Synthesis, X-Ray diffraction data, and 1H and 13C NMR spectra of N-(N-Arylsulfonylimidoyl)-1,4-benzoquinonimines derived from N-Aroyl(acetyl)-1,4-benzoquinonimines

Article abstract of DOI:10.1023/A:1012430601142

Oxidation of N-(N-arylsulfonylimidoyl)-4-aminophenols gave the corresponding N-[N-arylsulfonylimidoyl)-1,4-benzoquinonimines, derivatives of N-aroyl-and N-acetyl-1,4-benzoquinonimines. The structure of the products was studied by the X-ray diffraction met

Full text of DOI:10.1023/A:1012430601142

Russian Journal of Organic Chemistry, Vol. 37, No. 7, 2001, pp. 991 1000. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 7, 2001,
pp. 1043 1051.
Original Russian Text Copyright
2001 by Avdeenko, Pirozhenko, Yagupol’skii, Marchenko.
Synthesis, X-Ray Diffraction Data, and 1H and 13C NMR Spectra
of N-(N-Arylsulfonylimidoyl)-1,4-benzoquinonimines Derived
from N-Aroyl(acetyl)-1,4-benzoquinonimines
A. P. Avdeenko1, V. V. Pirozhenko2, L. M. Yagupol’skii2, and I. L. Marchenko1
1
Donbass State Machine-Building Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
2
Institute of Organic Chemistry, National Academy of Sciences of Ukraine
Received November 10, 1999
Abstract Oxidation of N-(N-arylsulfonylimidoyl)-4-aminophenols gave the corresponding N-[N-arylsulfonyl-
imidoyl)-1,4-benzoquinonimines, derivatives of N-aroyl- and N-acetyl-1,4-benzoquinonimines. The structure
1
of the products was studied by the X-ray diffraction method and H and 13C NMR spectroscopy. N-(N-Arylsul-
fonylimidoyl)-1,4-benzoquinonimines were found to undergo fast (on the NMR time scale) Z,E isomerization
about the C N bond in the quinonimine fragment. N-(N-Arylsulfonylacetimidoyl)-1,4-benzoquinonimines
in solution give rise to dynamic Z,E-isomerization with respect to the C N bond in the N-arylsulfonylacet-
imidoyl fragment.
We previously studied the 1H and 13C NMR spectra
of N-aroyl-1,4-benzoquinonimines [1]. The results
showed a considerable reduction of the barriers to
It should be noted that correlation of the barriers
to Z,E isomerization with structural parameters of
various N-substituted 1,4-benzoquinonimines [5]
revealed opposite directions in the variation of Gk
and the bond angle C N X. This means that change
of the C N X angle in crystal is related to variation
of the rate of Z,E isomerization in solution.
Presumably, the C N C angle in N-aroyl-1,4-benzo-
Z,E isomerization of these compounds ( Gk
=
44 46 kJ/mol) relative to those found for the other
N-substituted p-benzoquinonimines (e.g., for N-aryl-
sulfonyl-1,4-benzoquinonimines, Gk = 65 80 kJ/mol
[2]; for N-arylthio-1,4-benzoquinonimines, Gk
=
75 80 kJ/mol [3]; for N-aryl-1,4-benzoquinonimines,
Gk = 75 95 kJ/mol [4]) and the absence of conjuga-
tion between -electron systems of the quinoid and
aroyl fragments. We presumed that molecules of
N-aroyl-1,4-benzoquinonimines have nonplanar struc-
ture, so that the -electron systems of the quinoid
and aroyl fragments are orthogonal. According to
the results of quantum-chemical calculations, just in
this case the interaction between the lone electron pair
*
on the nitrogen atom and
orbital of the C O bond
could lead to considerable reduction of the barrier to
Z,E isomerization. In order to prove this assumption,
we performed X-ray analysis of 2,6-di-tert-butyl-N-
(4-chlorobenzoyl)-1,4-benzoquinonimine (I).
Fig. 1. Absolute configuration of the molecule of N-(4-
chlorobenzoyl)-2,6-di-tert-butyl-1,4-benzoquinonimine (I)
according to the X-ray diffraction data.
1070-4280/01/3707-0991$25.00 2001 MAIK Nauka/Interperiodica

992
AVDEENKO et al.
N,N -Bis(trimethylsilyl)-1,4-benzoquinonediimine
(II) was assigned [8] a linear structure with sp-
hybridized nitrogen atoms, which is stabilized through
the exchange interaction nN dSi, i.e., via donation of
the nitrogen lone electron pair to the silicon d orbital.
This conclusion was drawn on the basis of spectral
1
data, including the H NMR spectra which showed
magnetic equivalence of all quinoid ring protons.
Fig. 2. Quinonimine fragment in the molecule of N-(4-
chlorobenzoyl)-2,6-di-tert-butyl-1,4-benzoquinonimine (I)
according to the X-ray diffraction data.
quinonimines in crystal is much greater than 120 ;
then, these compounds should be characterized by
a low energy of activation for Z,E isomerization.
According to the results of X-ray diffraction study,
the bond angle C N C(O) in molecule I is 124.6 .
This value approaches those found for the correspond-
ing N-aryl derivatives [6]. Therefore, reduction of the
barrier to topomerization of N-aroyl-2,6-di-tert-butyl-
1,4-benzoquinonimines does not correlate with the
We believe that in this case very fast (on the NMR
time scale) Z,E isomerization about the C N double
bond occurs; also, a considerable contribution of the
linear structure with sp-hybridized nitrogen atoms
is conceivable. Presumably, a significant contribution
of the linear structure exists in the case of N-aroyl-
1,4-benzoquinonimines.
N-(N-Arylsulfonylimidoyl)-1,4-benzoquinonimines
IV, some representatives of which were synthesized
by us previously [9], are derivatives of N-aroyl-
(acetyl)-1,4-benzoquinonimines in which the carbonyl
oxygen atom in the aroyl or acetyl moiety is replaced
by arylsulfonylimino group (ArSO2N ). We expected
C N C bond angle. The C N bond length (1.29
)
is typical for the other benzoquinonimine derivatives
[6, 7], which excludes the possibility for change of the
isomerization mechanism from inversion to rotational
in going to N-aroyl-1,4-benzoquinonimines.
1
that the structure and hence the H and 13C NMR
The absolute configuration of molecule I is shown
in Fig. 1. It supports the assumption made in [1] to
explain reduction of the barriers to Z,E isomerization.
In fact, the planes of the p-chlorophenyl substituent
and the quinoid fragment are almost orthogonal: the
corresponding dihedral angle is 86.1 which excludes
conjugation between -electron systems of the aroyl
and quinoid fragments. The quinoid ring (C1 C6) is
planar within 0.024 ; the deviations of the O1, N,
C7, C14, and C15 atoms from the mean-square plane
spectra of compounds IV should be similar to those
of N-aroyl(acetyl)-1,4-benzoquinonimines.
1
In the H NMR spectra of quinonimines IV signals
from the 2-H/6-H and 3-H/5-H protons appear as two
doublets, indicating that they are magnetically equiv-
alent in pairs (Table 1). Compounds IVa, IVb, and
IVf IVi show in the 13C NMR spectra two singlets
from C2/C6 and C3/C5; this means that C2/C6 and
C3/C5 are also equivalent (Table 2). Therefore, the
E,Z isomerization of N-(N-arylsulfonylimidoyl)-1,4-
benzoquinonimines IV with respect to the quinon-
imine C N bond in solution is very fast on the NMR
time scale and there is a considerable contribution
of the linear structure (linear transition state) in which
the quinonimine nitrogen atom has sp hybridization.
(C1 C6) are given in Fig. 2. The C7 carbonyl carbon
atom lies in the quinoid ring plane; this also follows
from the torsion angles C7NC4C3 (178.2 ) and
C7NC4C5 ( 2.6 ). The aroyl carbonyl group is ortho-
*
gonal to the quinoid ring plane, and the
orbital
of the C O bond is parallel to the orbital occupied
by the lone electron pair on the nitrogen (nN); such
arrangement favors interaction between *(C O) and
nN and reduces the energy of the latter; hence the
energy of the linear structure is also reduced.
Thus, the results of X-ray diffraction study of
compound I are fully consistent with our previous
assumption [1] on the reasons for reduced barrier to
Z,E isomerization in N-aroyl derivatives of 1,4-benzo-
quinonimines.
N-(N-Arylsulfonylimidoyl)-1,4-benzoquinonimines
IVa IVl were synthesized by oxidation of the corre-
sponding N-substituted 4-aminophenols IIIa IIIl with
lead tetraacetate in acetic acid. N-(N-Arylsulfonyl-
imidoyl)-4-aminophenols IIIa IIIl were prepared by
acylation of 4-aminophenols with appropriate N-aryl-
sulfonylbenz(or acet)imidoyl chlorides in a mixture
of DMF with acetic acid (1:3) in the presence of
anhydrous sodium acetate, following the procedure
reported in [9] (Scheme 1). The yields, melting points,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

SYNTHESIS, X-RAY DIFFRACTION DATA, AND 1H AND 13C NMR SPECTRA
993
Scheme 1.
X = H (a, c e), CH3 (b, f, j, l), Cl (k), Br (g i); R1 = H (a, b, d, f, g, i, k), CH3 (c, h, j), Cl (e, l); R2 = H (a c, e h, j, l),
CH3 (g, i, k); R3 = C6H5 (a e, g i), 4-ClC6H4 (f), CH3 (j l).
and elemental analyses of compounds IIIc IIIl and
IVc IVl are given in Table 3. Compounds IIIa, IIIb,
IVa, and IVb were described in [9].
which are almost orthogonal to each other (the corre-
sponding dihedral angle is 86.4 ). The quinoid frag-
ment and the aryl group in the ArSO2 moiety are
coplanar, i.e., they lie in parallel planes which form
a dihedral angle of 3.6 . The quinoid ring C1 C6 in
IVc is planar within 0.027 ; the deviations of the
O1, N1, C7, C20, and C21 atoms from the mean-square
plane are given in Fig. 4. In keeping with these data,
the C7 atom lies almost in the quinoid ring plane: the
X-Ray analysis of a single crystal of 2,6-dimethyl-
N-(N-phenylsulfonylbenzimidoyl)-1,4-benzoquinon-
imine (IVc) showed that the C N C bond angle in
the quinonimine fragment is 124.1 (cf. X-ray diffrac-
tion data for compound I). The absolute configuration
of molecule IVc is shown in Fig. 3. As in molecule I,
quinonimine derivative IVc lacks conjugation between
-electron systems of the aryl and quinoid fragments
torsion angles C7N1C4C3 and C7N1C4C5 are 3.1
and 176.5 , respectively. The C7 N2 group in the
Table 1. 1H NMR spectra ( , ppm) of N-(N-arylsulfonylimidoyl)-1,4-benzoquinonimines IVa IVl in CDCl3
Quinoid ring
Compound
R3
4-XC6H4
no.a
R1
R2
IVab
6.66 6.70 d (2H) 7.00 7.03 d (2H) 7.43 7.81 m (5H)
6.65 6.68 d (2H) 6.99 7.02 d (2H) 7.42 7.80 m (5H)
7.51 7.99 m (5H)
7.31 7.86 d.d (4H), 2.44 s (3H, CH3)
7.49 8.00 m (5H)
7.52 7.99 m (5H)
7.53 8.00 m (5H)
7.31 7.85 d.d (4H), 2.44 s (3H, CH3)
7.66 7.86 d.d (4H)
7.64 7.86 d.d (4H)
IVbc
IVc
IVd
IVe
IVfb
IVgb
IVh
IVi
2.06 s (6H, CH3) 6.74 br.s (2H)
6.49 br.s (2H) 2.07 s (6H, CH3) 7.44 7.80 m (5H)
7.22 br.s (2H) 7.44 7.80 m (5H)
7.41 7.82 m (5H)
6.65 6.69 d (2H) 6.97 7.00 d (2H) 7.40 7.74 d.d (4H)
6.68 6.71 d (2H) 7.00 7.04 d (2H) 7.43 7.80 m (5H)
2.07 s (6H, CH3) 6.73 br.s (2H)
7.42 7.81 m (5H)
6.51 s (2H) 2.10 s (6H, CH3) 7.45 7.78 m (5H)
7.65 7.87 d.d (4H)
IVj (Z, 25) 2.07 s (6H, CH3) 6.76 br.s (2H)
IVj (E, 75) 2.07 s (6H, CH3) 6.68 br.s (2H)
2.68 br.s (3H, CH3) 7.30 7.88 d.d (4H), 2.43 s (3H, CH3)
2.26 br.s (3H, CH3) 7.29 7.80 d.d (4H), 2.43 s (3H, CH3)
IVk (Z, 7) 6.48 br.s (2H)
IVk (E, 93) 6.48 br.s (2H)
IVl (Z, 34)
2.14 s (6H, CH3) 2.40 br.s (3H, CH3) 7.28 7.79 d.d (4H), 2.38 s (3H, CH3)
2.14 s (6H, CH3) 2.13 br.s (3H, CH3) 7.47 7.86 d.d (4H), 2.38 s (3H, CH3)
7.25 br.s (2H)
2.71 br.s (3H, CH3) 7.33 7.87 d.d (4H), 2.44 s (3H, CH3)
2.29 br.s (3H, CH3) 7.31 7.80 d.d (4H), 2.44 s (3H, CH3)
IVl (E, 66)
7.51 br.s (2H)
a
b
c
In parentheses is given the fraction (%) of the corresponding isomer.
J2,3 = 10.2 Hz. J2,3 = 9.9 Hz.
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994
AVDEENKO et al.
Table 2. 13C NMR spectra ( C, ppm) of N-(N-arylsulfonylimidoyl)-1,4-benzoquinonimines IVa, IVb, and IVf IVk
in CDCl3
Comp.
no.
Quinonimine fragment
R3 C N
4-XC6H4SO2
IVa 185.84 (C1), 135.02 (C2, C6), 168.28 (C N), 131.71 (C1), 129.08 (C2, C6), 141.14 (C1), 127.43 (C2, C6),
129.10 (C3, C5), 156.92 (C4) 128.84 (C3, C5), 134.28 (C4) 135.20 (C3, C5), 132.89 (C4)
IVb 185.80 (C1), 135.02 (C2, C6), 167.94 (C N), 131.87 (C1), 129.42 (C2, C6), 138.33 (C1), 127.53 (C2, C6),
129.03 (C3, C5), 156.89 (C4)
129.01 (C3, C5), 134.12 (C4)
135.09 (C3, C5), 143.74 (C4),
21.52 (CH3)
IVf
185.71 (C1), 134.89 (C2, C6), 166.84 (C N), 131.87 (C1), 129.45 (C2, C6), 138.15 (C1), 127.56 (C2, C6),
129.51 (C3, C5), 157.29 (C4)
130.29 (C3, C5), 140.97 (C4)
135.27 (C3, C5), 143.94 (C4),
21.56 (CH3)
IVg 185.77 (C1), 134.88 (C2, C6), 168.61 (C N), 131.26 (C1), 129.09 (C2, C6), 139.85 (C1), 128.92 (C2, C6),
132.09 (C3, C5), 156.91 (C4) 129.04 (C3, C5), 134.49 (C4) 135.29 (C3, C5), 127.99 (C4)
IVh 186.62 (C1), 144.70 (C2, C6), 169.05 (C N), 131.21 (C1), 129.17 (C2, C6), 140.46 (C1), 129.05 (C2, C6),
131.22 (C3, C5), 156.99 (C4), 129.02 (C3, C5), 134.16 (C4)
16.27 (2-CH3, 6-CH3)
132.05 (C3, C5), 127.78 (C4)
IVi
IVj
186.29 (C1), 133.42 (C2, C6), 164.84 (C N), 131.25 (C1), 129.24 (C2, C6), 140.71 (C1), 128.60 (C2, C6),
145.21 (C3, C5), 155.84 (C4), 128.38 (C3, C5), 133.97 (C4)
18.89 (3-CH3, 5-CH3)
132.15 (C3, C5), 127.59 (C4)
186.60 (C1), 144.30 (C2, C6), 173.03 (C N), 25.94 and 25.90 (CH3)
137.98 (C1), 127.65 (C2, C6),
131.13 (C3, C5), 143.75 (C4),
21.57 (CH3)
129.72 and 129.43 (C3, C5),
153.38 and 153.34 (C4), 16.26
(2-CH3, 6-CH3)
IVk 186.10 (C1), 133.30 and 133.14 168.00 (C N), 25.55 and 25.50 (CH3)
139.29 (C1), 128.54 (C2, C6),
129.16 (C3, C5), 139.29 (C4),
21.55 (CH3)
(C2, C6), 145.14 and 145.03
(C3, C5), 152.03 (C4), 18.78
and 18.66 (3-CH3, 5-CH3)
N-phenylsulfonylbenzimidoyl fragment is orthogonal
to the quinoid ring plane, and the antibonding
as a result, the barrier to isomerization about the C N
bond in the quinonimine fragment should be reduced
considerably.
*
orbital of the C7 N2 bond is parallel to the non-
bonding nN orbital of the nitrogen. Such arrangement
favors interaction between the orbitals and reduction
of the energy of nN. The greatest decrease in energy,
as with compound I, could be expected for the transi-
tion state where the bond angle C4 N1 C7 is 180 ;
In the case of N-(N-arylsulfonylimidoyl)-1,4-benzo-
quinonimines IVa IVl having one more C N group
in the imidoyl fragment, Z,E isomerization about that
1
group could be expected. However, our H NMR
study of 1,4-benzoquinonimines IVa IVi at various
Scheme 2.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

SYNTHESIS, X-RAY DIFFRACTION DATA, AND 1H AND 13C NMR SPECTRA
995
Table 3. Yields, melting points, and elemental analyses of N-(N-arylsulfonylimidoyl)-4-aminophenols IIIc IIIl and
1,4-benzoquinonimines IVc IVl
Comp. no.
Yield, %
mp,
C
Found N, %
Formula
Calculated N, %
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
IIIi
IIIj
IIIk
IIIl
IVc
IVd
IVe
IVf
IVg
IVh
IVi
76
86
90
86
93
65
89
79
57
47
88
61
75
85
88
66
87
86
83
62
190
7.12, 7.26
7.05, 7.31
6.39, 6.58
7.37, 7.45
6.22, 6.29
5.93, 6.07
5.84, 5.89
8.05, 8.31
8.09, 8.15
7.82, 7.97
7.16, 7.22
7.07, 7.39
6.68, 6.83
7.42, 7.48
6.39, 6.52
6.07, 6.22
6.02, 6.16
8.33, 8.42
7.78, 7.96
7.72, 7.77
C21H20N2O3S
C21H20N2O3S
7.37
7.37
6.65
6.99
6.50
6.10
6.10
8.43
7.94
7.84
7.41
7.41
6.67
7.02
6.53
6.13
6.13
8.48
7.99
7.88
252
182
255
258
125
263
220
195
175
175
142
181
130
163
173
160
189
170
160
C19H14Cl2N2O3S
C20H17ClN2O3S
C19H15BrN2O3S
C21H19BrN2O3S
C21H19BrN2O3S
C17H20N2O3S
C16H17ClN2O3S
C15H14Cl2N2O3S
C21H18N2O3S
C21H18N2O3S
C19H12Cl2N2O3S
C20H15ClN2O3S
C19H13BrN2O3S
C21H17BrN2O3S
C21H17BrN2O3S
C17H18N2O3S
IVj
IVk
IVl
C16H15ClN2O3S
C15H12Cl2N2O3S
Table 4. Crystallographic parameters, conditions of X-ray diffraction experiment, and divergence factors for compounds
I and IVc
Parameter
I
IVc
Parameter
I
IVc
Formula
Space group
C21H24ClNO2
C21H18N2O3S
Number of reflections:
total
P21/n
P1
3320
2677
2230
0.0305
323
2461
2271
1392
0.0272
244
Unit cell parameters:
independent
with I> 2 (I)
R(int)
Number of refined
parameters
a,
b,
c,
5.9113(6)
30.765(2)
10.805(1)
90
103.051(8)
90
1914.2(4)
4
20
1.24
1.865
760
8.281(2)
10.212(2)
11.363(2)
76.16(3)
87.08(3)
85.32(3)
929.4(3)
2
20
1.35
0.198
396
, deg
, deg
, deg
Number of reflections
per parameter
Divergence factors:
R1 (F)
6.90
5.70
3
V,
Z
0.0392
0.0991
1.033
0.0664
0.1519
0.995
Temperature,
C
RW (F2)
GOF
dcalc, g/cm3
1
, mm
Ratio of the maximal 0.150 (0.010)
(average) shift
0.007 (0.001)
F (000)
Crystal habit, mm
Spherical segment
0.46 0.27 0.22 0.31 0.25 0.19
to the error
6 h 6
24 k 34
12 l 11
60
0 h 8
10 k 10
11 l 11
22
Residual electron
density from the
difference Fourier
0.13
0.17
0.30
0.28
3
Limiting diffraction
angle , deg
series, e
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

996
AVDEENKO et al.
was the major one (Table 1). In the 1H NMR spectrum
of compound IVj recorded in CDCl3 or DMSO-d6
at 45 C we observed coalescence of signals from the
CH3 protons and signals from 3-H and 5-H of the
quinoid ring (coalescence temperature Tc = 318 K).
On further raising the temperature to 80 C (solution
in DMSO-d6) the broadened signals become narrower.
This pattern is typical of a dynamic process which is
likely to involve Z,E isomerization.
The 13C NMR spectra of compounds IVj and IVk
contain separate signals from C3 and C5 of the quinoid
ring (
0.1 0.3 ppm), indicating a weak magnetic
C
nonequivalence of the corresponding nuclei. The CH3
carbon atom of the R3 C N group also gives two
signals. Slightly nonequivalent signals from C2 and
C6 of the quinoid fragment (
0.16 ppm) were
C
also observed in the 13C NMR spectrum of compound
IVk. The C4 atom in the quinoid ring of IVj gives
two signals in the spectrum (Table 2).
EXPERIMENTAL
Fig. 3. Absolute configuration of the molecule of 2,6-di-
methyl-N-(N-phenylsulfonylbenzimidoyl)-1,4-benzoquinon-
imine (IVc) according to the X-ray diffraction data.
1
The H and 13C NMR spectra were recorded on
1
a Varian VXR-300 spectrometer at 300 MHz for H
and 75.4 MHz for 13C. The chemical shifts were
measured relative to TMS.
X-ray analysis of single crystals of compounds I
and IVc was performed at room temperature using
an Enraf Nonius CAD-4 automatic four-circle dif-
fractometer ( MoK irradiation, graphite mono-
chromator, scan rate ratio /2 = 1.2). The unit cell
parameters and crystal orientation matrices were
determined from 22 reflections with 28 < < 30 for
compound I and 12 < < 13 for compound IVc.
The structure was solved by the direct method and
was refined by the least-squares procedure in full-
matrix anisotropic approximation using SHELXS and
SHELXSL-93 programs [10, 11]. All hydrogen atoms
were visualized from the difference synthesis of
electron density and were included in the calcula-
tions with fixed positional and thermal parameters
Uiso = 0.08 2. The calculations were carried out on
a PC-AT/486. The principal crystallographic data for
compounds I and IVc and conditions for the X-ray
diffraction experiments are given in Table 4. The
coordinates of atoms in molecules I and IVc are listed
in Tables 5 and 6, respectively; the bond lengths and
bond angles, in Tables 7 and 8; and Tables 9 and 10
contain principal torsion angles in molecules I and
IVc, respectively.
Fig. 4. Structure of the quinonimine fragment in the
molecule of 2,6-dimethyl-N-(N-phenylsulfonylbenz-
imidoyl)-1,4-benzoquinonimine (IVc) according to the
X-ray diffraction data.
temperatures revealed no dynamic Z,E isomerization
process. These compounds exist in solution as a single
E isomer with more favorable trans arrangement
of the ArSO2 group with respect to the benzimidoyl
fragment. According to the X-ray diffraction data,
compound IVc in crystal also exists as a single E
isomer (Fig. 3).
Dynamic Z,E isomerization was observed for
N-(N-arylsulfonylacetimidoyl)-1,4-benzoquinonimines
IVj IVl in solution (Scheme 2). Compounds IVj IVl
showed in the 1H NMR spectra two broadened singlets
from the quinoid ring protons and CH3 C N group,
which indicates the presence of two isomers occurring
in a dynamic equilibrium. In all cases, the E isomer
N-(N-Arylsulfonylimidoyl)-4-aminophenols
IIIc IIIl. To a solution of 0.01 mol of appropriate
p-aminophenol and 0.011 mol of anhydrous sodium
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

SYNTHESIS, X-RAY DIFFRACTION DATA, AND 1H AND 13C NMR SPECTRA
Table 5. Coordinates of atoms ( 104) in molecule I
997
Atom
x
y
z
Atom
x
y
z
Cl
O1
O2
N
C1
C2
C3
C4
C5
C6
C7
C8
C9
1331(1)
4522(4)
10438(3)
8010(4)
5217(4)
5826(3)
6759(4)
7109(4)
6404(4)
5490(3)
8518(5)
6724(4)
7285(5)
70(1)
1998(1)
899(1)
7208(1)
15117(1)
11354(2)
11226(2)
14199(2)
13292(2)
12360(2)
12164(2)
13017(2)
13989(2)
10929(2)
9972(2)
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
5651(5)
3426(5)
2831(5)
4476(5)
5381(4)
4751(4)
2792(4)
6835(5)
6028(5)
6242(6)
2183(5)
5077(8)
199(1)
360(1)
750(1)
8626(2)
8263(2)
8728(2)
1477(1)
1873(1)
2197(1)
2045(1)
1584(1)
1273(1)
1397(1)
1051(1)
823(1)
979(1)
9576(2)
2676(1)
1075(1)
2751(1)
2835(1)
2953(1)
1147(1)
1141(1)
610(1)
13480(2)
14904(2)
13420(2)
14757(2)
12434(2)
16243(2)
14899(3)
14517(3)
430(1)
9482(2)
Table 6. Coordinates of atoms ( 104) in molecule IVc
Atom
x
y
z
Atom
x
y
z
S
1190(2)
4219(6)
1863(5)
1634(5)
956(6)
1684(5)
3456(8)
4356(7)
3546(7)
1812(7)
909(7)
186(2)
3661(5)
116(4)
2681(1)
1729(4)
1470(3)
3280(4)
2239(4)
3609(4)
867(6)
C9
2774(8)
3248(9)
3039(10)
2359(10)
1872(9)
911(7)
1817(8)
3436(10)
4224(10)
3352(11)
1698(8)
6161(8)
805(9)
4024(6)
5235(7)
6442(7)
6489(7)
5284(6)
98(5)
220(6)
360(8)
196(8)
121(7)
263(6)
3052(7)
3618(6)
5251(5)
6047(5)
5807(6)
4739(7)
3929(6)
2638(4)
3607(6)
3602(8)
2584(12)
1639(9)
1638(5)
1(6)
O1
O2
O3
N1
N2
C1
C2
C3
C4
C5
C6
C7
C8
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
803(4)
2888(5)
1650(5)
3385(6)
3105(6)
2933(6)
2986(5)
3175(5)
3370(5)
2779(6)
4054(6)
145(6)
1147(6)
1279(5)
259(5)
755(5)
3306(5)
4162(5)
1694(7)
1601(7)
2082(7)
1797(5)
Table 7. Bond lengths d and bond angles
in molecule I
Bond
d,
Bond
d,
Bond
d,
Bond
d,
Cl C11
O1 C1
O2 C7
N C4
1.730(3)
1.218(2)
1.217(3)
1.289(2)
1.398(3)
1.494(3)
1.498(3)
C2 C3
C2 C14
C3 C4
C4 C5
C5 C6
C6 C15
C7 C8
1.337(3)
1.520(3)
1.455(3)
1.453(3)
1.342(3)
1.531(3)
1.481(3)
C8 C13
C8 C9
C9 C10
C10 C11
C11 C12
C12 C13
1.387(3)
1.389(3)
1.376(4)
1.377(4)
1.377(3)
1.371(4)
C14 C18
C14 C16
C14 C17
C15 C21
C15 C19
C15 C20
1.531(3)
1.534(3)
1.532(3)
1.516(3)
1.531(3)
1.531(3)
N C7
C1 C6
C1 C2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

998
AVDEENKO et al.
Table 7. (Contd.)
Angle
, deg
Angle
, deg
Angle
, deg
Angle
, deg
C4NC7
124.6(2)
120.1(2)
119.8(2)
120.1(2)
117.5(2)
123.6(2)
118.9(2)
123.2(2)
124.0(2)
117.4(2)
C5C4C3
C6C5C4
C5C6C1
C5C6C15
C1C6C15
O2C7N
118.6(2)
122.2(2)
118.3(2)
123.0(2)
118.6(2)
120.3(2)
122.7(2)
116.6(2)
118.6(2)
122.4(2)
C9C8C7
118.9(2)
121.0(3)
119.0(2)
121.1(3)
119.8(2)
119.1(2)
119.4(3)
120.9(2)
111.1(2)
109.9(2)
C18C14C16
C2C14C17
C18C14C17
C16C14C17
C21C15C6
C21C15C19
C6C15C19
C21C15C20
C6C15C20
C19C15C20
107.4(2)
110.6(2)
107.7(2)
110.0(2)
111.2(2)
108.4(2)
109.2(2)
108.2(2)
109.8(2)
110.1(2)
O1C1C6
O1C1C2
C6C1C2
C3C2C1
C3C2C14
C1C2C14
C2C3C4
NC4C5
C10C9C8
C11C10C9
C10C11C12
C10C11Cl
C12C11Cl
C13C12C11
C12C13C8
C2C14C18
C2C14C16
O2C7C8
NC7C8
C13C8C9
C13C8C7
NC4C3
Table 8. Bond lengths d and bond angles
in molecule IVc
Bond
d,
Bond
d,
Bond
d,
Bond
d,
S O2
1.445(4)
1.426(4)
1.645(5)
1.737(6)
1.216(7)
1.290(7)
1.381(7)
1.287(7)
C1 C6
C1 C2
C2 C3
C2 C20
C3 C4
C4 C5
C5 C6
C6 C21
1.457(9)
1.497(8)
1.333(8)
1.500(9)
1.440(8)
1.469(7)
1.342(8)
1.507(8)
C7 C8
1.466(8)
1.371(8)
1.397(7)
1.387(9)
1.350(9)
1.376(9)
1.393(9)
1.389(8)
C14 C15
C15 C16
C16 C17
C17 C18
C18 C19
1.388(8)
S O3
C8 C13
C8 C9
1.344(10)
1.403(12)
1.352(12)
1.366(10)
S N2
S C14
O1 C1
N1 C4
N1 C7
N2 C7
C9 C10
C10 C11
C11 C12
C12 C13
C14 C19
Angle
, deg
Angle
, deg
Angle
, deg
Angle
, deg
O3SO2
O3SN2
O2SN2
O3SC14
O2SC14
N2SC14
C4N1C7
C7N2S
117.0(3)
105.0(2)
111.9(2)
108.4(3)
108.9(3)
105.0(2)
124.1(5)
122.0(4)
122.5(6)
119.1(6)
118.4(5)
C3C2C1
C3C2C20
C1C2C20
C2C3C4
N1C4C3
N1C4C5
C3C4C5
C6C5C4
C5C6C1
C5C6C21
C1C6C21
119.6(6)
122.2(6)
118.2(6)
121.8(6)
125.2(5)
115.9(5)
118.9(5)
120.6(6)
120.6(5)
121.8(6)
117.6(5)
N2C7N1
123.9(5)
119.7(5)
116.2(5)
118.6(5)
121.9(5)
119.5(5)
119.1(6)
121.8(6)
119.9(6)
119.2(6)
121.4(6)
C19C14C15
C19C14S
119.5(6)
121.8(5)
118.6(5)
121.3(7)
118.6(8)
120.5(8)
121.1(8)
118.9(7)
N2C7C8
N1C7C8
C15C14S
C13C8C9
C13C8C7
C9C8C7
C16C15C14
C15C16C17
C18C17C16
C19C18C17
C18C19C14
C10C9C8
C11C10C9
C10C11C12
C11C12C13
C8C13C12
O1C1C6
O1C1C2
C6C1C2
Table 9. Principal torsion angles
in molecule I
Angle
, deg
Angle
, deg
Angle
, deg
O1C1C2C3
C6C1C2C3
O1C1C2C14
C6C1C2C14
174.64(0.21)
4.58(0.28)
4.79(0.30)
175.99(0.18)
NC7C8C9
169.17(0.18)
0.23(0.33)
177.65(0.20)
0.54(0.34)
O1C1C6C15
C1C2C14C17
C2C1C6C15
C5C6C15C21
3.40(0.31)
C13C8C9C10
C7C8C9C10
C8C9C10C11
62.52(0.25)
177.39(0.18)
2.94(0.33)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

SYNTHESIS, X-RAY DIFFRACTION DATA, AND 1H AND 13C NMR SPECTRA
Table 9. (Contd.)
999
Angle
, deg
Angle
, deg
Angle
, deg
C1C2C3C4
C14C2C3C4
C7NC4C5
C7NC4C3
C2C3C4N
C2C3C4C5
NC4C5C6
C3C4C5C6
C4C5C6C1
C4C5C6C15
O1C1C6C5
C2C1C6C5
2.65(0.30)
177.95(0.19)
2.61(0.36)
178.17(0.22)
179.51(0.20)
0.25(0.31)
C9C10C11C12
C9C10C11Cl
C10C11C12C13
ClC11C12C13
C11C12C13C8
C9C8C13C12
C7C8C13C12
C3C2C14C18
C1C2C14C18
C3C2C14C16
C1C2C14C16
C3C2C14C17
1.03(0.35)
178.89(0.17)
0.72(0.36)
179.20(0.18)
0.08(0.36)
0.54(0.33)
177.26(0.21)
2.73(0.28)
177.88(0.19)
121.46(0.22)
59.15(0.24)
116.88(0.24)
C4NC7O2
92.47(0.29)
178.07(0.24)
94.44(0.26)
116.61(0.24)
174.06(0.22)
62.38(0.26)
13.03(0.29)
122.62(0.24)
3.73(0.31)
C1C6C15C21
C4NC7C8
C5C6C15C19
O2C7C8C13
C1C6C15C19
NC7C8C13
C5C6C15C20
O2C7C8C9
C1C6C15C20
179.42(0.21)
1.37(0.31)
0.59(0.30)
179.59(0.19)
175.64(0.21)
3.57(0.29)
58.39(0.26)
Table 10. Principal torsion angles
in molecule IVc
Angle
, deg
Angle
, deg
Angle
, deg
O3SN2C7
172.95(0.45)
45.04(0.51)
72.92(0.49)
173.43(0.58)
4.09(0.80)
5.52(0.84)
176.97(0.54)
1.04(0.85)
179.94(0.53)
3.12(0.88)
176.50(0.48)
176.79(0.53)
2.82(0.84)
O1C1C6C5
C2C1C6C5
O1C1C6C21
C2C1C6C21
SN2C7N1
174.22(0.55)
3.21(0.81)
4.14(0.87)
178.43(0.47)
6.31(0.76)
178.98(0.40)
97.95(0.69)
87.16(0.66)
173.72(0.57)
1.40(0.82)
6.16(0.81)
178.72(0.50)
1.07(0.90)
179.05(0.56)
0.96(1.03)
0.95(1.16)
1.06(1.18)
C9C8C13C12
C7C8C13C12
C11C12C13C8
O3SC14C18
1.23(0.99)
178.89(0.63)
1.22(1.15)
142.06(0.46)
13.75(0.54)
106.21(0.47)
34.43(0.52)
162.74(0.43)
77.31(0.49)
0.55(0.91)
O2SN2C7
C14SN2C7
O1C1C2C3
C6C1C2C3
O1C1C2C20
C6C1C2C20
C1C2C3C4
C20C2C3C4
C7N1C4C3
C7N1C4C5
C2C3C4N1
C2C3C4C5
N1C4C5C6
C3C4C5C6
C4C5C6C1
C4C5C6C21
O2SC14C19
SN2C7C8
N2SC14C19
C4N1C7N2
C4N1C7C8
N2C7C8C13
N1C7C8C13
N2C7C8C9
N1C7C8C9
C13C8C9C10
C7C8C9C10
C8C9C10C11
C9C10C11C12
C10C11C12C13
O3SC14C15
O2SC14C15
N2SC14C15
C19C14C15C16
SC14C15C16
C14C15C16C17
C15C16C17C18
C16C17C18C19
C17C18C19C14
C15C14C19C18
SC14C19C18
177.12(0.52)
0.83(1.04)
1.20(1.17)
1.30(1.21)
0.99(1.03)
0.60(0.84)
175.93(0.51)
3.72(0.77)
0.63(0.81)
177.66(0.49)
177.06(0.49)
acetate in 10 ml of a 1:3 dimethylformamide acetic
acid mixture, cooled in an ice bath, we added with
stirring a solution of 0.01 mol of the corresponding
N-arylsulfonylbenzimidoyl chloride. The mixture was
stirred for 30 min and diluted with 100 ml of ice
water. The precipitate was filtered off, washed with
water, dried, and recrystallized from acetic acid. The
yields, melting points, and elemental analyses of
compounds IIIc IIIl are given in Table 3.
added to a mixture of 0.01 mol of N-(N-arylsulfonyl-
imidoyl)-4-aminophenol IIIc IIIl in 15 ml of acetic
acid, and the mixture was vigorously stirred. The
reaction was exothermic. In the synthesis of com-
pounds IVf IVi, the mixture was additionally heated
to 50 60 C. When a solid separated, the mixture was
cooled, and 1 ml of ethylene glycol was added. The
yellow precipitate was filtered off, washed with acetic
acid and methanol, dried, and recrystallized from
acetic acid. The yields, melting points, and elemental
analyses of compounds IVc IVl are given in Table 3.
N-(N-Arylsulfonylimidoyl)-1,4-benzoquinon-
imines IVc IVl. Lead tetraacetate, 0.013 mol, was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001

1000
AVDEENKO et al.
Povet’eva, Z.P., Chetkina, L.A., and Kopylov, V.V.,
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