Reaction of trihalo(phenylenedioxy)phosphoranes with arylacetylenes: VII. Regiochemistry of reaction 2,2,2-tribromo-5-halobenzo[d]-[1,3, 2λ5]dioxaphospholes with arylacetylenes

Article abstract of DOI:10.1007/s11176-005-0269-z

It was for the first time shown that 2,2,2-tribromo- and 2,2-dibromo-2-fluoro-5-halobenzo[d]-[1,3,2λ⁵]dioxaphospholes react with arylacetylenes with preferential formation of heterocycles monohalogenated in the benzo fragment, viz. 4-aryl-2-bromo(fluoro)-7- halobenzo[e][1,2]oxaphosphinines. Their structure was established by NMR spectroscopy. By varying in such a way the nature of the halogen at the phosphorus atom one can obtain 6- or 7-halo-substituted regioisomers of benzo[e][1,2]oxaphosphinines. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11176-005-0269-z

Russian Journal of General Chemistry, Vol. 75, No. 4, 2005, pp. 541 548. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005,
pp. 579 586.
Original Russian Text Copyright
2005 by Mironov, Azancheev, Musin, Konovalov.
Reaction of Trihalo(phenylenedioxy)phosphoranes
with Arylacetylenes: VII.1 Regiochemistry
of Reaction 2,2,2-Tribromo-5-halobenzo[d]-
5
[1,3,2 ]dioxaphospholes with Arylacetylenes
V. F. Mironov, N. M. Azancheev, R. Z. Musin, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received October 1, 2003
Abstract It was for the first time shown that 2,2,2-tribromo- and 2,2-dibromo-2-fluoro-5-halobenzo[d]-
[1,3,2 5]dioxaphospholes react with arylacetylenes with preferential formation of heterocycles monohalo-
genated in the benzo fragment, viz. 4-aryl-2-bromo(fluoro)-7-halobenzo[e][1,2]oxaphosphinines. Their struc-
ture was established by NMR spectroscopy. By varying in such a way the nature of the halogen at the phos-
phorus atom one can obtain 6- or 7-halo-substituted regioisomers of benzo[e][1,2]oxaphosphinines.
We recently showed that the reactions of a readily
available P(V) halide, 2,2,2-trichlorobenzo[d][1,3,2 ]-
If starting trichlorobenzophosphole VII contains
a 5-Br substituent, chlorine is introduced in the pre-
ferentially formed benzophosphinine occurs so that
both halogens are ortho to each other and para to the
fused phosphinine ring [4].
5
dioxaphosphole (I), with arylacetylenes or propargyl
chloride give benzo[e][1,2]oxaphosphinines II and
III. The reactions occur in mild conditions and in-
volve formation of a phosphorus carbon bond and
phosphoryl group, as well as ipso-substitution of
oxygen by carbon in the benzene ring. Depending on
the nature of the alkyne, chlorine is regioselectively
introduced para (with phenylacetylene) or ortho (with
propargyl chloride) to the oxygen atom of the phos-
phinine ring [2, 3].
O
7
Br
Cl
O
O
P
PhC CH
[ HCl]
Cl
5
PCl3
6
Br
O
Ph
VII
VIII
In the present work we for the first time studied
reactions of P,P,P-tribromobenzophospholes halo-
substituted in the phenylene fragment (compounds Xa
and Xb) with arylacetylenes. Unlike what is observed
with their chlorine analogs, the bromine atom in such
tribromophosphoranes is not so favorably disposed
toward migration into the phenylene fragment of the
benzophosphinine formed, which might allow prepara-
tion of regioisomers (with respect to the position of
the halogen atom) of compounds II and V.
Cl
8
O
O
O
O
P
P
Cl
Cl
6
Cl
Ph
II
CH2Cl
III
Unlike compound I, 2,2,2-tribromobenzo[d]-
5
[1,3,2 ]dioxaphosphole (IV) reacts with arylacety-
lenes to form benzophosphinines V and VI, the latter
having no bromine in the benzene ring [1].
Phosphorane Xa (
188.5 ppm, CH2Cl2) con-
P
taining chlorine in the benzene ring and obtained from
derivative IXa reacts with phenylacetylene to form
preferentially (more than 65%) a single benzophos-
O
O
O
O
P
P
phinine. In the 31P NMR spectrum, the product gives
Br
Br
6
a signal at
5.8 ppm (2JPCH 27.0 Hz) and in the H
1
Br
P
Ar
Ar
NMR spectrum (250 MHz, CDCl3), a downfield
2
V
VI
doublet ( 6.20 ppm) with the same JPCH constant.
The 13C NMR spectrum of the reaction mixture freed
of volatile products in a vacuum, like the spectrum of
1
For communication VI, see [1].
1070-3632/05/7504-0541 2005 Pleiades Publishing, Inc.

542
MIRONOV et al.
13C NMR spectra ( C, ppm, J, Hz) of compounds XIa, XIIIa, XIIIc, XIVb, and XVIIa XIXa
Atom
XIa, CDCl3 CH2Cl2, 1: 1
XIIIa,a ethanol-d6 DMSO, 3: 1
C3
116.18 d (d.d) (141.8, PC3; 172.1, HC3)
155.02 d (m) (2.0, PCC4)
114.83 d (d.d) (174.6, PC3; 164.2, HC3)
153.60 d (m) (2.1, PCC4)
C4
C4a
120.01 d (m) (18.7, PCCC4a)
121.56 d (d.d.d.d) (16.5, PCCC4a; 7.8 8.0, HC6C5C4a;
7.8 8.0, HC3C4C4a; 4.9, HC8C8aC4a)
C5
C6
130.56 d (br.d) (166.7, HC5; 1.5, POC8aC4aC5)
130.58 d (br.d) (164.0, HC5; 1.2, POC8aC4aC5)
125.21 d (br.d.d) (169.8, HC6; 5.1, HC8C7C6; 1.0, 124.16 d (br.d.d) (169.8, HC6; 5.4, HC8C7C6; 0.8,
POC8aC4aC5C6)
137.72 s (m)
POC8aC4aC5C6)
C7
136.50 s (d.d.d) (12.0 12.1, HC5C6C7; 4.3 4.4, HCC7;
1.6, HCC7)
C8
119.88 d (d.m) (166.0, HC8; 8.4, POC8aC8; 9.8, 119.93 d (d.d.d) (168.4, HC8; 7.5, POC8aC8; 4.8,
HC6C7C8)
HC6C7C8)
C8a
C9
151.30 d (m) (8.4, POC8a)
152.64 d (d.d.d) (7.0 7.1, POC8a; 9.1, HC5C4aC8a; 4.6,
HC8C8a)
136.57 d (m) (20.9, PC3C4C9)
139.07 d (d.t.d) (18.8, PC3C4C9; 6.5, HC11C10C9; 6.0,
HC3C4C9)
C10
128.10 s (d.d) (162.6, HC10; 7.2, HCCC10; 6.9, HCCC10) 128.79 s (br.d.d.d) (160.5, HC10; 6.3, HC10 CC10; 6.2,
HC12CC10)
C11
C12
128.69 s (HC11; 7.1, HC11 CC11)
129.26 s (br.d.d) (160.6, HC11; 6.6, HC11 CC11)
129.59 s (d.t) (161.4, HC12; 7.4 7.5, HC10CC12)
129.74 s (d.d) (162.0, HC12; 6.7, HC10CC12)
the crystalline substance isolated from this reaction
mixture, contains doublet of doublets
bromine in the phenylene fragment. The fact that the
signal of C7 is downfield ( 137.72 ppm) from that of
C6 ( 130.41 ppm) [1] suggests that chlorine locates
in the 7 position of benzophosphinine XIa. Analog-
ously, compounds XIb and XIc are preferentially
formed from 5-chlorophosphole Xa and p-tolylacety-
lene, as well as from 5-bromophosphole Xb [pre-
pared from phosphorobromidite IXb] and phenyl-
acetylene.
a
(
C
1
116.18 ppm) with the coupling constants JPC 141.8
1
and JCH 172.1 Hz, whose values are close to those in
compounds V and VI [2]. The spectrum contains six
more signals belonging to carbon atoms directly
coupled with protons, and five signals of carbon
atoms not involved into such interaction. These spec-
tral data correspond to product XIa which contains no
8
O
8a
O
X
O
7
X
O
O
O
O
O
P
P
Br2
+
YC6H4C CH
[ HBr], [ Br2]
Br
Br
PBr
PBr3
4
9
Br
3
6
X
X
4a
5
C6H4Y
XIIa XIIc
10
11
IXa, IXb
Xa, Xb
12
Y
XIa XIc
X = Cl (IXa, Xa); Br (IXb, Xb); Y = H, X = Cl (a); Y = Me, X = Cl (b); Y = H, X = Br (c).
Compounds XIIa XIIc in small amounts (15
20%) were detected by spectral methods. In the 31P
NMR spectra, they give doublets (2JPCH 26.0
cis- trans-1,2-dibromo-1-phenylethenes and 1-bromo-
1-phenylethene, whose spectral parameters agree with
published data [2, 5].
27.5 Hz) at
4.8 (XIIa) and 4.7 ppm (XIIb, XIIc).
P
By hydrolysis in dioxane benzophosphinines XIa
XIc and XIIa XIIc were converted to hydroxy deriva-
tives XIIIa XIIIc and XIVa XIVc, respectively. The
Bromine and hydrogen bromide evolved in the
course of the reaction add to phenylacetylene to give
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REACTION OF TRIHALO(PHENYLENEDIOXY)PHOSPHORANES WITH ARYLACETYLENES: VII.
Table (Contd.)
543
Atom
C3
C4
XIIIc,b ethanol-d6 DMSO, 2: 1
XIVb,c DMSO-d6
115.51 d (d.d) (171.8, PC3; 164.0, HC3)
153.11 d (m) (2.0, PCC4)
118.15 d (d.d) (168.0, PC3; 161.8, HC3)
148.46 br.s (br.m)
C4a
122.10 d (d.d. d.d) (16.5, PCCC4a; 8.0, HC6CC4a; 8.0, 123.12 d (d.d. d) (16.7, PCCC4a; 8.1, HC3CC4a; 5.7,
HC3CC4a; 4.8, HC8CC4a) HC8CC4a)
C5
C6
C7
130.75 d (br.d.d) (160.8, HC5; 4.2, HC6C5; 1.2, 131.92 s (d) (167.4, HC5)
POCCC5)
127.09 d (br.d.d) (170.9, HC6; 7.3, HC8CC6; 0.9, 114.21 s (d.d) (5.1, HC8CC6; 3.6, HC5C6)
POCCCC6)
124.19 s (d.d.d) (13.5, HC5CC7; 4.1, HC8C7; 2.7, 134.02 s (d.d) (10.4, HC5CC7; 4.2, HC8C7)
HC6C7)
C8
122.84 d (d.d.d) (169.3, HC8; 7.3, POCC8; 5.7, HC6CC8; 120.86 d (d.d) (170.0, HC8; 7.0, POCC8)
1.3, HC5CCC8)
C8a
C9
152.66 d (d.d.d.d) (7.2, POC8a; 10.0, HC5CC8a; 4.3, 151.17 d (d.d.d) (7.2, POC8a; 10.0, HC5CC8a; 4.4,
HC8C8a; 1.7, HCCCC8a)
HC8C8a)
139.05 d (d.t.d) (18.6, PCCC9; 6.5, HC11C10C9; 6.5, 134.82 d (m) (18.2, PCCC9)
HC3C4C9)
C10
C11
129.32 s (br.d.d.d) (161.7, HC10; 6.7, HC10 CC10; 6.7 127.87 s (br.d.d.d) (160.5, HC10; 6.0 HC10 CC10)
7.0, HC12CC10)
128.86 s (br.d.m) (163.3, HC11; 6.9, HC11 CC11)
129.14 s (br.d.m) (160.0, HC11; 5.2 5.5, HC11 CC11;
5.2 5.5, HCCC11)
C12
Atom
C3
129.61 s (br.d.t) (161.5, HC12; 7.5, HC10CC12) 138.37 s (q.t) (7.0 7.1, HC10HC12; 7.0 7.1, HCC12)
XVIIa, CDCl3 CCl4, 1: 1
XVIIIa, CDCl3 CCl4, 1: 1
XIXa,a CDCl3 CCl4, 1: 1
107.62 d.d (d.d.d) (179.4, PC3; 169.7, 108.80 d.d (d.d.d) (178.9, PC3; 108.97 d.d (d.d.d) (178.6, PC3;
HC3; 28.2, FPC) 169.8, HC3; 28.2, FPC) 169.9, HC3; 28.8, FPC)
158.80 d.d (m) (2.5, PCC4; 2.6, 157.74 d.d (m) (2.5, PCC4; 2.5, 158.42 d.d (m) (2.8, PCC4; 3.4,
FPCC) FPCC) FPCC)
C4
C4a
119.76 d (d.d.d.d) (17.4, PCCC4a; 122.36 d (d.d.d) (17.5, PCCC4a; 8.4, 122.36 d (m) (17.1, PCCC4a)
8.0, HC6C5C4a; 8.1, HC3C4C4a; 4.6, HC3C4C4a; 5.3, HC8C8aC4a)
HC8C8aC4a)
C5
C6
C7
C8
C8a
130.57 d (br.d) (165.8, HC5; 1.2, 133.64 d (br.d) (170.0, HC5; 2.1, 130.81 d (d.m) (1.2, POC8aC4aC5)
POC8aC4aC5)
POC8aC4aC5)
124.90 s (d.d) (170.1, HC6; 5.4, 117.93 d (br.d.d) (8.2, HC8C7C6;
HC8C7C6) 2.1, POC8aC4aC5C6; 4.3, HCC6)
137.69 s (d.d.d) (12.9, HC5C6C7; 3.6, 137.81 s (d.d) (10.1, HC5C6C7; 4.6, 131.96 s (br.d.d) (169.8, HC7; 6.9,
HC6C7; 3.8, HC8C7) HC8C7) HC5CC7)
119.62 d (d.d.d) (170.1, HC8; 8.6, 121.09 d (d.d) (171.1, HC8; 8.3, 120.74 d (d.d) (168.2, HC8; 8.3,
POC8aC8; 5.0, HC6C7C8) POC8aC8) POC8aC8)
151.20 d (d.d.d.d) (7.6, POC8a; 9.6, 149.89 d (d.d.d) (7.9, POC8a; 10.7, 149.39 d.d. (d.d.d.d.d) (8.3, POC8a;
HC5C4aC8a; 5.0, HC8C8a; 1.1,
HC3C4C4aC8a; 0, FPOC)
HC5C4aC8a; 4.9, HC8C8a; 0, FPOC) 10.2, HC5C4aC8a; 8.6, HC7C8C8a;
4.4, HC8C8a; 1.0, FPOC)
C9
137.15 d.d (m) (18.6, PC3C4C9; 1.1, 136.54 d (m) (20.4, PC3C4C9; 7.2, 136.84 d (m) (20.4, PC3C4C9)
FPCCC; 7.1, HC11C10C9; 6.5,
HC3C4C9)
HC11C10C9; 6.5, HC3C4C9)
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544
MIRONOV et al.
Table (Contd.)
Atom
C10
XVIIa, CDCl3 CCl4, 1: 1
XVIIIa, CDCl3 CCl4, 1: 1
XIXa,a CDCl3 CCl4, 1: 1
128.06 s (br.d.m) (161.6 162.5, HC10; 127.97 s (br.d.m) (162.3, HC10; 128.03 s
5.6 6.0, HC10 CC10; 5.6 6.0,
HC12CC10)
5.6 6.0,
HC10 CC10;
5.6 6.0,
HC12CC10)
C11
C12
128.90 s (br.d. m) (162.5, HC11; 6.3, 129.01 s (br.d.m) (162.5, HC11; 6.3, 128.89 s
H
11 CC11)
H11 CC11)
129.82 s (d.t) (162.0, HC12; 7.6, 130.13 s (d.t) (162.1, HC12; 7.6, 129.92 s
HC10CC12)
HC10CC12)
a
1
3
2
b
1
67.31 s (t.t.t) [CH O (dioxane),
J
142.7,
J
2.1 2.2,
HCOC
J
2.1 2.2]. 67.09 s (t.t.t) [CH O (dioxane),
J
142.6,
CH
2
HC
HCC
2
3
c
1
3
J
2.1].
20.51 s (q.t) (CH ,
J
126.6,
J
4.2).
HCOC
3
HC
HCCC
31P NMR signal of these compounds appears slightly
upfield (3.0 3.5 ppm). The structure of the isolated
major products XIIIa and XIIIc is confirmed by their
13C NMR spectra (see the table). Hence, the chemical
shifts of the C5 (d.d.d.d), C6 (d.d.d), C7 (d.d.d), and
C10 (br.d) signals and the coupling constants with
protons and phosphorus are fully consistent with the
cyclic structure of compounds XIIIa and XIIIc, as
well as the meta position of chlorine (bromine) with
respect to the phosphinine oxygen atom.
O
O
X
O
X
O
H2O
P
P
+
OH
XIa, XIc + XIIa, XIIc
OH
[ HBr]
Br
C6H4Y
C6H4Y
XIIIa XIIIc
XIVa XIVc
X, Y = Cl, H (a); Cl, Me (b), Br, H (c).
We failed to isolate minor products XIVa and
XIVc pure but could obtain enriched fractions by frac-
tional crystallization. Parameters of the 13C NMR
spectra of compounds XIVa and XIVc agree with
those reported in [5]. Unlike phenyl derivatives XIVa
and XIVc, the minor isomer XIVb prepared from
p-tolylacetylene was isolated pure by crystallization
from dioxane. Its structure was established by means
of 13C NMR spectroscopy (see table). The spectrum
contains seven carbon signals not split by direct C H
spin spin coupling and four signals that show such
splitting. Such spectral pattern and the fairly upfield
location of the C6 signal (114.22 ppm), associated
with shielding from the ipso-bromine and para-
oxygen atoms, completely agree with structure XIVb.
of the products is preferred (53 60%). Its fraction in-
creases when the reaction is carried out in a more
dilute solution. In the 31P NMR spectrum, the prod-
ucts (reaction with phenylacetylene, synthesis in a
concentrated solution) are characterized by doublets
1
2
P1
of doublets with
4.1 (53%, JPF 1065.4, JP4dCH
1
2
P2
P3
19.3), 3.7 (24%, JPF 1064.8, JPCH 19.1), and
1
2
3.2 ppm (24%, JPF 1067.7, JPCH 18.7 Hz). Analog-
1
ous doublets are present in the H NMR spectrum
(250 MHz): 6.14 (2JPCH 19.5), 2 6.18 (2JPCH 19.0),
1
and
6.19 ppm (2JPCH 18.8 Hz). Since we failed to
3
isolate any of these compounds pure, the reaction
mixture freed of volatile products in a vacuum
(0.05 mm Hg) was investigated by mass spectrometry
and 13C NMR spectroscopy. The electron impact mass
spectra contain only two peaks at m/z 372 and 294,
assigned to the molecular ions [M1]+ and [M2]+ The
exact masses of these ions (given are ions containing
the most abundant isotopes) are 371.9230 and
293.9931, which is nicely consistent with those cal0
culated from the elemental compositions C14H8BrCl
FO2P and C14H9ClFO2P: 371.9118 (M1) and 294.0012
(M2), respectively. Considering the 13C NMR spectral
Unlike tribromophospholes Xa and Xb, 2,2-di-
bromo-5-chloro-2-fluorobenzo[d][1,3,2]dioxaphos-
phole (XVI) prepared from P(III) derivative XV reacts
with phenyl- and p-tolylacetylene in a more com-
plicated manner to give three benzophosphinines are
formed, whose ratio slightly varies, depending on the
concentration of the starting reagents. In any case, one
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REACTION OF TRIHALO(PHENYLENEDIOXY)PHOSPHORANES WITH ARYLACETYLENES: VII.
(a)
545
C3
C3
XVIIa
1JPC
C3
XVIIIa
XIXa
1JPC
1JHC
1JPC
1JHC
1JHC
2JFPC
2JFPC
2JFPC
111.0
109.5
108.0
106.5
C, ppm
(b)
C8
C6
3
6
XVIIa
3JPCCC8
JPCCC
C8
XVIIIa
C4a
C8
XVIIIa
3JPCCC8
XIXa
XVIIa
C4a
3JPCCC8
3JPCCC4a
XVIIIa
C4a
C6
3JPCCC4a
XIXa
3JPCCC4a
122.4
121.4
120.4
119.4
118.4
C, ppm
13
13
1
Fig. 1. Upfield regions of the (a) C and (b) C { H} NMR spectra of the mixture of compounds XVIIa XIXa.
data (see table), we assigned to the resulting com-
pounds the structures of benzophosphinines XVIIa
which allows the spectra to be assigned completely.
The major product XVIIa contains no other substi-
tuents in the phenylene fragment than 7-Cl, which is
easy to establish from the chemical shift of the C7
3
P1
XIXa (chemical shifts
P , respectively). Figu-
res 1a and 1b show the upfield regions of the 12C and
13C{1H} NMR spectra of the mixture of compounds
XVIIa XIXa. The signals are fairly well resolved,
signal (
137.69 ppm) and its muliplicity (d.d.d,
C
3
2
2
5
7
6
7
8 7
JHC CC 12.9, JHC C = JHC C 3.6 3.8 Hz). The
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

546
MIRONOV et al.
multiplicity of the C7 signal of compound XVIIIa (
137.81 ppm, d.d, JH CC 10.1 Hz, JHC C 4.6 Hz)
117.93 ppm). The presence of fluorine on phosphorus
C
3
2
5
7
8 7
in compounds XVIIa XIXa can also be inferred from
agrees with the presence of bromine in the 6 position.
the shape of the C4 signal ( 157.74 158.8 ppm, d.
C
The C6 signal appears upfield from the C7 signal (
d, JFCC 2.5 3.4 Hz, JPCC 2.5 Hz).
2
3
C
F
O
O
Br2
P F
PBr2
Cl
Cl
O
O
XV
XVI
[ HBr], [ Br2]
YC6H4C CH
O
F
O
O
O
F
7
7
O
Cl
Br
Cl
O
+
P
+
P
P
F
Cl
6
6
C6H4Y
XIX
C6H4Y
XVIII
C6H4Y
XVII
Y = H (a), Me (b).
Other parameters of the 13C NMR spectrum of
compound XIXa (see table) are much alike those of
compound II [2].
chloride, to migrate into the benzo fragment of the
benzophosphinine system in the course of reaction of
P,P,P-tribromo- and P,P,P-trichlorobenzo[d][1,3,2]-
dioxaphospholes with arylacetylenes and, on the other,
on selective ipso substitution of the oxygen atom
located para to the halogen atom that is already
present in the benzo fragment of the starting
phosphole.
Hydrolysis of the mixture of fluorophosphinanes
XVIIa XIXa gave hydroxy derivatives XIIIa and
XIIIb, XIVa and XIVb, and XXa and XXb, respec-
tively.
O
O
P
EXPERIMENTAL
OH
Cl
6
The IR spectra were measured on a Specord M-80
spectrometer for suspensions in mineral oil between
KBr plates. The NMR spectra were recorded on
Bruker MSL-400 (13C, 100.6; 31P 162.0 MHz) and
Bruker WM-250 (1H, 250 MHz) spectrometers in
CDCl3 or ethanol-d6 solutions at 20 C and in DMSO-
d6 solutions at 45 C. The mass spectrum was obtained
on an MX-1310 instrument (ionizing energy 70 eV,
collector current 30 A) with direct inlet (T 120 C).
The exact masses were measured automatically by the
reference peaks of perfluorokerosene.
C6H4Y
XXa, XXb
Y = H (a), Me (b).
By fractional crystallization we could only isolate
a small amount of phosphinane XIVb, as well as a
mixture of compounds XIII (most abundant), XIV,
and XX. The spectral parameters of 6-chloro-substi-
tuted hydroxyphosphinines XXa and XXb are similar
to those of the pure compounds prepared previously
[2].
2-Bromo-5-chlorobenzo[d][1,3,2]dioxaphosphole
(IXa). A mixture of 23.6 g of 4-chloropyrocatechol,
31.1 ml of PBr3, and 3-5 drops of water was heated
with strirring (90 110 C) for 40 min and then frac-
tionated. Yield of dioxaphosphole IXa 89%,
bp 82 84 C (0.1 mm Hg). 31P {1H} NMR spectrum:
Hence, the possibility of the preferential formation
of regioisomers of benzo[e][1,2]oxaphosphinanes
containing the chlorine atom para to the heteroring
carbon atom, via the use of tribromophosphoranes like
X and XVI that already have a halogen atom in the
benzene ring, has been demonstrated for the first time
This synthetic result is based, on the one side, on the
weaker ability of the bromide anion, compared to
177.6 ppm.
P
2,5-Dibromobenzo[d][1,3,2]dioxaphosphole
(IXb) was obtained analogously from 11.86 g of
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REACTION OF TRIHALO(PHENYLENEDIOXY)PHOSPHORANES WITH ARYLACETYLENES: VII.
547
4-bromopyrocatechol, 6.4 ml of PBr3, and 3 5 drops
of water. Yield 91%, bp 92 94 C (0.1 mm Hg). 31P
26.3 Hz) (XIIb. This material was dissolved in 25 ml
of dioxane, and 1.0 ml of H2O was added. After 5
7 days, a little (0.11 g) 6-bromo-7-chloro4-p-tolyl-
benzo[e][1,2 5]oxaphosphinin-2-ol 2-oxide (XIV)
{1H} NMR spectrum (CH2Cl2):
178 ppm.
P
5-Chloro-2-fluorobenzo[d][1,3,2]dioxaphosphole
(XV) was prepared by fluorination of 5-chloro-2-flu-
orobenzo[d][1,3,2]dioxaphosphole [3] (15.2 g) with
18 g of antimony trifluoride. Yield 61%, bp 72 75 C
1
precipitated as white crystals, mp > 300 C. H NMR
spectrum (400 MHz, DMSO-d6), , ppm (J, Hz):
7.58 s (H5), 7.26 m and 7.33 m (C6H4, AA XX spec-
3
3
trum, JAX = JA X 8.1), 7.31 s (H8), 6.29 d (PCH,
2JPCH 17.3), 2.40 s (CH3). 31P NMR spectrum
(DMSO-d6), P, ppm: 3.7 d (2JPCH 17.4 Hz). Found,
%: C 46.63; H 3.07. C15H11BrClO3P. Calculated, %:
C 46.69; H H 2.85. Prolonged crystallization of the
mother liquor (more than a month) gave 2.21 g of a
(15 mm). 31P {1H} NMR spectrum (CH2Cl2),
,
P
ppm: 125.4 d (1JPF 1313.7 Hz).
Reaction of 2,2,2-tribromo-5-chlorobenzo[d]-
5
[1,3,2 ]dioxaphosphole (Xa) with phenylacetylene.
Phenylacetylene, 6.1 ml, was added at 0 10 C under
vigorous bubbling of argon to 12.06 g of phosphorane
5
10:1 mixture of 7-chloro-4-p-tolylbenzo[e][1,2 ]-
Xa (
188.5 ppm, CH2Cl2) prepared from 7.39 g of
oxaphosphinin-2-ol 2-oxide (XIIIb) and compound
P
1
dioxaphosphole IXa and 1.57 ml of bromine in 25 ml
of CH2Cl2 ( 10 to 3 C), and the resulting mixture
was kept at 20 C for 8 h. 2-Bromo-7-chloro-4-phe-
nylbenzo[e][1,2 5]oxaphosphinine 2-oxide (XIa)
( 0.6 g) precipitated and was filtered off under argon,
washed with cold CH2Cl2 and dried. mp 174 175 C.
31P {1H} NMR spectrum (CH2Cl2), P, ppm: 5.8 d
(2JPCH 27.0 Hz). The filtrate was evaporated in a
vacuum (first at 12 and then 0.1 mm Hg). The glassy
residue and the crystals were dissolved in 20 ml of
dioxane, and 0.6 ml of water was added. After 5
XIVb. H NMR spectrum (400 MHz, DMSO-d6), ,
ppm (J, Hz) of compound XIIIb: 7.38 d.d (H8,
4
4
6
8
8
JH CCCH 2.2, JPOCCH 1.5), 7.25 m and 7.31 m
3
3
(C6H4, AA XX spectrum, JAX = JA X 8.1), 7.20 d.d
(H6, JH CCH 8.5, JH2CCCH 2.2), 7.12 d (H5, JH CCH
3
4
3
5
6
8
6
6
5
8.5), 6.23 d (PCH, JPCH 17.8), 2.39 s (CH3). 31P
NMR spectrum (DMSO-d6) of compound XIIIb,
,
P
ppm: 4.7 d (2JPCH 18.0 Hz).
5
Reaction of 2,2,2,5-tetrabromobenzo[d][1,3,2 ]-
dioxaphosphole (Xb) with phenylacetylene. Phenyl-
acetylene, 8.73 ml, was added at 0 10 C under vi-
gorous bubbling of argon to 18.23 g of phosphorane
5
10 days, 7-chloro-4-phenylbenzo[e][1,2 ]oxaphos-
phinin-2-ol 2-oxide (XIIIa) precipitated as white
Xb (
189.2 ppm, CH2Cl2) prepared from 11.86
crystals (adduct with dioxane), yield 2.2 g, mp 198
dioxapPhosphole IXb and 2.02 ml of bromine in 40
ml of CH2Cl2 ( 10 to 3 C). The solvent, dibromo-
styrenes, and excess acetylene were removed from the
reaction mixture in a vacuum first at 12 and then
0.1 mm Hg. The glassy residue, a 8:3 mixture of
2,7-dibromo-4-phenylbenzo[e][1,2 5]oxaphos-
phinine 2-oxide (XIc) and 2,6,7-dibromo-4-phenyl-
1
201 C. IR spectrum, , cm : 3056, 2540 2550 v.br,
2230 2290 v.br, 1625 1627, 1592, 1576, 1549, 1485,
1435, 1400, 1337, 1248, 1219, 1182 sh., 1078, 1020,
964, 930, 885, 860, 825, 758, 743, 725, 714, 699,
670, 651, 610, 578, 565, 542, 510, 474, 439, 412. 31P
NMR spectrum (DMSO), P, ppm: 3.5 d (2JPCH
17.5 Hz). Found, %: C 56.97; H 4.24; P 9.19; Cl
10.61. C14H10ClO3P 1/2C4H8O. Calculated, %: C
57.05; H 4.16; P 9.21; Cl 10.55. Additional crystal-
lization gave an additional 2.1 g of the dioxane adduct
of phosphinine XIIIa.
5
benzo[e][1,2 ]oxaphosphinine 2-oxide (XIIc), was
characterized by spectral methods. H NMR spectrum
1
(250 MHz, CDCl3) of compound XIc, , ppm (J, Hz):
2
6.26 d (PCH, JPCH 25.6). 31P {1H} NMR spectrum
(CH2Cl2), P, ppm: 3.8 d (2JPCH 25.0 Hz) (XIc, 6.47 d
(2JPCH 25.6 Hz) (XII. This material was dissolved in
20 ml of dioxane, and 1.0 ml of H2O was added. After
Reaction of dioxaphosphole Xa with p-tolyl-
acetylene. p-Tolylacetylene, 9.5 g, was added at 0
10 C under vigorous bubbling of argon to 16.48 g of
phosphorane Xa prepared from 10.1 g of phosphole
IXa and 2.0 g of bromine in 50 ml of CH2Cl2 ( 10 to
3$oC). The solvent, dibromostyrenes, and excess
acetylene were removed from the reaction mixture in
a vacuum first at 12 and then 0.1 mm Hg. The
glassy residue, a 7:1 mixture of 2-bromo-7-chloro-4-
5
9 12 days, 7-bromo-4-phenylbenzo[e][1,2 ]oxa-
phosphinin-2-ol 2-oxide (XIIIc) precipitated as white
crystals (adduct with dioxane), yield 2.2 g, mp 220
1
222 C. IR spectrum, , cm : 2670 v.br, 2530 2560
v.br, 2250 2300 v.br, 2150 v.br, 2150 v.br, 1643,
1590, 1576, 1545, 1400, 1340, 1250 1260, 1210,
1195, 1182, 1160, 1125, 1087, 1082, 1015, 1002, 964,
930, 895, 875, 865, 830, 768, 744, 725, 715, 700, 667,
644, 618, 575, 565, 525, 510, 475, 440. 1H NMR spec-
5
p-tolylbenzo[e][1,2 ]oxaphosphinine 2-oxide (XIb)
5
and 2,6-dibromo-7-chloro-4-p-tolylbenzo[e][1,2 ]-
oxaphosphinine 2-oxide (XIIb), was characterized
trum (300 MHz, ethanol-d6), , ppm (J, Hz): 7.48 m
4
by spectral methods. 31P {1H} NMR spectrum,
,
and 7.34 m (C6H5), 7.38 d (H8, JH CCCH 2.0),
6
8
P
ppm: 6.0 d (2JPCH 26.4 Hz) (XIb), 4.7 d (2JPCH
7.25 d.d (H6, JH CCCH 2.0, JH CCH 8.5), 7.06 d (H5,
4
3
6
8
5
6
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

548
MIRONOV et al.
3
2
JH CCH 8.5), 6.16 d (PCH, JPCH 17.9). 31P NMR
spectrum (DMF), P, ppm: 3.6 d (2JPCH 17.8 Hz).
Found, %: C 50.07; H 3.48; P 7.92; Br 21.51.
C14H10BrO3P 1/2C4H8O2. Calculated, %: C 50.39; H
3.67; P 8.14; Br 21.0. The mother liquor was evapo-
rated by half to obtain an additional 2.2 g of the di-
oxane adduct of phosphinine XIIIc.
water in dioxane. Subsequent crystallization gave
phosphinine XIVb and a mixture of benzophosphori-
nes XIIIb, XIVb, and XXb in various ratios.
6
5
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 03-03-
32542) and the Program for Support of Leading
Scientific Schools of the Russian Federation (project
no. NSh-2030.2004.3).
Reaction of 2,2-dibromo-5-chloro-2-fluoroben-
5
zo[d][1,3,2 ]dioxaphosphole (XVI) with phenylace-
tylene. Phenylacetylene, 16.49 ml, was added at 0
10 C under vigorous bubbling of argon to 26.22 g of
phosphorane XVI prepared from 14.32 g of dioxa-
phosphole XV and 3.8 ml of bromine in 25 ml of
CH2Cl2 ( 20 to 10 C). The reaction mixture was
consecutively evaporated at 12 and 0.5 mm Hg. The
glassy residue was dissolved in 30 ml of dioxane, and
1.5 ml of water was added. Over the course of 10
15 days, a mixture of benzophosphinines XIIIa, XIVa,
and XXa, containing 50 90% of compound XIIIa,
precipitated. The components were characterized by
spectral methods.
REFERENCES
1. Mironov, V.F., Shtyrlina, A.A., Varaksina, E.N., Gu-
baidullin, A.T., Azancheev, N.M., Dobrynin, A.B.,
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Obshch. Khim., 2004, vol. 74, no. 12, p. 1953.
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baidullin, A.T., Petrov, R.R., Shtyrlina, A.A., Zyabli-
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and Konovalov, A.I., Zh. Obshch. Khim., 2000, vol. 70,
no. 1, p. 160.
Reaction of dioxaphosphole (XVI) with p-tolyl-
acetylene was carried out analogously. A mixture of
7-chloro-2-fluoro-4-p-tolylbenzo[e][1,2 ]oxaphos-
5
4. 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.
phinine 2-oxide (XVIIb) (50%), 6-bromo-7-chloro-
2-fluoro-4-p-tolylbenzo[e][1,2 5]oxaphosphinine
2-oxide (XVIIIb) (35%), and 7-chloro-2-fluoro-4-p-
5
tolylbenzo[e][1,2 ]oxaphosphinine 2-oxide (XIXb)
(23%) was obtained. 31P {1H} NMR spectrum
(CH2Cl2), P, ppm (J, Hz): 2.1 d (1JPF 1055.0)
(XVIIb), 1.9 d (1JPF 1065.0) (XVIIIb), and 1.7 d
(1JPF 1069.3) (XIXb). The mixture was treated with
5. Mironov, V.F., Petrov, R.R., Shtyrlina, A.A., Gu-
baidullin, A.T., Litvinov, I.A., Musin, R.Z., and Kono-
valov, A.I., Zh. Obshch. Khim., 2001, vol. 1, no. 1,
p. 74.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005