Chlorination of N-(N-arylsulfonylarylimidoyl)-1,4-benzoquinone imines and their reduced forms

Article abstract of DOI:10.1023/A:1016555324390

The study of chlorination of N-(N-arylsulfonylarylimidoyl)-1, 4-benzoquinone imines and of N-(N-arylsulfonylarylimidoyl)-1,4-aminophenols revealed that the dominant stage in the process was the formation of cyclohexene structures, 4-(N-arylsulfonylarylimidoyl)imino-2,5,6-trichloro-2-cyclohexene-1-ones, resulting from addition of a Cl₂ molecule across the C=C bond of the quinoid ring. These substances suffer a prototropic rearrangements yielding N-(N-arylsulfonylarylimidoyl)-2,3,6-trichloro-4-aminophenols. The latter are the most common reaction products. The products of deeper chlorination were also obtained.

Full text of DOI:10.1023/A:1016555324390

Russian Journal of Organic Chemistry, Vol. 38, No. 4, 2002, pp. 546 552. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 4, 2002,
pp. 571 577.
Original Russian Text Copyright
2002 by Avdeenko, Marchenko, Konovalova.
Chlorination of N-(N-Arylsulfonylarylimidoyl)-1,4-benzoquinone
Imines and Their Reduced Forms
A. P. Avdeenko, I. L. Marchenko, and S. A. Konovalova
Donbass State Machinebuilding Academy, Kramatorsk, 184313 Ukraine
Received December 14, 2001
Abstract The study of chlorination of N-(N-arylsulfonylarylimidoyl)-1,4-benzoquinone imines and of
N-(N-arylsulfonylarylimidoyl)-1,4-aminophenols revealed that the dominant stage in the process was the
formation of cyclohexene structures, 4-(N-arylsulfonylarylimidoyl)imino-2,5,6-trichloro-2-cyclohexene-1-
ones, resulting from addition of a Cl2 molecule across the C=C bond of the quinoid ring. These substances
suffer a prototropic rearrangements yielding N-(N-arylsulfonylarylimidoyl)-2,3,6-trichloro-4-aminophenols.
The latter are the most common reaction products. The products of deeper chlorination were also obtained.
In the preceding investigation on chlorination of
N-arylsulfonyl-1,4-benzoquinone imines and N-aryl-
sulfonyl-1,4-aminophenols we demonstrated that
depending on the solvent, temperature, and molar
ratio of the initial substrate to chlorine the reaction
gave rise to N-arylsulfonyl-2,3,6-trichloro-4-amino-
The chlorination of N-aroyl-4-aminophenols
afforded only N-aroyl-2,3,6-trichloro-4-aminophenols
and
N-aroyl-2,3,5,6-tetrachloro-1,4-benzoquinone
imines [3]. The stability of N-aroyl-1,4-benzoquinone
imines unsubstituted in the ring is very low, and
therefore their reactivity, in particular in chlorination,
was not investigated.
phenols,
N-arylsulfonyl-2,3,6-trichloro-1,4-benzo-
quinone imines, and N-arylsulfonyl-2,3,5,6-tetra-
chloro-1,4-benzoquinone imines [1]. We failed to
isolate products containing one or two chlorine
atoms. We also obtained semiquinoid structures
resulting from addition of a Cl2 molecule across a
double bond of the quinoid ring, 2,3,5,6,6-penta-
chloro[2]- and 2,3,5,5,6,6-hexachloro[1]-4-arylsul-
fonylimino-2-cyclohexen-1-ones.
N-(N-Arylsulfonylarylimidoyl)-1,4-benzoquinone
imines are derivatives of N-aroyl-1,4-benzoquinone
imines where in the aroyl group the oxygen in C=O
is replaced by arylsulfonylimino group (ArSO2N=).
Therefore we expected to obtain similar results of
chlorination.
The target of this study was to investigate the
chlorination process of N-(N-arylsulfonylarylimido-
yl)-1,4-benzoquinone imines and reduced forms
thereof and to reveal by this example the intermediate
stages of the process that provides prevailingly
products containing three chlorine atoms.
Several schemes of multistage chlorination process
were suggested [1]. (1) N-Arylsulfonyl-4-amino-
phenols first are oxidized with Cl2 to the respective
quinone imines that further can add a Cl2 molecule
followed by dehydrochlorination or add HCl
molecule with subsequent oxidation. The above
chlorination products arise due to alternation of these
processes. (2) N-Arylsulfonyl-1,4-benzoquinone
imines first add a chlorine molecule to the C=C bond
of the quinoid ring followed by dehydrochlorination,
and the arising N-arylsulfonyl-2-chloro-1,4-benzo-
quinone imine can either add a chlorine molecule
attended by dehydrochlorination or take up HCl
molecule with subsequent oxidation.
The chlorination of N-(N-arylsulfonylarylimidoyl)-
1,4-aminophenols (Ia c) and N-(N-arylsulfonylaryl-
imidoyl)-1,4-benzoquinone imines (IIa, b) was per-
formed with a flow of chlorine gas through a solution
of a substrate at a rate of 15 20 ml per min. Acetic
acid, dimethylformamide, a mixture of acetic acid and
DMF (5: 1), and chloroform were used as solvents.
The amount of chlorine passed through the reaction
mixture was evaluated from the gained weight save at
the use of chloroform as solvent.
The reason why not a single chlorination experi-
ment with N-arylsulfonyl-1,4-benzoquinone imines
or their reduced forms yielded chlorination products
containing one or two chlorine atoms remained
unclarified.
In chlorination of N-(N-arylsulfonylarylimidoyl)-
1,4-aminophenols (Ia c) depending on the reaction
conditions individual compounds III X were isolated
(Scheme 1).
1070-4280/01/3804-546$27.00 2002 MAIK Nauka/Interperiodica

CHLORINATION OF N-(N-ARYLSULFONYLARYLIMIDOYL)-1,4-BENZOQUINONE
547
Scheme 1.
Ar = C6H5 (a), 4-CH3C6H4 (b, c); Ar = C6H5 (a, b), 4-ClC6H4 (c).
In chlorination runs with aminophenols Ia, c in
acetic acid, chloroform, and DMF at the molar ratio
substrate:chlorine of 1: 1 1: 2 we succeeded in isolat-
ing monochloro and dichloro derivatives of amino-
phenol and benzoquinone imine IIIa, IVa, Va, c.
fonylbenzimidoyl)-1,4-benzoquinone imine (XIa)
(Scheme 2). Both chlorination of aminophenols Ia c
and benzoquinone imines IIa, b usually afforded
N-(N-arylsulfonylarylimidoyl)-2,3,6-trichloro-4-
aminophenols VIa c.
In the only case at chlorination of N-(N-phenyl-
sulfonylbenzimidoyl)-1,4-benzoquinone imine (IIa)
formed a monochloro derivative of N-(N-phenylsul-
At considerable excess of chlorine form also
N-substituted 2, 3, 6-trichloro-1,4-benzoquinone
imines VIIa c, 2,3,5,6-tetrachloro-4-aminophenols
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

548
AVDEENKO et al.
Melting points and elemental analyses of compounds Xa c, XIVa, b, XVa, b
Found, %
Calculated, %
Compd.
no.
mp, oC (solvent for
recrystallization)
Formula
Cl
H
Cl
H
Xa
Xb
IXc
XIVa
XIVb
XVa
XVb
170 (CH3CO2H)
165 (CH3CO2H)
168 (CH3CO2H)
186 (CH3CO2H)
136 (C6H6)
37.68, 37.91
36.69, 37.07
40.11, 40.37
21.39, 21.41
20.39, 20.45
21.43, 21.49
20.55, 20.59
4.97, 5.13
4.82, 4.95
4.52, 4.73
4.21, 4.26
4.00, 4.11
4.24, 4.31
4.09, 4.12
C19H10Cl6N2O3S
C20H12Cl6N2O3S
C20H11Cl7N2O3S
C13H11Cl2NO3S
C14H13Cl2NO3S
C13H9Cl2NO3S
C14H11Cl2NO3S
38.05
37.12
40.85
21.34
20.48
21.47
20.60
5.01
4.89
4.61
4.22
4.05
4.24
4.07
178 (CH3CO2H)
149 (CH3CO2H)
VIIIa,
b,
2,3,5,6-tetrachloro-1,4-benzoquinone
N-(N-arylsulfonylarylimidoyl)-2,3,6-trichloro-1,4-
benzoquinone imines VIIa c. The latter on chlorina-
tion in acetic acid at heating and large chlorine excess
or in DMF furnish N-(N-arylsulfonylarylimidoyl)-
2,3,5,6-tetrachloro-1,4-benzoquinone imines IXa c
that can be converted into hexachloro semiquinoid
derivatives Xa c only by treating with large excess of
chlorine in DMF.
imines IXa c, and 4-(N-arylsulfonylarylimidoyl-
imino)-2,5,6-trichloro-2-cyclohexene-1-ones Xa c;
however these substances do not arise in all cases of
chlorination of aminophenols Ia c and benzoquinone
imines IIa, b (cf. Schemes 1 and 2).
Thus the chlorination of N-(N-arylsulfonylaryl-
imidoyl)-1,4-aminophenols (Ia c) and 1,4-benzo-
quinone imines IIa, b affords wider range of chlorin-
ation products than has been observed with N-aryl-
sulfonyl-1,4-benzoquinone imines [1] and N-aroyl-
1,4-benzoquinone imines [3], although in the most
cases N-(N-arylsulfonylarylimidoyl)-2,3,6-trichloro-
4-aminophenols VIa c are obtained.
We failed to prepare compounds VIIIa c by
chlorination of derivatives VIIa c. The formation of
tetrachloroquinone imines IXa, c from trichloro-
quinone imines VIIa, c evidences formation of a
semiquinoid structure, 4-(N-arylsulfonylarylimidoyl-
imino)-2,3,5,6,6-pentachloro-2-cyclohexene-1-one,
that is further dehydrochlorinated to yield tetrachloro-
quinone imines IXa, c.
Treating with chlorine in DMF solution of N-(N-
arylsulfonylarylimidoyl)-2,3,6-trichloro-4-amino-
phenols VIa c at moderate ratios chlorine:substrate
afforded oxidation products of the initial compounds,
N-(N-arylsulfonylarylimidoyl)-2,3,5,6-tetrachloro-
4-aminophenols VIIIa, b are oxidized by chlorine in
DMF into the corresponding quinone imines IXa, b.
Scheme 2.
The composition and structure of compounds Xa c
were proved by elemental analyses (see table), IR,
1H and 13C NMR spectra.
In the IR spectra of compounds Xa c the absorption
bands in the regions 1740 1730, 1695 1690, 1590
1
1585, 1335 1325 and 1170 1165 cm are present
characteristic of groups C=O, C=N and SO2 re-
1
spectively. In the H NMR spectra of compounds
Xa, b the corresponding signals from Ar and Ar
groups (CDCl3), , ppm: IXa 7.44 7.80 m (5H,
C6H5 C=N), 7.52 7.06 m (5H, C6H5SO2); IXb
7.43 7.80 m (5H, C6H5 C=N), 7.32 7.93 d.d (4H,
4-CH3C6H4SO2), 2.44 s (3H, CH3) are observed.
In the 13C NMR spectra of compounds Xa, b
appear two signals in the region 89 90 ppm char-
acteristic of two sp3-hybridized carbon atoms of the
Ar = C6H5 (a), 4-CH3C6H4 (b).
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CHLORINATION OF N-(N-ARYLSULFONYLARYLIMIDOYL)-1,4-BENZOQUINONE
549
semiquinoid structure; the other signals are in agree-
ment with the assumed structure , ppm: Xa 172.53
(C=O), 147.14 (C=N), 140.69 (C2), 138.25 (C3),
90.00 (C6), 89.11 (C5) (cyclohexene ring); 162.25
(C=N), 134.07 (C4), 131.24 (C1), 129.10 (C2, C6),
128.81 (C3, C5) (C6H5 C=N), 138.86 (C1), 132.95
(C4), 128.35 (C3, C5), 127.21 (C2, C6) (C6H5SO2);
Xb 172.59 (C=O), 147.03 (C=N), 143.86 (C2),
138.20 (C3), 90.32, 89.99 (C6), 89.44, 89.17 (C5)
(cyclohexene ring), 161.99 (C=N), 133.99 (C4),
129.44 (C2, C6), 129.07 (C3, C5) (C6H5 C=N),
138.92 (C1), 137.74 (C4), 128.37 (C3, C5), 127.35
(C2, C6), 21.55 (CH3) (4-CH3C6H4SO2).
Scheme 3.
Scheme 4.
The other chlorination products according to IR
spectra are identical to previously synthesized com-
pounds [1, 4] with the known structure.
The chlorination of N-(N-arylsulfonylbenzimido-
yl)-2-chloro-1,4-benzoquinone imines XIa, b with
equimolar amount of chlorine afforded N-(N-aryl
sulfonylbenzimidoyl)-2,3,6-trichloro-4-aminophenols
VIa, b in high yield. At the double excess of chlorine
formed N-(N-arylsulfonylbenzimidoyl)-2,3,6-trichloro-
1,4-benzoquinone imines VIIa, b. The reduction of
the ratio Cl2:substrate resulted in lower yield of
aminophenols VIa, b, in the reaction mixture re-
mained unreacted initial quinone imine, but no com-
pounds IVa, b or Va, b containing two chlorine
atoms were formed (Scheme 3).
Ar = C6H5 (a, d), 4-CH3C6H4 (b), 4-ClC6H4 (c); Œ=
CH3 (a, b), Cl (c, d).
shows that in the formation of the corresponding
2,3,6-trichloro-4-aminophenols neither the alternation
of oxidation and hydrochlorination nor addition of
Cl2 to the C=C bond of the quinone imine followed
by dehydrochlorination play the major role in the
general scheme of transformations during the chlorin-
ation of p-quinone imines and their reduced deriv-
atives as has been presumed in [1].
Besides in the course of quinone imines XIa, b
chlorination into aminophenols VIa, b unstable
intermediate compounds XIIa, b of light yellow color
appeared that decolorized within several minutes
during filtration. Compounds XIIa, b obviously
possessed semiquinoid structure: 4-(N-arylsulfonyl-
benzimidoyl)imino-2,5,6-trichloro-2-cyclohexene-1-
ones. We failed to characterize these unstable com-
pounds in any way, even registering of IR or NMR
spectra was impossible.
We additionally supported our assumption on the
dominant role in the chlorination of the N-substituted
p-quinone imines and the reduced forms thereof of
the Cl2 addition across the C=C bond in the quinoid
ring followed by prototropic rearrangement by the
study of chlorination of 2-substituted N-arylsulfonyl-
1,4-benzoquinone imines XIIIa d (Scheme 4).
At equimolar ratio of chlorine to the substrate
aminophenols XIVa d were obtained in high yield.
The increase in the ratio Cl2:substrate to 2: 1 resulted
in formation of the corresponding N-arylsulfonyl-1,4-
benzoquinone imines XVa d, at the reduced ratio the
yield of aminophenols XIVa d decreased, and in the
reaction mixture were found unreacted quinone
imines XIIIa d.
Thus we established that one of the dominant
stages in the chlorination of N-(N-arylsulfonylaryl-
imidoyl)-1,4-benzoquinone imines (II) and their
reduced forms I is formation of semiquinoid struc-
tures by addition of a chlorine molecule across the
C=C bond of the quinoid ring. These intermediate
compounds further undergo prototropic rearrange-
ment affording 2,3,6-trichloro-4-aminophenols VI. It
is therefore understandable why the chlorination of
compounds I and II, also of N-arylsulfonyl-1,4-benzo-
quinone imines, their reduced forms, and N-aroyl-4-
aminophenols results in the corresponding 2,3,6-tri-
chloro-4-aminophenols [1, 3]. The above reasoning
The composition and structure of compounds
XIVa, b, XVa, b was proved by elemental analyses,
1
IR and H NMR spectra. In the IR spectra of com-
pounds XIVa, b are present absorption bands in the
range 3515 3480, 3260 3240, 1340 1330 and 1180
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 4 2002

550
AVDEENKO et al.
1
1170 cm characteristic of OH, NH, and SO2 groups
respectively, in the IR spectra of compounds XVa, b
the bands in the range 1670 1660, 1585 1575, 1560
N-(N-Arylsulfonylarylimidoyl)-2,6-dichloro-4-
aminophenols (IVa, b). Through a solution of 0.5 g
of aminophenol Ia, b in 3 ml of acetic acid or CHCl3
was passed at 20 25 C a flow of chlorine gas till the
gained weight corresponded to the desired ratio sub-
strate: chlorine, 1: 2. The reaction product IVa, b
precipitated after the end of chlorination. The product
was recrystallized from acetic acid, yield of di-
chloride IVa 63%, that of dichloride IVb 42%.
1
1550, 1330 1325 and 1170 1165 cm appear
characteristic of C=O, C=C, C=N and SO2 groups
respectively. In the H NMR spectra of compounds
1
XVa, b appears a characteristic quartet of the H3
proton from the quinoid ring neighboring to a CH3
group. The other signals are in agreement with the
assumed structure (CDCl3), , ppm: XVa 8.04q (1H,
H3), 2.22 d (3H, CH3), 7.58 7.08 m (5H, C6H5SO2);
XVb 8.09 q (1H, H3), 2.21 d (3H, CH3), 7.38
7.94 d.d (4H, 4-CH3C6H4SO2), 2.48 s (3H, CH3).
In CHCl3 aminophenol IVa was prepared at 20 C.
The molar ratio substrate: chlorine was not de-
termined, and chlorine was passed till the product
started to precipitate. Yield of compound IVa 45%.
Compounds XIVc, d, XVc, d according to IR
spectra are identical to the samples with the known
structure described in [1, 4].
N-(N-Arylsulfonylarylimidoyl)-2,6-dichloro-1,4-
benzoquinone imines (Va, c). To a solution of 0.5 g
of aminophenol Ia, c in 3 ml of acetic acid or DMF
was passed a flow of chlorine gas till the gain in
weight corresponded to the desired ratio substrate:
chlorine, 1: 2. Quinone imine Va was obtained by
chlorination in DMF at 40 C. The reaction product
was precipitated by adding water and recrystallized
from acetic acid, yield 52%. Quinone imine Vc was
obtained by chlorination in acetic acid at 25 C. The
reaction product precipitated after the end of chlorin-
ation. The product was recrystallized from acetic
acid, yield 42%.
EXPERIMENTAL
IR spectra were recorded on spectrophotometer
1
UR-20 from KBr pellets. H and 13C NMR spectra
were registered on Varian VXR-300 instrument at
operating frequencies 300 and 75.4 MHz respectively
with TMS as external reference.
Reaction mixtures were analyzed by TLC on
Silufol UV-254 plates. Chloroform was used as
solvent, as eluents were used mixtures of alcohol
chloroform, 1: 1, and benzene hexane, 10: 1,
development under UV irradiation.
N-(N-Arylsulfonylarylimidoyl)-2,3,6-trichloro-4-
aminophenols(VIa c). (a)Through a solution of 0.5 g
of aminophenol Ia c in 3 ml of acetic acid or a mix-
ture of DMF and acetic acid, 1: 5, was passed a flow
of chlorine gas till the gain in weight corresponded to
the desired ratio substrate: chlorine. Aminophenols
VIa c were prepared in the acetic acid at the molar
ratio substrate: chlorine from 1: 2 to 1: 4 and at a
temperature 20 90 C. The highest yield of product
VIa (58%) was obtained at 30 C and molar ratio
substrate: chlorine = 1: 3, for product VIb the yield
of 67% was obtained at 20 C and the molar ratio 1: 4,
for compound Vc the yield of 56% was reached in
reaction performed at 90 C and molar ratio 1: 4.
Compound VIa in the mixture DMF acetic acid, 1: 5,
was prepared at the following temperatures and molar
ratios substrate: chlorine: 30 50 C, 1: 1.5 1: 2.5.
The best yield (46%) was obtained at 30 C and molar
ratio substrate: chlorine 1: 1.5.
The initial compounds were synthesized by
procedures described in [5], by acylation of p-amino-
phenol with appropriate N-arylsulfonylarylimidoyl
chlorides in a mixture DMF acetic acid, 1: 3, follow-
ed by oxidation with lead tetraacetate in acetic acid.
In reaction were brought recrystallized substances and
dried solvents.
N-(N-Phenylsulfonylbenzimidoyl)-2-chloro-4-
aminophenol (IIIa). Through a solution of 0.5 g of
aminophenol Ia in 3 ml of acetic acid was passed at
20 C a flow of chlorine gas till the gained weight cor-
responded to equimolar ratio substrate: chlorine. The
reaction product precipitated after the end of chlorin-
ation. The product was recrystallized from acetic
acid, yield 56%.
N-(N-Phenylsulfonylbenzimidoyl)-2-chloro-1,4-
benzoquinone imine (XIa). Through a solution of
0.5 g of quinone imine IIa in 3ml of a mixture DMF
acetic acid, 1: 5, was passed at 20 C a flow of chlorine
gas till the gained weight corresponded to equimolar
ratio substrate: chlorine. The reaction product
precipitated after the end of chlorination. The product
was recrystallized from acetic acid, yield 35%.
(b) The chlorination of quinone imines IIa, b was
carried out similarly to the above described proce-
dures. Aminophenols VIa, b were prepared in acetic
acid, in a mixture DMF acetic acid, 1: 5, and in
CHCl3. In the acetic acid at 20 C and the molar ratio
substrate: chlorine 1: 2 the aminophenols were pre-
pared in the following yields: VIa, 41%; VIb, 39%.
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CHLORINATION OF N-(N-ARYLSULFONYLARYLIMIDOYL)-1,4-BENZOQUINONE
551
In the mixture DMF acetic acid, 1: 5, aminophenols
VIa, b were chlorinated at 20 50 C and molar ratio
substrate: chlorine from 1: 1 to 1: 2. The highest
yields were reached at the following temperature and
molar ratio: VIa, 20 C, 1: 1, 83%; VIb, 35 C, 1: 1,
79%. Compound VIa was prepared in CHCl3 in the
temperature range 20 35 C at molar ratio of the
reagents from 1: 1 to 1: 5. The best yield (42%) of
chloride VIa was obtained at 35 C and molar ratio of
the reagents 1: 5.
the end of chlorination. The highest yield (71%) of
compound VIIb was obtained at 30 C and the
reagents ratio 1: 5.
(c) Quinone imines VIIa, b were prepared by
oxidation with chlorine of the corresponding amino
phenols VIa, b along the procedures similar to the
above described. The process was carried out in DMF
at 20 C and the molar ratio substrate: chlorine 1: 3
for compound VIIa, 1: 1 for compound VIIb. The
reaction products were precipitated by adding water
and were recrystallized from acetic acid. Yield of
compound VIIa 96%, of compound VIIb 93%.
(c) Compounds VIa, b were obtained by chlorina-
tion of quinone imines XIa, b along procedure
similar to the above described. The reaction was
carried out in acetic acid at 60 70 C and molar ratio
substrate: chlorine from 1: 0.5 to 1: 1.5. The highest
yields of aminophenols VIa, b was obtained at molar
ratio substrate: chlorine 1: 1: for compound VIa
89%, for compound VIb 70%.
N-(N-Arylsulfonylarylimidoyl)-2,3,5,6-tetra-
chloro-4-aminophenols (VIIIa, b). (a) Aminophenol
VIIIb was prepared from aminophenol Ib in a similar
way as above in a mixture DMF CH3COOH, 1: 5, at
35 50 C and the molar ratio of the reagents from
1: 2 to 1: 4. The reaction product precipitated to the
end of chlorination. The highest yield (5%) of amino-
phenol VIIIb was obtained at 35 C and reagents ratio
1: 4.
In all experiments the reaction products VIa c
precipitated to the end of chlorination and were
recrystallized from acetic acid.
N-(N-Arylsulfonylarylimidoyl)-2,3,6-trichloro-
1,4-benzoquinone imines (VIIa c). (a) The chlorin-
ation of aminophenols Ia c was carried out as de-
scribed above in acetic acid, DMF, and a mixture
DMF acetic acid, 1: 5. Quinone imine VIIa was pre-
pared by chlorination in CH3COOH at 30 C and
molar ratio substrate: chlorine 1: 4. The reaction
product was precipitated by water addition, yield
49%. In DMF the quinone imines VIIa c were
obtained at 30 45 C and the molar ratios of substrate
to chlorine from 1: 2 to 1: 6. The reaction product
precipitated after completion of the chlorination. The
highest yields were obtained at the following tempera-
tures and molar ratios of the reagents: compound
VIIa, 30 C, 1: 4, 73%; VIb, 35 C, 1: 6, 92%; VIIc,
35 C, 1: 4, 79%. In the mixture DMF acetic acid,
1: 5, the yields obtained at the following temperatures
and molar ratios of the reagents were as follows:
compound VIIa, 50 C, 1: 3, 48%; compound VIIc,
30 C, 1: 2, 53%. Reaction products VIIa c preci-
pitated to the end of chlorination and were recrystal-
lized from acetic acid.
(b) Aminophenols VIIIa, b were synthesized from
the corresponding quinone imines IIa, b in the
similar way as described above in CH3COOH or
CHCl3. In the acetic acid aminophenols VIIIa, b
were prepared in the temperature range 25 80 C and
at molar ratio substrate:chlorine from 1: 1 to 1: 5.
The best yield was obtained at 80 C and 1: 5 ratio
(41% for compound VIIIa and 45% for compound
VIIIb). In CHCl3 compounds VIIIa, b were obtained
at 40 C and reagents molar ratio 1: 5 in 39 and 35%
yield respectively. The products precipitated to the
end of chlorination and were recrystallized from
acetic acid.
N-(N-Arylsulfonylarylimidoyl)-2,3,5,6-tetra-
chloro-1,4-benzoquinone imines (IXa c). (a)
Quinone imines IX were prepared from aminophenols
Ia, c in a similar way as above in DMF or a mixture
DMF CH3COOH, 1: 5. Reaction in DMF occurred
at 35 50 C and the molar ratio of the reagents from
1: 4 to 1: 6. The highest yield of chlorides was
obtained at the following temperature and reagents
ratio: for compound IXa, 35 C, 1: 5, 66%; for com-
pound IXc, 40 C, 1: 6. 81%. In the DMF
CH3COOH mixture, 1: 5, compound IXc was pre-
pared at 30 C and substrate:chlorine ratio 1: 4 in
30% yield. The products precipitated to the end of
chlorination and were recrystallized from acetic acid.
(b) The chlorination of compound IIb was carried
out along the above described procedures. Quinone
imine VIIb was prepared by chlorination in DMF at
30 C and molar ratio substrate: chlorine 1: 2, from
the reaction mixture the product was precipitated with
water and recrystallized from acetic acid, yield 39%.
The process was performed also in the mixture
DMF acetic acid, 1: 5, at 25 30 C and the reagents
ratio from 1: 4 to 1: 5. Product VIIb precipitated to
(b) Quinone imines IXa, b were prepared from the
corresponding quinone imines IIa, b in a similar way
as above in a mixture DMF CH3COOH, 1: 5 at
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552
AVDEENKO et al.
30 80 C and the reagents ratio from 1: 3 to 1: 5. The
products were precipitated from the reaction mixture
with water and recrystallized from acetic acid. The
best yield of the reaction products was obtained at
temperature and molar ratio of the initial compounds:
of 30 C and 1: 4, 80 and 1: 3 for compounds IXa
(90%) and IXb (52%) respectively.
ed in DMF at the following temperatures and molar
ratios of the reagents: compound Xa, 25 C, 1: 6,
yield 67%; Xb, 45 C, 1: 5, yield 50%; Xc, 50 C,
1: 7, yield 67%. The chlorination products were pre-
cipitated from reaction mixture with water.
N-Arylsulfonyl-2-methyl(chloro)-5,6-dichloro-4-
aminophenols (XIVa d). The synthesis was carried
out by chlorination of the corresponding quinone
imines XIIIa d along procedures described above in
CH3COOH or a mixture DMF acetic acid, 1: 5, at
equimolar amounts of substrate and chlorine in the
temperature range 25 60 C. The reaction products
were either precipitated from the reaction mixture
with water, or the compound precipitated spontaneous-
ly within 24 h. The yields were as follows: compound
XIVa, 50%; compound XIVb, 82%; compound
XIVc, 74%; compound XIVd, 77%. The melting
points and elemental analyses of aminophenols
XIVa, b first obtained are presented in the table.
(c) Quinone imines IXa c were prepared from the
corresponding quinone imines VIIa c in a similar
way as above in DMF at 20 C and the molar reagents
ratio 1: 3. The products were precipitated from the
reaction mixture with water and recrystallized from
acetic acid. The yield of the products was as follows:
IXa, 91%; IXb, 87%; IXc, 81%.
(d) Quinone imines IXa, b were prepared from the
corresponding aminophenols VIIIa, b in a similar
way as above in DMF at 30 C and the molar reagents
ratio 1: 8. Quinone imine IXa was obtained in 90%
yield when the chlorination was carried out at 25 C
and reagents ratio 1: 3; quinone imine IXb was
obtained in 98% yield. The isolation and purification
of compounds IXa, b was performed as above.
N-Arylsulfonyl-2-methyl(chloro)-5,6-dichloro-
1,4-benzoquinone imines (XVa d) were obtained
from the corresponding quinone imines XIIIa d as
above, by chlorination in acetic acid or the mixture
DMF CH3COOH, 1: 5, at the molar reagents ratio
1: 2 in the temperature range 30 60 C. The reaction
product precipitated after storage of the reaction mix-
ture for 24 h, or it was precipitated by water addition.
Yields were as follows: XVa, 96%; XVb, 75%;
XVc, 82%; XVd, 81%. The melting points and
elemental analyses of quinone imines XVa, b first
obtained are presented in the table.
4-(N-Arylsulfonylarylimidoylimino)-2,3,5,5,6,6-
hexachloro-2-cyclohexene-1-ones, (Xa c). (a) Com-
pounds Xa c were obtained by procedure similar to
the above described in DMF or a mixture DMF
CH3COOH, 1: 5. Semiquinoid substance Xb was
obtained in 48% yield by chlorination in DMF at
80 C and molar ratio substrate: chlorine 1: 5. Com-
pounds Xa c were prepared in the mixture DMF
CH3COOH, 1: 5, in the temperature range 45 80 C
and molar reagents ratio from 1: 3.5 to 1: 6.5. The
highest yields were obtained at the following tempera-
tures and molar ratios of the reagents: compound Xa,
50 C, 1: 4, 50%; Xb, 60 C, 1: 6.5, 68%; Xc, 50 C,
1: 6, 67%. The products precipitated to the end of
chlorination and were recrystallized from acetic acid.
REFERENCES
1. Avdeenko, A.P., Velichko, N.V., Romanenko, E.A.,
Pirozhenko, V.V., and Shurpach, V.I., Zh. Org. Khim.,
1991, vol. 27, no. 11, pp. 2350 2361.
2. Avdeenko, A.P. and Zhukova, C.A. , Zh. Org. Khim.,
1999, vol. 35, no. 3, pp. 412 420.
(b) The chlorination of quinone imine IIa was per-
formed by procedure similar to the above described in
DMF at 100 C and molar ratio substrate: chlorine
1: 5. Reaction product Xa was precipitated from
reaction mixture with water. Yield 96%. Melting
points of compounds Xa c are given in the table.
3. Avdeenko, A.P. and Marchenko, I.L., Zh. Org. Khim.,
2001, vol. 37, no. 6, pp. 869 876.
4. Avdeenko, A.P. and Velichko, N.V., Zh. Org. Khim.,
1993, vol. 29, no. 6, pp. 1167 1169.
5. Avdeenko, A.P., Pirozhenko, V.V., Yagupol,skii, L.M.,
and Marchenko, I.L., Zh. Org. Khim., 2001, vol. 37,
no. 7, pp. 1043 1051.
(c) The chlorination of quinone imines IXa c was
performed by procedure similar to the above describ-
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