
(0.8 0.9, POC6C7C8)
131.78 d (d)
(1.9, POC6C7C8C9)
131.95 d (d)
(2.6, PC3C4C5C10)
C10
147.46 s (s)
147.44 s (s)
130.44 d (d)
130.93 d (br.d)
(1.8, PC3C4C5C10)
(2.0, POC6C5C10;
1.2, HC3C4C5C10)
137.15 d (d.d.t)
C11
138.38 d (d.t.d)
(19.4, PC3C4C11;
7.1 7.2,
133.73 d (m)
134.82 d (m)
140.13 d (d.d.t)
(18.3, PC3C4C11;
7.0, HC13C12C11;
6.0 5.0, HC3C4C11)
(25.4, PC3C4C11) (19.2, PC3C4C11) (21.0, PC3C4C11;
7.6, HC13C12C11;
5.0, HC3C4C11)
HC13C12C11;
5.8 6.0, HC3C4C11)
C12, 126.70 s (d.d.d)
126.99 s (br.d.m) 126.56 s (br.d.m) 125.38
s
(br.d.d.d)
125.73 s (br.d.d.d)
(159.5, HC12;
C16
(161.4, HC12;
(161.3, HC12;
6.4 6.6,
HC16C11C12,
HC14C13C12)
(161.3, HC12;
(159.1, HC12;
6.7, HC16C11C12;
6.2, HC14C13C12)
6.4, HC16C11C12, 5.0 6.0, HC16C11C12; 6.7, HC16C11C12;
HC14C13C12)
5.0 6.0, HC14C13C12) 6.0, HC14C13C12)
C13, 129.02 br.s
C15
128.67 s (br.d.d) 129.17 s (br.d.d) 127.31 s (br.d.d)
(162.3, HC13; (162.3, HC13; (161.0, HC13;
7.0, HC15C14C13) 7.0, HC15C14C13) 7.8, HC15C14C13)
128.87 s (br.d.d)
(160.0, HC13;
6.6, HC15C14C13)
(br.d.d) (163.1,
HC13; 5.0 6.0,
HC15C14C13)
C14
129.87 s (d.t)
(161.8, HC14;
7.3, HC12,16CC14)
131.97 s (d.t)
(162.3, HC14;
131.49 s (d.t.t)
(162.5, HC14;
127.97 s (d.t)
(161.0, HC14;
127.62 s (d.t)
(161.2, HC14;
7.2, HC12,16CC14)
7.0, HC12,16CC14) 7.0, HC12,16CC14; 7.2, HC12,16CC14)
2.2, HCC)
a
12 14
13
The signals of C
C
can overlap; data for the C NMR spectrum taken without proton decoupling are given in parentheses.
b
c
+
63.89 s (t.t.t) (dioxane; 143.0, HC; 3.7, HCC; 2.0, HCOC). H N CH CH CH CH . 38.14 s (t.m) (NCH ; 151.2 152.0, HC;
3
2
2
2
3
2
4.2, HCC), 28.71 s (t.m) (NCCH ; 126.0 126.2, HC; 4.0 4.3, HCC), 19.02 s (t.m) ( -CH ; 125.3, HC; 3.3, HCC), 12.95 s (q.m)
2
2
(CH ; 124.9, HC; 4.0 4.2, HCC).
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
1767
Table 2. Selected bond ( , deg) and torsion ( , deg) angles
and bond lengths (d, ) in the molecule of VIII
C14
C13
C12
Angle
Angle
Cl2P2O1
Cl2P2O2
Cl2P2C3
O1P2O2
O1P2C3
O2P2C3
C5C4C11
C4C5C10
C6C5C10
103.6(1)
112.4(1)
107.0(1)
112.4(2)
101.8(1)
118.2(2)
120.9(3)
124.8(3)
115.9(3)
P2O1C6
P2C3C4
C3C4C5
C3C4C11
Cl8C8C7
Cl8C8C9
C4C5C6
O1C6C5
O1C6C7
120.1(2)
119.6(3)
120.7(3)
118.0(3)
120.5(3)
120.6(3)
119.4(3)
121.0(3)
116.2(3)
C15
C11
C16
Cl10
C9
Cl9
Cl8
C10
C7
C4
C5
C3
C8
C6
O1
Cl7
Angle
Angle
P2
Cl2P2O1C6
O2P2O1C6
C3P2O1C6
Cl2P2C3C4
O1P2C3C4
O2P2C3C4
P2O1C6C5
P2O1C6C7
P2C3C4C5
P2C3C4C11
66.5(2) C3C4C5C6
171.9(2) C11C4C5C6
44.5(3) C11C4C5C10
80.6(3) C3C4C11C12
27.8(4) C3C4C11C16
151.4(3) C5C4C11C12
29.9(4) C5C4C11C16
151.9(3) C4C5C6O1
3.5(5) C4C5C6C7
25.9(5)
147.6(3)
31.7(5)
128.2(4)
49.3(5)
45.4(5)
137.0(4)
9.5(5)
O2
Cl2
Fig. 1. Geometry of VIII in the crystal.
and O2 [0.273(2) ] from the least-squares plane
C3C4C5C6O1; this group is planar within 0.146(3)
according to PLATON calculations [12]. Such an
arrangement of the substituents corresponds to the
anomeric effect of the endocyclic O1 atom. The con-
formation along the P C bond is favorable for the
conjugation of the bond C3=C4 with the antibonding
168.6(3)
171.1(3)
170.2(3) C10C5C6O1
Bond
d
Bond
d
*
orbital P Cl. The P Cl bond length [2.018(1) ] is in
Cl2 P2
Cl7 C7
Cl8 C8
Cl9 C9
Cl10 C10
P2 O1
2.018(1)
1.719(4)
1.698(4)
1.714(4)
1.726(4)
1.597(3)
1.456(3)
1.750(4)
1.411(6)
1.377(5)
C5 C10
C6 C7
C7 C8
C4 C5
C4 C11
C5 C6
O1 C6
C3 C4
C11 C12
C11 C16
1.410(5)
1.382(5)
1.392(6)
1.474(5)
1.479(5)
1.405(6)
1.382(5)
1.358(5)
1.405(4)
1.392(5)
agreement with the lengths (1.997 2.011 ) of the
axially oriented P Cl bond in 2-chloro-2-oxo-1,3,2 -
dioxaphosphorinane derivatives [13 16]. The torsion
angle (C5C4C11C12) is 45.4(5) , which shows that
the plane of the phenyl group at the 4-position of the
phosphorine heteroring is appreciably turned relative to
the C5C4C3P2 plane, so that the conjugation between
the phenyl group and the C3=C4 bond is improbable.
5
P2 O2
P2 C3
C8 C9
C9 C10
It is interesting that in chlorophosphorine VIII, as
in the previously studied phosphorines II, the chemical
shifts of the C3 C10 atoms clearly alternate with in-
creasing distance from phosphorus along the possible
conjugation chain (C3, C4, C5, C6, C7, C8, C9, C10),
so that the nuclei with the odd numbers (starting from
C3) give signals in appreciably higher fields than the
nuclei with the even numbers (starting from C4). The
carbon carbon bond lengths also noticeably alternate
along this chain, which is consistent with the sug-
gested conjugation model.
H12 (phenyl) atoms, with the parameters C H 1.07(3),
H O 2.47(3), C O 3.448(5) C H O 152(2) ,
,
results in formation of a dimer from two symmetry-
related (1 x, y, 1 z) molecules (Fig. 2). The sec-
ond interaction in the dimer is that between the Cl7
and H3 atoms [Cl7 H3 2.97(4)
,
C3 H3 Cl7
123(3) ]. Other numerous intermolecular contacts of
the type C H Cl give rise to an infinite two-dimen-
sional hydrogen-bonded structure. A bilayered supra-
molecular structure consisting of dimeric pairs and
oriented parallel to the b0c crystallographic plane is
formed. The majority of chlorine atoms appear to be
localized between the adjacent bilayered structures.
In the crystals of VIII, classical hydrogen bonds
are absent. Among other interactions, we should note
the intermolecular contacts C H O and C H Cl.
The first of these interactions between the O12 and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1768
MIRONOV et al.
Table 3. Atomic coordinates in VIII, equivalent
Cl2
Cl8
C8
isotropic temperature factors of nonhydrogen atoms B =
C9
C7
C6 P2
3
4/33
(aiaj)B(i,j) ( )2, and isotropic temperature factors
Cl9
Cl7
O2
i=1 j=1
2
C10
of hydrogen atoms Biso
(
)
Cl10
C16
C15
C5
O1
C3
H3
C1
B or
Biso
Atom
x
y
z
C11
C12
Cl2
Cl7
Cl8
Cl9
0.1436(1)
0.43999(9)
0.2876(1)
0.0955(1)
0.02620(7) 0.16883(8) 2.39(2)
0.23023(6) 0.33312(8) 2.07(2)
0.35862(6) 0.46994(9) 2.52(2)
0.27950(6) 0.61169(9) 2.14(2)
0.07483(6) 0.64143(8) 1.70(2)
0.05468(6) 0.30584(8) 1.68(2)
0.0423(2) 0.3588(2) 1.77(5)
0.1057(2) 0.2492(2) 2.33(5)
0.0989(2) 0.4460(3) 1.68(7)
0.0421(2) 0.5348(3) 1.46(6)
0.0559(2) 0.5105(3) 1.38(6)
0.0951(2) 0.4305(3) 1.64(7)
0.1873(2) 0.4214(3) 1.64(7)
0.2451(2) 0.4818(3) 1.75(7)
0.2078(2) 0.5493(3) 1.61(7)
0.1157(2) 0.5632(3) 1.48(6)
0.0803(2) 0.6626(3) 1.48(6)
0.0413(2) 0.7850(3) 1.55(7)
0.0802(2) 0.9043(3) 1.92(7)
0.1549(3) 0.9020(3) 2.24(8)
0.1934(2) 0.7811(4) 2.05(7)
0.1574(3) 0.6624(3) 1.82(7)
C13
C14
Cl10 0.07257(9)
P2
0.3267(1)
0.3880(3)
0.4145(3)
0.2950(4)
0.2681(3)
0.2575(4)
0.3268(4)
0.3414(4)
0.2735(4)
0.1892(4)
0.1825(4)
0.2642(4)
0.3415(4)
0.3372(4)
0.2571(4)
0.1822(4)
0.1876(4)
0.690(4)
Fig. 2. Formation of hydrogen-bonded dimers in the
crystal of VIII. Hydrogen bonds are denoted by dashed
lines.
O1
O2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
H3
0.159(3)
0.020(2)
0.042(4)
0.180(3)
0.253(3)
0.182(3)
0.538(4)
0.785(3)
0.022(4)
0.020(3)
0.720(4)
0.410(4)
2.4(9)
0.8(7)
4(1)
1.6(8)
2.6(9)
3(1)
H12 0.396(3)
H13 0.610(5)
H14 0.752(4)
H15 0.853(4)
H16 0.862(4)
structure is formed, which makes the crystals of VIII
anisometric. This results in fairly close packing of
molecules in the crystals; according to calculations,
the crystal contains no free space.
The electron impact mass spectrum of the product
mixture after separation of the major fraction of VIII
contains, along with the molecular peak of VIII, also
an additional peak of a larger mass, m/z 484. The
accurately measured mass of this ion, 483.8116, is
well consistent with the value of 483.7895, calculated
for the ion [C14H635Cl637ClO2P]+ . As judged from
the relative intensity of this peak, the content of the
corresponding compound IXb is low. Therefore, the
accurate mass could be determined only for the peak
Fig. 3. Fragment of the bilayered structure of the crystal
of VIII. Hydrogen bonds are denoted by dashed lines.
View along the 0z crystallographic axis.
Their fairly close packing is indicated by the large
number of short Cl Cl contacts, with the distances
from 3.543(1) to 3.632(1) (Fig. 3). However, there
are no other intermolecular contacts between the ad-
jacent layers. Thus, the hydrophilic fragments in the
crystal are localized, and a bilayered supramolecular
at m/z 484 corresponding to 635Cl + 137Cl. An addi-
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REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
1769
tional evidence of the formation of IXb is the intensity
ciably. The highest-field signal,
120.23 ppm, lo-
C
ratio of the peaks at m/z 484 and 486 (535Cl + 237Cl),
equal to 1 : 1 and corresponding to the presence of
seven chlorine atoms.
cated closely to the signal of C3 in VIII (120.63 ppm),
belongs, apparently, to C3 in the Z isomer (IXa), since
the surrounding of C3 (cis) in IXa is similar to that in
VIII. The signal of C3 in the E isomer (IXb) is located
in lower fields (123.73 ppm). The direct coupling con-
In the 31P NMR spectrum, the open-chain products
IXa and IXb give downfield doublets (CH2Cl2,
1
1
P
stants JPC and JHC for the cyclic (VIII) and acyclic
(IXa, IXb) compounds are close. The acyclic structure
24.7 and 21.7 ppm) with the coupling constants
2JPCH of 30.5 and 24.0 Hz, respectively, in a 1 : 1
ratio, which varies insignificantly in various experi-
of vinylphosphonic chlorides IXa and IXb also fol-
3
5
lows from the constants JPCCC , 8.4 9.9 Hz, which
ments. On heating, the signal at
24.7 ppm disap-
P
are approximately two times lower than in VIII. The
signals of C5 and C11 in IX and IXb were assigned on
the basis of the known fact that the coupling constants
3JPC=CC at trans arrangement of the coupled nuclei
are higher than at their cis arrangement [19]. Since
in both VIII and IXa the configuration of substituents
at the double bond is similar (Z), the signal at
152.87 ppm, located close to signal of C4 in VIII
(155.38 ppm), was assigned to the similar carbon
atom in cis-vinylphosphonic dichloride IXa, and the
higher-field signal at 150.90 ppm was assigned to the
pears, and the signal of phosphorine VIII with
15.2 ppm grows. This is indicative of the cis arrangeP-
ment of the quinoid and dichlorophosphoryl substit-
uents in the compound giving the signal with
24.7 ppm, since only the Z isomer can undergo therP-
mal cyclization fo VIII. This fact is consistent with
the relatively low content of the compound giving a
molecular pear at m/z 484, according to mass spec-
trometry. Our calculation of the chemical shifts of the
proton at the double bond in the Z and E isomers of
IX, performed according to [17], gave for these iso-
mers the values of 6.86 and 6.53 ppm, respectively.
In the experimental spectrum, the sequence is similar
C4 atom in the trans isomer IXb. The assignment of
the signals of the phenyl ring (Table 1) is tentative,
since the ratio of IXa and IXb is close to 1 : 1.
2
(7.80 ppm, Z; 7.17 ppm, E). Calculation of JPCH for
these isomers according to [18] gives the value of
30.1 Hz, close to the experimental values (24.0 Hz, Z;
30.5 Hz, E).
The quinoid structure of the chlorinated substituent
also unambiguously follows from the spectrum owing
to the presence of very characteristic downfield
(171.37, 171.36 ppm, C6) and upfield (79.71 ppm,
CCl2) signals. The carbon signals of the chlorinated
quinoid substituents proved to be less sensitive to the
configuration of the vinyl C=C bond. The most diffi-
cult problem in the analysis of the structure of this
substituent is determination of the relative arrange-
ment of the CCl2 fragment and carbonyl group.
The presence of the conjugated carbonyl group in
isomers IXa and IXb was confirmed by IR spectros-
copy. The spectrum of the reaction mixture in methyl-
ene chloride contains strong absorption bands at 1681,
1
1588, and 1568 cm , belonging to the stretching
vibrations of the C=O and C=C groups.
13C NMR spectroscopy also proved to be very use-
ful for determining the structures of IXa and IXb,
despite the fact that these compounds were not iso-
lated pure. In the 13C NMR spectrum of the reaction
mixture from which the crystalline precipitate of VIII
was preliminarily removed, the signals of VIII have
decreased intensity. These signals can be readily iden-
tified by comparison with the spectrum of pure VIII.
The remaining signals in the spectrum of the filtrate
form a doubled set typical of stereoisomers. The
difference between the isomers was manifested to the
greatest extent in the signals of the C4=C3 moiety and
in the signals of the C5 and C11 atoms directly bonded
to this fragment. This fact confirms the assumed iso-
merism with respect to the double bond. Figure 4
shows two fragments of the 13C NMR spectrum of
the reaction mixture of phosphorane VII with phenyl-
acetylene, recorded in a CDCl3 solution after removal
of the major portion of VIII. It is seen that the signals
of C3, C5, and C11 in VIII, IXa, and IXb differ appre-
Cl
Cl Cl
7
6
8
O
8
O
Cl
Cl
Cl
6
5
Cl9
9
5
10
Cl
10
Cl
Cl
Ph
Ph
A
B
First, it should be noted that, in both isomers, the
structure of this substituent is similar; otherwise, the
number of signals in the 31P and 13C NMR spectra
would be considerably larger. Furthermore, if the
observed differences between the spectral parameters
of the olefinic carbon atoms C3 and C4 were due to
isomerism in the chlorinated substituent (structures A
and B), these differences would not be so significant,
as the vinyl fragment is remote from the CCl2 group.
The choice of structure A was primarily based on
the available data on regiochemistry of chlorination
of the phenylene ring in the reactions of both substi-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1770
MIRONOV et al.
C11
C5
C11
IXb
IXa
C11
C8
VIII
IXa
VIII
138.0
137.0
136.0
135.0
134.0
C, ppm
C3
IXb
IXa C3
C3
VIII
VIII
C7
C5
VIII
125.0
124.0
123.0
122.0
121.0
C, ppm
13
1
Fig. 4. Fragments of the C { H} NMR spectrum of a mixture of VIII, IXa, and IXb.
tuted and unsubstituted phenylenedioxytrichlorophos-
phoranes with arylacetylenes (to the p-position rela-
tive to the oxygen atom of the phosphorine heteroring)
[1, 6, 9]. Unfortunately, the 13C NMR spectra do not
allow unambiguous choice between structures A and
B. The p-quinoid substituent in A is more symmetri-
cal, and the electronic effects of the carbonyl and
dichloromethylene groups on C8 and C10 are approx-
imately equal. In accordance with the M effect of the
carbonyl group, the C8 and C10 nuclei should give
signals in lower fields as compared to C7 in both
isomers of IX with structure A. Therefore, we as-
131.31 ppm, to C7 in isomers IXa and IXb of
structure A. In structure B, larger differences should
be expected between the chemical shifts of C8 , C9 ,
and C10, since the structure is unsymmetrical.
C
Thus, the whole set of spectral data is consistent
with the formation of relatively stable vinylphosphon-
ic chlorides IX containing the quinoid substituent of
structure A. The isomerism of IX is determined by
arrangement of the radicals about the acyclic double
bond. Formation of such structures was postulated
previously [1, 6, 9], and only with perchlorinated
phosphorane VII they could be detected experimental-
ly. This may be due to the steric hindrance to both
signed signals with
146.6 147.5 ppm to C8 and
C
C10 (these signals can overlap), and the signal with
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REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
1771
ipso substitution of oxygen and cyclization into phos-
phorine, produced by the o-chlorine atoms in the phen-
ylene substituent of VII. It should be noted that, in
competing reaction with phenylacetylene, phosphor-
ane VII is less reactive in than unsubstituted com-
pound I. For example, in the reaction of a mixture of
phosphoranes I and VII with phenylacetylene (molar
ratio 1 : 1 : 1), the ratio of the unchanged halides I and
VII is 1 : 2. Since phosphorine VIII is formed under
very mild conditions (0 10 C) and quinoid phospho-
nate IXa undergoes cyclization only on heating, phos-
phorin VIII is hardly formed via IXa, at least at this
low temperature. The formation of the E isomer IXb
also suggests that phosphorine VIII under mild condi-
tions is formed by a different pathway. Apparently,
formation of the cis and trans isomers of IX implies
formation of certain intermediates with free rotation
around the P C bond. This is possible only if this
bond is single. In view of this fact, taking also into
account published data [1, 6, 9], we propose the fol-
lowing reaction scheme.
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
O
O
O
Cl
Cl
O
O
Cl
Cl
PCl3
VII + Ph C CH
Cl
Cl
P
Cl
O P
+C=CH
Cl
Cl
Ph
Cl
Ph
XI
PhC CH
X
XI
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
O
Cl
Cl
O
Cl
Cl
O
O^
O
P
Cl
Cl
+
P
+
Cl
Cl
+
Cl
Cl
Cl
Ph
P
Cl
Ph
Ph
Cl
O
XIII
XIV
XV
Cl
Cl
Cl
Cl
Cl
Cl
O
Cl
Cl
O
O
P
Cl
Cl
Cl
+
+
Cl
Ph
P
Cl
Ph
Cl
O
XVI
XVII
IXb
VIII
IXa
Cl2
The first step apparently involves formation of
complex X of the phosphorane as an acid with phenyl-
acetylene as a Lewis base. Then this complex trans-
forms into intermediate phosphorane XI, which gives
quinoid phospholine XII (postulated in [6]) by the
attack of the carbon atom at the carbanionic center.
Intermediate XII can occur in equilibrium with phos-
phonium salt XIII, which contains a quaternary carbon
atom and therefore can readily undergo further trans-
formations resembling the elimination stage in the
Arbuzov reaction. Such a transformation can yield
intermediate allyl cations XIV and XV containing
dichlorophosphoryl and quinoid substituents. We
believe that specifically this step is responsible for
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1772
MIRONOV et al.
the formation of a mixture of cis and trans isomers of
the final acyclic phosphonates IXa and IXb. The other
mesomeric forms of phosphorylated allyl cations XIV
and XV are divinyl carbanions with localization of the
charge in the chlorinated rings, XVI and XVII. Migra-
tion of the chloride anion to this ring yields the final
products IXa and IXb.
presence of heavy atoms with the weaker spin orbital
coupling (Cl). In the process, the chlorine atoms at
phosphorus are successively substituted by phenoxy
groups to give finally phosphoranyl radicals similar
to those described in [21], with the characterstic split-
ting from phosphorus ( 4 Oe). However, the contribu-
tion of this process is low, and it can be detected only
thanks to the stability of the arising radicals and to the
high sensitivity of ESR.
Phosphorine VIII is, apparently, formed from quino-
id phosphonium salt XIII containing a phospholine
ring. This transformation may involve the halophilic
attack of the chloride anion resulting in elimination
of molecular chlorine, intramolecular attack of the
carbonyl oxygen atom at the phosphonium center, and
formation of the phosphoryl group. Chlorine adds to
excess phenylacetylene, yielding isomeric dichloro-
styrenes whose spectral parameters are described esle-
where [1].
Hydrolysis of VIII yields acyclic phosphonic acid
XIX. By treatment of a mixture of VIII and IX with
water, followed by crystallization, we were able to
isolate only one isomer of XIX also. In the process,
the perchlorinated quinoid substituent transforms into
the tetrachlorohydroxyphenyl group. Monochloro-
substituted phosphorines II give cyclic products [6].
Attempts to perform hydrolysis with an equimolar
amount of water did not result in isolation of pure
cyclic acid XX, as this acid is hydrolyzed extremely
1
readily. Hydroxyphosphorine XX was detected by H
and 31P NMR spectroscopy. The spectrum of a fresh-
ly prepared DMSO-d6 solution of the reaction mixture
after hydrolysis with an equimolar amount of water
contained, along with the H3 signal ( 6.67 ppm, d,
2JPCH 13.4 Hz) belonging to XIX, also a weaker
doublet with 6.53 ppm, with the coupling constant
2JPCH 17.8 Hz characteristic of cyclic compound XX.
Along with the heterolytic reaction pathway dis-
cussed above, the homolytic pathway via biradical
XVIII is also possible. In XVIII, one of the radical
centers is localized on the chlorinated phenyl group,
and the other, on the vinyl group.
The 31P NMR spectrum contains a doublet with
P
2
3.7 ppm with the same coupling constant JPCH
.
Cl
O
OH
H
Cl
Cl
O
H2O
HCl
P
Cl
VIII
O
Cl
Cl
Cl
Cl
Cl
X
XII
Cl Ph
O P
XX
Cl
C-CH
Cl
7
Ph
XVIII
8
6
Cl
OH
O
5
Cl 9
3
4
CH P(OH)2
H2O
11
It should be noted, however, that the stability of
vinyl radicals is low; furthermore, they are gener-
ated as cis and trans isomers in equal amounts and do
not tend to isomerize [20]. Due to steric factors, radi-
cal XVIII with the cis arrangement of the phenyl
group and phosphorus-containing substituent will
polymerize rather than cyclize, yielding vinyl oligo-
mers, which was not observed in our case. Thus, we
can conclude that the pathway of formation of VIII
and IX is mainly heterolytic.
10Cl
12
13
14
XIX
1
The structure of XIX was determined by 31P, H,
and 13C NMR spectroscopy (Table 1). In the 31P
NMR spectrum (162.0 MHz, ethanol-d6), vinylphos-
phonic acid XIX gives a signal with P 10.7 ppm. The
1H NMR spectrum (ethanol-d6) contains, along with
signals of XIX [ , ppm: 7.62 s (5H, C6H5), 6.59 d
When monitoring the reaction by ESR, we detected
formation of long-lived phenoxy radicals. They give
weak broad lines with the g-factors depending on the
2
(1H, JPCH 13.5 Hz)], also a signal of dioxane
(3.95 ppm) with which compound XIX forms a stable
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REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
1773
Table 4. Atomic coordinates in XIX (dioxane solvate),
equivalent isotropic temperature factors of nonhydrogen
C14
C15
3
3
atoms
B
=
4/3
(aiaj)B(i, j) ( )2, and isotropic
C13
i=1 j=1
2
C16
Cl3
temperature factors of hydrogen atoms Biso
(
)
C12
C11
Cl6
B or
Biso
Atom
x
y
z
C10
C8
C9
C6
O4
Cl7
Cl8
Cl9
0.56158(6)
0.67751(6)
0.67665(5)
0.24684(5) 0.34532(5)
0.24227(5) 0.41345(7) 10.58(4)
8.74(4)
C4
C5
Cl7
C7
C3
0.23209(6) 0.54737(7)
0.23461(5) 0.61192(5)
0.12476(4) 0.54033(4)
0.24813(9) 0.4187(1)
0.11622(9) 0.50913(9)
0.1015(1) 0.5050(1)
0.0960(1) 0.6003(1)
9.24(4)
6.67(3)
3.80(2)
4.83(6)
4.02(6)
5.57(7)
5.52(6)
Cl5
Cl10 0.55811(5)
P1
P2
0.44099(4)
0.4554(1)
0.49693(9)
0.3893(1)
0.4421(1)
O2
O1
O1
O2
O3
O4
O3
O30 0.5776(2)
0.2493(2) 0.6913(2) 11.7(1)
C3
0.4227(1)
0.4533(2)
0.5081(2)
0.5088(2)
0.5603(2)
0.6123(2)
0.6132(2)
0.5604(2)
0.4328(1)
0.4064(2)
0.3892(2)
0.3985(2)
0.4254(2)
0.4432(2)
0.5784(4)
0.5783(4)
0.7817(5)
0.7495(4)
0.4661
0.1977(1) 0.5536(1)
0.2449(1) 0.5403(1)
0.2426(1) 0.5087(2)
0.2451(1) 0.4493(2)
0.2440(2) 0.4198(2)
0.2405(2) 0.4498(2)
0.2379(2) 0.5092(2)
0.2389(1) 0.5391(2)
0.3036(1) 0.5589(2)
0.3124(2) 0.6107(2)
0.3668(2) 0.6269(2)
0.4142(2) 0.5939(2)
0.4061(2) 0.5422(2)
0.3515(2) 0.5241(2)
3.53(9)
3.61(9)
3.68(9)
4.5(1)
5.8(1)
6.2(1)
5.8(1)
4.9(1)
3.91(9)
5.6(1)
6.5(1)
6.9(1)
7.7(1)
6.1(1)
C4
C5
C31
C6
C7
O30
C8
C9
C32
C10
C11
C12
C13
C14
C15
C16
C31
C32
C51
C52
H1
Fig 5. Molecular structure of the dioxane solvate of XIX,
with the atom numbering. The disordered dioxane
molecule is not shown.
4 : 3 solvate. The C3 signal appears in considerably
lower field as compared to cyclic hydroxyphosphor-
ines, in the range typical of aromatics. The coupling
1
0.1973(3) 0.7222(3) 15.0(3)
0.3000(3) 0.7240(3) 16.1(3)
0.2392(5) 0.8164(5) 10.7(3)
constant JPC is very large, 190.0 Hz, and untypical of
cyclic hydroxyphosphorines [1, 6, 9]. When the phos-
phorin ring is opened, the geminal constant JPCC
which is close to zero in hydroxyphosphorines, in-
creases to 3.7 Hz, whereas the vicinal coupling con-
stant JPCCC decreases by a factor of 2 (to 7.5 Hz);
this value corresponds to the cis arrangement of the
phosphorus-containing group and chlorinated phenyl.
The large constant JPCCC , 21.0 Hz, is also consis-
tent with the trans arrangement of the phenyl and
dihydroxyphosphoryl groups. Naturally, in the open
system XIX the coupling of phosphorus with C7 dis-
appears. Similarly to phosphorines, C7 gives a signal
in higher fields as compared to the other atoms of the
chlorinated phenyl group. It should be noted also that
the C5 signal (126.86 ppm) is shifted downfield rela-
tive to phosphorines [1, 6, 9].
2
4
,
0.1906(5) 0.7124(5)
9.4(3)
0.2604
0.2017
0.0644
0.2797
0.3709
0.4516
0.4385
0.3475
0.1045
0.1769
0.1771
0.3231
0.3176
0.3810
0.5741
0.6255
0.6367
0.6658
0.6048
0.5156
0.4856
0.5207
0.7085
0.7110
0.7110
0.7136
4
4
4
7
9
9
9
7
7
3
5
H3
H4
0.3859
0.4722
H12 0.4013
H13 0.3681
H14 0.3862
H15 0.4337
H16 0.4627
H31 0.3505
H311 0.5443
H312 0.6112
H321 0.6064
H322 0.5397
3
11
18
18
19
19
Thus, the above-considered spectroscopic data for
XIX suggest its acyclic structure and the Z configura-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1774
MIRONOV et al.
Table 5. Selected bond angles ( , deg), torsion angles ( , deg), and bond lengths (d, ) in molecules of phosphonic acid
XIX and salt XXIV
Angle
XIX,
XXIV,
Angle
XIX,
XXIV,
O1C6C5
O2P2O3
O2P2O4
O2P2C3
O3P2O4
O3P2C3
O4P2C3
119.3(3)
111.6(1)
111.4(1)
114.7(1)
109.8(1)
103.9(1)
105.1(1)
114.4(7)
109.5(4)
114.8(4)
110.0(4)
109.9(4)
107.7(4)
104.6(4)
C6O1H1
P2O3H31
P2O4H4
P2C3C4
C3C4C5
C3C4C11
C5C4C11
130
130
107.1(4)
85
136.6(7)
121.6(7)
125.1(8)
113.0(7)
119.4(2)
137.0(2)
127.9(3)
122.9(3)
120.4(3)
116.7(3)
Angle
XIX,
XXIV,
Angle
XIX,
XXIV,
O2P2C3C4
O3P2C3C4
O4P2C3C4
P2C3C4C5
P2C3C4C11
C3C4C5C6
C3C4C5C10
1.7(4)
123.8(3)
120.9(3)
3.2(5)
175.6(3)
89.5(4)
91.7(4)
103(1)
16(1)
133(1)
3(2)
171.0(9)
77(1)
107(1)
C6C5C4C11
91.7(4)
87.1(4)
36.9(5)
146.4(4)
141.9(4)
34.8(5)
97.7(9)
79(1)
138(1)
39(1)
36(1)
146.9(9)
56(1)
C10C5C4C11
C3C4C11C12
C3C4C11C16
C5C4C11C12
C5C4C11C16
N18C17C20C25
Bond
XIX, d
XXIV, d
Bond
XIX, d
XXIV, d
Cl7 C7
Cl8 C8
Cl9-C9
Cl10 C10
P2 O2
1.727(4)
1.731(4)
1.720(4)
1.690(4)
1.496(2)
1.546(3)
1.540(3)
1.768(3)
1.426(4)
1.741(9)
1.722(9)
1.716(9)
1.73(1)
1.488(7)
1.575(7)
1.501(6)
1.742(9)
1.37(1)
O1 H1
0.95
0.97
1.17
1.338(5)
1.468(5)
1.502(4)
1.27
1.18
O3 H31
O4 H4
C3 C4
1.33(1)
1.51(1)
1.46(1)
1.45(1)
1.17
C4 C5
P2 O3
C4 C11
N18 C17
N18 H181
N18 H183
P2 O4
P2 C3
O1 C6
1.00
tion of substituents at the double bond. This conclu-
sion was confirmed by single crystal X-ray diffraction
study of XIX. Figure 5 shows the geometry of the
dioxane solvate of XIX. The atomic coordinates and
selected bond angles, torsion angles, and bond lengths
are listed in Tables 4 and 5.
field (to 130 ppm) relative to acid XIX, which is due
to a change in the electron density on the phosphorus
Cl
O
NH R
H
Cl
Cl
O
P
2R NH2
VIII
R NH2 HCl
Amides XXI and XXII prepared by us from chloro-
phosphorine VIII and appropriate amines are viscous
oils very susceptible to hydrolysis. In the course of
their attempted isolation without special precautions
against moisture, we obtained more stable crystalline
ammonium phosphonates XXIII and XXIV.
Cl Ph
XXI, XXII
Cl
Cl
Cl
Cl
OH
O
P
2H2O
O
+
NH3
R
OH
1
The structure of these salts was determined by H
Ph
NMR (see Experimental) and IR spectroscopy. The
parameters of the 13C NMR spectrum of butylammo-
nium salt XXIII are listed in Table 1, and a fragment
if this spectrum is shown in Fig. 6. Its interesting
feature is that the C3 signal is strongly shifted down-
XXIII, XXIV
R = CH2CH2CH2CH3 (XXI, XXIII), CH(CH3)C6H5
(XXII, XXIV).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
1775
C10
C13
C8
C14
C3
C5
132.0
131.2
130.4
129.6
128.8
128.0
127.2 C, ppm
13
Fig. 6. Fragment of the C NMR spectrum of butylammonium salt XXIII.
atom in XXIII (an anion instead of a neutral mole-
cule). On the contrary, the C4 signal is shifted upfield
(to 144 ppm), with the difference between the chem-
the double bond does not exceed 3 ). In XIX, the con-
formation of the O=P C=C fragment is eclipsed, and
in salt XXIV the O P and C=C bonds are eclipsed
(see torsion angles in Table 5). It should be noted that
two independent molecules in the structure of XXV
have different conformations: In one of them, the O=P
and C=C bonds (torsion angle O=P C=C 9.2 ), and in
the other, the O P and C=C bonds (torsion angle
O=P C=C 151 ) are eclipsed. In XXVI and XXVII,
ical shifts [ (C4)
(C3)] in XIX being almost two
times larger ( 28 ppm) than in butylammonium salt
XXIII ( 14 ppm). Passing from acid XIX to salt
XXIII also affects the sequence of the chemical shifts
of the phenyl carbon atoms. For example, in XIX the
C14 atom is the most deshielded, whereas in XXIII
the most deshielded are the carbon atoms in the m-
positions relative to the acyclic double bond (C13, 15).
O2
The structure of 1-phenylethylammonium salt
XXIV was determined by single crystal X-ray diffrac-
tion. Figure 7 shows the molecular geometry of XXIV
in the crystal, and the selected bond lengths, bond
angles, and torsion angles and the atomic coordinates
are listed in Tables 5 and 6.
Cl8
C8
O3
Cl7
C6
C7
P2
C3
Cl9
C23
O4
C9
O1
C4
10 C5
Cl
A search in the Cambridge Structural Database [22]
revealed no published structural data for 2-diaryl-
substituted derivatives of vinylphosphonic acid.
Among monoaryl-substituted vinylphosphonic acids,
data are available on -phenylvinylphosphonic acid
XXV [23], dimethyl (Z)-1-formamido-2-phenylethen-
ylphosphonate XXVI [24], and dimethyl 2-phenyl-1-
hydroxyethenylphosphonate XXVII [25].
C22
C11
C24
C21
C20
C17
N18
C25
C12 C16
C15
C13
C19
C14
Despite the presence of bulky substituents, the con-
formation of the ethene fragments in XIX and XXIV
is planar: The torsion angle P1C3C4C5 in them is
3.2(5) and 3(2) , respectively. In structures XXV
XXVII, the conformation is also planar (twisting of
Fig. 7. Geometry of XXIV in the crystal, with atom
numbering.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1776
MIRONOV et al.
Table 6. Atomic coordinates in ammonium salt XXIV, equivalent isotropic temperature factors of nonhydrogen atoms
3
3
2
B = 4/3
(aiaj)B(i, j) ( )2, and isotropic temperature factors of hydrogen atoms Biso
(
)
i=1 j=1
B or
Biso
B or
Biso
Atom
x
y
z
Atom
x
y
z
Cl7
Cl8
Cl9
Cl10
P2
0.5877(4) 0.2517(2) 0.9884(1)
0.3704(5) 0.4057(2) 1.0035(1)
0.0558(5) 0.4320(2) 0.9323(1)
0.2462(5) 0.3107(2) 0.8354(1)
0.1240(4) 0.0650(2) 0.9273(1)
4.84(8)
5.21(9)
5.47(9)
4.19(8)
2.39(7)
3.4(2)
3.5(2)
3.5(2)
3.7(2)
3.2(2)
2.6(3)
2.2(3)
1.1(2)
3.0(3)
3.0(3)
3.1(3)
2.9(3)
2.5(3)
2.9(3)
3.3(3)
4.4(3)
5.7(4)
6.0(4)
3.9(3)
5.0(3)
4.8(3)
C20
C21
C22
C23
C24
C25
H1
0.470(1)
0.645(2)
0.691(2)
0.553(2)
0.382(2)
0.342(2)
0.5106
0.1775
0.2942
0.3178
0.0529
0.2364
0.2721
0.5335
0.7493
0.8153
0.5706
0.2907
0.2131
0.0326
0.4612
0.4075
0.2383
0.3112
0.1131
0.2009
0.0590(5) 0.7997(4)
0.0791(6) 0.7733(5)
0.0542(6) 0.7110(5)
0.0075(6) 0.6791(5)
0.0160(6) 0.7045(5)
0.0105(6) 0.7679(5)
3.1(3)
4.9(3)
6.2(4)
6.5(4)
7.7(4)
5.8(4)
O1
0.367(1)
0.1473(3) 0.8902(3)
O2
0.3361(9) 0.0756(4) 0.9468(3)
0.1698
0.0769
0.2344
0.2408
0.1950
0.1443
0.1325
0.1269
0.1102
0.0652
0.0106
0.0500
0.0054
0.0722
0.0168
0.0623
0.0177
0.1888
0.1314
0.1709
0.9303
0.8139
0.7548
0.6359
0.5661
0.6082
0.7221
0.8821
0.7972
0.6871
0.6303
0.6803
0.7890
1.0291
0.9320
0.9588
0.9003
0.8317
0.8381
0.9027
6
2
4
6
7
6
4
7
6
9
7
8
5
6
6
6
3
6
5
5
O3
0.028(1)
0.060(1)
0.375(1)
0.097(1)
0.016(1)
0.078(1)
0.279(2)
0.354(1)
0.257(2)
0.069(2)
0.017(1)
0.012(2)
0.182(2)
0.196(2)
0.040(2)
0.131(2)
0.141(2)
0.416(2)
0.248(2)
0.1067(3) 0.9788(3)
0.0153(3) 0.9205(3)
0.0382(4) 0.9160(4)
0.1039(5) 0.8487(4)
0.1658(5) 0.8247(4)
0.2257(4) 0.8705(4)
0.2145(5) 0.9039(4)
0.2706(5) 0.9458(4)
0.3364(5) 0.9539(5)
0.3493(5) 0.9200(5)
0.2932(5) 0.8794(5)
0.1803(5) 0.7539(4)
0.2127(5) 0.7258(5)
0.2186(5) 0.6569(4)
0.1921(6) 0.6168(5)
0.1596(6) 0.6397(6)
0.1572(5) 0.7081(5)
0.0932(5) 0.8655(5)
0.1492(5) 0.8590(5)
H3
O4
H12
H13
H14
H15
H16
H17
H21
H22
H23
H24
H25
H31
H181
H182
H183
H191
H192
H193
N18
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C19
the corresponding fragments have the transoid and
anticlinal conformations, respectively. Apparently, the
rotation about the P C bond in such molecules is vir-
tually free, and the conformation along this bond in
crystals is governed by intermolecular interactions.
The C3=C4 bond length in the molecules of phos-
phonates XIX and XXIV [1.338(5) ] is characteristic
of nonconjugated C=C bonds. In XXV XXVII, the
bond length in the ethene moiety varies from 1.334
to 1.348 . The aromatic fragments are turned relative
to the ethene moiety by different angles: The tetra-
chlorophenyl rings are almost orthogonal to the plane
of the ethene moiety [torsion angles C3C4C5C6 in
XIX and XXIV 89.5(4) and 77(1) , respectively],
and the phenyl rings are in the gauche conformation
conjugation between the aromatic fragments and the
double bond.
The phosphonate fragments in XIX and XXIV have
a common geometry with the distorted tetrahedral co-
ordination of phosphorus. The single (P2 O3, P2 O4)
and double (P2=O2) phosphorus oxygen bonds in acid
XIX are clearly distinguished by the length. In XXIV,
only the P2 O3 bond is single, and the P2 O4 and
P2 O2 bonds are intermediate (bond order 1.5),
suggesting delocalization of the negative charge. In
XIX, the P2 C3 bond [1.768(3) ] is longer than in
the anion of salt XXIV [1.742(9) ] and is typical of
neutral vinylphosphonic acids XXV XXVII (1.730
1.803 ).
[they are turned about the C4 C11 bond by 36.9(5)
and 39(1) , respectively]. At the same time, the C4 C5
bond in XIX [1.468(5) ] is shorter than the C4 C11
bond [1.502(4) ]. This fact shows that there is no
The geometries of the aromatic fragments in XIX
and XXIV and ammonium ion in XXIV are usual.
The geometric parameters of dioxane solvation mole-
cules in XIX were determined with a poor accuracy,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
probably because of their disordering and large libra-
1777
tion amplitudes.
The crystal structures of XIX and XXIV are char-
acterized by a developed system of hydrogen bonds of
various types. In the molecules of XIX, the hydroxy
groups of the phosphonate moiety form intermolecular
hydrogen bonds: O4 H O2 ( 1/2 + z, 1/2 + x, 1 y),
O4 H 1.17, H O2 1.64, O1 O2 2.584(3) , angle
O4 H O2 134 ; O3 H Cl7 (1/2
y, z, 1/2
x),
O3 H 0.97, H Cl7 2.71, O3 Cl7 3.631(3) , angle
O3 H Cl7 159 . The hydroxy group of the tetra-
chlophenolic moiety forms a bifurcate hydrogen
bond: an intramolecular bond with the Cl7 atom and
an intermolecular bond with the O30 atom (1/2 y,
1/2 z, x) of the dioxane solvation molecule. The pa-
rameters of the H bonds are as follows: O1 H1 Cl7,
O1 H1 0.95, H1 Cl7 2.38, O1 Cl7 2.989(3) , angle
O1 H1 Cl7 122 ; O1 H1 O30 (1/2 y, 1/2 z, x),
O1 H1 0.95, H1 O30 1.98, O1 O30 2.660(4) , angle
O1 H1 O30 127 .
It is interesting that, in the crystal of XIX, the areas
containing dioxane solvation molecules and phos-
phorus-containing moiety are separated as a result of
mutual association. Owing to the above-noted hydro-
gen bonds, six phosphonate molecules arranged
around the symmetry centers on the cell edges form
a local hydrogen-bonded spherical associate. Figure 8
shows a fragment of such a spherical aggregate (for
simplicity sake, only three molecules are shown). At
the same time, association of dioxane molecules near
the symmetry centers in lattice points also gives rise
to spherical aggregates shown in Fig. 9. Thus, the
supramolecular structure of XIX can be represented
as close packing of spherical associates of different
diameters, similar to packing in NaCl cubic crystal.
This was probably the cause of crystallization of XIX
in the cubic system, seldom for organic compounds.
Experimental data show that the remaining disordered
dioxane molecules also form such aggregates, but the
Fig. 8. Formation of associate from six molecules of
phosphonic acid XIX (only three molecules are shown).
The hydrogen bonds are shown by dashed lines.
in the crystal, potentially accessible for solvation
molecules. Note that the different types of associates
in the crystal are mutually bound by a number of
other revealed intermolecular contacts.
In the crystal of XXIV, there are also an intramo-
lecular hydrogen bond O1 H1 Cl7 with the param-
eters O1 H1 1.27, H1 Cl7 1.91, O1 Cl7 3.011(7)
,
angle O1 H1 Cl7 142 , and six intermolecular
hydrogen bonds (Table 7).
Intermolecular contacts in the crystal of XXIV
result in formation of hydrogen-bonded centrosym-
metrical tetramers consisting of anion cation pairs
(Fig. 10). Two intermolecular interactions involving
the ammonium group bind these tetramers in an infi-
arrangement of the molecules in the aggregates is dis-
3
ordered, as indicated by a large free volume (389.5
)
Table 7. Parameters of intermolecular hydrogen bonds in the structure of XXIV
Symmetry code of acceptor
D H A,
deg
Bond
d(D H),
d(H A),
d(D A),
atom
O1 H1 O2
1 + x, y, z
1.27
1.18
1.17
1.17
0.97
1.00
1.98
1.43
2.54
1.71
1.99
2.04
2.540(8)
2.591(8)
3.349(9)
2.823(9)
2.86(1)
101
165
125
157
147
144
O3 H31 O4
N18 H181 O1
N18 H181 O2
N18 H182 O2
N18 H183 O4
x, 1
y, 1
z
1
x, 1/2 + y, 1/2
x, 1/2 + y, 1/2
z
z
1 + x, 1/2
y, 1/2 + z
1
x, 1/2 + y, 1/2
z
2.91(1)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1778
MIRONOV et al.
Fig. 9. Spherical associates of dioxane molecules in points of the cubic lattice of the crystal solvate of phosphonic acid XIX.
View along the major diagonal of the unit cell.
nite stack along the 0x crystallographic direction, so
that supramolecular ensembles are formed, having the
shape of infinite cylinders with the inner hydrophilic
region and outer hydrophobic shell consisting of poly-
chlorinated and unsubstituted phenyl groups. The
three-dimensional steric structure of the crystals of
XXIV can be considered as parallel packing of the
cylnidrical substructures along the crystallographic
direction 0x in the tetragonal fashion, as shown in
Fig. 11. It is seen that the groups in the internal part
of the cylinders are hydrogen bonded; there are no
specific interactions between the hydrophobic shells
of the adjacent cylinders. With such an arrangement,
the maximally close crystal packing is attained.
O4
O3
O1
P2
O2
Structural analysis of the compounds under consid-
eration allows certain generalizations. The concepts
of segregation and microphase separation are well
known in the polymer physics [26 28]. For example,
block copolymers in the solid or gel-like state form
structures with segregated domains consisting of
Fig. 10. Anion cation tetramer in the crystal of XXIV.
Hydrogen bonds are shown by dashed lines. Numbering
is given for the phosphorus and oxygen atoms only.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
1779
Fig. 11. Molecular packing in the crystal of XXIV (view along the 0x direction). Hydrogen bonds are shown by dashed lines.
blocks of only one type (phase). Typical examples of
such structures (before the phase inversion point) are
shown in Fig. 12 [29].
fested in localization of hydrophilic and hydrophobic
regions, gives rise to supercrystalline structures in
which the repeating unit is not a separate atom or
molecule but their associate. To some extent, such a
consideration decreases the crystal symmetry, i.e.,
the number of symmetry elements describing the
crystal structure. Note also that the pronounced struc-
tural anisotropy of the crystals of XIX and XXIV
should give rise to anisotropy of their physical pro-
perties. Studies in this direction will be continued.
For such structures, S.Ya. Frenkel suggested the
term superlattice or supercrystal [30], which is quite
justified, since in many cases segregated domains
form regular three-, two-, or unidimensional structures
(one structure transforms into another when changing
the ratio of the blocks). A similar pattern is observed
with localization of hydrophilic and hydrophobic
regions in the crystals that we studied (see also
[31 34]). The three compounds whose structures were
determined in this work cover the whole range of
possible superstructures: lamellar (layered) packing
(the most frequent superstructure in crystals with
separated fydrophilic and hydrophobic regions),
packing of cylinders, and packing of spherical
domains. The arising supramolecular structures are
exclusively due to intermolecular interactions, i.e.,
the thermodynamic incompatibility of phases, mani-
EXPERIMENTAL
The IR spectra were recorded on a Specord IR-75
spectrometer (mulls in mineral oil or solutions in
CH2Cl2). The NMR spectra were taken on Bruker
MSL-400 (13C, 13C {1H}, 100.6 MHz; 31P, 31P {1H},
162.0 MHz) and Bruker WM-250 (1H, 250 MHz)
spectrometers relative to internal HMDS and external
1
H3PO4. The H and 13C NMR spectra were recorded
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1780
MIRONOV et al.
Reaction of phosphorane VII with phenyl-
(a)
(b)
(c)
acetylene. A solution of 4.2 ml of phenylacetylene in
5 ml of CH2Cl2 was added in small portions with stir-
ring and cooling (10 15 C) to a solution of 4.8 g of
phosphorane VII in 20 ml of CH2Cl2. The solution
color rapidly changed from light yellow to dark brown.
The mixture was stirred for 2 h (in the process, the
color became light brown), evaporated in a vacuum,
and dried to remove volatiles at 120 140 C (0.06 mm).
A mixture of 2-oxo-4-phenyl-2,5,6,7,8-pentachloro-
Fig. 12. Schemes of supercrystal structures with se-
gregated domains: (a) lamellar, (b) hexagonal packing of
cylindrical domains, and (c) spherical domains.
5
benzo[e]-1,2 (2H)-oxaphosphorine VIII and E and Z
isomers of 2-(2,3,4,4,5-pentachlorocyclohexadienon-
6-yl)-2-phenylvinylphosphonic dichloride IXa and
IXb was obtained as a light brown glass. 31P NMR
spectrum (CH2Cl2), P, ppm (J, Hz): 15.2 d (2JPCH
25.6) (VIII, 42%), 24.7 d (2JPCH 30.5) and 21.7 d
(2JPCH 24.0) (IXa, IXb, 56%). Mass spectrum, m/z
(Irel, %), ion composition: 486 (1.7), 484 (1.7)
at 45 C. The ESR spectra were measured on a Radio-
pan SE/X-2544 spectrometer.
The mass spectra were taken on an MKh-1310
spectrometer interfaced with an SM-4 computer. The
ionizing electron energy was 70 eV, and the collector
current, 30 A. Samples were introduced with a direct
inlet system at 120 C. The accurate weights were
determined automatically from the reference peaks of
[C14H635Cl637ClO2P]+ ([MIX]+ ); 420 (1.8), 419
(1.8), 418 (10.2), 417 (5.6), 416 (35.8), 414 (52.1),
413 (5.3), 412 (33.3) [C14H6Cl5O2P]+ ([MVIII]+ );
384 (1.3), 383 (10.9), 381 (47.4), 380 (16.2), 379
(100), 378 (18.5), 377 (76.1) [C14H6Cl4O2P]+ . The
glassy product was then dissolved in chloroform (10
15 ml) and kept at 0 5 C for 3 5 days. A crystalline
precipitate of VIII formed; yield 15 18%, mp 179
180 C (from chloroform). Vacuum distillation of the
residue (220 230 C/0.04 mm) followed by crys-
tallization from chloroform gave an additional crop
of VIII. Total yield 23 25%. 1H NMR spectrum
(CDCl3), , ppm (J, Hz): 7.54 m (5H, C6H5), 6.82 d
perfluorokerosene. The relative error did not exceed
5
5
10 amu.
Single crystal X-ray diffraction study of VIII,
XIX, and XXIV was performed with an Enraf Nonius
CAD-4 automatic four-circle diffractometer. The re-
flection intensities were measured using the /2
scanning mode at variable scanning rate in the range
1
1 16.4 deg min with respect to ; no corrections for
the decay of intensity of the check reflections were
made. The structures were solved by the direct method
using the SIR program [35]; treatment of the experi-
mental data and structure refinement were performed
on an Alpha Station 200 computer using MolEN soft-
ware [36]. In the structure of XIX, we revealed a dis-
ordered solvent molecule identified by spectroscopic
methods as a dioxane molecule. It is randomly dis-
ordered in the crystal and occupies a special position
on the interception of three twofold axes. The C51 and
2
(1H, PCH, JPCH 25.3). Found, %: C 40.47; H 1.57;
Cl 43.08; P 7.27. C14H6Cl5O2P. Calculated, %: C
40.53; H 1.45; Cl 42.82; P 7.48.
2-(2-Hydroxy-3,4,5,6-tetrachlorophenyl)-2-
phenylvinylphosphonic acid XIX. A mixture of
VIII and IX (dark brown glassy substance, 8.1 g),
treated to remove chlorostyrenes and phenylacetylene
(150 C, 0.05 mm), was dissolved in 30 ml of dioxane
and treated with excess water (2 ml). The resulting
solution was poured into 200 ml of water; a light
yellow oily substance precipitated, which was crys-
tallized from chloroform with addition of a small
amount of dioxane. Phosphonic acid XIX was ob-
tained as a 4 : 3 solvate with dioxane; yield 62%, mp
C
52 atoms were set with a 1/2 multiplicity; the hydro-
gen atoms of this molecules were not revealed. The
intermolecular contacts, including hydrogen bonds in
the crystals, were analyzed using the PLATON pro-
gram [12]. The crystal parameters and conditions of
structure refinement are listed in Table 8.
5
1
2,2,2,4,5,6,7-Heptachlorobenzo[d]-1,3,2 -dioxa-
169 171 C (dec.). IR spectrum, , cm : 466, 494,
phosphole VII. A solution of 3.7 ml of PCl3 in 50 ml
of CH2Cl2 was added to a solution of 9.58 g of tetra-
chloro-o-quinone in 32 ml of CH2Cl2 at 20 C. The
resulting solution was heated for 1 day, the solvent
was distilled off, and the residue was sublimed in a
vacuum (120 130 C/0.06 mm Hg; published data
575, 588, 620, 683, 695, 725, 760, 789, 823, 840, 870,
900, 941, 990, 1025 1028, 1080, 1130, 1160, 1190,
1220, 1260, 1270, 1280, 1290, 1310, 1320, 1560,
1612, 2250 2350 v.br, 2650 2750 v.br, 3100
1
3200 v.br. H NMR spectrum (ethanol-d6), , ppm (J,
2
Hz): 7.34 br.s (5H, C6H5), 6.59 d (1H, PCH, JPCH
[11]: mp 160 165 C); yield 87%. 31P NMR spectrum
13.4), 3.67 s (6H, C4H8O2). 1H NMR spectrum
(CH2Cl2):
22.9 ppm.
(acetone-d6), , ppm: (J, Hz): 7.41 br.s (5H, C6H5),
P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES... : IV.
1781
Table 8. Parameters of the crystals of VIII, XIX, and XXIV and conditions of X-ray diffraction experiments (standard
deviations of the last digit are given in parentheses)
Parameter
VIII
XIX
XXIV
Empirical formula
Color, habit
C14H6O2PCl5
Colorless needles
140
4 C14H9O4PCl4 3C4H8O2
C14H8O4PCl4 C8H12N+
Colorless prisms
Colorless needles
T,
C
20
Cubic
Pn3
20
Crystal system
Space group
Monoclinic
P21/c
Monoclinic
P21/c
a,
b,
c,
, deg
Volume,
Z
10.370(5)
14.828(5)
10.588(4)
109.24(4)
1537(1)
4
23.157(5)
6.587(2)
17.835(4)
20.035(5)
93.85(2)
2348(1)
4
3
12418(2)
24
Formula weight
414.44
1.79
10.53
303.73
1.49
6.7
499.16
1.41
5.91
3
dcalc, g cm
1
, cm
F(000)
824
5663
1016
Radiation ( ,
Range of , deg
Scanning angle
)
MoK ,
2.12
0.71073
27.4
0.68 + 0.4tan
Two for orientation check and three for intensity check after collection of every 200 reflections
Standard reflections
Range of measured
indices
12
13
18
h
k
l
0,
12,
18
0
h
k
l
38,
0,
47
6
0
19
4773
1385
h
k
l
6,
17,
19
33
47
14816
Number of reflections
measured
Number of reflections
observed with I > 3 (I)
Absorption
6593
4892
4284
Taken into account empirically
Not taken into account
Not taken into account
Setting and refinement of
hydrogen atoms
Revealed from the
difference series, refined in
Revealed from the difference series, not refined
isotropic approximation
R
RW
0.067
0.079
2.690
0.01
0.048
0.054
1.508
0.18
0.045
0.044
1.039
0.06
Fitting parameter
/
Number of parameters
refined
223
243
289
Number of reflections in
final cycles of least-
squares treatment
Maximal peak in dif-
4505
3921
1383
0.22(2)
0.20(1)
0.24(3)
3
ference series, e/
2
6.74 d (1H, PCH, JPCH 13.3), 3.61 s (6H, C4H8O2).
chlorophenyl)-2-phenylvinylphosphonate
XXIII.
31P NMR spectrum (ethanol-d6):
13.5). Found, %: C 42.73; H 3.54; Cl 29.67; P 6.37.
4C14H9Cl4O4P 3C4H8O2. Calculated, %: C 42.50; H
3.13; Cl 29.58; P 6.46.
9.8 ppm, d (2JPCH
n-Butylamine, 1.3 g, was added with stirring at 20 C
to a solution of 4.0 g of chlorophosphorine VIII in
30 ml of absolute benzene. The mixture was stirred
for 2 h, the precipitate was filtered off, and the filtrate
was concentrated to 15 ml, washed with water, dried
over MgSO4, and evaporated. The oily residue was
P
n-Butylammonium 2-(2-hydroxy-3,4,5,6-tetra-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002

1782
MIRONOV et al.
crystallized from CCl4. Yield of XXIII 2.53 g; color-
less crystals, mp 160 161 C. 1H NMR spectrum
(60 MHz, CD3OD), , ppm (J, Hz): 7.23 br.s (5H,
6. Mironov, V.F., Konovalov, A.I., Litvinov, I.A., Gu-
baidullin, A.T., Petrov, R.R., Shtyrlina, A.A., Zyab-
likova, T.A., Musin, R.Z., Azancheev, N.M., and
Il’yasov, A.V., Zh. Obshch. Khim., 1998, vol. 68,
no. 9, p. 1482.
2
C6H5), 6.67 d (1H, PCH, JPCH 12.0), 2.81 m (2H,
NCH2), 1.55 1.59 m and 1.15 t (7H, CH2CH2CH3).
31P NMR spectrum (acetone-d6):
10.1 ppm, d
7. Pudovik, M.A., Ovchinnikov, V.V., Cherkasov, R.A.,
and Pudovik, A.N., Usp. Khim., 1983, vol. 52, no. 4,
p. 640.
P
(2JPCH 12.3 Hz). Found, %: C 44.51; H 4.34; Cl
29.08; N 3.06; P 6.25. C18H20Cl4NO4P. Calculated,
%: C 44.35; H 4.11; Cl 29.16; N 2.87; P 6.36.
8. Polezhaeva, N.A. and Cherkasov, R.A., Usp. Khim.,
1-Phenylethylammonium 2-(2-hydroxy-3,4,5,6-
tetrachlorophenyl)-2-phenylvinylphosphonate
XXIV. A mixture of 1.9 g of 1-phenylethylamine and
1.6 g of triethylamine in 10 ml of CH2Cl2 was added
to a solution of 6.6 g of chlorophosphorine VIII in
40 ml of CH2Cl2 at 20 C. The resulting mixture was
allowed to stand for 12 h, after which it was washed
with water and aqueous sodium carbonate and dried
over MgSO4; the solvent was removed in a vacuum.
The resulting yellow oily substance was crystallized
from acetone ether. Yield 4.0 g (47%), mp 184
1983, vol. 52, no. 11, p. 1899.
9. Mironov, V.F., Litvinov, I.A., Shtyrlina, A.A., Gu-
baidullin, A.T., Petrov, R.R., Konovalov, A.I., Azan-
cheev, N.M., and Musin, R.Z., Zh. Obshch. Khim.,
2000, vol. 70, no. 7, p. 1117.
10. Mironov, V.F., Gubaidullin, A.T., Petrov, R.R., Litvi-
nov, I.A., Shtyrlina, A.A., Zyablikova, T.A., Azanche-
ev, N.M., Konovalov, A.I., and Musin, R.Z., Phosp-
horus, Sulfur, Silicon Relat. Elem., 1999, vols. 144
146, p. 377; Petrov, R.R., Shtyrlina, A.A., Miro-
nov, V.F., and Konovalov, A.I., Abstracts of Papers,
Molodezhnaya nauchnaya shkola po organicheskoi
khimii (Workshop on Organic Chemistry for Young
Scientists), Yekaterinburg, 1999, p. 72; Mironov, V.F.,
Petrov, R.R., Shtyrlina, A.A., Zyablikova, T.A., Mu-
sin, R.Z., and Konovalov, A.I., Abstracts of Papers,
III Vserossiiskaya konferentsiya Novye dostizheniya
YaMR v strukturnykh issledovaniyakh (III Russian
Conf. New Achievements of NMR in Structural
Studies ), Kazan, 2000, p. 115.
1
185 C. IR spectrum, , cm : 465, 533, 545, 571, 596,
625, 580, 696, 725, 765, 785, 810, 855, 865, 928, 975,
990, 1043, 1093 sh, 1120, 1160, 1200, 1235, 1270,
1332, 1430, 1556, 1612, 1645, 2350 v.br, 2650
2750 v.br, 2950 3050 v.br. 31P NMR spectrum
(DMF):
7.2 ppm, d (2JPCH 12.4 Hz). Found, %: C
P
49.12; H 3.49; Cl 26.41; N 2.59; P 5.88. C22H20Cl4
NO4P. Calculated, %: C 49.35; H 3.74; Cl 26.54; N
2.62; P 5.79.
11. Gloede, J. and Gross, H., J. Pr. Chem., 1970, vol. 312,
ACKNOWLEDGMENTS
p. 326.
12. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
The study was supported by the Russian Founda-
tion for Basic Research (project nos. 00-03-32835 and
98-03-33266).
no. 1, p. 34.
13. Silver, L. and Rudman, R., Acta Crystallogr., Sect. B,
1972, vol. 28, no. 2, p. 574.
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