Chlorinations of derivatives of 2,2,2-trichlorobenzo-1,3,2-dioxaphospholes

Article abstract of DOI:10.1134/S1070428008070087

By ³¹P, ¹³C, ¹³C-{¹H}, and ¹H NMR spectroscopy the chlorination of 4-and 5-methyl-2,2,2- trichlorobenzo-1,3,2-dioxaphosphols was shown to provide in quantitative yield 4-methyl-2,2,2,5-tetrachloroand

Full text of DOI:10.1134/S1070428008070087

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 7, pp. 988−999. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © E.N. Varaksina, V.F. Mironov, A.A. Shtyrlina, A.B. Dobrynin, K.Yu. Cherkin, A.T. Gubaidullin, I.A. Litvinov, A.I. Konovalov, 2008,
published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 7, pp. 999−1010.
Chlorinations of Derivatives
of 2,2,2-Trichlorobenzo-1,3,2-dioxaphospholes
E. N. Varaksina, V. F. Mironov, A. A. Shtyrlina, A. B. Dobrynin,
K. Yu. Cherkin, A. T. Gubaidullin, I. A. Litvinov, and A. I. Konovalov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
Kazan, 420088 Russia
Received August 30, 2007
1
Abstract—By 31P, 13C, 13C-{1H}, and H NMR spectroscopy the chlorination of 4- and 5-methyl-2,2,2-
trichlorobenzo-1,3,2-dioxaphosphols was shown to provide in quantitative yield 4-methyl-2,2,2,5-tetrachloro-
and 6-methyl-2,2,2,5-tetrachlorobenzo-1,3,2-dioxaphosphols. Their hydrolysis led to the formation of difficultly
available 4-methyl-5-chloro- and 3-methyl-4-chloro-1,2-dihydroxybenzenes. The structure of the latter compound
was established by XRD analysis. The 5-methyl-2-chlorobenzo-1,3,2-dioxaphosphol treated with excess chlorine
was converted in succession into 5-methyl-2,3,4,5,6,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate and 5-
methyl-1,2,4,4,5,6-hexachlorocyclohex-1-en-3-yl dichlorophosphate. The hydrolysis resulted in 5-methyl-
2,3,4,5,6,6-hexachlorocyclohex-2-en-1-yl dihydrophosphate. The configuration of three chiral carbon atoms in
the latter was established by XRD study. In the course of the chlorination the aromaticity of the ortho-phenylene
fragment was distorted and 3,3-sigmatropic shift of the dichlorophosphoryl group occurred. The reaction with
chlorine of 5-tert-butyl-2,2,2-trichlorobenzo-1,3,2-dioxaphosphol and 2,2,2-trichloro-benzo-1,3,2-dioxaphosphol
was not selective: The reaction product obtained in excess chlorine transformed on hydrolysis into
tetrachloropyrocatechol. Its solvates with water and dioxane were studies by XRD analysis.
DOI: 10.1134/S1070428008070087
1,2-Dihydroxybenzenes (catechols or pyrocatechols)
and their derivatives play an important part in organic
sysnthesis and in the synthesis of natural substances and
also in the metabolism of aromatic hydrocarbons [1–7].
Despite the enormous number of publications concerning
their preparation the problem of selective introduction
of functional groups, in particular, of halogen, into the
catechol molecule remains urgent [8–10]. The
electrophilic substitution with chlorine and bromine in
the 2-methoxy-4-methylphenol is known to proceed
nonselectively, and in the halogen excess form the
corresponding 2,5,6-trihaloderivatives [11, 12]. Mono-
and dihaloderivatives of some pyrocatechols were later
obtained in moderate yields using milder halogenating
agents (SOCl2, SO2Cl2, CH3COCl etc.) in various
solvents [13]. The application of cyclic ethers based on
pyrocatechol, like benzo[d]-1,3-dioxolane, proved to be
efficient [14–17]. At the use of methyl-substituted
anilines and phenols alongside the common substitution
a rare process occurred of a distortion of the benzene
ring aromaticity, and already in the conventional
conditions mixtures of diastereomers of polychlorinated
cyclohexen-3-ones were obtained [18]. The distortion
of aromaticity was also observed at benzene chlorination
under UV irradiation to provide cyclohexane and
cyclohexene derivatives [19–22] and at phenol chlorina-
tion in alkaline medium [23]. No examples are known
of clean and selective halogenation of cyclic systems with
the catechol moiety included into a P-heterocycle (benzo-
1,3,2-dioxaphosphol) (a review on the chemical properties
of these compounds, see [24]).
In this study aiming at the preparation of chloro-
catechols we brought into the chlorination reaction
3
2-chlorobenzo-λ -1,3,2-dioxaphosphols I–IV. The reac-
tion with chlorine of these compounds occured in several
stages but in all events at equimolar reagents ratio
according to reports cited in [24] first formed penta-
coordinate phosphorus derivatives, 2,2,2-trichlorobenzo-
5
λ -1,3,2-dioxaphospholes V–VIII that could be isolated
in high yield and purified by vacuum distillation.
988

CHLORINATIONS OF DERIVATIVES OF 2,2,2-TRICHLOROBENZO-1,3,2-DIOXAPHOSPHOLES
989
OH
OH
Cl2
methyl made it possible to unambiguously assign the
signals of C4,7 and C3a,7a in phosphol X. In the latter
case the assignment was additionally supported by the
multiplicity of signals from C7 and C7a in the 13C NMR
spectrum due to the couplings with the protons of methyl
group.
O
O
PCl3
R
PCl
R
_2 HCl
I_IV
O
R
PCl3
The regiochemistry of chlorination is consistent with
the electrophilic character of the reaction and can be
ascribed to the joint orientation from two ortho-para
directing substituents (methyl group and one of the
oxygen atoms). In the ordinary reactions of electrophilic
chlorination of aromatic compounds iron or aluminum
chlorides are as a rule used as catalysts, but the
halogenation of phenols or dihydroxy benzenes does not
require catalysts. The easily proceeding chlorination of
benzo-1,3,2-dioxaphosphol that has not been formerly
known [24] is an uncommon event and it is evidently
due to the catalytic effect of the pentacoordinate phos-
phorus atom acting as a Lewis acid on the polarization
of the chlorine molecule.
O
V_VIII
R = H (I, V), 4-Me (II, VI), 5-Me (III, VII), 5-Bu-t (IV,
VIII).
We revealed for the first time that phosphols VI and
VII were capable to undergo regioselective chlorination
into the benzene ring leading to the formation of
compounds IX and X in high yields. In their 31P-{1H}
NMR spectra characteristic signals appeared at δP –22.8
and –24.1 ppm.
Me
4
Me
Cl
3
O
The chlorination of benzophosphols V and VII with
equimolar quantity of chlorine followed by hydrolysis
of compounds IX and X can be regarded as a convenient
selective synthesis of methyl-substituted 4- and 5-chloro-
pyrocatechols XI and XII.
Cl
3a
7a
OH
OH
2
H2O
_3 HCl,
_H3PO4
Cl2
_HCl
5
6
PCl3
VI
1
O
7
IX
XI
4
3
O
Cl
The structure of 3-methyl-4-chloropyrocatechol (XI)
was proved by XRD analysis. Four independent
molecules (a, b, c, d) differing from each other in the
experimental error limits are present in the unit cell
(Fig. 1). The bond distances C–C, C–Cl, and C–O are
within the standard limits of this type bonds (Table 1).
Only in one molecule the C–Cl bond is somewhat
3a
Cl
OH
OH
2
Cl2
_HCl
H2O
5
VII
PCl3
_3 HCl,
1
O
6
_H3PO4
7a
Me
7
X
Me
XII
The introduction of a chlorine atom into the benzene
ring is proved by H and 13C NMR spectra. In the
1H NMR spectrum of compounds IX and X in the
downfield region a spectral pattern is observed character-
istic of 1,2,3,4- and 1,2,4,5-tetrasubstituted benzenes. In
the 13C-{1H}NMR spectra of substances IX and X four
signals of carbon atoms appear in the downfield region
which have no direct coupling with protons, and of two
carbon atoms whose signals are split in doublets at
recording the 13C NMR spectra. For phosphol IX the
resonance of atom C7 in the spectrum 13C–{1H} is
1
°
shortened [1.579(8) A] because of the partial occupancy
observed as a doublet with the coupling constant 3JPOCC
7
17.4 Hz. The nuclei of ipso-atoms C3a and C7a are also
easily distinguished not only due to the considerable
difference in the summary effect of chlorine and methyl
(stronger deshielding of C3a atom), but by the multiplicity
of signals in the 13C NMR spectrum (a doublet of doublets
for C7a and a multiplet for C3a). The same difference in
the deshielding para- and ortho-effects of chlorine and
Fig. 1. Four independent molecules (a–d) of 3-methyl-4-
chloropyrocatechol (XI) in the crystal.
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VARAKSINA et al.
990
(50%) of this position of the chlorine atom. Benzene rings
°
of all molecules are flat within 0.01 A; the substituents
are a little deviated from the plane of the rings in the
opposite directions (alternation of substituents in the
1,2,3,4-tetrasubstituted benzene). The exocyclic angeles
at the methyl group in the four independent molecyles
of the substituted pyrocatechol are within the limits of
an ideal value for an sp2-hybridized carbon atom. The
bond angles Cl4C4C5 at the chlorine atom in molecules
XIa, XIb, XId are slightly diminished, and in molecule
XIc this angle is within the standard limits.
In the crystal of compound XI form numerous classic
...
...
and nonclassical hydrogen bonds O–H O and C–H Cl
(Table 2) that result in appearance of a spiral structure
of infinite chain of molecules bound by the hydrogen
bonds along 0x axis (Fig. 2). These spiral structures
penetrate into each other by their coils. Therewith the
chlorine atoms are outside of these spiral structures
forming “chlorine channels.” Owing to the classic
Fig. 2. The formation of supramolecular cylindrical aggregates
...
of molecules XI with classic hydrogen bonds O–H O, along
0x axis (only hydrogens involved in bonds formation are
...
shown).
hydrogen bonds O–H O supramolecular cylindrical
°
Table 1. Main geometrical parameters of compound XI (four independent molecules): bond distances d (A), bond ϕ and torsion
τ angles (deg)
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CHLORINATIONS OF DERIVATIVES OF 2,2,2-TRICHLOROBENZO-1,3,2-DIOXAPHOSPHOLES
991
Table 2. Parameters of hydrogen bonds in the crystal of compound XI
and C7a are distinguished thanks to the difference in the
electronic effect of the chloromethylene and alkenyl
substituents (stronger deshielding of C3a atom). The
signal of another sp3-hybridized atom (C4) appeared in
13C-{1H} as a doublet with a characteristic trans-constant
3JPCCC 18.9 Hz. In the spectrum registered without
decoupling from protons the latter signal additionally
split into a doublet of quartets that was possible only in
case a methyl was attached to C5. The nultiplicity of the
remaining signals corresponded to a double bond C6=C7.
aggregates arise; one such aggregate is shown in Fig. 2
(view along 0x axis, only hydrogens involved in bonds
formation are shown).
Compound XII was formerly obtained by more
complex method [25], and also isolated as a metabolism
product of some microorganisms [26, 27]. Its dichloro-
dioxolane derivative also was known [17]. Catechol XI
was not previously synthesized but it was described as a
metabolism product of 3-chloro-2-methylaniline in
bacteria Phodococeus prodochrous [25] and also as a
metabolism product of 2-chlorotoluene [20, 28, 29].
No further chlorine addition occurred to the double
bond of compound XIII. Dioxaphosphol XIII at storage
for 3–4 days (20°C) gradually transformed into a thick
colorless oily phosphate XIV (δP –1.3 ppm) along the
route of the nonclassical version of Arbuzov reaction.
Its structure was established from the 13C and 13C−{1H}
NMR spectra. Unlike compound XIII phosphate XIV has
in the spectrum a single peak characteristic of the moiety
OC(Cl)C and belonging to C3 (doublet, 2JPOC 15.2 Hz).
Two downfield signals corresponding to the carbon atoms
at the double bond in this case appear as doublets owing
to the coupling with the phosphorus nucleus. Besides
the atoms C4, C5, and C6 involved into coupling with the
protons of methyl resonated upfield in the region
characteristic of sp3-hybridized carbon atoms. In this
stage alongside the allylic rearrangement a regioselective
rupture of the C3a–O bond occurred with the formation
of a phosphoryl group. The regiochemistry of the process
presumably is governed by the stability of the
intermediately arising allyl carbocation with the positive
charge rather on C3a and not on C7a atom.
Dioxaphosphol X is capable of further reaction with
chlorine under mild conditions with the distortion of the
aromaticity of the benzo fragment. We succeeded to
monitor the process by 31P NMR spectroscopy and
demonstrated that the stages are sufficiently different in
kinetics; the latter made it possible to establish the
structure of some intermediate compounds by means 13C
NMR spectroscopy. In the first stage as shown by the
peak with the chemical shift δP –31.5 ppm formed a
compound with a pentacoordinate phosphorus XIII. The
distortion of the aromaticity of the benzene ring and
formation of a single diastereomer at arising of four chiral
centers (C3a, C4, C5, C7a) was established based on the
13C-{1H} and 13C NMR spectra of this compound. In
molecule XIII five of the seven carbon nuclei resonate
in the strong field characteristic of sp3-hybridized carbon
atoms. The presence of two signals in the region 95–101
ppm indicates the addition of chlorine across the ð-bond
OC3a=C7aO resulting in formation of a fragment
OC3a(Cl)C7a(Cl)O [30]. The nuclei of the ipso-atoms C3a
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VARAKSINA et al.
992
Compound XVI crystallized as a salt of alkyl-
In phosphate XIV at long storage (20°C) or at heating
phosphoric acid with a DMSO molecule XVII and
formed a solvate with a water molecule. XRD data for
salt XVII (Fig. 3, Table 3) show the presence in the single
crystal of two enantiomers A and B in the ratio 1:1 of
a configuration C3 C5 C6 /C3 C5 C6 . The carbocycle
an uncommon 3,3-sigmatropic shift of the dichloro-
phosphate group occurred formerly unknown from
publications. It may be regarded as a version of Claisen
3,3-rearrangement [31].According to NMR spectra, phos-
phate XV formed as a single diastereomer with a P–O
bond stable against hydrolysis.
R
S
S
S
R
R
in molecule A occurs in a semichair conformation: Four-
°
Table 3. Main geometrical parameters of solvate XVII (two independent molecules): bond distances d (A), bond ϕ and torsion
τ angles (deg)
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CHLORINATIONS OF DERIVATIVES OF 2,2,2-TRICHLOROBENZO-1,3,2-DIOXAPHOSPHOLES
993
4
Cl
3a
7a
5
O
O
PCl3
6
Me
7X
Cl
7
1
O
1
Cl
Cl
Cl
6
2
Cl
6
Cl
2
Cl2
*
*
7a
3a
O
PCl3
5
3
5
3
O
*
*
*
*
*
Cl
Me
O PCl2
4
4
Me
Cl
Cl
Cl
Cl
XIII
XIV
O
O
O PCl2
O P(OH)2
Cl
Cl
3
3
*
4
Δ
2
4
2
Cl
Cl
Cl
Cl
Cl
Cl
H2O
*
5
5
*
*
Fig. 3. Structure of phosphate salt with DMSO XVII (solvate
with water) in the crystal.
*
Cl
Me
*
1
1
Cl
6
6
Me
Cl
Cl
°
XV
XVI
Cl2A–C2A 1.68(1), Cl1B–C1B 1.71(1), Cl2B–C2B 1.65(1)A].
Inasmuch as in the crystal lattice four solvate molecules
are present (2DMSO and 2H2O) numerous classic
°
atom fragment C6C1C2C3 is planar within 0.08(1) A ,
atoms C4 and C5 deviate in different directions from this
...
hydrogen bonds O–H O form in the crystal that result
°
plane by –0.31(1) and 0.31(1) A; in molecule Β the carbo-
in infinite layers along one of the crystallographic axes.
The system of hydrogen bonds in molecule XVII is
shown in Fig. 4. The intra- and intermolecular hydrogen
cycle takes semichair conformation, nearly sofa: Four-
°
atom fragment C6C1C2C3 is planar within 0.02(1) A,
atoms C5 and C4 deviate from this plane by –0.50(2) and
...
...
bonds O–H O and O–H Cl lead to the formation of
a bilayer structure alond the 0y axis. Parameters of the
bonds are given in Table 4.
°
0.17(1) A respectively. The deviation of these atoms in
different directions just permits the nomination of this
conformation as semichair. However the minimal
Unlike 5-methyl-2,2,2,6-tetrachlorobenzo[d]-1,3,2-
dioxaphosphol (X), 4-methyl-2,2,2,5-tetra-chlorobenzo-
[d]-1,3,2-dioxaphosphol (IX) did not react with excess
chlorine under the common conditions. 5-tert-Butyl-
2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphol (VIII) and
unsubstituted compound I underwent a nonselective
chlorination, and at the equimolar reagents ratio formed
°
deviation of atom C4B [0.17(1) A ] from the plane
C6BC1BC2BC3B also permits to regard the five-atom
fragment C6BC1BC2BC3BC4B as nearly planar and the cycle
conformation, as sofa. Bond lengths C–Cl at the double
bond C=C are shortened due to the effect of the
phosphorus substituent at atom C1 [Cl1A–C1A 1.67(1),
Table 4. Parameters of hydrogen bonds in the crystal of salt XVII (solvate with water)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

VARAKSINA et al.
994
°
Table 5. Geometric parameters of tetrachloropyrocatechol solvate with dioxane XIX: bond distances d (A) and bond angles ϕ
(deg)
a complex mixture of chlorinated benzophosphols. The
O
prolonged passing of chlorine in a large excess through
solutions of phosphol VIII in dichloromethane resulted
in the formation of 2,2,2,4,5,6,7-heptachlorobenzo[d]-
Cl
PCl3
PCl3
O
Cl
Cl
O
O
4Cl2
VIII
PCl3
5
λ -1,3,2-dioxaphosphol (XVIII). In the course of the
O
process the tert-butyl group suffered an ipso-replacement,
and the arising tert-butyl chloride was identified in the
1H NMR spectrum. In the 31P NMR spectrum phosphol
XVIII gave rise to an upfield singlet at δ –22.9 ppm.
Cl
XVIII
O
I
Cl
By hydrolysis of compound XVIII we obtained
tetrachloropyrocatechol XIX whose structure was
established by XRD analysis of two types of single
crystals obtained: solvate with dioxane a and solvate with
water b. The general view of solvates with dioxane a
Cl
Cl
OH
OH
H2O
_3 HCl,
_H3PO4
Cl
XIX
and with water b are presented on Figs. 5 and 6
respectively. The parameters of cataechol XIX (bond
distances and bond angles) are compiled in Table 5.
In the crystal of solvate a with dioxane of tetrachloro-
pyrocatechol XIX an intramolecular and intermolecular
hydrogen bonds exist. The bifurcate intramolecular
...
hydrogen bond O1–H1 O2 has the following parameters:
°
...
...
O1–H1 0.73(3), H1 O2 2.15(3), O1 O2 2.655(2) A, angle
...
O1–H1 O2 127(2)°. Another hydrogen bond is of three-
center character and is involved into an intra-molecular
contact O2–H2 Cl3 [O2–H2 0.76(3), 2.72(3), O2 Cl3
...
...
°
3.020(1) A, angle 106(2)°] and anintermolecular contact
...
...
O2–H2 O11 with parameters: O2–H2 0.76(3), H2 O11
°
...
...
1.92(3), O2 O11 2.630(2) A, angle O2–H2 O11 156(3)°.
In the crystal of solvate b of tetrachloropyrocatechol
Fig. 4. Hydrogen bonds system in the crystal of salt XVII
(view along 0°C axis).
with water (Fig. 6) a complex three-dimensional network
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CHLORINATIONS OF DERIVATIVES OF 2,2,2-TRICHLOROBENZO-1,3,2-DIOXAPHOSPHOLES
formed because of intermolecular hydrogen bonds O–
995
...
...
H
O and O–H Cl (Fig. 7). Tetrachloropyrocatechol
formed crystalline adducts with triphenylphosphine oxide
[32], triphenylphosphine oxide and water [32],
triphenylarsine oxide [33], and 2,2-bis(diisopropyl-
amino)-5-[bis(diisopropylamino)phosphinyl]-6,7,8,9-
5
tetrachloro-1,3,4,2-λ -benzoxazaphosphepine and
dichloromethane [34] where also various types of intra-
and intermolecular hydrogen bonds were present.
Thus it was shown for the first time that the trans-
formation of an ortho-hydroxy fragment into a cyclic
phosphol resulted in an increased regio- and stereo-
selectivity of chlorination of substituted benzenes. This
procedure can be a convenient method for chloro-
catechols preparation.
Fig. 5. Molecule of tetrachloropyrocatechol XIX solvate a
with dioxane in the crystal (hydrogen bonds are shown by
dotted lines).
EXPERIMENTAL
The solvents and reagents used were purified and
dried by conventional methods.All reactions were carried
out under an atmosphere of dry argon. NMR spectra were
registered on spectrometers Bruker MSL-400 [400 (1H),
162.0 (31P), 100.6 MHz (13C)], Bruker WM-250 [250
MHz (1H)], Bruker CXP-100 [36.48 MHz (31P)]. The δP
values were measured relative to an external reference
(H3PO4), δC and δH values, with respect to internal
reference (HMDS). Parameters of X-ray diffraction
experiments are compiled in Table 6.
Fig. 6. Molecule of tetrachloropyrocatechol XIX solvate b
with water in the crystal (hydrogen bonds are shown by dotted
lines).
5-Methyl-2-chlorobenzo-1,3,2-dioxaphosphol
(III). A mixture of 10 g of 4-methylpyrocatechol, 22.2
ml of PCl3, and several drops of water was stirred for 1 h
at 100–110°C, then it was maintained in a vacuum to
remove excess PCl3. The residue was distilled. Yield 13.7
g (91%), bp 65°C (1 mm Hg). 31P-{1H} NMR spectrum:
δP 176.6 ppm
4-Methyl-2,2,2-trichlorobenzo-1,3,2-dioxaphos-
phol (VI). To a solution of 3.85 g of dioxaphosphol II in
15 ml of dichloromethane was added at stirring under
an argon atmosphere while cooling (–70°C) a solution
4-Methyl-2-chlorobenzo-1,3,2-dioxaphosphol (II).
A mixture of 12.8 g of methylpyrocatechol, 14 ml of
PCl3, and several drops of water was stirred for 1.5 h at
100°C. Excess PCl3 was removed in a vacuum (12 mm
Hg), the residue was distilled. Yield 17.3 g (89%), bp
65°C (1 mm Hg), nD 1.5630. 1H NMR spectrum
20
(CDCl3), δ, ppm: 2.41 s (3H, CH3), 6.99–7.10 m (3H,
H5–7, AΒC). 31P-{1H} NMR spectrum (36.46 MHz,
CDCl3): δP 174.2 ppm.
Fig. 7. Hydrogen bonds system in the crystal of tetrachloropyrocatechol XIX solvate with water.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

VARAKSINA et al.
996
Table 6. Crystal parameters of compounds XI, XVII, and XIX, and the conditions of XRD experimentsa
a Diffractometer Enraf-Nonius CAD-4; scanning ω/2θ; variable scanning rate, 1–16.4 deg/min by θ; no correction of intensity of control
reflexions was done; applied programs of XRD analysis MolEN, AlphaStation 200 [35]. bStructure solved by the direct method, program
SIR [36]; refinement by full-matrix least-squares method. The intermolecular contacts, in particular, hydrogen bonds, in the crystals were
c
analyzed with the use of PLATON software [37]. Structure solved by the direct method, program SIR [36]; refinement by SHELX
d
e
program [38]. Figures in parentheses are standard deviations. The extiction was not taken into account because of weakly reflecting
crystal.
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CHLORINATIONS OF DERIVATIVES OF 2,2,2-TRICHLOROBENZO-1,3,2-DIOXAPHOSPHOLES
997
3
6.2 Hz], 129.02 d.q.d (s) [C5, J(HC7CC5) 10.7,
of 1.45 g of chlorine in 10 ml of dichloromethane. The
reaction mixture was maintained in a vacuum to remove
excess chlorine and solvent. Yield 97%. Thick yellowish
3J(HCCC5) 5.4, J(HC6C5) 4.4 Hz], 122.89 d (s) [C6,
2
1J(HC6) 168.5 Hz], 108.77 d.d (d) [C7, J(HC7) 170.2,
1
1
3J(POCC7) 17.4 Hz], 140.33 br.d.d (br.s) [C7a,
oily substance, bp 97–101°C (0.8 mm Hg). H NMR
spectrum (CDCl3), δ, ppm: 2.41 s (CH3), 7.17 br.d (H7,
3J(HC6CC7a) 12.0, J(HC7C7a) 3.6 Hz], 12.74 q.d (d)
2
3JH CCH
6
7 8.8 Hz), 6.99–7.04 br.m (H5, H6, 3JH CCH
6
5 8.5
[CH3, 1J(HC) 129.9, 4J(POCCC) 1.1 Hz]. 31P-{1H} NMR
spectrum (162.0 MHz, CDCl3): δP –22.8 ppm
Hz). 13C NMR spectrum [here and hereinafter the form
of signal indicated in parentheses corresponds to the
spectrum 13C-{1H}] (CDCl3), δ, ppm: 140.10 m (d) [C3a,
6-Methyl-2,2,2,5-tetrachlorobenzo-1,3,2-dioxa-
phosphol (X). To a solution of 6.2 g of phosphite III in
30 ml of dichloromethane was added at stirring while
cooling (–60°C) a solution of 5 g of chlorine in 25 ml of
dichloromethane. The reaction mixture was slowly
warmed to 20°C and left standing for 3 days. The solvent
and excess chlorine were removed in a vacuum. Yield
9.3 g (96%). Thick yellowish oily substance. 13C NMR
spectrum (CDCl3), δ, ppm: 141.04 d.d.d (d) [C3a,
3
2J(POC3a) 1.3 Hz], 121.28 d.d.q.d (d) [C4, J(POCC4)
3
3
2
17.0, J(HCCC4) 6.7–6.8, J(HC6CC4) 7.1, J(HC5C4)
2.0 Hz], 124.81 d.d.q (s) [C5, 1J(HC5) 160.4, 3J(HC7CC5)
7.6, 3J(HCCC5) 5.0 Hz], 122.74 d (s) [C6, 1J(HC6) 163.9
Hz], 107.99 d.d.d (d) [C7, J(HC7) 167.6, J(POCC7)
1
3
3
18.0, J(HC5CC7) 8.8 Hz], 142.23 br.d (br.s) [C7a,
3J(HC6CC7a) 10.2 Hz], 14.62 br.q.d (d) [CH3, J(HC)
1
128.2, J(POCCC) 1.1 Hz]. 31P-{1H} NMR spectrum
3
3
2
2J(POC3a) 0.9, J(HC7CC3a) 7.5, J(HC4C3a) 4.3 Hz],
111.62 d.d (d) [C4, J(HC4) 170.8, J(POCC4) 17.7,
4J(HCCCC4) 0.8–0.9 Hz], 131.28 q.d (s) [C6, 2J(HC4CC6)
12.0, 2J(HCC6) 6.0 Hz], 128.08 d.q.d (s) [C5, 3J(HC7CC5)
10.3, 2J(HC4C5) 5.1, 3J(HCCC5) 5.2 Hz], 112.63 d.d.q.d
(d) [C7, 1J(HC7) 166.4, 3J(POCC7) 17.3, 3J(HCCC7) 5.2,
4J(HC4CCC7) 1.3 Hz], 141.11 d.d.d.q (d) [C7a,
1
3
(162.0 MHz, CDCl3): δP –25.7 ppm.
5-Methyl-2,2,2-trichlorobenzo-1,3,2-dioxa-
phosphol (VII). To 7.4 g of phosphite III at –60°C was
added a solution of 2.8 g of chlorine in 15 ml of
dichloromethane, then the solvent and excess chlorine
were removed. Yield 97%. Thick yellowish oily
substance, bp 95–100°C (0.8 mm Hg). 13C NMR
spectrum (CDCl3), δ, ppm: 142.84 d.d.d (d) [C3a,
3J(HC4CC7a) 7.5, J(HC7C7a) 4.3, J(POC7a) 1.6,
2
2
4J(HCCCC7a) 0.9–1.0 Hz], 20.03 q.d (s) [CH3, J(HC)
1
132.6, J(HC7CC) 3.0 Hz]. 31P-{1H} NMR spectrum
3
2
2
3J(HC7CC3a) 7.1, J(HC4C3a) 3.6, J(POC3a) 0.8 Hz],
(162.0 MHz, CDCl3): δP –24.1 ppm.
111.32 d.d.q.d (d) [C4, 3J(POCC4) 17.6, 3J(HC6CC4) 7.7,
3J(HCCC4) 5.1, J(HC7CCC4) 1.4 Hz], 133.81 d.q (s)
4
3-Methyl-4-chloropyrocatechol (XI). Into a mixture
of 7 ml of water and 1.5 ml of HCl was carefully added
dropwise at stirring (20°C) 5.4 g of phosphol IX.Astrong
heat evolution and hydrogen chloride liberation was
observed. The reaction product was extracted with
hexane at boiling. From the separated hexane layer in
some time crystals precipitated. The crystals were filtered
off and dried in a vacuum (12 mm Hg). Yield 1.1 g (38%),
mp 53–54°C. IR spectrum, ν, cm–1: 454, 544, 584, 655,
727, 817, 839, 854, 893, 1003, 1034, 1113, 1143, 1185,
1209, 1295, 1377, 1461, 1509, 1603, 2855, 2925, 3299.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.19 s (3H, CH3),
6.656–6.70 m (2H, H5, H6, AΒ, 3J 8.6 Hz), 8.54 br.s and
9.37 br.s (2H, OH). Found, %: C 53.11; H 4.77.
C7H7ClO2. Calculated, %: C 53.0; H 4.42.
[C5, 3J(HC7CC5) 7.8, 2J(HCC5) 6.1 Hz], 123.51 d.d.q.d
(C) [C6, 1J(HC6) 161.4, 3J(HC4CC6) 7.0, 3J(HCCC6) 5.1,
2J(HC7C6) 1.1 Hz], 110.43 d.d (d) [C7, J(HC7) 166.7,
1
3J(POCC7) 17.7 Hz], 140.40 m (d) [C7a, 2J(POC7a) 0.8
Hz], 21.21 q.d.d (d) [CH3, 1J(HC) 127.2, 3J(HC4CC) 4.7,
3J(HC6CC) 4.7 Hz]. 31P-{1H} NMR spectrum (162.0
MHz, C6H6): δP –27.3 ppm
4-Methyl-2,2,2,5-tetrachlorobenzo-1,3,2-di-
oxaphosphol (IX). To a solution of 3.6 g of
dioxaphosphol II in 15 ml of dichloromethane was added
at stirring while cooling (–60°C) a solution of excess
chlorine (4 g) in 20 ml of dichloromethane. The reaction
mixture was slowly warmed to 20°C and left standing
for 6 days. The solvent and excess chlorine were removed
in a vacuum (12 mm Hg). Yield 97%. Thick yellowish
oily substance. 1H NMR spectrum (CDCl3), δ, ppm: 2.32 s
4-Methyl-5-chloropyrocatechol (XII). To a solution
of 10.0 ml of water and 0.5 ml of hydrochloric acid was
added at vigorous stirring (20°C) 9.3 g of phosphorane
X. The reaction mixture was heated at stirring on a water
bath (60°C) for 1 h. The crystals precipitated on cooling
were filtered off and recrystallized from hexane. Yield
2.3 g (46%), mp 106–107°C. IR spectrum, ν, cm–1: 453,
544, 586, 656, 726, 817, 837, 857, 892, 943, 1002, 1035,
3
4
(CH3), 6.87 br.d.d [H7, J(H6CCH7) 8.6, J(POCCH7)
1.0 Hz], 7.04 br.d.d [H6, 3J(H6CCH7) 8.6, 5J(POCCCH7)
1.4 Hz]. 13C NMR spectrum (CDCl3), δ, ppm: 141.87 m
(d) [C3a, J(POC3a) 2.1 Hz], 120.27 d.d.q (d) [C4,
3J(POCC4) 16.5, J(HC6CC4) 6.0–6.2, J(HCC4) 6.0–
2
3
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

VARAKSINA et al.
998
(C5), 65.39 br.d (br.s) [C6, 1J(HC6) 163.4 Hz], 25.63 br.q
1113, 1143, 1185, 1209, 1292, 1350, 1377, 1462, 1511,
1603,1658, 1721, 1932, 2855, 2925, 2955 3298. H NMR
spectrum (DMSO-d6), δ, ppm: 2.16 s (3H, CH3), 6.71 s
and 6.77 s (2H, H4, H6). Found, %: C 53.17; H 4.59.
Calculated, %: C 53.0; H 4.42.
1
(br.s) [C7H3, J(HC7) 132.8 Hz]. 31P NMR spectrum
1
(162.0 MHz, CDCl3), δ, ppm: 13.2 d (3JPOCH 12.0 Hz).
5-Methyl-2,3,4,5,6,6- hexachlorocyclohex-1-en-3-
yl dihydrophosphate (XVI) was obtained by hydrolysis
of phosphate XV in aqueous acetone. After prolonged
crystallization from aqueous DMSO colorless crystals
of phosphate XVI were obtained as solvate XVII with
Chlorination of dioxaphosphol (X). To a solution
of 6.5 g of phosphol X in 20 ml of CH2Cl2 while stiring
under an argon atmosphere was added a solution of
1.9 g of chlorine in 20 ml of CH2Cl2 at –50°C. After
3 days a mixture was obtained of compounds XIII
(δP –23.2 ppm) and XIV (δP –1.3 ppm) in a ratio 3:2;
after 6 days the ratio reached 1:6. Compound XIII
completely converted in phosphate XIV within two
weeks (25°C).
1
DMSO and water, mp 211°C. H NMR spectrum (400
MHz, DMSO-d6), δ, ppm: 2.08 br.s (3H, CH3), 5.60 d
3
6
(1H, H6, JPOCH 12.6 Hz), 5.69 d (1H, H3, JPOCCCCH
1.1 Hz). Found, %: C 21.63; H 3.32; P 6.19.
C7H6Cl6O4P·C2H7OS·H2O. Calculated, %: C 21.82;
H 3.03; P 6.26.
Chlorination of 2,2,2-trichlorobenzo-1,3,2-
dioxaphosphol (V). Through a solution of 4.1 g of
compound V in 10 ml of CH2Cl2 at –60°C was passed
excess chlorine. Dichloromethane was distilled off in
a vacuum, to the residue 10 ml of H2O and 1.5 ml of HCl
was added, and the mixture was boiled for 2.5 h. The
water and organic layers separated. From the water layer
precipitated crystals of solvate b of tetrachloro-
pyrocatechol XIX with water, mp 183°C. Crystals for
XRD analysis were obtained by recrystallization of
compound XIX from water and dioxane [solvate a with
dioxane, mp 176–179°C (decomp.)].
5-Methyl-2,2,2,3a,4,5,6,7a-octachloro-3a,7a,4,5-
tetrahydrobenzo-1,3,2-dioxaphosphol (XIII).
Yellowish oily substance. 13C NMR spectrum (CDCl3),
δ, ppm: 95.35 d.d.d (d) [C7a, 3J(HC4CC7a) 2.3, 2J(POC7a)
1.2, 2J(HC7C7a) 1.0–1.1 Hz], 122.94 d.d (s) [C7, 1J(HC7)
4
177.5, J(HC4CCC7) 1.4 Hz], 139.22 d.q (s) [C6,
3
2J(HC7C6) 5.4, J(HC8CC6) 4.3 Hz], 69.95 m (s) (C5),
1
3
69.12 d.d.q (d) [C4, J(HC4) 156.1, J(POCC4) 18.9,
3J(HC8CC4) 3.5 Hz], 100.77 d.d.d (d) [C3a, J(POC3a)
2
5.9, 3J(HC7CC3a) 5.9, 2J(HC4C3a) 2.5 Hz], 25.38 d.q (s)
[C8H3, J(HC8) 132.7, J(HC4CC8) 3.1 Hz]. 31P-{1H}
1
3
NMR spectrum (162.0 MHz, CDCl3): δP –31.5 ppm.
5-Methyl-2,3,4,5,6,6-hexachlorocyclohex-1-en-3-yl
dichlorophosphate (XIV). Colorless oily substance.
13C NMR spectrum (CDCl3), δ, ppm: 132.30 d.d (d) [C1,
1J(HC1) 180.4, 4J(POCCC1) 1.4 Hz], 130.13 d.d (d) [C2,
2J(HC4C2) 5.1, 3J(POCC2) 3.0 Hz], 96.91 d.d.d (d) [C3,
Chlorination of 5-tert-butyl-2,2,2-trichlorobenzo-
1,3,2-dioxaphosphol (VIII). Through a solution of 8.5
g of compound VIII in 20 ml of CH2Cl2 at –40°C was
passed excess chlorine. The solvent was removed in a
vacuum, to the residue 15 ml of H2O and 5 ml of HCl
was added dropwise. The reaction mixture was boiled
for 2.5 h, and then dark-brown oily organic layer
separated from the water layer. From the water layer
gradually precipitated transparent needle crystals that
were filtered off and recrystallized from water. Yield of
solvate b of tetrachloropyrocatechol XIX 0.12 g, mp 183–
184°C (decomp.).
3
2
2J(POC3) 15.2, J(HC4CC3) 11.3, J(HCC3) 1.2 Hz],
1
3
71.16 d.d.q (d) [C4, J(HC4) 158.5, J(POCC4) 3.5,
2J(HCC4) 3.3 Hz], 75.37 d.d.q (s) [C5, 3J(HC4CC5) 5.3,
2J(HCC5) 5.3, J(HCC5) 4.2 Hz], 87.97 m (s) [C6,
2
3J(HC7CC6) 4.2, J(HCCC6) 2.7, J(HCC6) 1.5 Hz],
3
2
23.00 d.d (s) [C7, J(HC7) 132.7, J(HC4CC7) 4.4 Hz].
31P-{1H} NMR spectrum (162.0 MHz, CDCl3): δP –1.3
ppm.
1
3
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant
no. 07-03-00180) and of grant MK-1434.2006.3.
5-Methyl-1,2,4,4,5,6-hexachlorocyclohex-1-en-3-yl
dichlorophosphate (XV) was obtained by heating
(180°C, 5 min) of phosphate XIV. Yellow transparent
viscous fluid containing 90% of compound XV (3.5 g),
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 7 2008

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