Reaction in a three-component system tetrachloro-o-benzoquinone-arylacetylene-phosphorus trichloride

Article abstract of DOI:10.1023/A:1020909828276

Reaction in a three-component system tetrachloro-o-benzoquinone-arylacetylene-phosphorus trichloride was investigated with the use of NMR and IR spectroscopy and high resolution mass spectrometry. It was established that prevailingly formed 4-aryl-2-oxo-2,5,6,7,8-pentachlorobenzo[e]-l,2-oxaphosphorin-3-enes which on hydrolysis furnished 2-aryl-2-(1-hydroxy-2,3,4,5-tetrachlorophenyl)vinyl-phosphonic acids.

Full text of DOI:10.1023/A:1020909828276

Russian Journal of Organic Chemistry, Vol. 38, No. 8, 2002, pp. 1183 1188. From Zhurnal Organicheskoi Khimii, Vol. 38, No. 8, 2002,
pp. 1235 1239.
Original English Text Copyright
2002 by Mironov, Baronova, Konovalov, Aznacheev, Alekseev, Zyablikova, Musin.
Reaction in a Three-component System
Tetrachloro-o-benzoquinone Arylacetylene Phosphorus
Trichloride*
V. F. Mironov, T. A. Baronova, A. I. Konovalov, N. M. Aznacheev,
F. F. Alekseev, T. A. Zyablikova , and R. Z. Musin
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received March 1, 2002
Abstract Reaction in a three-component system tetrachloro-o-benzoquinone arylacetylene phosphorus
trichloride was investigated with the use of NMR and IR spectroscopy and high resolution mass spectro-
metry. It was established that prevailingly formed 4-aryl-2-oxo-2,5,6,7,8-pentachlorobenzo[e]-1,2-oxa-
phosphorin-3-enes which on hydrolysis furnished 2-aryl-2-(1-hydroxy-2,3,4,5-tetrachlorophenyl)vinyl-
phosphonic acids.
Reactions of substituted o-benzoquinones with
P(III) derivatives are known to provide in a quantit-
ative yield relatively stable compounds of penta-
oxaphosphorin-3-ene (II) [5 7]. In the course of the
reaction not only fairly readily formed a phosphorus
carbon bond and a phosphoryl group, but also occur-
red an uncommon ipso-substitution of an oxygen by
a carbon atom and regioselective chlorination of the
benzo-substituent in the para-position with respect to
the endocyclic oxygen of the phosphorine heterocycle
(II).
5
coordinate phosphorus, benzo[d]- -1,3,2-dioxaphos-
pholes [1, 2], that can be further used in the organic
synthesis [3]. For instance, the products of reaction
with phosphorus trichloride, substituted in the
5
aromatic ring 2.2.2-trichlorobenzo[d]- -1,3,2-di-
oxaphospholes, are fairly effective agents for replace-
ment of a carbonyl group by a gem-dichloroalkyl
moiety [4].
In some cases the preparation of initial phos-
phorane I is unfavorable because of its instability that
puts a limit on this procedure. To avoid the necessity
of phosphorane I synthesis from the corresponding
pyrocatechol it seemed promising to use in reaction
with arylacetylenes instead of compound I a combin-
ation of o-benzoquinone with phosphorus trichloride.
Among available o-quinones the most interesting one
is the sufficiently stable tetrachloro-o-benzoquinone.
In reactions with phosphites this compound under
very mild conditions provides P(V) derivatives, the
corresponding monocyclic phosphoranes [8, 9]. The
reaction with phosphorus trichloride occurs at heating
and also yields a phosphorane, 2,2,2,4,5,6,7-hepta-
We recently demonstrated that substituted in the
5
aromatic ring 2.2.2-trichlorobenzo[d]- -1,3,2-di-
oxaphospholes (I) were capable to enter into an
unusual reaction with arylacetylenes that resulted in
4
formation of a heterocyclic system benzo[e]- -1,2-
5
chlorobenzo[d]- -1,3,2-dioxaphosphole (III) [10].
In this study we were first to show that a similar
4
synthetic result, i.e., formation of benzo[e]- -1,2-
oxaphosphorin-3-ene derivative, was actually possible
at the use of the three-component system tetrachloro-
o-benzoquinone arylacetylene phosphorus trichloride
(preliminary communications see [11, 12]. The addi-
tion of phosphorus trichloride to a mixture of
o-chloranil with arylacetylene in dichloromethane at
X = H, Cl, Br.
Deceased.
*
The study was carried out under financial support from the Rus-
sian Foundation for Basic Research (grant no. 00-03-32835).
1070-4280/02/3808-1183$27.00 2002 MAIK Nauka/Interperiodica

1184
MIRONOV et al.
10 15 C furnished prevailingly products that in the
formed due to a loss of chlorine atom. The relative
intensity of peaks caused by isotopes for all above
ions corresponds to that calculated from their
empirical formulas.
31P {1H} NMR spectra gave singlet signals at
P
19 21 ppm. In the 31P NMR spectra registered
without decoupling from protons the signals appear
2
as doublets with coupling constants JPCH 25 27 Hz.
The chlorine evolved in the course of the reaction
added to excess acetylene yielding the corresponding
cis- and trans-isomers of dichlorostyrenes that were
identified by spectral methods (spectral parameters of
some among these compounds we had described
before [7]).
2
The doublets with a similar coupling constant JPCH
are also observed in the downfield part (5.5 6.5 ppm)
1
of H NMR spectra of the reaction mixtures. The
content of these compound in the reaction mixture in
different experiments amounts to 60 80%. In reaction
with phenylacetylene we succeeded to isolate the main
product as crystals easily suffering hydrolysis in air.
Since we failed to isolate compounds IVb, c in the
pure state the reaction mixtures after heating to 150
170 C in a vacuum of 0.1 mm Hg were subjected to
hydrolysis in dioxane with the goal to separate
individual reaction products. The compounds thus
obtained were sufficiently easily crystallized from
The chemical shift
indicates that the compounds
obtained have a P CPbond. Taking in consideration
the 1H and 31P NMR spectra (see the table) we
assigned to the main products a structure of 3-aryl-
4
2,5,6,7,8-pentachlorobenzo[e]- -1,2-oxaphosphorin-
benzene or acetone, and according to 31P {1H} NMR
spectra these were also phosphonates. The structure
of these phosphonates and also that obtained by
hydrolysis of phosphorine IVa was determined from
1H and 13C NMR spectra (see the table). According to
the spectral data the compounds formed are acyclic
vinylphosphonic acids VIa c. Thus the hydrolysis did
not stop at the stage of phosphorines V formation.
3-enes (IV).
X = H (a, Me (b, Cl (c.
In the 13C {1H} NMR spectra of the reaction mix-
tures taken after removing volatile impurities in the
strong field a doublet belonging to C3 carbon was
observed . In the spectrum registered without proton
decoupling the signal became a doublet of doublets
1
with characteristic coupling constants JPC (158.2
158.8 Hz) and JHC (173.0 175.0 Hz). The assign-
1
X = H (a), Me (b), Cl (c).
ment of the other signals in the spectra was carried
out taking in consideration the published spectral data
of similar in structure compounds [5 7].
In the 13C NMR spectra of compounds VI the
signal from C3 carbon appears as a doublet of
1
doublets with larger coupling constants JPC (170
The structure of benzophosphorines IVa, c was
also confirmed by mass spectra obtained under the
electron impact. In the mass spectra were observed
peaks of m/z 412 and 446 corresponding to molecular
ions [MIVa+ ] and [MIVc+ ]. In the spectrum of
190 Hz) than in the spectra of phosphorines IV.
Acyclic structure of phosphonic acids VI is also
evidenced by the value of the vicinal coupling con-
3
stant JPCCC4a (7.0 7.5 Hz) that is half as large as
analogous constant in benzophosphorines IV. In the
latter the coupling occurs by two channels, P O1
C8a C4a and P C3 C4 C4a.
compound
IVc
the
peak
of
maximum
intensity was that of ion [M Cl]+ with m/z 411 that
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

REACTION IN A THREE-COMPONENT SYSTEM
1185
Data of 13C NMR spectra of compounds IV (40 C, CDCl3) and VI (DMSO-d6, 50 C), , ppm, J, Hza
Atom
C3
Compound IVa
Compound IVbb
Compound IVc
120.63 d (d.d) (158.2, PC3; 173.1, 119.39 d (d.d) (158.8, PC3; 175.0, 120.96 d (d.d) (158.3, PC3; 173.0,
HC3) HC3) HC3)
155.38 s (br.m) (4.1, HC10C9C4; 155.35 s (d.t) (4.3, HC10C9C4; 3.4, 154.08 c (br.d.t) (4.3, HC10C9C4;
3.9, HC3C4) HC3C4) 3.6, HC3C4)
C4
C4a
121.91 d (d.d) (18.7, PC3C4C4a; 121.74 d (d.d) (18.7, PC3C4C4a; 8.8, 121.53 d(d.d) (18.6, PC3C4C4a; 8.7,
8.8, HC3C4C4a)
HC3C4C4a)
HC3C4C4a)
C5
C6
C7
C8
C8a
C9
131.95 d (d) (2.6, PC3C4C4aC5) 131.77 d (d) (2.6, PC3C4C4aC5)
131.72 d (d) (2.6, PC3C4C4aC5)
131.78 d (d) (1.9, POC8aC4aC5C6) 131.50 d (d) (1.8, POC8aC4aC5C6) 131.89 d (d) (1.9, POC8aC4aC5C6)
136.25 d (d) (0.8 0.9, POC8aC8C7) 135.88 s (s)
136.52 d (d) (0.9, POC8aC8C7)
124.89 d (d) (7.5, POC8aC8)
146.22 d (d) (9.7, POC8a)
124.75 d (d) (7.4, POC8aC8)
146.23 d (d) (9.5, POC8a)
124.53 d (d) (7.5, POC8aC8)
145.89 d (d) (9.4, POC8a)
138.38 d (d.t.d) (19.4, PC3C4C9; 135.10 d (m) (19.6, PC3C4C9; 7.8, 136.86 d (m) (19.9, PC3C4C9; 7.8,
7.1 7.2, HC11C10C9; 5.8 6.0,
HC3C4C9)
HC11C10C9; 6.7, HC3C4C9)
HC11C10C9; 6.6, HC3C4C9)
C10
C11
C12
126.70 s (d.d.d) (161.4, HC10; 6.7, 128.53 s (d.d) (159.7, HC10; 6.2, 129.29 s (d.d) (162.2, HC10; 6.5,
HC12C11C10; 6.2, HC10C9C10)
HC10C9C10)
HC10C9C10)
129.02 br.s (br.d.d) (163.1, HC11; 129.37 br.s (br.d.m) (159.6, HC11) 128.06 br.s (d.d) (162.2, HC11; 6.5,
5.0 6.0, HC11C12C11)
HC11C12C11)
129.87 s (d.t) (161.8, HC12; 7.3, 139.59 s (m)
HC10C11C12)
136.16 s (t.t) (10.5, HC10C11C12;
3.5, HC11C12)
Atom
C3
Compound VIa (DMF d7)c
Compound VIbd
Compound VIc
119.93 d (d.d) (190.0, PC3; 152.0, 129.43 d (d.d) (170.2, PC3; 148.5, 123.78 d (d.d) (183.6, PC3; 151.1,
HC3)
HC3)
HC3)
C4
147.71 d (d.d.t) (3.7, PC3C4; 3.7 144.69 d (d.d.t) (3.7, PC3C4; 3.9, 144.85 d (m) (4.4, PC3C4)
4.0, HC10C9C4; 3.7 4.0, HC3C4) HC10C9C4; 3.9, HC3C4)
C4a
C5
126.86 d(d.d) (7.5, PC3C4C4a; 10.5, 131.90 d (d.d) (7.0, PC3C4C4a; 11.1, 127.91 d (d.d) (7.3, PC3C4C4a; 10.5,
HC3C4C4a)
HC3C4C4a)
HC3C4C4a)
130.44 d (d) (2.0, PC3C4C4aC5; 1.2, 131.0 d (d) (1.8, PC3C4C4aC5)
131.15 d (br.s) (2.0, PC3C4C4aC5)
HC3C4C4aC5)
C6
C7
C8
C8a
C9
122.09 s (s)
130.52 s (s)
119.89 s (s)
149.72 s (s)
124.63 s (s)
130.0 s (s)
119.72 s (s)
155.39 s (br.s)
121.87 s (s)
130.83 s (s)
120.64 s (s)
151.22 d (br.s) (1.5, PC3C4C4aC8a)
137.15 d (d.t.d) (21.0, PC3C4C9; 138.01 d (d.t.d) (18.3, PC3C4C9; 136.59 d (d.t.d) (21.0, PC3C4C9;
7.6, HC11C10C9; 5.0, HC3C4C9)
7.7, HC11C10C9; 6.8, HC3C4C9)
7.0, HC11C10C9; 6.5, HC3C4C9)
C10
125.38 s (br.d.d.d) (159.1, HC10; 125.91 s (d.d) (158.0, HC10; 6.5, 128.80 s (d.d) (167.8, HC10; 5.3,
5.0 6.0, HC10C9C10; 5.0 6.0,
HC12C11C10)
HC10C9C10)
HC10C9C10)
C11
C12
127.31 s (br.d.d) (161.0, HC11; 129.05 s (d.m) (158.0, HC11; 6.2, 128.50 s (d.d) (162.3, HC11; 6.9,
7.8, HC11C12C11)
127.97 s (d.t) (161.0, HC12; 7.2, 137.29 s (m) (6.8, HC10CC12; 6.5, 133.86 s (t.t) (10.6, HC10CC12; 2.9,
HC10C11C12) HC11C12) HC11C12)
HC11C12C11; 6.1, HCC12C11)
HC11C12C11)
a
b
c
d
Multiplicity in 13C NMR spectrum without decoupling from protons is given in parentheses.
CH3, 20.93 s (q.d) (126.8, HC; 4.3, HC11C12C).
63.89 s (t.t.t) (dioxane; 143.0, HC; 3.7, HCC; 2.0, HCOC).
CH3, 20.71 s (q.t) (126.3, HC; 4.3, HC11C12C).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

1186
MIRONOV et al.
Thus the reaction in the three-component system
tetrachloro-o-benzoquinone phosporus trichloride
31P NMR spectrum (162.0 MHz, CDCl3), , ppm:
1
15.2 d (2JPCH 25.6 Hz). H NMR spectrum (CD-Cl3),
arylacetylene provides a possibility to prepare in one
stage vinylphosphonic acids derivatives and extends
the synthetic opportunities of the procedure described
in [5 7].
, ppm, J, Hz: 7.54 m (5H, C6H5), 6.82 d (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
The crystals and oily residue after chloroform
removal were dissolved in 20 ml of dioxane and
treated with excess water (2 ml). The solution formed
was poured into 200 ml of water; the separated light-
yellow oily substance was crystallized from chloro-
form containing a little amount of dioxane.
EXPERIMENTAL
NMR spectra were measured on the following
instruments: Bruker MSL-400 (13C, 13C {1H},
100.6 MHz; 31P, 31P {1H}, 162.0 MHz), Bruker
WM-250 (1H, 250 MHz), Bruker CXP-100
(36.48 MHz, 31P, 31P {1H}) relative to HMDS as
internal reference and H3PO4 as external reference.
2-(1-Hydroxy-2, 3, 4, 5-tetrachlorophenyl)-2-
phenylvinylphosphonic acid (VIa) was obtained as
a solvate with dioxane of 4:3 composition, yield 62%,
The H and 13C NMR spectra were registered at 30 C
1
if not indicated otherwise. IR spectra were recorded
on spectrophotometer Specord IR 75 from mulls in
mineral oil placed between KBr plates. Mass spec-
trum of benzophosphorine IVa was measured on
MKh-1310 instrument at ionizing electrons energy
70 eV, current of electrons collector 30 A, sample
input directly into the ion source at 120 C. The
precise measurement of ion mass was performed auto-
matically by reference peaks of perfluorokerosene.
1
mp 169 171 C (decomp.). IR spectrum, cm : 466,
494, 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,
1
3100 3200 v.br. H NMR spectrum (ethanol-d6), ,
ppm, J, Hz: 7.34 br.s (5H, C6H5), 6.59 d (1H, PCH,
2JPCH 13.4), 3.67 s (6H, C4H8O2). 1H NMR spectrum
(acetone-d6), , ppm, J, Hz: 7.41 br.s (5H, C6H5),
5
Relative error was no more than 5 10 amu. The
2
mass spectrum of benzophosphorine IVc was
obtained on Finnigan MAT-212 instrument under the
same conditions. The processing of mass spectra was
performed with the use of software MASPEC 2
system.
6.74 d (1H, PCH, JPCH 13.3), 3.61 s (6H, C4H8O2).
31P NMR spectrum (162.0 MHz, ethanol-d6), , ppm:
9.8 d (2JPCH 13.5 Hz). Found, %: C 42.73; H 3.54;
Cl 29.67; P 6.37. 4C14H9Cl4O4P 3C4H8O2. Cal-
culated, %: C 42.50; H 3.13; Cl 29.58; P 6.46.
Reaction of tetrachloro-o-benzoquinone with
phosphorus trichloride and phenylacetylene. To a
solution of 6.2 g (0.025 mol) of tetrachloro-o-benzo-
quinone in 50 ml of benzene was added at stirring
2.6 ml (0.025 mol) of phenylacetylene and then drop-
wise 2.2 ml (0.026 mol) of phosphorus trichloride.
Therewith the color of the reaction mixture turned
from light-yellow to dark-brown and then gradually
to light-brown. The reaction mixture was stirred at
10 15 C for 1 h, then the solvent was distilled off,
and the residue was maintained in a vacuum of
0.1 mm Hg at heating to 160 C to remove excess
acetylene and isomeric 1-phenyl-1,2-dichloroethenes.
Then the glass-like substance obtained was dissolved
in chloroform (20 ml) and kept at 0 5 C for 3 5 days.
Therewith precipitated crystalline oxaphosphorine
IVa, yield 27%, mp 179 180 C (from chloroform).
Mass-spectrum, m/z (Irel, %), ion composition: 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]+ ;
384 (1.3), 383 (10.9), 381 (47.4), 380 (16.2), 379
(100), 378 (18.5), 377 (76.1) [C14H6Cl4O2P]+ .
Reaction of tetrachloro-o-benzoquinone with
phosphorus trichloride and p-methylphenylacetyl-
ene. To a solution of 5 g (0.02 mol) of tetrachloro-o-
benzoquinone in 20 ml of benzene was added at stir-
ring 2.35g (0.02mol) of p-methylphenylacetylene and
then dropwise 1.9 ml (0.022 mol) of phosphorus tri-
chloride. The reaction mixture was stirred at 10 15 C
for 1 2 h, then the solvent was distilled off, and the
residue was maintained in a vacuum of 0.1 mm Hg at
heating to 160 C to remove excess acetylene and iso-
meric 1-(p-methylphenyl)-1,2-dichloroethenes. Then
the glass-like light-brown substance containing 82%
of
4-p-methylphenyl-2-oxo-2,5,6,7.8-pentachloro-
benzo[e]-1,2-oxphosphorin-3-ene (IVb) was char-
acterized by spectral methods. 31P NMR spectrum
(162.0 MHz, CDCl3), , ppm: 16.3 d (2JPCH
27.2 Hz). The oily compound was further dissolved
in dioxane and treated with excess water. Dioxane
and excess water were removed by distillation, the
residue was dissolved in 20% solution of KOH, and
then acidified with HCl to pH 5.0. Therewith partial-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

REACTION IN A THREE-COMPONENT SYSTEM
1187
ly formed a precipitate and separated an oily sub-
stance, both were separated and crystallized from
benzene and acetone. 2-(1-Hydroxy-2,3,4,5-tetra-
chlorophenyl)-2-(p-methylphenyl)vinylphosphonic
acid (VIb) was obtained in 47% yield, mp 176
178 C. 31P NMR spectrum (36.48 MHz, DMSO-d6),
yield 42%, mp 136 128 C. 31P NMR spectrum
(36.48 MHz, DMSO-d6), , ppm: 9.4 d (2JPCH
1
11.7 Hz). H NMR spectrum (DMSO-d6, 50 C), ,
ppm, J, Hz: 7.41 and 7.34 two m [4H, AA BB -spec-
3
2
trum, J(HAHB) 8.9], 6.63 d (1H, PCH, JPCH 11.5).
1
IR spectrum, cm : 3290 3340 v.br, 2710 2730 v.br,
1
, ppm: 9.7 d (2JPCH 12.0 Hz). H NMR spectrum
2280 2290 v.br, 2170 2180 sh, v.br, 1604, 1590,
1546, 1493, 1425, 1403, 1329, 1272, 1234, 1186,
1189 sh, 1159, 1094, 1077, 1013, 985, 974, 949,
860, 815 sh, 817 sh, 811, 780, 757, 740, 722, 709,
689, 678, 618, 567, 532, 500, 461, 428. Found, %:
C 37.42; H 1.93; Cl 40.02; P 6.79. C14H8Cl5O4P.
Calculated, %: C 37.46; H 1.78; Cl 39.78; P 6.91.
(DMSO-d6, 50 C), , ppm, J, Hz: 7.07 and 6.94
two m [4H, AA BB -spectrum, 3J(HAHB) 8.1],
2
6.48 d (1H, PCH, JPCH 11.8), 2.25 s (3H, CH3).
1
IR spectrum, cm : 2250 2350 v.br, 2730 2780 v.br,
2360 2330 v.br, 1716, 1608, 1550, 1511, 1316,
1311, 1274, 1266 sh, 1158, 1092, 1108 sh, 1056,
985, 967, 922, 898, 830, 802, 754, 722, 677, 616,
564, 500, 484, 472. Found, %: C 41.92; H 2.81;
Cl 33.23; P 7.49. C15H11Cl4O4P. Calculated, %:
C 42.05; H 2.57; Cl 33.18; P 7.27.
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Reaction of tetrachloro-o-benzoquinone with
phosphorus trichloride and p-chlorophenylacetyl-
ene. To a solution of 4.8 g (0.019 mol) of tetra-
chloro-o-benzoquinone in 40 ml of benzene was
added at stirring 2.7 g (0.02 mol) of 4-chlorophenyl-
acetylene and then dropwise 2.0 ml (0.023 mol) of
phosphorus trichloride. The reaction mixture was
stirred at 10 15 C for 1 2 h, then the solvent was
distilled off, and the residue was maintained in a
vacuum of 0.1 mm Hg at heating to 160 C to remove
excess acetylene and isomeric 1-(p-chlorophenyl)-1,2-
dichloroethenes. Then the glass-like light-brown
substance containing 77% of 2-oxo-4-p-chlorophenyl-
2-oxo-2,5,6,7.8-pentachlorobenzo[e]-1,2-oxphos-
phorin-3-ene (IVc) was characterized by spectral
methods. 31P NMR spectrum (162.0 MHz, CDCl3),
3. Cherkasov, R.A. and Pudovik, M.A., Usp. Khim.,
1994, vol. 63, no. 12, pp. 1087 1113.
4. Gloede, J., Z. Chem., 1982, vol. 22, no. 4,
pp. 126 134.
1
, ppm: 15.2 d (2JPCH 25.5 Hz). H NMR spectrum
(CDCl3), , ppm: 6.57 d (2JPCH 25.3 Hz). Mass
spectrum, m/z (Irel, %), ion composition: 446 (46.1)
[M] + , 447 (9.4), 448 (70.5), 449 (12.0), 450 (63.1),
451 (11.7), 452 (24.2), 453 (5.5), 454 (7.4), 411
(72.8) [M Cl]+ , 412 (17.4), 413 (100.0), 414 (18.3),
415 (66.2), 416 (11.6), 417 (22.8). The oily sub-
stance was dissolved in dioxane and treated with
excess water. The water-dioxane solution obtained
was poured into 100 ml of 20% KOH solution and
heated to 70 C. Insoluble resin was separated, and
the water-dioxane mixture was acidified with HCl to
pH 5 and then extracted with warm benzene (30
40 C). The benzene layer was separated, at cooling to
20 C formed a precipitate that was filtered off and
washed with ether. 2-(1-Hydroxy-2,3,4,5-tetrachloro-
phenyl)-2-(p-chlorophenyl)vinylphosphonic acid (VIc)
obtained was recrystallized from benzene and acetone,
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