Reactions of phenylenedioxytrihalophosphoranes with arylacetylenes: VII. Reaction of 2,2,2-trichloro-4-fluoro-1,3,2λ5- benzodioxaphosphole with phenylacetylene

Article abstract of DOI:10.1007/s11178-005-0102-5

2,2,2-Trichloro-4-fluoro-1,3,2λ⁵-benzodioxaphosphole reacts with phenylacetylene to give 2,7-dichloro-5-fluoro-4-phenyl-2H-1, 2λ⁵-benzoxaphosphinine 2-oxide. Hydrolysis of the latter leads to opening of the oxaphosphinine ring with formation of (E)-2-(4-chloro-2- fluoro-6-hydroxyphenyl)-2-phenylethenylphosphonic acid.

Full text of DOI:10.1007/s11178-005-0102-5

Russian Journal of Organic Chemistry, Vol. 40, No. 12, 2004, pp. 1798–1803. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004,
pp. 1846–1851.
Original Russian Text Copyright © 2004 by Mironov, Shtyrlina, Varaksina, Efremov, Konovalov.
Reactions of Phenylenedioxytrihalophosphoranes
with Arylacetylenes: VII.* Reaction of 2,2,2-Trichloro-4-fluoro-
5
1,3,2λ -benzodioxaphosphole with Phenylacetylene
V. F. Mironov, A. A. Shtyrlina, E. N. Varaksina, Yu. Ya. Efremov, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received October 2, 2003
Abstract—2,2,2-Trichloro-4-fluoro-1,3,2λ5-benzodioxaphosphole reacts with phenylacetylene to give 2,7-di-
chloro-5-fluoro-4-phenyl-2H-1,2λ5-benzoxaphosphinine 2-oxide. Hydrolysis of the latter leads to opening of
the oxaphosphinine ring with formation of (E)-2-(4-chloro-2-fluoro-6-hydroxyphenyl)-2-phenylethenylphos-
phonic acid.
We previously showed [2] that reactions of tri-
chloro(phenylenedioxy)phosphorane with arylacety-
lenes lead to formation of unexpected products, deriva-
tives of 2H-1,2λ5-benzoxaphosphinine 2-oxide which
may be regarded as a phosphorus-containing analog
of coumarin, the latter being a natural heterocyclic
system. With the goal of elucidating the mechanism
of formation of such compounds, in particular the
regioselectivity of the ipso-substitution of the oxygen
atom by carbon and chlorination of the phenylene
fragment, we examined reactions of arylacetylenes
with 4-methyl- and 4-chlorocarbonyl-2,2,2-trichloro-
1,3,2λ5-benzodioxaphospholes [1, 3]. The results
showed that the regioselectivity in the formation of
the benzoxaphosphinine system, as well as the site of
halogen entry into the phenylene fragment, is largely
determined by the substituent nature.
fluoro-1,3,2λ5-benzodioxaphosphole (I), with phenyl-
acetylene. Compound (I) was synthesized in two steps
via phosphorylation of 3-fluoro-1,2-benzenediol with
phosphorus trichloride, followed by chlorination of
intermediate 2-chloro-4-fluoro-1,3,2-benzodioxaphos-
phole (II) (Scheme 1). Compound I characteristically
31
showed in the P NMR spectrum an upfield signal at
δP –23.7 ppm.
2,2,2-Trichloro-4-fluoro-1,3,2λ5-benzodioxaphos-
phole (I) reacted with phenylacetylene under fairly
mild conditions (CH2Cl2, 10–15°C) to afford mainly
one product with δP 17.5 ppm, d (2JPH = 24.2 Hz). The
observed 31P chemical shift and the coupling constant
2JPH suggest a phosphonate nature of this compound.
Removal of volatile substances (initial phenylacetylene
and chlorostyrenes) from the reaction mixture under
reduced pressure (150°C) left a vitreous material
1
While extending studies in this line, i.e., elucidating
the effect of substituents in the phenylene fragment of
the initial benzodioxaphospholes on the direction of
their reactions with arylacetylenes, in the present work
we were the first to react an unsymmetrically sub-
stituted phenylenedioxyphosphorane, 2,2,2-trichloro-4-
which was analyzed by NMR spectroscopy. Its H
NMR spectrum (see Experimental) contained a down-
field doublet signal corresponding to proton of the
P(O)CH=C fragment. Taking into account the 13C and
13C–{1H} NMR data (see table), the product was as-
signed a 1,2λ5-benzoxaphosphinine structure. Analysis
Scheme 1.
F
F
F
OH
OH
O
O
O
O
PCl3
Cl2
Cl
Cl
Cl
P
Cl
P
–HCl
II
I
* For communication VI, see [1].
1070-4280/04/4012-1798 © 2004 MAIK “Nauka/Interperiodica”

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ...: VII.
1799
Scheme 2.
F
8
8
O
O
2 P
3 Cl
Cl
O1
O1
8a
4a
8a
4a
F
7
6
2P
7
6
3 Cl
O
O
Cl
Cl
Cl
Cl
4
4
9
5
5
+
P
Ph
C
CH
or
–HCl
F
10
11
12
I
III
IV
(δC 114.44 ppm) should be assigned to C6. Thus the
analysis of the NMR data indicates formation of
structure III.
Presumably, the formation of isomer III may be
explained in terms of greater stability of intermediate
V in which negative charge on the oxygen atom (or on
the carbon atom linked to the other oxygen atom) is
delocalized due to negative inductive effect of the
fluorine atom. Alternative intermediate structure VI is
destabilized by positive mesomeric effect of the
fluorine atom.
of the spectral data shows that the phenylene fragment
contains a chlorine atom, for signals from the aromatic
carbon atoms resemble those observed in the spectra
of 4-phenyl-1,2-benzoxaphosphinine derivatives syn-
thesized previously [1–3]. In keeping with the signal
multiplicities, the product has the structure of either
2,7-dichloro-5-fluoro-4-phenyl-1,2λ5-benzoxaphosphi-
nine 2-oxide (III) or 2,6-dichloro-8-fluoro-4-phenyl-
1,2λ5-benzoxaphosphinine 2-oxide (IV) (Scheme 2).
Structures III and IV can be distinguished by the
chemical shifts of C5–C8 and carbon–fluorine coupling
constants. First of all, it should be noted that the signal
from the carbon atom attached to fluorine should
appear either as a doublet (C5 in structure III) with
a direct coupling constant 1JFC or a doublet of doublets
O
OH
Cl
Cl
Cl
CH
Cl
Cl
Cl
CH
P
P
O
O
C
C
1
3
(C8 in structure IV) with JFC and JPC couplings. In
the experimental 13C NMR spectrum we observed
a slightly broadened downfield doublet (δC 159.65 ppm)
F
F
Ph
Ph
V
1
F
with a constant JFC indicating direct coupling with
fluorine; this pattern corresponds to structure III. The
signal from the C7 atom, which is attached to chlorine,
should appear in a fairly weak field (δP 136–138 ppm)
[3, 4]. In fact, a signal at δC 138.25 ppm was present
in the spectrum. The signal from the C6 atom in IV
should be located in a stronger field (δC 130–132 ppm)
due to π-electron-donor effect of the oxygen atom in
the para position [2, 4]. Finally, the small J(F–C8a)
value is better consistent with carbon–fluorine cou-
pling through three bonds rather than two bonds as
in IV. It is interesting that the carbon atoms located
symmetrically with respect to fluorine show different
coupling constants with the latter: the spin–spin cou-
plings in the bond sequence F–C5–C6–C7 are stronger
O
O
Cl
Cl
Cl
CH
P
C
Ph
VI
A more difficult problem is to rationalize the regio-
selectivity of chlorination of the phenylene fragment.
First of all, it is reasonable to consider a probable reac-
tion scheme. It is generally similar to that proposed
previously [2]. It includes formation of a complex by
the phosphorane as Lewis acid and phenylacetylene
as base. This complex may also be represented as
structure V with separated charges. Intramolecular ipso
attack by the cationic center gives rise to formation
of a new carbon–carbon bond (intermediate spiro oxa-
phosphole VII; Scheme 3). Structurally related quinoid
oxaphospholes with a tetrahedral phosphorus atom
were obtained by us previously in the reaction of
phenanthrenequinone with phosphorus trichloride in
3
(2JFC = 26.3, JFC = 13.2 Hz) than in the sequence
3
F–C5–C4a–C8a (2JFC = 12.2, JFC = 5.6). Signals corre-
sponding to the C6 and C8 nuclei can be identified on
3
2
the basis of the coupling constants JPC and JFC: the
latter is considerably greater (26.3 Hz). Taking into
account the effects of the oxygen and fluorine atoms in
the para and ortho positions, the more upfield signal
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

MIRONOV et al.
1800
Scheme 3.
O
O
Oδ–
O
O
Cl
Cl
Cl
Cl
Cl
O
P
P
Cl Cl–
Cl
P
Cl–
V
F
F
F
Ph
H
Ph
Ph
VII
Cl
VIII
IX
Cl
O
O
O
O
H
Cl
Cl
Cl–
III
P
P
Cl
–HCl
F
F
Ph
Ph
XI
X
Scheme 4.
O
O
P
O
O
Cl
P
VIII
Cl
Cl
–HCl
Cl
Cl
H
F
Ph
F
Ph
XII
XIII
the presence of arylacetylenes [5]. Insofar as inter-
mediate VII is a five-coordinate phosphorus derivative
possessing a P–Cl bond, it can occur in equilibrium
with quasiphosphonium structure VIII. The latter can
be transformed into phosphorane IX via intramolecular
attack by the carbonyl oxygen atom on the phospho-
nium center. The benzene fragment in IX may be
regarded as a nonclassical divinyl-like cation. The sub-
sequent attack by chloride ion on that cation gives
dichlorophosphorane X which is converted into final
product III through equilibrium with quasiphospho-
nium salt XI. The formation of intermediate IX is very
consistent with the observed chlorination direction.
Had quinoid oxaphosphole VII been converted into
open quinoid structure XII, as it was proposed in [1],
the final product would be compound XIII as a result
of chlorine migration to the para position with respect
to the oxygen atom (Scheme 4).
We failed to isolate compound III in the pure state,
and the obtained vitreous material was subjected to
hydrolysis with an equimolar amount of water in
diethyl ether. We thus isolated 7-chloro-5-fluoro-2-
hydroxy-4-phenyl-2H-1,2λ5-benzoxaphosphinine
2-oxide (XIV) (Scheme 5). The cyclic structure of
1
product XIV was proved by the H and 13C NMR
1
spectra (see table). In the H NMR spectrum of XIV
(400 MHz, DMSO-d6), the 3-H signal appeared at
2
δ 6.14 ppm as a doublet with a coupling constant JPH
of 17.0 Hz, which is typical of a cyclic structure. The
13C NMR spectrum revealed spin–spin couplings
Scheme 5.
Cl
Cl
OH
P(O)(OH)2
H2O
∆, –H2O
O
Cl
O
P
H2O
F
Ph
OH
III
XV
–HCl
O
O
O
O
Cl
F
Ph
P
P
∆
–H2O
XIV
O
F
Ph
Ph
F
XVI
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ...: VII.
13C and 13C–{1H} NMR spectra of compounds III–Va
Chemical shifts δC, ppm (J, Hz)
1801
Atom
IV (CD3CN + 10% DMSO-d6)
[DMSO-d6 + 10% CDCl3]
V (CD3CN + 10% DMSO-d6)
[DMSO-d6 + 10% CDCl3]
III (CDCl3)
C3
116.77 d (d.d)a (156.0, 120.49 d (d.d) (170.5, PC3; 165.1, HC3) 122.75 d (d.d) (190.0, PC3; 151.8, HC3)
PC3; 172.2, NC3)
[119.85 d (d.d) (170.0, PC3; 165.3, [122.71 d (d. d) (186.0, PC3; 150.0, HC3)]
HC3)]
C4
152.88 br.s (br.m)
149.34 br.s (br.m) [147.31 d.d (m) (2.7, 147.24 d (m) (3.6, PCC) [144.31 d (m) (4.2,
FCC4; 2.5–2.6, PCC4)]
PCC4)]
C4a 110.50 d.d (m) (18.3, 112.72 d.d (m) (16.7, PCCC5; 12.8, 115.30 d.d (m) (19.9, FCC4a; 7.5, PCCC4a)
PCCC4a; 12.2, FCC4a) FCC4a) [111.22 d.d (m) (16.7, PCCC4a; [113.90 d.d (m) (19.4, FCC4a; 7.2,
12.2, FCC4a)] PCCC5)]
159.65 d (br.d.d) (262.2, 160.75 d (d.d) (255.0, FC5; 4.5, HC6C5) 161.37 d (d.d) (244.5, FC5; 4.6, HC6C5)
FC5; 1.8–2.0, HC6C5) [159.20 br.d (br.d.d) (258.9, FC5; 4.5– [160.50 (br.d.d) (245.2, FC5; 5.0,
5.0, HC6C5)] HC6C5)]
C5
C6
C7
d
114.44 d (d.d.d) (171.2, 113.91 d (d.d.d) (171.0, HC6; 26.9, FCC6; 107.84 d (d.d.d) (170.4, HC6; 26.6, FCC6;
HC6; 26.3, FCC6; 5.7, 6.1, HC8CC6) [112.84 d (d.d.d) (171.0, 4.7, HC8CC6) [106.25 d (d.d.d) (170.3,
HC8CC6)
HC6; 26.7, FCC6; 6.0, HC8CC6)]
HC6; 26.8, FCC6; 5.5, HC8CC6)]
138.25 d (d.d.d) (13.2, 136.78 d (d.d.d) (14.4, FCCC7; 4.4–4.5, 134.89 d (d.d.d) (14.4, FCCC7; 4.5, HC8C7;
FCCC7; 4.5–4.6, HC8C7; HC8C7; 4.4–4.5, HC6C7) [135.18
d
4.5, HC6C7) [132.83 d (d.d.d) (14.2,
4.5–4.6, HC6C7)
(d.d.d) (14.7, FCCC7; 4.4, HCC7; 3.2, FCCC7; 4.3–4.4, HCC7; 4.3–4.4, HCC7)]
HCC7)]
C8
116.50
(173.1,
d.d
HC8;
(d.d.d.d) 117.25 d.d (d.m) (171.8, HC8; 6.3, 113.60
d
(br.d.m) (166.3, HC8; 2.0,
8.0, POCC8; 5.2, HC6CC8; 3.2, FCCCC8) FCCCC8) [111.64 d (br.d.m) (163.2, HC8;
ROCC8; 8.3, HC6CC8; [116.07 d.d (d.d.d) (172.0, HC8; 6.3, 2.0, FCCCC8)]
3.8, FCCCC8)
POCC8; 5.3, HC6CC8; 3.3, FCCCC8)]
C8a 151.40 d.d (d.d.d) (9.7, 154.19 d.d (br.d.d) (7.0, POC8a; 4.6, 158.19 d (br.d) (8.8, FCCC8a) [156.96 d
ROC8a; 5.6, FCCC8a; 4.5, FCCC8a) [152.79 d.d (d.d.d) (7.0, POC8a; (br.d) (9.2, FCCC8a)]
HCC8a)
7.0, FCCC8a; 4.5, HCC8a)]
C9
138.37 d.d (m) (19.4, 141.53 d.d (d.t.d.d) (17.7, PCCC9; 6.5, 140.59
d
(d.t.d) (21.3, PCCC9; 7.7,
PCCC9; 4.2, FCCCC9)
HC11CC9; 5.6, HC3CC9; 2.0, FCCCC9) HC11CC9; 6.2, HC3CC9) [139.38 d.d (m)
[139.96 d.d (m) (19.1, PCCC9; 3.0, (21.1, PCCC9; 7.5, HC11CC9; 5.6,
FCCCC9)]
HC3CC9)]
C10 126.63 br.s (d.m) (160.5, 127.95 br.s (d.m) (161.7, HC10) [126.66 d 127.54 s (d.d.d) (159.7, HC10; 5.0–6.8,
HC10)
(d.m) (161.0, HC10; 2.6, FCCCCC10)]
HC10'CC10; 5.0–6.8, HC12CC10) [126.12 s
(br.d.m) (159.0, HC10; 5.8–6.0, HCCC10;
6.2, HC12CC10)]
C11 128.45
s
(d.d) (161.9, 129.37
HC11'CC11) [128.23 s (br.d.m) (161.3, [128.49 s (br.d.d) (161.1, HC11; 4.7–5.0,
HC11; 5.5, HC11'CC11)] HC11'CC11)]
(d.t) (161.3, HC12; 7.0, 130.22 s (d.t) (161.2, HC12; 6.8, HC10CC12)
s
(d.d) (161.5, HC11; 6.5, 129.66 s (d.d) (160.9, HC11; 6.8, HC11'CC11)
HC11; 7.1, HC11'CC11)
C12 129.63
s
(d.t) (161.3, 129.82
s
HC12; 7.2, HC10CC12)
HC10CC12) [128.49 s (d.t) (160.0–161.5, [128.77 s (d.t) (158.5, HC12; 6.9–7.1,
HC12; 7.0, HC10CC12)]
HC10CC12)]
a
In parentheses is given the shape of the signal in the 13C NMR spectrum.
between the phosphorus atom and C8a and C8. The
coupling constant J(PC4a) = 18.3 Hz also indicates the
existence of two coupling channels, P–C3–C4–C4a and
P–O–C8a–C4a, i.e., the cyclic structure of the corre-
sponding fragment. When the hydrolysis of III was
performed under more severe conditions, e.g., in di-
oxane or acetone using excess water, we isolated
vinylphosphonic acid XV. Unlike compound III, the
31P signal of acid XV is located in a weaker field,
2
δP 8.8 ppm, and the coupling constant JPH is smaller,
13.2 Hz. The 13C and 13C–{1H} NMR data obtained in
two solvents (see table) suggest E configuration of the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

MIRONOV et al.
1802
5
double bond in XV. Phosphonic acid XV can readily
be converted back into cyclic ester XIV by dehydra-
tion on heating in benzene with removal of water as
azeotrope. Taking into account the low volatility of
compound XIV and the possibility for secondary proc-
esses due to the presence of a hydroxy group, its mass
spectra were recorded in the temperature range from
100 to 400°C. Up to 300°C, the molecular ion peak
(m/z 310) was the most abundant in the region of large
a.m.u. values, though its absolute intensity was small.
The presence of a chlorine atom gives rise to ion
peak with m/z 312; the intensity ratio of the peaks with
m/z 310 and 312 (3:1) coincides with the theoretical
occurrence of 35Cl and 37Cl isotopes. The exact mass
number is 309.996 (calculated value 309.9961).
Further heating of compound XIV results in elimina-
tion of one more water molecule and formation of
dimeric structure XVI having a P(O)–O–P(O) frag-
ment. Bis-phosphonate XVI showed in the mass spec-
trum the molecular ion cluster with m/z 602/604/606
(intensity ratio 9:6:1), in keeping with the presence of
two chlorine atoms in the molecule.
Thus the reaction of phenylacetylene with 2,2,2-tri-
chloro-4-fluoro-1,3,2λ5-benzodioxaphosphole, as well
as with unsubstituted 2,2,2-trichloro-1,3,2λ5-benzodi-
oxaphosphole, leads to formation of 1,2λ5-benzoxa-
phosphinine 2-oxide derivative in which the fluorine
atom appears in the ortho position with respect to the
endocyclic oxygen atom. The process is accompanied
by regioselective chlorination of the benzo fragment at
the meta position with respect to the fluorine atom and
oxygen atom in the oxaphosphinine ring.
2,2,2-Trichloro-4-fluoro-1,3,2λ -benzodioxaphos-
phole (I). A mixture of 5 g (0.039 mol) of 3-fluoro-
1,2-benzenediol and 5 ml (0.057 mol) of phosphorus
trichloride was stirred for 1 h at 80°C. Excess phos-
phorus trichloride was removed under reduced pres-
sure (12), and the residue was distilled to isolate 4.1 g
(55%) of benzodioxaphosphole II as a colorless
mobile liquid, bp 28–30°C (0.2 mm). 31P NMR spec-
trum (CDCl3): δP 177.7 ppm. Compound II, 4.1 g
(0.021 mol), was dissolved in 30 ml of methylene
chloride, the solution was cooled to –20°C, and a solu-
tion of 1.7 g (0.023 mol) of chlorine in 20 ml of
methylene chloride, cooled to –10°C, was added under
stirring in a stream of argon. The mixture was kept
under reduced pressure (12 mm) to remove excess
chlorine, and the residue was brought into further
syntheses without additional purification. According
to the NMR data, the yield of I was quantitative.
31P NMR spectrum (CH2Cl2): δP –23.7 ppm.
Reaction of phosphorane (I) with phenylacety-
lene. Phenylacetylene, 4.7 ml, was added dropwise to
a solution of 5.6 g (0.021 mol) of phosphorane I in
50 ml of methylene chloride while continuously bub-
bling argon through the mixture (10°C). The mixture
was stirred for 3 h, the solvent was distilled off, and
excess phenylacetylene and chlorostyrenes were re-
moved under reduced pressure (0.1 mm, 150–170°C).
The residue was 6.5 g (93%) of 2,7-dichloro-5-fluoro-
4-phenyl-2H-1,2λ5-benzoxaphosphinine 2-oxide (III)
1
as a vitreous material. H NMR spectrum (250 MHz,
CDCl3), δ, ppm: 7.32–7.44 m (C6H5), 7.21 d.d (8-H,
4JHH = 2.2, 5JPH = 1.9 Hz), 6.99 d.d.d (6-H, 3JFH = 10.7,
4JHH = 2.2 Hz), 6.34 d (3-H, 2JPH = 25.1 Hz). 31P NMR
spectrum (CDCl3): δP 17.5 ppm, d (2JPH = 24.2 Hz).
EXPERIMENTAL
Hydrolysis of 2,7-dichloro-5-fluoro-4-phenyl-2H-
1,2λ -benzoxaphosphinine 2-oxide (III). Compound
The NMR spectra were obtained on Bruker MSL-
5
1
400 (400 MHz for H, 100.6 MHz for 13C and
13C–{1H}, and 162.0 MHz for 31P and 31P–{1H}) and
III, 6.5 g, was dissolved in 15 ml of diethyl ether, and
0.4 ml of water was added. After 24 h, the precipitate
was filtered off. Yield of 7-chloro-5-fluoro-2-hydroxy-
4-phenyl-2H-1,2λ5-benzoxaphosphinine 2-oxide (XIV)
2.9 g (44%), mp >360°C. IR spectrum, ν, cm–1: 3628,
3375–3500 v.br, s (POH), 3094, 3025 (C–Harom), 1975,
1957, 1890, 1637, 1611, 1594, 1573, 1545 (C=C,
C=Carom), 1490, 1462, 1445, 1415, 1334 (δC–H),
1297, 1226, 1202, 1141, 1085, 1048, 999, 969, 938,
921, 903, 857, 838, 813, 779, 760, 749, 701, 681,
1
Bruker WM-250 (250 MHz, H) spectrometers. The
chemical shifts were measured relative to HMDS
(1H, 13C) as internal reference and H3PO4 (31P) as
external reference. The NMR spectra of solutions in
DMSO-d6 were recorded at 40°C, and in the other
solvents, at 20°C. The IR spectra were recorded on
a Bruker Vector-22 Fourier spectrometer from samples
prepared as KBr pellets (compound IV) or dispersed
in mineral oil (V). The mass spectra were run on
a Finnigan MAT-202 high-resolution mass spectrom-
eter (60 eV, emission current 0.5 mA; direct sample
admission into the ion source; continuous recording);
The relative error in the determination of m/z values
did not exceed 5×10–5 a.m.u.
1
631, 573, 504, 453. H NMR spectrum (400 MHz,
DMSO-d6), δ, ppm: 7.33–7.34 m (3H, 11-H, 12-H),
7.23 m (2H, 10-H, 3JHH = 7.7 Hz), 6.95 d.d.d (1H, 8-H,
5
4
4JHH = 1.6, JFH = 1.3, JPH = 0.8 Hz), 6.88 d.d.d (1H,
3
4
6
6-H, JFH = 11.2, JHH = 1.6, JPH = 0.7 Hz), 6.14 d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004

REACTIONS OF PHENYLENEDIOXYTRIHALOPHOSPHORANES ...: VII.
1803
2
1
2
(1H, 3-H, JPH = 17.0 Hz). H NMR spectrum
(250 MHz): in CD3CN + 10% DMSO-d6: δ, ppm:
6.46 d (3-H, JPH = 13.0 Hz). 31P NMR spectrum
(DMSO-d6): δP 8.8 ppm, d (2JPH = 13.2 Hz). Found, %:
C 51.37; H 3.71. C14H11ClFO4P. Calculated, %: C 51.14;
H 3.35.
4
5
7.28 d.d (8-H, JHH = 2.0, JFH = 1.8 Hz), 7.10 d.d
(6-H, JFH = 11.1, JHH = 2.0 Hz), 6.33 d (3-H, JPH
3
4
2
=
18.8 Hz); in CDCl3: 11.22 br.s (OH), 7.15 d.d (8-H,
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 03-03-32542 and 03-03-06559).
5
3
4JHH = 1.8, JFH = 1.7 Hz), 6.88 d.d (6-H, JFH = 10.8,
4JHH = 1.7 Hz), 6.19 d (3-H, 2JPH = 19.1 Hz). 31P NMR
spectrum: in DMSO-d6: δP –1.1 ppm, d (2JPH
=
17.0 Hz); in acetone: δP –0.3 ppm, d (2JPH = 17.1 Hz).
Found, %: C 54.23; H 3.19. C14H9ClFO3P. Calculated,
%: C 54.11; H 2.90.
REFERENCES
1. Mironov, V.F., Shtyrlina, A.A., Varaksina, E.N., Gubai-
dullin, A.T., Azancheev, N.M., Dobrynin, A.B., Litvi-
nov, I.A., Musin, R.Z., and Konovalov, A.I., Zh. Obshch.
Khim., 2004, vol. 74, p. 1953.
The ether filtrate was evaporated, and the residue
was heated in aqueous acetone. Removal of acetone
gave a yellow oily substance which was recrystallized
from benzene–petroleum ether (1:1) to obtain 1.6 g of
(E)-2-(4-chloro-2-fluoro-6-hydroxyphenyl)-2-phenyl-
ethenylphosphonic acid (XV), mp 198–200°C. IR
spectrum, ν, cm–1: 3380–3390, 3166, 3061, 2606,
2566, 2526, 2244, 2163 v.br (O–H, PO–H, CHarom),
1618, 1591, 1574, 1544, 1509, 1413, 1332, 1246,
1205, 1183, 1162, 1083, 1056, 1026, 943, 921, 859,
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1
450. H NMR spectrum (400 MHz, DMSO-d6), δ,
ppm: at 20°C: 7.33–7.34 m (11-H, 12-H), 7.29 m
4
5
(10-H), 6.69 d.d (8-H, JHH = 2.0, JFH = 1.3 Hz),
3
4
6.78 d.d (6-H, JFH = 8.8, JHH = 2.0 Hz), 6.47 d (3-H,
5. Mironov, V.F., Baronova, T.A., Gubaidullin, A.T., Mu-
sin, R.Z., Azancheev, N.M., Latypov, Sh.K., Dobry-
nin, A.B., Alekseev, F.F., Litvinov, I.A., and Konova-
lov, A.I., Dokl. Ross. Akad. Nauk, 2002, vol. 385, p. 196.
2JPH = 12.9 Hz); at 42°C: 7.32–7.34 m (11-H, 12-H),
4
5
7.30 m (10-H), 6.71 d.d (8-H, JHH4 = 2.0, JFH
=
3
1.3 Hz), 6.75 d.d (6-H, JFH = 8.8, JHH = 2.0 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 12 2004