Reactions of phenylenedioxytrihalophosphoranes with arylacetylenes: III. Features of reactions of 5,6-Dihalo-2-chlorobenzo[d]-1,3,2-dioxaphosphole 2,2-Dichloride with arylacetylenes

Article abstract of DOI:10.1023/A:1012381423101

According to the NMR, IR, and high-resolution mass spectra, the major products of the reactions of 5,6-dibromo-2-chlorobenzo[d]-1,3,2-dioxaphosphole 2,2-dichloride with arylacetylenes are 4-aryl-6,7-dibromo-2-chloro-5,6-benzo[e]-1,2-oxaphosphorin-3-ene 2-oxides. The steric structure of one of the hydrolysis products, 2-hydroxy-6,7-dibromo-4-phenyl-5,6-benzo[e]-1,2-oxaphosphorin-3-ene 2-oxide, was studied by single crystal X-ray diffraction.

Full text of DOI:10.1023/A:1012381423101

Russian Journal of General Chemistry, Vol. 71, No. 1, 2001, pp. 67 74. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 1, 2001,
pp. 74 82.
Original Russian Text Copyright
2001 by Mironov, Petrov, Shtyrlina, Gubaidullin, Litvinov, Musin, Konovalov.
Reactions of Phenylenedioxytrihalophosphoranes
with Arylacetylenes:
III.1 Features of Reactions of 5,6-Dihalo-2-chlorobenzo[d]-
1,3,2-dioxaphosphole 2,2-Dichloride with Arylacetylenes
V. F. Mironov, R. R. Petrov, A. A. Shtyrlina, A. T. Gubaidullin, I. A. Litvinov,
R. Z. Musin, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received October 26, 1999
Abstract According to the NMR, IR, and high-resolution mass spectra, the major products of the reactions
of 5,6-dibromo-2-chlorobenzo[d]-1,3,2-dioxaphosphole 2,2-dichloride with arylacetylenes are 4-aryl-6,7-
dibromo-2-chloro-5,6-benzo[e]-1,2-oxaphosphorin-3-ene 2-oxides. The steric structure of one of the hydrol-
ysis products, 2-hydroxy-6,7-dibromo-4-phenyl-5,6-benzo[e]-1,2-oxaphosphorin-3-ene 2-oxide, was studied
by single crystal X-ray diffraction.
We found previously that reactions of phenylenedi- chloride (II) readily reacts with phenyl- and p-chlo-
rophenylacetylenes to give, according to the 31P NMR
oxytrichlorophosphorane (I) with arylacetylenes unex-
pectedly yield derivatives of benzo[e]-1,2-oxaphos-
phorin-3-ene, an organophosphorus analog of couma-
rin [2, 3]. The result of the reaction under mild condi-
tions formally resembles that of the Arbuzov reaction:
formation of the phosphoryl group and a P C bond.
However, the initial compound is a phosphorane, and
the phosphoryl group is formed by ipso substitution
of carbon for oxygen. The reaction also involves
another unusual process: regioselective chlorination
of the benzene ring at the p-position relative to
the oxygen atom of the newly formed oxaphosphorine
heteroring. When the benzo fragment of the initial
phosphorane contains a halogen, derivatives of 6,7-
dihalobenzo[e]-1,2-oxaphosphorin-3-ene are formed;
in the product, the halogen atom initially present in
the ring is at the m-position relative to the oxygen
atom of the oxaphosphorine ring, and the second halo-
gen atom migrating to the aromatic ring, at the p-posi-
tion [1].
data, two phosphorus-containing products in the ratio
from 8 : 1 to 10 : 1. The two bromine atoms present
in the benzene ring do not prevent the reaction.
From the reaction mixture, we distilled off a mix-
ture of cis- and trans-dichlorostyrenes (see Experi-
mental), which are probably formed by addition of
a chlorine molecule released in the reaction to ex-
cess acetylene. The electron impact mass spectrum of
the residue obtained after removal of volatiles con-
tains peaks at m/z 432 and 388. The precisely meas-
ured weights of ions giving these peaks (431.8284
and 387.8729) are consistent with the formulas
C14H8Br2ClO2P (431.8317) and C14H8BrCl2O2P
(387.8822). Taking into account also the 1H (see
Experimental) and 13C (Table 12) NMR data, we iden-
tified these compounds as 6,7-dibromo-4-phenyl-2-
chloro- and 7-bromo-4-phenyl-2,6-dichlorobenzo[e]-
1,2-oxaphosphorin-3-ene 2-oxides IIIa and IVa.
The main fragmentation pathway of IIIa and IVa
under electron impact involves cleavage of the P Cl
bond to give ions with m/z 397 and 353, respectively.
Here we report on the reaction of arylacetylenes
with phenylenedioxytrichlorophosphoranes containing
halogen atoms at the p-position relative to the oxygen
atoms. We found that previously unknown 5,6-di-
bromo-2-chlorobenzo[d]-1,3,2-dioxaphosphole 2,2-di-
2
In the tables and hereinafter in the text, the atom numbering
is arbitrary; it is shown in the structural formulas of III, V,
VIII, and IX.
1
For communication II, see [1].
1070-3632/01/7101-0067$25.00 2001 MAIK Nauka/Interperiodica

68
MIRONOV et al.
7
8
9
6
Br
Br
Br
Br
Br
Cl
O
O
O
O
Cl
H
O
O
Cl
H
P
P
XC6H4C CH
HCl
+
PCl3
5
3
10
16
15
4
11
C6H4X
IVa, IVb
12
13
II
14
X
IIIa, IIIb
X = H (a), 4-Cl (b).
The 13C NMR spectrum of IIIa contains four sig-
occurrence of ipso substitution of chlorine for bromine
at the p-position relative to the oxaphosphorinane
oxygen atom. The structure of phosphorines IV was
readily determined by comparison of the spectral pa-
rameters with those of compound IVa prepared previ-
ously [1]. In reactions of phosphorane II with phe-
nals of ipso-C atoms, which suggests the presence of
only two bromine atoms in the benzo substituent.
Apparently, in this limiting case the third halogen
atom is not incorporated. Another very interesting re-
sult of the reaction of I with arylacetylenes is partial
Table 1. 13C NMR spectra [ , ppm (J, Hz)] of III, V, IX, and XI (100.6 MHz, 35 C)
Atom
IIIa (CDCl3)
Va (DMF-d7)
C3
115.92 da (d.d)b (153.9, PC3; 172.0, HC3)
155.39 s (br.s)
117.31 d (d.d) (169.2, PC3; 163.5, HC3)
149.65 br.s (br.m)
C4
C5
122.54 d (d.d.d) (18.2, PCCC5; 7.9 8.1,
HC3CC5; 5.7 5.8, HC7CC5)
123.16 d (d.d.d) (16.6, PCCC5; 9.3, HC3CC5;
5.3 5.5, HC7CC5)
C6
150.16 d (d.d.d) (10.6, POC6; 9.8 10.1,
HC10C5C6; 5.0, HC7C6)
150.59 d (m) (7.0, POC6)
C7
125.21 d (d.d) (171.8, HC7; 8.2, POCC7)
128.74 s (d.d) (9.9, HC10CC8; 4.4, HC7C8)
121.28 br.s (br.d.d) (8.7, HC7CC9; 4.2, HC10C9)
134.01 s (d) (169.6, HC10)
123.83 d (d.d) (169.9, HC7; 6.1, POCC7)
124.73 s (d.d) (10.5, HC10CC8; 4.2, HC7C8)
116.94 s (d.d) (8.5, HC7CC9; 4.0, HC10C9)
131.81 s (d) (167.7, HC10)
C8
C9
C10
C11
136.63 d (d.t.d) (20.6, PCCC11; 7.1, HC13CC11;
6.5, HC3CC11)
137.46 d (d.t.d) (18.2, PCCC11; 7.2 7.4,
HC13CC11; 5.0 6.0, HC3CC11)
C12, C16 128.63 s (d.d) (163.1, HC12; 6.7, HC16CC12; 5.7,
HC14CC12)
127.81 s (d.d.d) (160.4, HC12; 6.6,
HC16CC12; 6.0, HC14CC12)
C13, C15 129.63 s (d.d) (163.1, HC13; 6.5, HC15CC13)
128.24 s (d.d) (161.5, HC13; 6.5, HC15CC13)
128.55 s (d.t) (161.6, HC14; 7.3, HC12, 16CC14)
C14
130.77 s (d.t) (162.1, HC14; 7.2, HC12, 16CC14)
Atom
IX (CDCl3)
XI (DMF-d7)
C3
C4
C5
C6
C7
C8
C9
C10
C11
115.47 d (153.5, PC3)
154.96 d (1.1, PCC4)
121.78 d (18.4, PCCC5)
149.43 d (9.7, POC6)
121.61 d (8.8, POCC7)
137.96 s
117.21 d (d.d) (169.5, PC3; 163.6, HC3)
150.14 s (br.m)
122.70 d (m) (16.6, PCCC5)
150.47 d (m) (6.9, POC6)
121.09 d (d.d) (170.0, HC7; 7.3, POCC7)
134.77 s (m)
114.18 s (m)
118.47 s
133.89 s
132.33 s (d) (167.0, HC10)
137.76 d (m) (18.2, PCCC11)
128.09 s (d.m) (160.5 161.0, HC12)
128.54 s (d.m) (160.7 161.3, HC13)
128.86 s (d.t) (161.4, HC14; 7.3, HC12, 16CC14)
136.27 d (20.5, PCCC11)
C12, C16 128.38 s
C13, C15 129.27 s
C14
130.44 s
a
b
With proton decoupling.
Without proton decoupling.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES WITH ARYLACETYLENES: III.
69
nylacetylene, the ratio of products IIIa and IVa de-
pends on the concentration of the reactants in the ini-
tial solution. As the concentration of the initial phos-
phorane is decreased in the series 1.44, 0.72, 0.48,
0.36, 0.288, and 0.07 M (at a constant reactant ratio
of 1 : 2), the ratio of IIIa and IVa varies, respective-
ly, as follows: 79.0 : 21.0, 77.6 : 22.4, 73.2 : 26.8,
73.2 : 26.8, 72.7 : 27.3, 71.6 : 28.4, and 63.3 : 36.7,
i.e., the relative content of the ipso substitution
product IVa slightly increases, probably owing to in-
creased contribution of the intramolecular mechanism
of chlorine migration. It should be noted also that di-
bromo-substituted phosphorane II and unsubstituted
phenylenedioxytrichlorophosphorane I show a similar
reactivity in concurrent reaction with phenylacetylene.
Fig. 1. Structure of the complex of benzophosphorine Va
with dioxane in the crystal.
occupies the equatorial position [the O2 atom devi-
ates from the O1C6C5C4 plane by 0.026(8) ], and
the hydroxy group, the axial position [the O3 atom
deviates from the O1C6C5C4 plane by 2.119(8) ],
Hydrolysis of IIIa, IIIb, IVa, and IVb in dioxane
gave the corresponding phosphonic acids Va, Vb,
VIa, and VIb. The major products Va and Vb were
isolated by fractional crystallization.
which is consistent with the anomeric effect of O3.
The P2 O3 bond is somewhat longer [1.544(8) ] as
compared to the related 2-hydroxy-4-phenyl-6,7-di-
chlorobenzo[e]-1,2-oxaphosphorin-3-ene 2-oxide (VII)
[1.525(5) ] and VIa [1.519(3) ] [1], which are
isostructural. Similar to VIa and VII, this is due to
realization of the conformation favorable for interac-
tion of the system of the C3=C4 bond with the P2 O3
antibonding orbital [ (O3P2C3C4) 92(1) ]. The length
of the endocyclic P2 O1 bond [1.593(9) ] coin-
cides within the limits of the experimental error with
the corresponding bond lengths in VIa and VII
[1.596(5) and 1.590(4) , respectively] [1].
2
1
2
O
Br
Br
O
P
3
OH
H2O
HCl
III, IV
H
C6H4X
Va, Vb
Br
Cl
O
O
OH
H
P
+
C6H4X
VIa, VIb
The phenyl substituent is turned relative to the di-
bromophenylene ring plane by an angle as large as
63(2) [ (C5C4C11C16)], which rules out any conju-
gation between them. The heterocyclic moiety contains
another planar [within 0.01(1) ] fragment, P2C3C4C5,
from which the C6 and O1 atoms deviate in the same
direction by 0.244(11) and 0.529(9) , respectively.
The O2 and O3 atoms deviate from the P2C3C4C5
1
The structure of V and VI was determined by H,
31P, and 13C NMR and IR spectroscopy (see Experi-
mental; Table 1) and by comparison with the spectral
parameters of a sample of VIa prepared by indepen-
dent synthesis [1] (the mass spectrum of this com-
pound is discussed in the Experimental).
Data in Table 1 suggest that hydrolysis lefts intact
the phosphorine ring. This conclusion is confirmed
by the single crystal X-ray diffraction data for Va.
The atomic coordinates for the dioxane solvate of Va
and the selected bond lengths, bond angles, and tor-
sion angles are listed in Tables 2 and 3. The steric
structure of the complex of Va with dioxane in
the crystal is shown in Fig. 1. It is seen that the acid
molecule is cyclic, with the positions of both bromine
atoms preserved. The phosphorine ring has the dis-
torted boat conformation: The O1C6C5C4 fragment is
planar within 0.01(1) , and the P2 and C3 atoms
deviate in the same direction by 0.596(3) and
0.237(11) , respectively. The phosphoryl group
ring in different directions by 0.870(8) 1.447(7)
.
The planar fragments are turned relative to each other
about the C4 C5 bond by 13(2) . The solvent (dioxane)
molecule has a usual chair conformation; the distances
between the dioxane and benzophosphorine molecules
correspond to van der Waals contacts.
Figure 2 shows the system of hydrogen bonds
in the crystal of the complex of Va with dioxane.
The benzophosphorine molecules form an infinite
chain of intermolecular hydrogen bonds O3 H30 O2 =
P(x 1, y, z), directed along the x-axis, with the pa-
rameters O3 H30 1.08, O2 H30 1.43, O3 O2
2.475(10) , angle O3 H30 O2 160 .
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001

70
MIRONOV et al.
3
3
2
Table 2. Atomic coordinates, equivalent isotropic temperature factors of nonhydrogen atoms
,
)
B = 4/3
(ai aj)B(i, j) (
i = 1 j = 1
and isotropic temperature factors of hydrogen atoms Biso
B or
(
2) for Va
B or
Atom
x
y
z
Atom
x
y
z
Biso
Biso
Br1
Br2
P2
1.0194(4)
1.1632(4)
0.1938(7)
0.280(2)
0.095(2)
0.406(1)
0.815(2)
0.243(2)
0.402(2)
0.547(2)
0.486(2)
0.625(2)
0.832(2)
0.894(2)
0.757(2)
0.442(2)
0.559(3)
0.589(3)
0.0936(1)
0.3486(2)
0.3949(3)
0.3057(7)
0.3811(7)
0.3677(7)
0.0014(9)
0.522(1)
0.534(1)
0.428(1)
0.318(1)
0.220(1)
0.231(1)
0.335(1)
0.432(1)
0.644(1)
0.720(1)
0.831(1)
0.6559(1)
0.5568(1)
0.9169(2)
0.8479(5)
0.9517(6)
0.9950(5)
0.9282(7)
0.8497(8)
0.7770(8)
0.7457(7)
0.7837(8)
0.7568(8)
0.6903(8)
0.6499(8)
0.6798(8)
0.7239(9)
0.7648(9)
0.718(1)
4.68(4) C14
4.87(4) C15
2.01(8) C16
0.498(3)
0.383(3)
0.355(3)
0.795(3)
1.099(4)
0.1447
0.5020
0.8118
0.5439
0.6674
0.5321
0.2890
0.2883
0.6038
0.9056
1.1243
1.2282
0.3795
0.856(1)
0.781(1)
0.676(1)
0.087(1)
0.051(1)
0.5903
0.1498
0.5064
0.7301
0.8866
0.9351
0.7849
0.6229
0.1231
0.1488
0.1094
0.0048
0.6133
0.628(1)
0.5891(9)
0.6340(9)
0.979(1)
0.928(1)
0.8712
0.7770
0.6522
0.8315
0.7535
0.5948
0.5236
0.6073
0.9871
0.9582
0.8870
0.9012
1.0150
4.7(4)
3.6(4)
2.7(3)
5.9(5)
O1
O2
O3
O17
C3
2.4(2)
2.7(2)
2.3(2)
5.6(3)
1.5(3)
1.8(3)
1.6(3)
1.9(3)
2.0(3)
2.0(3)
2.0(3)
1.7(3)
2.2(3)
3.5(4)
4.7(4)
C18
C19
H3
6.5(5)
1
6
2
6
5
6
6
6
8
8
7
7
4
H7
H10
H12
H13
H14
H15
H16
H181
H182
H191
H192
H30
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
Table 3. Selected bond lengths (d, ), bond angles ( , deg), and torsion angles ( , deg) in the molecule of Va
Bond
d
Bond
d
Angle
Angle
Br1 C8
Br2 C9
P2 O1
P2 O2
P2 O3
P2 C3
1.89(1)
1.87(1)
1.593(9)
1.483(8)
1.544(8)
1.73(1)
1.36(1)
1.34(2)
1.43(2)
1.31(2)
0.98(1)
1.48(2)
1.46(2)
1.42(2)
1.38(2)
1.37(2)
1.38(2)
1.09(1)
C8 C9
1.37(2)
1.38(2)
0.98(1)
1.35(2)
1.40(2)
1.42(2)
1.02(1)
1.40(2)
1.02(2)
1.32(2)
1.03(1)
1.35(2)
1.08(1)
0.89(1)
0.98(2)
0.97(2)
0.98(2)
1.00(2)
O1P2O2
O1P2O3
O1P2C3
O2P2O3
O2P2C3
O3P2C3
P2O1C6
C18O17C19
P2C3C4
P2C3H3
C4C3H3
C3C4C5
C3C4C11
C5C4C11
C4C5C6
C4C5C10
C6C5C10
108.7(5)
107.4(4)
100.9(5)
110.4(5)
117.3(5)
111.2(5)
123.4(8)
109(1)
126.4(9)
114.6(9)
119(1)
118(1)
124(1)
O1C6C5
120(1)
117(1)
122(1)
118(1)
109(1)
121(1)
122(1)
116.9(8)
121.4(9)
121.3(9)
119.8(9)
122(1)
120(1)
118(1)
118(1)
124(1)
118(1)
C9 C10
O1C6C7
C10 H10
C11 C12
C11 C16
C12 C13
C12 H12
C13 C14
C13 H13
C14 C15
C14 H14
C15 C16
C15 H15
C16 H16
C18 H181
C18 H182
C19 H191
C19 H192
C5C6C7
C6C7C8
C6C7H7
C14C15C16
C11C16C15
Br1C8C7
Br1C8C9
Br2C9C8
Br2C9C10
C5C10C9
C5C10H10
C9C10H10
C4C11C12
C4C11C16
C12C11C16
O1 C6
O17 C18
O17 C19
C3 C4
C3 H3
C4 C5
C4 C11
C5 C6
C5 C10
C6 C7
C7 C8
C7 H7
118(1)
122(1)
122(1)
116(1)
Angle
Angle
Angle
Angle
O2P2O1C6
O3P2O1C6
C3P2O1C6
O1P2C3C4
O1P2C3H3
O2P2C3C4
O2P2C3H3
158.67(0.85) C11C4C5C10
81.85(0.92) C3C4C11C12
34.69(0.96) C3C4C11C16
21.90(1.18) C5C4C11C12
160.83(0.86) C5C4C11C16
139.80(1.04) C4C5C6O1
42.92(1.11) O1C6C7H7
12.60(1.64) O3P2C3C4
61.58(1.71) O3P2C3H3
115.43(1.45) P2O1C6C5
119.51(1.29) P2O1C6C7
63.47(1.60) C3C4C5C6
3.14(1.66) C3C4C5C10
17.35(1.50) C11C4C5C6
91.82(1.14) C5C6C7H7
85.45(0.96) H7C7C8Br1
29.31(1.44) H7C7C8C9
152.01(0.89) C4C11C12H12
161.30(1.03)
23.27(1.76)
155.56(1.22)
30.23(2.12)
9.41(1.67) C16C11C12H12 146.96(1.43)
168.42(1.11) H12C12C13C14 153.79(1.36)
169.57(1.07) H12C12C13H13
23.76(1.91)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES WITH ARYLACETYLENES: III.
71
The most interesting was the reaction pattern in
the case of disubstituted trichlorophosphorane VIII
containing two different halogen atoms, chlorine and
bromine, in the phenylene ring. We obtained three
chlorophosphorines IVa, IX, and X in a 3 : 5 : 2
ratio.
7
8
6
Br
O
PCl3 + Ph C CH
5
9
O
Cl
10
VIII
Br
Cl
O
O
Cl
H
P
HCl
Ph
IVa
7
8
9
6
Cl
Br
Cl
O
P
O
Cl
O
O
Cl
H
P
+
+
5
Cl
H
10
Ph
Ph
Fig. 2. System of hydrogen bonds in the complex of ben-
zophosphorine Va with dioxane in the crystal.
IX
X
The structure of IVa and X was determined by
comparison of the 13C NMR spectra of the reaction
mixture with those of authentic samples of IVa and X,
prepared and discussed in detail previously [1]. Hy-
drolysis of the reaction mixture gave phosphonic acids
VIa, VII, and XI. We failed to isolate the individual
acids by the subsequent fractional crystallization of
the precipitate and obtained only fractions rich in one
or another product. Table 1 gives the 13C NMR data
for phosphorine IX and phosphonic acid XI. Since
the orientation of the halogen atoms in the aromatic
ring in these compounds differs from that in IVa and
VIa, the chemical shifts of the corresponding carbon
atoms (C8 and C9) are significantly different. The C8
signal in the spectra of IX and XI is shifted downfield
relative to IVa, X, VIa, and VII owing to the total de-
shielding effect of ipso-Cl, o-Br, and p-vinyl substitu-
ents (134 138 ppm), whereas the C9 signal is shifted
upfield (114 118 ppm) owing to the strong shielding
effect of the ipso-Br and p-O atoms. It should be
noted also that, owing to the deshielding effect of
bromine on the o-position, the C7 signal in the spectra
of IVa and Va is shifted downfield relative to phos-
phorines IX and XI.
Thus, we obtained a very notable result: The bro-
mine atom prefers, to some extent, the p-position rela-
tive to the oxaphosphorine oxygen atom, and the chlo-
rine atom, the m-position. The reaction also yields
a noticeable amount of the product of ipso subtitution
of chlorine for bromine, which is also an indirect
evidence of the preferable location of bromine at
the p-position relative to oxaphosphorine oxygen.
Taking into account the possible reaction schemes
suggested in [1, 3], we can tentatively explain the pre-
ferableness of ipso substitution of oxygen by carbon
at the p-position relative to the chlorine atom in
the benzo fragment of the initial phosphorine. The pos-
sible key intermediates of the reaction are phosphorane
structures with separated charges of types XII and
XIII, whose formation is followed by the attack of
the carbocation at the ipso-C atom to give quinoid
phospholenes XIV and XV. These compounds under-
go cyclization with release of Cl2 and formation of
IVa and IX. Apparently, intermediate XIII is more
preferable owing to greater stabilization of the active
center with the electron-withdrawing m-Cl substituent
and to the weaker destabilizing mesomeric effect of
the p-Br atom. Structure XII is less stable because of
the weaker electron-withdrawing effect of the m-Br
atom and stronger destabilizing mesomeric effect of
the p-Cl atom. This explanation is consistent with
the pKa values of m- and p-bromine- and -chlorine-
substituted phenols [4].
H2O
IVa, IX, X
VIa
HCl
Cl
Cl
O
OH
H
Cl
O
O
O
OH
H
P
P
+
+
Br
Ph
Ph
VII
XI
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001

72
MIRONOV et al.
5
error 5 10 ) in the automatic mode using reference
peaks of perfluorokerosene.
Br
Cl
Cl
Br
O Cl
O Cl
Cl
Cl
Cl
Cl
P
P
O
O
Single crystal X-ray diffraction study of Va,
2 : 1 solvate with dioxane, C14H9Br2O3P 1/2C4H8O2.
Triclinic crystals, space group P1. Unit cell param-
eters (at 20 C): a 4.7932(3), b 11.912 (2), c
CH
CH
+
+
C
C
XII
XIII
Ph
Ph
14.930(2)
;
81.74(1) ,
88.11(1) , 82.78(1) ;
3
V 836.8(2) 3; Z 2; dcalc 1.83 g cm . The unit cell
parameters and the intensities of 3802 reflections,
1146 of which had I 3 , were measured on an Enraf-
Nonius CAD-4 automated four-circle diffractometer
( MoK radiation, graphite monochromator, /2
Br
Cl
Cl
Br
O
O
O
O
Cl
P
Cl
P
Cl
Cl
Cl
Cl
C CH
C CH
XIV
XV
Ph
Ph
scanning,
26.9 ). No decrease in the intensity of
Cl2
Cl2
the three check reflections was observed during the ex-
periment. The absorption was taken into account em-
pirically ( Mo 49.06 cm ): seven reflections with
IVa
IX
1
80 were measured with the -vector rotation with
a 10 step. The structure was solved by the direct
method using the SIR program [5] and refined first in
the isotropic and then in the anisotropic approxima-
tion. The hydrogen atoms were revealed from the dif-
ferential electron density series. Their contribution to
structural amplitudes was taken into account with
fixed positional and isotropic thermal parameters.
The structure was refined to R 0.051 and RW 0.057
It should be noted also that the product X of ipso
substitution of chlorine for bromine can form only
from structure XV in which bromine is in the p-posi-
tion relative to oxygen. Therefore, the ratio of prod-
ucts IVa and IX formed by the competing pathways
is actually 3 : 7, i.e., the p-bromine-substituted isomer
IX prevails.
Thus, dihalo-substituted trichlorophosphoranes II
and VIII react with arylacetylenes as readily as does
unsubstituted phenylenedioxytrichlorophosphorane I,
yielding six-membered heterocycles, benzophospho-
rines. A distinctive feature of the reactions is release
of chlorine and partial formation of phosphorines by
regioselective ipso substitution of chlorine for bro-
mine. When the initial trichlorophosphorane contains
two halogen atoms in the benzo fragment, the prefer-
able pathway is ipso substitution of oxygen by carbon
at the p-position relative to chlorine.
(from 1059 unique reflections with F2
3 ). All
calculations were performed with an AlphaStation
200 computer using the MolEN program package [6].
The intermolecular interactions were analyzed and
the structure drawings obtained using the PLATON
program [7]. The atomic coordinates are given in Ta-
ble 2, and the main geometric parameters, in Table 3.
The molecular geometry and the system of hydrogen
bonds in the crystal are shown in Figs. 1 and 2.
5,6-Dibromo-2-chlorobenzo[d]-1,3,2-dioxaphos-
phole 2,2-dichloride (II). 4,5-Dibromopyrocatechol
(38.1 g) was added in small portions over a period
of 1.5 2 h to a stirred solution ot 29.6 g of PCl5 in
150 ml of benzene. After the evolution of HCl ceased,
the solvent was distilled off, and the residue was
fractionated. Yield of phosphorane II 78%, bp 137
141 C (0.1 mm Hg), mp 84 86 C. IR spectrum, ,
EXPERIMENTAL
The IR spectra were taken on a Specord IR-75
spectrometer (mulls in mineral oil). 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; 31P, 31P {1H}, 101.6 MHz)
spectrometers relative to internal HMDS and external
H3PO4. The 13C NMR spectra were taken at 30 35 C.
1
cm : 1130, 1100, 960 980 (POC); 870, 760, 710. 1H
NMR spectrum (250 MHz, CH2Cl2), , ppm: 7.25. 31
P
NMR spectrum (162.0 MHz, CH2Cl2), P, ppm: 24.5.
Found, %: Br 39.85; Cl 26.30. C6H2Br2Cl3O2P. Cal-
culated, %: Br 39.65; Cl 26.39.
The mass spectra were measured with an MKh-
1310 device interfaced with an SM-4 computer.
The ionizing electron energy was 70 eV, and the elec-
tron collector current, 30 A. The samples were intro-
duced through the direct inlet system heated to 120 C.
Reaction of phosphorane II with phenylacety-
lene. A mixture of 6.8 ml of phenylacetylene and 6 ml
of CH2Cl2 was added dropwise at 10 15 C over a pe-
riod of 10 15 min to a solution of 13.37 g of II in
The m/z values were measured accurately (relative 25 ml of CH2Cl2, bubbled with argon. The resulting
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES WITH ARYLACETYLENES: III.
73
2
mixture was allowed to stand for 8 h at 20 C, after
which the solvent was distilled off. Vacuum distilla-
tion of the residue gave a mixture of isomeric 1,2-
dichlorostyrenes, bp 60 65 C (0.1 mm Hg), with
the characteristics consistent with the published data
[8]. The viscous glassy residue consisting of 88% 6,7-
dibromo-4-phenyl-2-chlorobenzo[e]-1,2-oxaphosphorin-
3-ene 2-oxide (IIIa) and 12% 7-bromo-4-phenyl-
2,6-dichlorobenzo[e]-1,2-oxaphosphorin-3-ene 2-oxide
(IVa) was examined spectroscopically. Mass spectrum,
m/z (Irel, %)3: 439 (2.4), 438 (16.5), 437 (11.9), 436
ppm (J, Hz): 6.27 d (PCH, JPCH 23.0). 31P NMR
spectrum (162.0 MHz, CH2Cl2), P, ppm (J, Hz):
16.2 d (2JPCH 23.0). Compound IVb. 31P NMR
spectrum (162.0 MHz, CH2Cl2), P, ppm (J, Hz):
15.1 d (2JPCH 23.0).
Hydrolysis of the mixture of IIIb and IVb in diox-
ane gave a mixture of 90 92% 6,7-dibromo-2-hy-
droxy-4-(p-chlorophenyl)benzo[e]-1,2-oxaphosphorin-
3-ene 2-oxide (Vb) and 8 10% 7-bromo-2-hydroxy-
4-(p-chlorophenyl)-6-chlorobenzo[e]-1,2-oxaphospho-
rin-3-ene 2-oxide (VIb). Phosphorine Vb was isolated
in a 37% yield by crystallization from dioxane; mp
(74.3), 435 (17.7), 434 (100), 433 (10.3), 432 (44.5)
.
[C14H8Br2ClO2P] [MIIIa]+ ; 395 (1.9), 394 (4.1), 393
1
312 315 C. IR spectrum, , cm : 2540 2580, 2250
(4.1), 392 (26.7), 391 (9.5), 390 (52.5), 389 (7.2),
2300 (POH); 1600, 1590, 1535 (C=C, C=Carom);
1490, 1375, 1330 [ (CH)]; 1250, 1200 1211, 1133,
1115, 1098, 1020 1030, 970, 920, 892, 859, 847,
.
388 (37.1) [C14H8BrCl2O2P] [MIVa]+ ; 404 (0.35),
403 (2.3), 402 (1.3), 401 (9.8), 399 (20.1), 398 (3.8),
397 (12.5) [MIIIa Cl]+; 359 (1.5), 358 (0.46), 357
1
812, 720, 585, 555, 530, 500. H NMR spectrum
(3.4), 356 (3.4), 355 (14.9), 354 (11.9), 353 (14.6)
(400 MHz, ethanol-d6 + 30% DMSO), , ppm (J, Hz):
1
[MIVa
Cl]+. Compound IIIa. H NMR spectrum
7.51 and 7.20 two s (2H, H7 and H10); 7.43 and 7.29
(250 MHz, CDCl3), , ppm (J, Hz): 7.52 and 7.40
3
3
two m (4H, Cl C6H4, AA XX pattern, JAX = JA X
=
two s (H7, H10); 7.43 and 7.28 two m (C6H5); 6.30 d
8.5); 6.23 d (1H, PCH, 2JPCH 17.2). 31P NMR spectrum
(162.0 MHz, DMSO), P, ppm: 3.52. Found, %: C
37.24; H 1.83; P 6.42. C14H8Br2ClO3P. Calculated, %:
C 37.29; H 1.78; P 5.42. From the mother liqour,
after separation of Vb and evaporation followed by
crystallization, we obtained a mixture of Vb and VIb
2
(PCH, JPCH 23.8). 31P NMR spectrum (162.0 MHz,
CDCl3), P, ppm (J, Hz): 17.3 d (2JPCH 24.0).
A mixture of IIIa and IVa (7.2 g) was dissolved in
20 ml of dioxane and treated with 0.3 ml of H2O.
A white clotted precipitate formed, consisting of
90 92% 6,7-dibromo-2-hydroxy-4-phenylbenzo[e]-1,2-
oxaphosphorin-3-ene 2-oxide (Va) and 8 10% 7-bro-
mo-2-hydroxy-4-phenyl-6-chlorobenzo[e]-1,2-oxaphos-
phorin-3-ene 2-oxide (VIa), which was filtered off
and washed with diethyl ether. Recrystallization from
dioxane and ethanol yielded phosphonic acid Va
as a dioxane complex; yield 47%, mp 220 222 C.
1
in a 3 : 1 ratio. Compound VIb. H NMR spectrum
(400 MHz, ethanol-d6 + 30% DMSO), , ppm (J, Hz):
7.52 and 7.06 two s (2H, H7 and H10); 7.43 and 7.29
3
3
two m (4H, Cl C6H4, AA XX pattern, JAX = JA X
=
8.5); 6.24 d (1H, PCH, JPCH 17.0). 31P NMR spec-
2
trum (162.0 MHz, DMSO), P, ppm: 3.6.
5-Bromo-2,6-dichlorobenzo[d]-1,3,2-dioxaphos-
phole 2,2-dichloride (VIII). A solution of 15.03 g of
4-bromo-5-chloropyrocatechol in 100 ml of benzene
was added dropwise with stirring to a solution of
21.9 g of PCl5 in 200 ml of benzene. After the evolu-
tion of HCl ceased, the solvent was distilled off, and
the residue was fractionated. Yield of phosphorane
VIII 69%, bp 156 158 C (0.2 mm Hg). 13C NMR
spectrum (100.6 MHz, CDCl3), C, ppm (in paren-
1
IR spectrum, , cm : 2500 2600, 2250 (POH);
1580, 1536, 1260 1270, 1215, 1187, 1120, 1005,
1
975, 900, 870, 805, 760, 720, 705. H NMR spectrum
(250 MHz, DMF-d7), , ppm (J, Hz): 7.70 s (1H,
H10); 7.50 and 7.46 two m (5H, C6H5); 7.36 s (1H,
2
H7); 6.38 d (1H, PCH, JPCH 17.0); 3.53 s (4H, di-
oxane); 11.30 br. s (1H, OH). 31P NMR spectrum
(162.0 MHz, DMF-d7), P, ppm (J, Hz): 3.0 d (2JPCH
17.0). Found, %: C 41.51; H 2.78; Br 35.07; P 7.01.
C14H9Br2O3P 1/2C4H8O2. Calculated, %: C 41.73;
H 2.82; Br 34.78; P 6.73.
theses are the
values, ppm, calculated according to
C
[9] with the use of base chemical shifts of 2-chloro-
benzo[d]-1,3,2-dioxaphosphole 2,2-dichloride instead
of benzene) (J, Hz): 141.28 (143.2) s (br. d.d) (C5,
By a similar procedure, starting from 6.01 g of II
and 4.05 g of p-chlorophenylacetylene, we obtained
a mixture of 92% 6,7-dibromo-2-chloro-4-( p-chlo-
rophenyl)benzo[e]-1,2-oxaphosphorin-3-ene 2-oxide
(IIIb) and 8% 7-bromo-4-phenyl-2,6-dichlorobenzo-
[e]-1,2-oxaphosphorin-3-ene 2-oxide (IVb). Com-
7
5
10C5
JHC CC 8.0, JHC
4.4); 141.94 (143.3) d (d.d.d)
(C6, JHC
8.0, JHC C 4.5, JPOC 1.1); 112.45
10CC6
7
6
6
(113.3) d (d.d.d) (C7, JPOC C 17.6, JHC 173.0,
6
7
7
1.2); 128.69 (129.8) s (d.d) (C8, JHC
10CCC7
JHC
10CC8
8.6, JHC C 4.5); 115.49 (114.9) s (d.d) (C9, JHC CC
1
7
8
7
9
pound IIIb. H NMR spectrum (60 MHz, CCl4), ,
10C9
8.0, JHC
4.2); 115.54 (116.1) d (d.d.d) (C10,
JPOC C 17.4, JHC 173.6, JHC CCC 0.9). 31P NMR
3
5
10
10
7
10
The ions containing the most abundant isotopes are given.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001

74
MIRONOV et al.
spectrum (162.0 MHz, CH2Cl2), P, ppm: 24.3.
Found, %: Cl 39.87. C6H2BrCl4O2P. Calculated, %:
Cl 39.55.
[MVIa Cl Br]+, 199 (36.8), 163 (100.0) [C13H7]+,
88 (90.4) [C4H8O2]+.
ACKNOWLEDGMENTS
Reaction of phosphorane VIII with phenylacetyl-
ene. A solution of 2.6 ml of phenylacetylene in 40 ml
of CH2Cl2 was added dropwise at 10 15 C over
a period of 10 15 min to a solution of 8.8 g of VIII
in 80 ml of CH2Cl2, bubbled with argon. The mixture
was allowed to stand at 20 C for 8 h, after which
the solvent was distilled off. Vacuum distillation of
the residue gave a mixture of isomeric 1,2-dichloro-
styrenes. The glassy residue was a mixture of 31%
7-bromo-4-phenyl-2,6-dichlorobenzo[e]-1,2-oxaphos-
phorin-3-ene 2-oxide (IVa), 51% 6-bromo-4-phenyl-
2,7-dichlorobenzo[e]-1,2-oxaphosphorin-3-ene 2-oxide
(IX), and 18% 4-phenyl-2,6,7-trichlorobenzo[e]-1,2-
oxaphosphorin-3-ene 2-oxide (X). The products were
The study was financially supported by the Russian
Foundation for Basic Research (project no. 98-03-
33266) and Academy of Sciences of Tatarstan [pro-
ject no. 17-11/99 (F)].
REFERENCES
1. Mironov, V.F., Litvinov, I.A., Shtyrlina, A.A., Gubai-
dullin, A.T., Petrov, R.R., Konovalov, A.I., Azan-
cheev, N.M., and Musin, R.Z., Zh. Obshch. Khim.,
2000, vol. 70, no. 7, pp. 1117 1132.
2. Mironov, V.F., Zyablikova, T.A., Konovalova, I.V.,
Musin, R.A., and Khanipova, M.G., Izv. Ross. Akad.
Nauk, Ser. Khim., 1997, no. 2, pp. 368 370.
1
identified spectroscopically. Compound IX. H NMR
3. Mironov, V.F., Konovalov, A.I., Litvinov, I.A., Gubai-
dullin, A.T., Petrov, R.R., Shtyrlina, A.A., Zyabliko-
va, T.A., Musin, R.Z., Azancheev, N.M., and Il’ya-
sov, A.V., Zh. Obshch. Khim., 1998, vol. 68, no. 9,
pp. 1482 1509.
4. Tablitsy konstant skorosti i ravnovesiya geteroliti-
cheskikh organicheskikh reaktsii (Tables of Rate and
Equilibrium Constants of Heterolytic Organic Reac-
tions), Palm, V.A., Ed., Moscow: VINITI, 1975.
5. Altomare, A., Cascarano, G., Giacovazzo, C., and
Viterbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47,
no. 4, pp. 744 748.
6. Straver, L.H. and Schierbeek, A.J., MolEN. Structure
Determination System, Nonius B.V., 1994, vols. 1 3.
spectrum (250 MHz, CDCl3), , ppm (J, Hz): 6.38 d
2
(PCH, JPCH 23.8). 31P NMR spectrum (CDCl3),
,
P
ppm: 15.4.
The mixture of IVa, IX, and X was dissolved in
100 ml of dioxane and treated with 0.3 ml of water.
Within 5 10 h, an abundant white precipitate formed,
consisting of phosphorines VI, VII, and XI; it was
recrystallized from ethanol, methanol, and dioxane.
Mixtures of VI, VII, and XI (complexes with di-
oxane) in various ratios were obtained. Compound
1
XI. H NMR spectrum (250 MHz, ethanol-d6), , ppm
2
(J, Hz): 6.10 d (PCH, JPCH 17.6). 31P NMR spectrum
(ethanol-d6), P, ppm (J, Hz): 4.36 d (2JPCH 17.6).
Compounds VIa and VII were obtained by indepen-
dent synthesis according to [1]. Mass spectrum of
the complex of VIa with dioxane, m/z (Irel, %): 375
7. Spek, A.L., Acta Crystallogr., Sect. A, 1990, vol. 46,
no. 1, pp. 34 39.
8. Debon, A., Masson, S., and Thuillier, A., Bull. Soc.
Chim. Fr., 1975, nos. 11 12, pp. 2493 2498.
(1.8), 374 (12.0), 373 (8.2), 372 (50.4), 371 (9.3), 370
.
(38.7) [MVIa]+ , 369 (3.0) [MVIa
[MVIa
H]+, 353 (3.0)
Cl]+, 256 (23.7)
9. Ewing, D.F., Org. Magn. Reson., 1979, vol. 12, no. 9,
OH]+, 335 (2.1) [MVIa
pp. 499 524.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 1 2001