Synthesis and 13C NMR spectra of N-substituted para-quinone imines: II. N-arylthio- and N-arylsulfonyl-l,4-benzoquinone imines with enhanced electron-withdrawing character of the quinoid ring

Article abstract of DOI:10.1023/A:1020945308712

Introduction of chlorine substituents into quinone imine fragment results in virtually the same variations in the chemical shifts of the quinoid ring carbons both in N-arylthio and N-arylsulfonyl-1,4-benzoquinone imines as compared to the unsubstituted analogs. In both classes of chloro-substituted compounds the effect of substituents in the benzene ring on the character and the range of chemical shifts variations for the carbon signals from the quinoid ring also turned out to be identical. Any differences observed may be due to the change in the geometry of the molecules, in particular, to the increase in the bond angle C=N-S.

Full text of DOI:10.1023/A:1020945308712

Russian Journal of Organic Chemistry, Vol. 38, No. 8, 2002, pp. 1142 1148. From Zhurnal Organicheskoi Khimii, Vol. 38, No. 8, 2002,
pp. 1192 1199.
Original English Text Copyright
2002 by Pirozhenko, Avdeenko, Yusina, Konovalova.
13
Synthesis and C NMR Spectra of N-Substituted para-Quinone
Imines: II.* N-Arylthio- and N-Arylsulfonyl-1,4-benzoquinone
Imines with Enhanced Electron-withdrawing Character
of the Quinoid Ring
V. V. Pirozhenko1, A. P. Avdeenko2, A. L. Yusina2, and S. A. Konovalova2
1Institute of Organic Chemistry, National Academy of Sciences of the Ukraine
2Donbass State Machine-building Academy, Kramatorsk, 84313, Ukraine
Received March 27, 2002
Abstract Introduction of chlorine substituents into quinone imine fragment results in virtually the same
variations in the chemical shifts of the quinoid ring carbons both in N-arylthio and N-arylsulfonyl-1,4-
benzoquinone imines as compared to the unsubstituted analogs. In both classes of chloro-substituted com-
pounds the effect of substituents in the benzene ring on the character and the range of chemical shifts
variations for the carbon signals from the quinoid ring also turned out to be identical. Any differences
observed may be due to the change in the geometry of the molecules, in particular, to the increase in the
bond angle C=N S.
Previous investigations of 13C NMR spectra of un-
substituted N-arylthio and N-arylsulfonyl-1,4-benzo-
quinone imines [1] demonstrated that the electronic
effects of substituents in the benzene ring were trans-
mitted to the quinoid part of the molecule similarly
both through the sulfur(II) atom and through SO2
group. This fact was unexpected for according to UV
spectral data the bivalent sulfur atom in contrast to
SO2 group was capable of conjugation with the
quinone imine moiety [2]. We carried out investiga-
tion in more detail of the specific features of electron
effects transmission in both types of compounds. To
this end we synthesized and measured 13C NMR
spectra of several series of N-arylthio and N-arylsul-
fonyl-1,4-benzoquinone imines substituted by chlorine
in the quinoid ring. The choice of chlorine as a sub-
stituent was determined by its electron-withdrawing
character since at the growing electron-acceptor
quality of the quinoid ring the degree of the assumed
conjugation between the thioaryl fragment and the
quinone imine part should have increased. To avoid
difficulties in the assignment of signals in 13C NMR
spectra in case of the presence of Z- E-isomers we syn-
thesized and investigated symmetrically substituted
benzoquinone imines and 2,3,6-trichlorobenzoquinone
imines that existed in a single conformation.**
R = CH3O (a), CH3 (b), H (c), Cl (d), NO2 (e); X =
Cl (I VI), (VII); Y = Cl (III VII), H (I, II); Z =
Cl (V VII), H (I IV).
Note that this study is also of independent interest
for as far as we know this class of compound has not
been subjected to systematic investigation by NMR
spectroscopy.
The results of NMR spectra analysis are presented
in Table 1.
As seen from Table 1, the replacement of hydro-
gens by chlorine in positions 2, 6 (compounds I and
II) in both series of compounds results in virtually
equal displacement of carbon signals in the quinone
imine as well as in the aryl fragments compared to
their position in the spectra of compounds unsub-
stituted in the quinoid ring. Therewith the character
of these changes in the chemical shift values is nearly
insensitive to the nature of the substituents in the
benzene ring. The latter, as seen from the data
obtained, affect the range of changes insignificantly.
*
For communication I, see [1].
The results of the study on conformational stability of
**
substituted benzoquinone imines will be published elsewhere.
1070-4280/02/3808-1142$27.00 2002 MAIK Nauka/Interperiodica

Table 1. Chemical shift values in 13C NMR spectra of N-arylthio- (I, III, V, VII) and N-arylsulfonyl- II, IV, VI 1,4-benzoquinone imines, CDCl3,
TMS, C, ppm
Compd.
Ia
C1
C2
C3
C4
C5
C6
C1
C2
C3
C4
R
173.42
( 14.29)a
173.49
( 14.06)
173.46
( 14.15)
173.44
( 14.03)
173.24
( 13.97)
172.10
( 13.79)
172.04
( 13.77)
172.00
( 13.73)
171.92
( 13.71)
171.76
( 13.66)
172.17
( 15.54)
172.22
( 15.33)
172.16
( 15.45)
172.04
( 15.43)
171.90
( 15.31)
170.59
( 15.30)
170.59
133.52
(+5.15)
133.44
(+4.77)
133.68
(+5.09)
133.95
(+5.11)
134.94
(+5.35)
141.00
(+5.88)
141.11
(+5.95)
141.26
(+6.00)
141.49
(+5.99)
142.01
(+6.22)
133.1 br
(+4.73)
133.19
(+4.82)
133.32
(+4.73)
133.60
(+4.76)
133.16
(+3.57)
139.21
(+4.09)
139.35
(+4.19)
139.47
136.17
( 3.03)
136.20
( 2.83)
136.21
( 2.97)
136.13
( 2.93)
136.05
( 2.92)
137.75
( 2.79)
137.65
( 2.60)
137.55
( 2.77)
137.39
( 2.82)
137.00
( 2.77)
141.49
(+2.29)
141.7
(+2.67)
141.60
(+2.42)
141.55
(+2.49)
141.62
(+2.65)
143.10
(+2.56)
143.08
(+2.83)
143.00
(+2.68)
150.19
( 3.39)
150.22
( 3.42)
150.49
( 3.39)
150.78
( 3.39)
152.02
( 3.33)
159.66
( 3.61)
160.03
( 3.61)
160.38
( 3.52)
160.62
( 3.62)
161.48
( 3.56)
144.77
( 8.81)
144.97
( 8.67)
145.23
( 8.65)
145.53
( 8.64)
146.71
( 8.64)
155.54
( 7.73)
156.03
( 7.61)
156.39
( 7.51)
123.60
( 2.88)
123.75
( 2.78)
123.87
( 2.81)
123.98
( 2.80)
124.26
( 2.74)
127.43
( 2.69)
127.54
( 2.62)
127.64
( 2.60)
127.61
( 2.67)
127.75
( 2.61)
123.64
( 2.84)
123.78
( 2.75)
123.89
( 2.79)
123.97
( 2.81)
124.16
( 2.84)
127.11
( 3.01)
127.28
( 2.88)
127.35
( 2.89)
138.10
(+6.53)
138.01
(+6.44)
138.23
(+6.48)
138.50
(+6.52)
139.35
(+6.66)
142.45
(+6.93)
142.55
(+7.00)
142.68
(+7.06)
142.90
(+7.03)
143.38
(+7.22)
136.40
(+4.83)
136.64
(+5.07)
136.82
(+5.07)
137.13
(+5.15)
137.99
(+5.30)
141.39
(+5.87)
141.54
(+5.99)
141.71
(+6.09)
127.36
( 0.42)
133.09
( 0.57)
136.41
( 0.56)
134.86
( 0.61)
144.40
( 0.93)
130.59
( 0.55)
136.31
( 0.41)
139.29
( 0.41)
137.74
( 0.48)
144.68
( 0.50)
127.77
( 0.01)
133.57
( 0.09)
136.78
( 0.19)
134.75
( 0.78)
144.48
( 0.85)
130.36
( 0.78)
136.12
( 0.60)
139.14
( 0.56
129.21
( 0.23)
126.09
( 0.15)
125.58
( 0.07)
126.75
( 0.03)
115.15
(+0.20)
130.12
(+0.15)
129.39
(+0.14)
129.60
(+0.16)
160.83
(+0.45)
139.24
(+0.78)
128.68
(+0.60)
134.71
(+0.72)
147.36
(+0.58)
164.24
(+0.35)
145.35
(+0.44)
134.10
(+0.35)
140.92
(+0.39)
150.83
(+0.65)
160.66
(+0.28)
139.17
(+0.71)
128.65)
(+0.57)
135.17)
(+1.18)
147.35
(+0.57)
164.11
(+0.22)
145.42
(+0.51)
134.18
(+0.43)
55.54
21.26
Ib
Ic
Id
Ie
124.58, 124.52
(+0.22) (+0.16)
IIa
130.20
(+0.22) (+0.18)
127.84 129.93
(+0.20) (+0.15)
127.76 129.29
(+0.12) (+0.14)
129.23 129.63
(+0.12) (+0.08)
129.11 124.47
(+0.16) (+0.13)
127.81
( 1.63)
125.30
( 0.94)
124.91
( 0.74)
126.18
( 0.60)
124.61,
114.58
55.82
21.71
IIb
IIc
IId
IIe
IIIa
IIIb
IIIc
IIId
IIIe
IVa
IVb
IVc
115.23
(+0.28)
130.25
(+0.38)
129.51
(+0.26)
129.74
(+0.30)
124.43
55.57
21.25
(+0.25) (+0.07)
130.11 114.50
(+0.13) (+0.10)
127.75 129.94
(+0.11) (+0.16)
55.77
21.79
( 15.22)
170.54
( 15.19)
127.64
0.0)
129.32
(+0.17)
(+4.21)

Table 1. Contd.
Compd.
C1
C2
C3
C4
C5
C6
C1
C2
C3
C4
R
IVd
IVe
Va
170.45
( 15.18)
170.20
( 15.22)
169.90
( 17.81)
169.90
( 17.65)
169.92
( 17.69)
169.81
( 17.66)
169.70
( 17.51)
169.27
( 16.62)
169.21
( 16.60)
169.16
( 16.57)
169.07
( 16.56)
168.89
( 16.53)
182.61
( 5.10)
182.73
( 4.82)
182.51
( 5.10)
182.50
( 4.97)
182.35
( 4.86)
139.69
(+4.19)
140.08
(+4.29)
136.95
(+8.19)
136.06
(+7.69)
136.09
(+7.50)
136.03
(+7.19)
136.13
(+6.54)
139.73
(+4.61)
139.91
(+4.75)
139.88
(+4.62)
140.05
(+4.55)
140.64
(+4.85)
130.28
(+1.91)
130.44
(+2.07)
130.79
(+2.20)
130.84
(+2.00)
131.28
(+1.69)
142.83
(+2.62)
142.44
(+2.67)
141.64
(+2.44)
141.80
(+2.77)
141.89
(+2.71)
141.75
(+2.69)
141.83
(+2.86)
140.10
( 0.44)
139.69
( 0.56)
139.84
( 0.48)
139.69
( 0.52)
139.53
( 0.24)
145.22
(+6.02)
145.47
(+6.44)
145.3 in
(+6.12)
145.0 in
(+5.94)
145.28
(+6.31)
156.67
( 7.57)
157.54
( 7.50)
137.20
( 16.38)
137.43
( 16.21)
137.70
( 16.18)
138.04
( 16.13)
139.24
( 16.11)
149.62
( 13.65)
149.83
( 13.81)
150.11
( 13.79)
150.42
( 13.82)
151.31
( 13.73)
139.41
( 14.17)
139.69
( 13.95)
140.25
( 13.63)
140.31
( 13.86)
141.34
127.31
( 2.97)
127.33
( 3.03)
132.03
(+5.55)
132.20
(+5.67)
132.39
(+5.71)
132.67
(+5.89)
133.45
(+6.45)
140.10
(+9.98)
139.69
(+9.53)
139.84
(+9.60)
139.69
(+9.41)
139.53
(+9.17)
139.30
141.97
(+6.10)
142.48
(+6.32)
135.38
137.65
( 0.57)
144.60
( 0.58)
131.97
129.14
(+0.03) (+0.13)
129.68
140.93
(+0.40)
150.75
(+0.57)
160.68
(+0.30)
139.41
(+0.95)
128.92)
(+0.84)
135.01)
(+1.02)
147.66)
(+0.88)
163.65
( 0.24)
144.37
( 0.54)
133.38
( 0.37)
139.93
( 0.60)
150.57
( 0.39)
160.41
(+0.03)
138.89
(+0.43)
128.47)
(+0.39)
134.68)
(+0.69)
147.40
(+0.62)
128.93
( 0.02)
126.41
( 3.03)
124.42
( 1.82)
124.27
( 1.38)
125.55
( 1.23)
124.50
(+0.16)
115.15
(+0.20)
130.20
(+0.23)
129.50
(+0.25)
129.69
(+0.25)
55.59
21.31
(+3.81) (+4.19)
135.55 137.43
(+3.98) (+3.77)
135.79 140.37
(+4.04) (+3.40)
136.10 138.79
(+4.12) (+3.32)
136.87 147.45
(+4.18) (+2.12)
139.73 133.87
(+4.21) (+2.73)
139.91 138.88
(+4.36) (+2.16)
139.88 141.78
(+4.26) (+2.08)
140.05 140.27
(+4.18) (+2.05)
140.64 147.41
Vb
Vc
Vd
Ve
124.38, 124.64
(+0.02), +0.28)
VIa
VIb
Vlc
VId
VIe
VIIa
VIIb
VIlc
Vlld
VIIe
129.36
( 0.62)
126.93
( 0.71)
126.87
( 0.77)
128.35
( 0.76)
124.43
114.30
( 0.10)
129.69
( 0.09)
129.10
( 0.05)
129.42
( 0.13)
128.24
( 0.71)
115.06
(+0.11)
130.09
(+0.12)
129.59
(+0.34)
129.61
(+0.17)
124.52
(+0.16)
55.75
21.68
(+4.48) (+2.23) (+0.09)
126.58
( 4.99)
126.71
( 4.86)
127.06
( 4.69)
127.11
( 4.87)
127.62
( 5.05)
132.15
(+4.37)
137.62
(+3.96)
140.25
(+3.28)
139.10
(+3.63)
147.87
(+2.54)
126.37
( 3.07)
124.49
( 1.75)
125.51
( 0.14)
125.57
( 1.21)
124.12
( 0.24)
55.52
21.20
(+12.82)
139.45
(+12.92)
139.4 m
(+12.72)
139.4 m
(+12.62)
139.37
( 14.01)
(+12.37)
a
The changes in chemical shift values occurring on substitution of quinone imines with chlorine in the quinone ring are given in parentheses

SYNTHESIS AND 13C NMR SPECTRA OF N-SUBSTITUTED para-QUINONE IMINES: II.
1145
Note that whereas for C3 and C5 atoms the changes
in the chemical shifts values at introduction of a
chlorine atom are virtually the same, for both atoms
and in both series of compounds (ArS and ArSO2),
6
by tert-butyl group might be ascribed to increased
transfer of the electron density from the sulfur atom
to the quinoid ring. However we performed a similar
comparison for N-methylsulfonyl-2,6-dichloro-1,4-
benzoquinone imine and quinone imine IIc where no
conjugation was possible, and the change in the
chemical shift values was similar.
the variation of chemical shift
is in both series of
compounds more significant thCan
. Variation of
2
substituents in the benzene ring in boCth series of com-
pounds (N-arylthio and N-arylsulfonyl derivatives)
affects the chemical shifts of carbons in the quinone
imine moiety to the same extent as in the unsubstitut-
ed benzoquinone imines. This fact is an evidence of
insignificant conjugation of the bivalent sulfur with
the -system of the quinoid ring. In the reverse case
the changes in the chemical shift values for N-arylthio
derivatives should be larger than for N-arylsulfonyl
derivatives. This conclusion is also supported by ana-
lysis of 13C NMR spectra of trichloro-substituted
benzoquinone imines (compounds III and IV).
It should be noted that introduction of chlorine
atoms into the quinoid ring differently affects the
chemical shifts of carbon atoms in the benzene ring of
arylsulfonyl and arylthio derivatives. For instance, in
the dichloro- and trichloro-substituted arylsulfonyl
derivatives the largest displacement of signal from
C1 atom suffers the compound with R = OMe,
whereas in the arylthio derivatives the largest shift
occurs in the compound with R = NO2.
In derivatives with four chlorine atoms in the
quinone imine fragment (compounds V and VI) the
chemical shifts of carbons suffer great changes both
in quinoid and aryl parts of the molecules. As seen
from Table 1, in contrast to arylsulfonyl compounds
in the spectra of the arylthio derivatives occur con-
4
As show the data in Table 1, the introduction of
one more chlorine into the quinone imine fragment
does not bring significant additional change in the
chemical shifts of carbon atoms in the compound
series under investigation. Note that the lack of con-
siderable conjugation between bivalent sulfur and
quinone imine fragment follows also from compari-
son of carbon chemical shifts in quinone imine frag-
ments of N-phenylthio-1,4-benzoquinone imine [1]
and of N-tert-butylthio-1,4-benzoquinone imine [3].
siderably larger changes in the
values as com-
pared to quinone imines unsubstCitited in the ring.
Thus whereas in sulfonyl derivatives VI this value
alters by 13.7 ppm, in the thiocompounds V this
change exceeds 16 ppm. Even larger alterations are
observed in the chemical shifts of C1 atom. There-
with the character of the changes is opposite to that
observed in 2,6- and 2,3,6-substituted compounds.
For instance, whereas in the latter the signal of C1
atom is shifted upfield, this signal in the tetrachloro
derivatives is displaces downfield as compared to
compounds unsubstituted in the ring. It may be
assumed that the presence of four chlorine atoms in
the quinoid part of the ArS derivatives resulted in
decreased interaction of sulfur with the benzene ring
and consequently its enhanced interaction with the
quinone imine fragment, However the data in Table 1
show that analogous changes in the chemical shift of
C1 atom are observed also in tetrachlorosulfonyl
derivatives VI. Apparently the difference observed is
caused mostly by the changes in the geometry of the
molecules at introduction of substituents into posi-
tions 3 and 5 (namely, by increase in the angle
C=N S [4]) and not by electronic effects due to the
presence of four chlorine atoms. This assumption is
also supported by the analysis of 13C NMR spectra of
3,5-dichlorosubstituted N-arylthio-1,4-benzoquinone
imines VII. As seen from Table 3, the presence of
only two chlorine atoms results in virtually identical
shift of the signal from C1 atom as is observed in the
spectra of tetrachloro derivatives.
The observed upfield shift of the signal from imino
group C=N carbon when the benzene ring is replaced
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

1146
PIROZHENKO et al.
Table 2. Parameters of correlation equations
Correlation
Number of points,
Compounds
a
b
factor, r
n
137.89
139.28
1.36 (0.06)
0.997
0.992
5
6
0.99 (0.07)
I
II
136.80
138.92
137.03
138.88
140.63
141.62
140.84
1.22 (0.03)
1.03 (0.07)
1.20 (0.02)
1.01 (0.07)
1.11 (0.02)
0.97 (0.03)
1.12 (0.04)
0.999
0.993
0.999
0.993
0.999
0.999
0.998
5
5
5
5
5
5
5
III
IV
V
VI
VII
a
Data from [1].
To reveal the specific features of interaction
between the fragment
character of interaction between the sulfur and benz-
ene ring is first of all caused by the altered geometry
of molecules due to the presence of bulky substituents
in the ortho-position with respect to nitrogen [4].
The use of
constants permitted [1] quantitative
p
estimation of transfer of electronic effect from sub-
stituent R on the quinoid fragment in the molecules of
unsubstituted benzoquinone imines. As indicator
center there was chosen C4 atom. We also calculated
analogous correlations in order to establish the extent
of substituents influence on the transmission of the
electronic effects. As a result the equations given
below were obtained describing the variation of
chemical shift of C4 atom as a function of substituent
R character.
and benzene ring we calculated correlations suggested
in [5] of the following kind:
1
= a + b ,
C
C
is chemical shift value of C1 atom in the
C1
where
benzoquinone imines under study,
are the cor-
responding chemical shifts of carbonCs in the para-
position of monosubstituted benzenes C6H5R.
The equations obtained revealed some increase in
transmission of the electronic effects of the R sub-
stituents through the bivalent sulfur but this increase
is comparable with that observed for arylsulfonyl
derivatives. This fact confirms the absence of a
unified conjugation system in the N-arylthio-1,4-
benzoquinone imines.
Parameters of the correlation equations obtained
are given in Table 2.
The presented data show that for all N-arylsulfonyl
derivatives under study the factor b practically equals
unity thus giving an evidence of a barrier character of
SO2 group in transmission of electronic effects along
a -system. The pattern is quite different with N-aryl-
thio-1,4-benzoquinone imines. The deviation of the
b factor from unity demonstrates the nonadditive
character of the interaction between the moiety neigh-
boring to the benzene ring and the -electron orbitals
of the C1 atom. We believe that the increase in this
factor means the less efficient interaction of the sulfur
atom with the benzene ring. The least values of the b
factor observed for tetrachloro and 3,5-dichloro
derivatives VI, VII evidence that the change in the
Apparently in both compounds classes the increase
4
in sensitivity of
value to the nature of the
C
character of R substituent as compared to the sub-
stances unsubstituted in the quinoid ring is due to
stronger polarization of -bond C=N to the carbon;
as a result the range of chemical shifts variation
increases. The decrease of the factor for tetrachloro-
sulfonyl derivatives VI may be caused by structural
changes.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

SYNTHESIS AND 13C NMR SPECTRA OF N-SUBSTITUTED para-QUINONE IMINES: II.
1147
Scheme 1.
Scheme 2.
Thus the analysis of chemical shift values in
chloro-substituted 1,4-benzoquinone imines I VII
testifies to the absence of the conjugation between the
bivalent sulfur atom and -system of the quinone
imine moiety.
substituted p-aminophenols with the corresponding
arylsulfenyl chlorides in the presence of triethyl-
amine. Here the intermediate N-arylthio-1,4-amino-
phenols were oxidized by air oxygen into the cor-
responding quinone imines (Scheme 1).
The assignment of carbon signals in the 13C NMR
spectra was carried out basing on the data of [1]. To
perform more exact attribution of carbon signals in
the spectra of N-arylthio-3,5-dichloro-1,4-benzo-
quinone imines (VIIa e) and N-arylthio-2,3,5,6-tetra-
chloro-1,4-benzoquinone imines (Va e) we measured
1H and 13C NMR spectra of N-4-chlorophenylthio-
2,3,5-trichloro-1,4-benzoquinone imine [2]. Accord-
The yield of the target products was very low, and
besides in the reaction mixture arise considerable
amounts of diaryl disulfides presumably formed by a
parallel reaction along Scheme 2.
The concurrent characteristics of the newly
obtained quinone imines are presented in Table 3.
1
ing to H NMR spectrum the compound exists as a
EXPERIMENTAL
mixture of Z,E-isomers in 0.37: 0.63 ratio. In the
13C NMR spectrum of the compound the signal of C6
atom attached to a proton appears as two signals at
129.4 ppm (less intensive) and at 126.0 ppm (more
intensive). Our quantum-chemical calculations by
PM3 method revealed that as expected the more
favored was E-isomer. Therefore its signal in the
13C NMR spectrum should be that at 126.0 ppm.
Consequently the signal of C6 atom in the Z-isomer
is located at 129.4 ppm.
13C NMR spectra were registered on spectrometers
Varian VXR-300 and Gemini-200 from solutions in
CDCl3. The chemical shifts were measured relative
to TMS with an accuracy 0.05 ppm.
Compound Ic was prepared by procedure describ-
ed in [9], compounds IIb, c, IVb, c by procedure
from [10], compounds IId, IVd, VIb d by that from
[8], compounds IIId, Va, b, d, e by that from [11],
preparation of compound Vc was published in [12],
that of compound VIa in [13].
N-Arylsulfonyl-2,6-dichloro-1,4-benzoquinone
imines IIa, e, and N-arylsulfonyl-2,3,6-trichloro-1,4-
benzoquinone imines IVa, e were prepared for the
first time from the corresponding N-arylsulfonyl-1,4-
aminophenols by successive oxidation with lead tetra-
acetate and hydrochlorination with gaseous hydrogen
chloride in chloroform or dimethylformamide by
procedures similar to those described in [6, 7].
N-4-Nitrophenylsulfonyl-2,3,5,6-tetrachloro-1,4-
benzoquinone imine (VIe). Through a suspension of
1 g of N-4-nitrophenylsulfonyl-1,4-aminophenol in
6 ml of a mixture DMF CH3COOH (1: 5) at room
temperature was passed a stream of chlorine at a rate
1
15 20 ml min till separated a colorless precipitate
N-4-Nitrophenylsulfonyl-2,3,5,6-tetrachloro-1,4-
benzoquinone imine VId was obtained for the first
time by chlorination of N-4-nitrophenylsulfonyl-1,4-
aminophenol by procedure similar to that published
in [8].
of
4-(4-nitrophenyl)sulfonylimino-2,3,5,6,6-penta-
chloro-2-cyclohexen-1-one. The precipitate was
filtered off and washed with small portions of acetic
acid. In air within 24 h the 4-(4-nitrophenyl)sulfonyl-
imino-2, 3, 5, 6,6-pentachloro-2-cyclohexen-1-one
underwent dehydrochlorination to furnish orange N-4-
nitrophenylsulfonyl-2,3,5,6-tetrachloro-1,4-benzo-
quinone imine (VId).
Chloro-substituted in the quinoid ring N-arylthio-
1,4-benzoquinone imines Ia, b, d, e, IIIa c, e,
VIIa e were first synthesized by acylation of chloro-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 8 2002

1148
PIROZHENKO et al.
Table 3. Yields, melting points, and elemental analyses of N-arylthio-1,4-benzoquinone imines Ia e, IIIa c, e, VIIa e
and N-arylsulfonyl-1,4-benzoquinone imines IIa, e, IVa, e, VIe substituted with chlorine in the quinoid ring
Compd.
no.
mp, C (solvent
for crystallization)
Yield, %
Found S, %
Formula
Calculated S, %
Ia
Ib
Ic [10]
Id
Ie
25
21
28
32
37
76
64
23
29
16
26
73
68
64
30
23
25
27
23
153 (CH3CO2H)
9.98, 10.07
10.71, 10.80
11.07, 11.21
10.06, 10.11
9.68, 9.75
9.51, 9.64
8.91, 8.99
9.22, 9.31
9.53, 9.60
9.99, 10.04
8.79, 8.84
8.39, 8.45
7.98, 8.08
7.22, 7.36
10.20, 10.22
10.66, 10.73
11.15, 11.24
10.02, 10.08
9.71, 9.75
C13H9Cl2NO2S
C13H9Cl2NOS
C12H7Cl2NOS
C12H6Cl3NOS
C12H6Cl2N2O3S
C13H9Cl2NO4S
C12H6Cl2N2O5S
C13H8Cl3NO2S
C13H8Cl3NOS
C12H6Cl3NOS
C12H5Cl3N2O3S
C13H8Cl3NO4S
C12H5Cl3N2O5S
C12H4Cl4N2O5S
C13H9Cl2NO2S
C13H9Cl2NOS
C12H7Cl2NOS
C12H6Cl3NOS
C12H6Cl2N2O3S
10.19
10.74
11.27
10.05
9.73
9.68
8.88
9.20
9.64
10.06
8.82
8.42
8.11
7.46
10.19
10.74
11.27
10.05
9.73
184 (CH3CO2H)
186 (CH3CO2H)
168 (CH3CO2H)
262 (CH3CO2H)
123 (CH3CO2H)
135 (CH3CO2H)
169 (CH3CO2H)
220 (CH3CO2H)
203 (CH3CO2H)
256 (decomp.) (CH3CO2H)
(CH3CO2H)
IIa
IIe
IIIa
IIIb
IIIc
IIIe
IVa
IVe
VIe
VIIa
VIIb
VIIc
VIId
VIIe
(CH3CO2H)
194 (CH3CO2H)
167 (CH3CO2H)
109 (CH3CO2H)
213 (n-C7H16)
217 (n-C7H16)
171 (CH3CO2H)
N-Arylthio-1,4-benzoquinone imines Ia e, IIIa e,
VIIa e substituted with chlorine in the quinone ring.
To suspension of 2 mmol of chloro-substituted
p-aminophenol in 20 ml of anhydrous ethyl ether
were added equimolar amounts of an appropriate aryl-
sulfonyl chloride and triethylamine. The arising
precipitate of triethylamine hydrochloride was filtered
off, the filtrate was evaporated in a vacuum of a
water-jet pump. The precipitate of N-arylthio-1,4-
benzoquinone imine formed was washed with
methanol and acetic acid.
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