Reaction of N-sulfonyl derivatives of 1,4-benzoquinone monoimine with substituted hydrazines

Article abstract of DOI:10.1134/S1070428016050055

Reaction direction of N-sulfonyl derivatives of 1,4-benzoquinone monoimine with substituted hydrazines depends on the redox potential of the quinone imine and on the basicity of the hydrazine. Aryl (alkyl)hydrazines of high basicity favor the reduction of

Full text of DOI:10.1134/S1070428016050055

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 5, pp. 644–649. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © S.A. Konovalova, A.P. Avdeenko, S.A. Goncharova, V.V. D’yakonenko, S.V. Shishkina, 2016, published in Zhurnal Organicheskoi
Khimii, 2016, Vol. 52, No. 5, pp. 659–664.
Reaction of N-Sulfonyl Derivatives of 1,4-Benzoquinone
Monoimine with Substituted Hydrazines
S. A. Konovalovaa, A. P. Avdeenkoa*, S. A. Goncharovab,
V. V. D’yakonenkoc, and S. V. Shishkinac,d
a Donbass State Engineering Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
*е-mail: chimist@dgma.donetsk.ua
b Sumy State University, Sumy, Ukraine
c Institute of Single Crystals, National Academy of Sciences of Ukraine, Kharkiv, Ukraine
d Karazin Kharkiv National University, Kharkiv, Ukraine
Received February 10, 2016
Abstract—Reaction direction of N-sulfonyl derivatives of 1,4-benzoquinone monoimine with substituted
hydrazines depends on the redox potential of the quinone imine and on the basicity of the hydrazine. Aryl
(alkyl)hydrazines of high basicity favor the reduction of quinone monoimine. In reactions with less basic
aroylhydrazones N'-(4-oxocyclohexa-2,5-dienylidene)aroylhydrazides were obtained only from the alkyl-
substituted in the quinoid ring N-sulfonyl derivatives possessing a lower redox potential.
DOI: 10.1134/S1070428016050055
Reactions of quinoid compounds with substituted
hydrazine were extensively studies for their products
may be used as acid-base indicators [1], pharmaceuti-
cals [2, 3], insecticides, fungicides, pesticides, plant
growth regulators, dyes, antioxidants [2], rubber
modifyers [4].
initial and final products: the reaction proceeds in the
direction of formation of compounds possessing lower
redox potential. Yet the reactions were carried out
under different conditions that might affect their
course: the aroylhydrazones of 1,4-benzoquinones
were obtained at room temperature, and the reduction
of the initial quinone monoimines occurred at boiling
in ethanol. Reactions of N-arylsulfonyl-1,4-benzo-
quinone monoimines having alkyl substituents in the
ring (beside the 2,6-diisopropyl derivative) with
substituted hydrazines were not explored up till now.
Lately in reaction of 1,4-benzoquinone derivatives
with substituted hydrazine the corresponding 1,4-
benzoquinone hydrazones were isolated [5–7]. In the
case of N-substituted derivatives of 1,4-benzoquinone
monoimine the corresponding hydrazones were
obtained only from 2,6-diisopropyl derivatives [8]
having lower redox potential than the other N-sulfonyl
derivatives [9], whose reactions with hydrazines
provided only reduction products [10].
This study was aimed at exploring the regularities
in reactions of different N-sulfonyl derivatives of 1,4-
benzoquinone monoamine with aryl-, alkyl-, and
aroylhydrazines.
In case of 1,4-naphthoquinone imine derivatives
possessing a lower redox potential than the 1,4-
benzoquinone monoimines [9] reactions with aroyl-
hydrazines along with 1,4-naphthoquinone aroyl-
hydrazones afforded also 1,4-addition products [11].
As
a result of reactions of N-aryl(methyl,
trifluoromethyl)sulfonyl-1,4-benzoquinone monoimi-
nes 1а–1р with phenyl-, 2,4-dinitrophenyl-, and ethyl-
hydrazines 2а–2c in ethanol, acetonitrile, and acetic
acid both at boiling and at room temperature we
obtained the corresponding N-aryl(methyl, trifluoro-
methyl)sulfonyl-4-aminophenols 3а–3р (Scheme 1)
that were reduced forms of initial quinone mono-
imines, therefore a common redox process occurred.
It was concluded in [8, 10] that the direction of
reaction between N-arylsulfonyl-1,4-quinone mono-
imines and hydrazines depends on the basicity of the
hydrazine and the ratio of the redox potentials of the
644

REACTION OF N-SULFONYL DERIVATIVES OF 1,4-BENZOQUINONE MONOIMINE
645
Scheme 1.
R1
R2
R1
R2
YNHNH2
XSO2N
+
XSO2HN
O
OH + N2 + YH
R4
R3
R4
R3
1a_1p
2a_2c
3a_3p
1, 3, X = Ph (а, d, e, g), 4-MeC6H4 (f, j, m, р), Me (b, h, k, n), CF3 (c, i, l, o); R1 = R2 = R3 = R4 = Н (а–c), R2 = R3 = R4 = Н,
R1 = Mе (d), R1 = R3 = R4 = Н, R2 = Mе (e), R3 = R4 = Н, R1 = R2 = Mе (f), R2 = R4 = Н, R1 = R3 = Mе (g–i), R2 = R3 = Н, R1 =
R4 = Mе (j–l), R1 = R4 = Н, R2 = R3 = Mе (m–o), R2 = R3 = Н, R1 = R4 = i-Pr (р); 2, Y = Et (а), Ph (b), 2,4-(NO2)2C6H3 (c).
The reaction of unsubstituted in the ring 1,4-
benzoquinone monoimines 1a–1c with aroylhydrazines
4а–4c in ethanol or chloroform at room temperature
also resulted in their reduction to the corresponding
aminophenols 3a–3c (Scheme 2) in agreement with the
findings of [10]. 1,4-Benzoquinone monoimines with
alkyl substituents in the ring 1d–1r reacted with
aroylhydrazines 4а–4с in ethanol, chloroform, or
acetonitrile affording the corresponding aroylhydrazo-
nes of 1,4-benzoquinone monoimine 5а–5l (Scheme 2).
Along with compounds 5а–5l also arylsulfamides 6а–
6d were isolated, and we failed to separate the mixture
of compounds 5b and 6b.
(chloroform, dichloromethane, acetone) compared to
compounds 5а and 5b with a single methyl group.
Introducing isopropyl or tert-butyl groups in the
positions 2 and 6 of the quinoid ring of compounds 5i–5l
even more increases their solubility. Besides the
acceptor substituents in the para-position of the
aromatic ring decrease the solubility in aprotic
solvents. We presume that this behavior is due to the
azo-hydrazone tautomerism of these compounds in
solutions [12].
To confirm this assumption we performed a
complete geometry optimization for quinonehydrazone
form (A) and azoform (B) of aroylhydrazones of 1,4-
benzoquinones 5g, 5h, 5m, and 5n (Scheme 3). Ac-
cording to obtained data in all compounds the
quinonehydrazone forms A possess a lower energy
[–1044.492978 (5g), –839.984944 (5h), –761.341322
(5m), –997.239054 (5n) а.u.] than azaforms B
[–1044.484833 (5g), –839.976010 (5h), –761.337894
(5m), –997.228628 (5n) а.u.], and the introduction of
alkyl groups in the quinoid ring of compounds 5g, 5h,
and 5n leads to the increase in the energy difference
We obtained for the first time the aroylhydrazone
of 3,5-dimethyl-1,4-benzoquinone 5f containing subs-
tituents in both ortho-positions with respect to the
imine carbon atom. Previous attempts to obtain such
compounds proceeding from alkyl-substituted 1,4-
benzoquinones were unsuccessful due to the steric
hindrances from the alkyl groups.
Compounds 5c–5h containing two methyl groups in
the quinoid ring are better soluble in aprotic solvents
Scheme 2.
3a_3c
R2
R1
1a_1r
+
Y
C
O
NH
NH2
Y
C
O
NH
N
O + XSO2NH2
4a_4c
R3
R4
6a_6d
5a_5l
1, X = Ph, R2 = R3 = Н, R1 = R4 = t-Bu (q); X = 4-MeC6H4, R2 = R4 = Н, R3 = Mе, R1 = i-Pr, (r); 4, Y = H (а), Cl (b), NO2
(c); 5, Y = H (c, h), Cl (e, j), NO2 (а, b, d, f, g, i, k, l); R2 = R3 = R4 = Н, R1 = Mе (а); R1 = R3 = R4 = Н, R2 = Mе (b); R3 =
R4 = Н, R1 = R2 = Mе (c); R2 = R4 = Н, R1 = R3 = Mе (d, e), R1 = R4 = Н, R2 = R3 = Mе (f); R2 = R3 = Н, R1 = R4 = Mе (g, h);
R2 = R3 = Н, R1 = R4 = i-Pr (i, j); R2 = R3 = Н, R1 = R4 = t-Bu (k); R2 = R4 = Н, R3 = Mе, R1 = i-Pr (l); 6, X = Ph (а),
4-MeC6H4 (b), Me (c), CF3 (d).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

KONOVALOVA et al.
646
Scheme 3.
R
R
R
Y
C
O
N
N
OH
Y
C
O
NH
N
O
R
A
B
5g, 5h, 5m, 5n
Y = NO2, R = Me (g); Y = H, R = Me (h); Y = R = H (m); Y = H, R = i-Pr (n).
between these forms [ΔE = E(B) – E(А) 21.39 (5g),
23.46 (5h), 27.38 (5n) kJ mol–1], namely, quinine-
hydrazone form A becomes even more feasible by
energy, and its prevalence favors the solubility of
compounds in aprotic solvents. The results obtained
are well consistent with the data of [12] where it has
been found that the content of the quinonehydrazone
form in compounds 5m and 5n equals 87.5 ± 2.5 and
98.1 ± 0.2%. The introduction of acceptor substituents
in the para-position of the aromatic ring affects the
difference in these energies significantly weaker that
the introduction of alkyl substituents in the quinoid
ring. The obtained data confirm our assumption on the
growth of the solubility of 1,4-benzoquinones aroyl-
hydrazones 5а–5l in aprotic solvents at increasing
content of the quinonehydrazone form.
The obtained results are also confirmed by 1Н NMR
spectra of compounds 5а–5l. In the 1Н NMR spectra of
compounds 5а and 5b containing one alkyl substituent
in the quinoid ring the majority of peaks appear as very
broadened singlets showing that in solutions of these
compounds a dynamic process occurs of mutual
transformation of forms A and B. The relative content
of these forms may be evaluated only from the integral
intensities of the peaks of protons from NH and ОН
groups: the broadened singlet of the NH group proton
observed in the region δ 12.21–12.31 ppm, the singlet
of the proton of the ОН group belonging to azoform B
appears in the region δ 11.03–11.96 ppm. In the
spectra of compounds 5c–5l containing two alkyl
substituents in the ring only the singlet from NH group
is present corresponding to form A. IR spectra of
compounds 5а–5l contain an absorption band in the
region 3367–3435 cm–1 characteristic of the NH group.
1
Since the Н NMR spectra were of complicated
pattern the unambiguous proof of the structure of the
prepared hydrazones 5 was obtained from X-ray
diffraction (XRD) analysis of the single crystal of
compound 5l (see the figure).
The carbamide group is present in the ар-
conformation with respect to the endocyclic С8–С13
bond of the benzoquinone fragment [torsion angle
С13С8N3N2–1.7(2) deg]. para-Nitrophenyl substituent
is present in the sp-conformation with respect to the
N2–N3 bond [torsion angle С4С7N2N3 –1.9(1) deg] and
slightly deviates from the plane of the amide fragment
[torsion angle С3С4C7N2 –19.8(1) deg], apparently due
to the presence of an intramolecular hydrogen bond
C3–H3···N3 (H···N 2.26 Å, CНN angle 122 deg) and of
a shortened intramolecular contact О3···Н5 2.38 Å (sum
of van der Waals radii 2.46 Å [13]). The isopropyl
substituent is turned with respect to the plane of the
benzene ring at a torsion angle C11C12C15H15 of 47 deg.
corresponding to quinonehydrazone form
A is
In the crystal the molecules 5l form double columns
along the crystallographic direction [100]. The mole-
cules are bound in the column by stacking interactions
(the distance between the contiguous molecules is 3.6 Å),
the neighbor columns are bound by intermolecular
hydrogen bonds N2–H2···O3' (–1/2 + x, –1,5 –y, –z)
(H···O 2.13 Å, NНO angle 156.8 deg).
O2
C14
C10
C9
O4
N1
C6
C11
C2
C1
C16
C3
N3
O1
C8
C13
C7
C12
C17
C4
O3
C5
C15
N2
Hence, the hydrazones of 1,4-benzoquinone mono-
amine may be obtained by reaction of alkyl-substituted
in the quinoid ring N-sulfonyl derivatives of 1,4-
benzoquinone monoamine with aroylhydrazines. This
is due to the lower redox potential of these quinone
Structure of N'-(5-isopropyl-2-methyl-4-oxocyclohexa-2,5-
dienylidene)-4-nitrobenzohydrazide 5l according to XRD
data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

REACTION OF N-SULFONYL DERIVATIVES OF 1,4-BENZOQUINONE MONOIMINE
647
monoimines compared to the unsubstituted in the ring
N-sulfonyl derivatives and to the lower basicity of
aroylhydrazine than that of aryl- and alkylhydrazines.
Therewith the nature of the solvent and the
temperature conditions do not significantly affect the
course of the reaction. The results obtained agree well
with the data of [10], which has shown that the
increase in the redox potential of the initial quinone
monoamine and in the basicity of the hydrazine favor
the proceeding of the redox process.
reaction mixture was stirred for 12 h, the separated
precipitate of compounds 3а–3р was filtered off.
When the precipitate did not form, the solution was
poured on ice or the solvent was partially evaporated
in a vacuum. The product was recrystallized from
ethanol, or from benzene–hexane mixture, 1 : 2, or
from acetic acid.
b. To a solution of 2 mmol of quinone imine 1а–1r
in 10 mL of ethanol, chloroform, or acetonitrile was
added dropwise a solution of 2 mmol of hydrazine 4а–4c
in appropriate solvent at room temperature (1а, 1b,
1d–1h, 1j, 1k, 1m, 1n, and 1р–1r) or at cooling to
–10°C (1c, 1i, 1l, and 1o). The reaction mixture was
stirred for 2 h, the separated precipitate was filtered
off. When the precipitate did not form the solvent was
partially evaporated in a vacuum. The product was
recrystallized from ethanol.
EXPERIMENTAL
IR spectra of synthesized compounds were
recorded on a spectrophotometer Vertex–70 from
pellets with KBr (5a–5h) or solution in CHCl3 (5i–5l).
1Н NMR spectra were registered on a spectrometer
Varian VXR-300 at operating frequency 300 MHz,
reference TMS. 13С NMR spectrum of compound 5i
was taken on a spectrometer Varian VXR-300 at
operating frequency 75.4 MHz. The purity of quinone
imines and their reaction products was checked by
TLC on Silufol UV-254 plates using as solvents
chloroform, acetone, THF, as eluents, ethanol–chlo-
roform, 1 : 10, benzene–hexane, 10 : 1, hexane–ethyl
acetate, 1 : 2, spots visualized under UV irradiation.
N'-(3-Methyl-4-oxocyclohexa-2,5-dienylidene)-4-
nitrobenzohydrazide (5а). Yield 51%, mp 245–247°C.
1Н NMR spectrum (DMSO-d6), δ, ppm: 2.02 br.s (3Н,
3-Mе), 6.59 br.s (1Н, Н5), 7.30 br.s (1Н, Н2), 8.01 br.s
(1Н, Н6), 8.18 br.s (2Н, 4-NO2C6H4), 8.37 d (2Н,
4-NO2C6H4, J 8.7 Hz), 11.96 br.s [1Н, ОН, 22% (B)],
12.31 br.s [1Н, NH, 78% (A)]. Found, %: N 14.65,
14.74. C14H11N3O4. Calculated, %: N 14.73.
Quantum-chemical calculations were carried out
using FireflyQC software [14] based partially on the
initial code of program package GAMESS (US) [15].
The optimization of quinonehydrazone form (A) and
azoform (B) of aroylhydrazones of 1,4-benzoquinones
5g, 5h, 5m, and 5n was performed along all geometry
parameters by DFT (B3LYP) method using basis set 6-
31+G(d).
N'-(2-Methyl-4-oxocyclohexa-2,5-dienylidene)-4-
nitrobenzohydrazide (5b). 1Н NMR spectrum
(DMSO-d6), δ, ppm: 2.02 s (3Н, 2-Mе), 7.08–7.11 d.d
(1Н, Н5, J 1.2, 8.4 Hz), 7.15 d (1Н, Н3, J 1.2 Hz), 8.14 d
(1Н, Н6, J 8.4 Hz), 8.32 d (2Н, 4-NO2C6H4, J 9.3 Hz),
8.41 d (2Н, 4-NO2C6H4, J 9.3 Hz), 11.03 br.s [1Н, ОН,
25% (B)], 12.21 br.s [1Н, NH, 75% (A)].
N'-(2,3-Dimethyl-4-oxocyclohexa-2,5-dienylide-
ne)benzohydrazide (5с). Yield 64%, mp 203–204°C.
1Н NMR spectrum (DMSO-d6), δ, ppm: 1.93 s (3Н, 3-
Mе), 2.17 br.s (3Н, 2-Mе), 6.47 d (1Н, Н5, J 9.9 Hz),
7.54–7.91 m (5H, Ph), 8.07 d (1Н, Н6, J 9.9 Hz), 12.13
br.s (1Н, NH). Found, %: N 11.00, 11.10. C15H14N2O2.
Calculated, %: N 11.02.
Characteristics of compounds 1а, 3a [16], 1b, 1c,
1h, 1i, 1k, 1l, 1n, 1o, 3b, 3c, 3h, 3i, 3k, 3l, 3n, 3o [17],
1d, 1e, 3d, 3e [18], 1f, 3f [19], 1g, 1r, 3g, 3r [20], 1j,
1m, 3j, 3m [21], 1р, 3р [22], 1q, and 3q [23] are in
agreement with the data published in the mentioned
references.
Reaction of quinone monoimines (1а–1r) with
hydrazines 2а–2c and 4а–4c. a. To a solution of
2 mmol of quinone imine 1а–1р in 10 mL of ethanol
or acetonitrile, glacial acetic acid, a mixture of acetic
acid with chloroform was added dropwise a solution of
4 mmol of hydrazine 2а–2c in appropriate solvent at
room temperature or at the boiling point of the solvent
(1а, 1b, 1d–1h, 1j, 1k, 1m, 1n, and 1р), or at cooling
to –10°C (1а–1c, 1h, 1i, 1k, 1l, 1n, and 1o). The
N'-(2,5-Dimethyl-4-oxocyclohexa-2,5-dienylide-
ne)-4-nitrobenzohydrazide (5d). Yield 78%, mp 259–
1
260°C. Н NMR spectrum (DMSO-d6), δ, ppm: 1.97 s
(3Н, 5-Mе), 2.10 br.s (3Н, 2-Mе), 6.41 s (1Н, Н3), 7.94
s (1Н, Н6), 8.12 d (2Н, 4-NO2C6H4, J 7.2 Hz), 8.37 d
(2Н, 4-NO2C6H4, J 7.2 Hz), 12.30 br.s (1Н, NH).
Found, %: N 13.90, 13.98. C15H13N3O4. Calculated, %:
N 14.04.
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KONOVALOVA et al.
648
N'-(2,5-Dimethyl-4-oxocyclohexa-2,5-dienyl-
3.01–3.13 m (1Н, 3-Pr-i), 3.13–3.26 m (1Н, 5-Pr-i),
6.93 br.s (1Н, Н2), 7.41 br.s (1Н, Н6), 7.48 d (2Н, 4-
ClC6H4, J 7.5 Hz), 7.88 d (2Н, 4-ClC6H4, J 7.5 Hz),
11.51 br.s (1Н, NH). Found, %: N 8.00, 8.15.
C19H21ClN2O2. Calculated, %: N 8.12.
idene)-4-chlorobenzohydrazide (5е). Yield 75%, mp
1
258–260°C. Н NMR spectrum (DMSO-d6), δ, ppm:
1.97 s (3Н, 5-Mе), 2.11 s (3Н, 2-Mе), 6.42 s (1Н, Н3),
7.63 d (2Н, 4-ClC6H4, J 8.1 Hz), 7.94 d (2Н, 4-
ClC6H4, J 8.1 Hz), 7.94 s (1Н, Н6), 12.04 br.s (1Н,
NH). Found, %: N 9.60, 9.69. C15H13ClN2O2. Calcu-
lated, %: N 9.70.
N'-(3,5-Di-tert-butyl-4-oxocyclohexa-2,5-dienyl-
idene)-4-nitrobenzohydrazide (5k). Yield 96%, mp
1
222–224°C. Н NMR spectrum (CDCl3), δ, ppm: 1.28
s (9Н, 3-t-Bu), 1.33 s (9Н, 5-t-Bu), 6.80 br.s (1Н, Н2),
7.42 br.s (1Н, Н6), 8.04 d (2Н, 4-NO2C6H4, J 9.0 Hz),
8.36 d (2Н, 4-NO2C6H4, J 9.0 Hz), 11.03 br.s (1Н,
NH). Found, %: N 10.90, 10.93. C21H25N3O4.
Calculated, %: N 10.96.
N'-(2,6-Dimethyl-4-oxocyclohexa-2,5-dienyl-
idene)-4-nitrobenzohydrazide (5f). Yield 52%, mp
1
268–270°C. Н NMR spectrum (DMSO-d6), δ, ppm:
1.88 s (6Н, 2-Mе), 1.89 s (6Н, 6-Me), 6.82 s (1Н, Н5),
7.92 s (1Н, Н3), 8.16 d (2Н, 4-NO2C6H4, J 8.2 Hz),
8.44 d (2Н, 4-NO2C6H4, J 8.2 Hz), 11.98 br.s (1Н,
NH). Found, %: N 13.99, 14.00. C15H13N3O4.
Calculated, %: N 14.04.
N'-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-
dienylidene)-4-nitrobenzohydrazide (5l). Yield 88%,
1
mp 191–192°C. Н NMR spectrum (CDCl3), δ, ppm:
N'-(3,5-Dimethyl-4-oxocyclohexa-2,5-dienyl-
idene)-4-nitrobenzohydrazide (5g). Yield 81%, mp
1.15 d (6Н, i-Pr, J 6.6 Hz), 2.04 br.s (3Н, 2-Me), 3.08–
3.21 m (1Н, i-Pr), 6.40 s (1Н, Н6),7.54 s (1Н, Н3), 8.06
d (2Н, 4-NO2C6H4, J 8.7 Hz), 8.34 d (2Н, 4-NO2C6H4,
1
267–268°C. Н NMR spectrum (DMSO-d6), δ, ppm:
1.98 s (3Н, 3-Mе), 2.00 s (3Н, 5-Mе), 7.15 s (1Н, Н2),
7.97 s (1Н, Н6), 8.15 d (4Н, 4-NO2C6H4, J 7.2 Hz),
8.36 d (4Н, 4-NO2C6H4, J 7.2 Hz), 12.20 br.s (1Н,
NH). Found, %: N 14.00, 14.09. C15H13N3O4.
Calculated, %: N 14.04.
1
J 8.7 Hz), 11.48 br.s (1Н, NH). Н NMR spectrum
(DMSO-d6), δ, ppm: 1.11 d (6Н, i-Pr, J 5.7 Hz), 2.04
br.s (3Н, 2-Me), 2.95–3.12 m (1Н, i-Pr), 6.39 s (1Н,
Н6), 7.81 s (1Н, Н3), 8.08 d (2Н, 4-NO2C6H4, J 6.9 Hz),
8.36 d (2Н, 4-NO2C6H4, J 6.9 Hz), 12.55 br.s (1Н,
NH). Found, %: N 12.78, 12.80. C17H17N3O4. Calcu-
lated, %: N 12.84.
N'-(3,5-Dimethyl-4-oxocyclohexa-2,5-dienyl-
idene)benzohydrazide (5h). Yield 85%, mp 219–
1
220°C. Н NMR spectrum (DMSO-d6), δ, ppm: 1.96 s
XRD analysis. Crystals of compound 5l rhombic,
at 21°C a 4.989(3), b 12.313(5), c 25.566(6) Å, α = β =
γ = 90 deg, V 1570.4(9) Å3, M 327.33, Z 4, space
group P212121, dcalc 1.384 g/cm3, μ(MoKα) 0.101 mm–1,
F(000) 688. The parameters of the unit cell and
intensities of 9677 reflections (2859 independent, Rint
0.183) were measured on a diffractometer Xcalibur-3
(MoKα radiation CCD-detector, graphite monochroma-
tor, ω-scanning, 2θmax 50 deg).
(3Н, 3-Mе), 2.00 s (3Н, 5-Mе), 7.18 s (1Н, Н2), 7.52–
7.93 m (5H, Ph), 8.01 s (1Н, Н6), 11.96 br.s (1Н, NH).
Found, %: N 10.90, 10.99. C15H14N2O2. Calculated, %:
N 11.02.
N'-(3,5-Diisopropyl-4-oxocyclohexa-2,5-dienyl-
idene)-4-nitrobenzohydrazide (5i). Yield 89%, mp
1
199–200°C. Н NMR spectrum (CDCl3), δ, ppm: 1.12
d (6Н, 3-Pr-i, J 8.4 Hz), 1.15 d (6Н, 5-Pr-i, J 8.4 Hz),
3.05–3.16 m (1Н, 3-Pr-i), 3.13–3.26 m (1Н, 5-Pr-i),
6.79 br.s (1Н, Н2),7.59 br.s (1Н, Н6), 8.09 d (2Н,
4-NO2C6H4, J 8.4 Hz), 8.35 d (2Н, 4-NO2C6H4, J
8.4 Hz), 11.48 br.s (1Н, NH). 13C (CDCl3), δ, ppm:
21.75 (2Mе, 3-Pr-i), 21.96 (2Mе, 5-Pr-i), 26.79 (CH,
3-Pr-i), 27.50 (CH, 5-Pr-i), 115.61 (C3',5'), 123.18
(C2',6'), 132.38 (C3,5), 138.12 (C1'), 148.97 (C4'), 149.71
(C=N), 152.18 (C2,6), 183.15 (NHC=O), 185.66 (C=O).
Found, %: N 11.70, 11.80. C19H21N3O4. Calculated, %:
N 11.82.
The structure was solved by the direct method
using program package SHELXTL [24]. Positions of
hydrogen atoms were found from the difference
synthesis of electron density and refined in the rider
model with Uiso = nUeq (n = 1.5 for methyl groups, 1.2
for the other hydrogen atoms) of the nonhydrogen
atom bound to this hydrogen. The structure was
refined with respect to F2 by the full-matrix least-
squares method in anisotropic approximation for
nonhydrogen atoms till wR2 0.062 for 2859 reflections
[R1 0.039 for 660 reflections with F > 4σ(F), S 0.438].
Atomic coordinates and full tables of bond lengths and
bond angles are deposited in the Cambridge
Crystallographic Data Center (CCDC 1443421).
N'-(3,5-Diisopropyl-4-oxocyclohexa-2,5-dienyli-
dene)-4-chlorobenzohydrazide (5j). Yield 95%, mp
1
174–177°C. Н NMR spectrum (CDCl3), δ, ppm: 1.12
d (6Н, 3-Pr-i, J 6.0 Hz), 1.16 d (6Н, 5-Pr-i, J 6.9 Hz),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

REACTION OF N-SULFONYL DERIVATIVES OF 1,4-BENZOQUINONE MONOIMINE
649
13. Zefirov, Yu.V. and Zorkii, P.M., Russ. Chem. Rev.,
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