Reaction of N-chloro-1,4-benzoquinone imines with thiols

Article abstract of DOI:10.1134/S1070428016090062

N-Chloro-1,4-benzoquinone imines reacted with arenethiols to give different products, depending on the conditions and initial quinone imine structure. N-(Arylsulfanyl)-1,4-benzoquinone imines were obtained as a result of nucleophilic substitution of the chlorine atom, and 1,4-benzoquinone imines containing an aryl-sulfanyl substituent in the quinoid ring were formed according to the radical mechanism. The reactions of N-chloro-1,4-benzoquinone imines with heterocyclic thiols afforded only the corresponding chlorine substitution products.

Full text of DOI:10.1134/S1070428016090062

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 9, pp. 1287–1296. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © S.A. Konovalova, A.P. Avdeenko, A.A. Santalova, E.N. Lysenko, K.S. Burmistrov, 2016, published in Zhurnal Organicheskoi Khimii,
2016, Vol. 52, No. 9, pp. 1300–1308.
Reaction of N-Chloro-1,4-benzoquinone Imines with Thiols
S. A. Konovalovaa, A. P. Avdeenkoa,* A. A. Santalovaa, E. N. Lysenkoa, and K. S. Burmistrovb
a Donbass State Engineering Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
*e-mail: chimist@dgma.donetsk.ua
b Ukrainian State University of Chemical Technology, pr. Gagarina 8, Dnepropetrovsk, 49005 Ukraine
Received May 11, 2016
Abstract—N-Chloro-1,4-benzoquinone imines reacted with arenethiols to give different products, depending
on the conditions and initial quinone imine structure. N-(Arylsulfanyl)-1,4-benzoquinone imines were obtained
as a result of nucleophilic substitution of the chlorine atom, and 1,4-benzoquinone imines containing an aryl-
sulfanyl substituent in the quinoid ring were formed according to the radical mechanism. The reactions of
N-chloro-1,4-benzoquinone imines with heterocyclic thiols afforded only the corresponding chlorine
substitution products.
DOI: 10.1134/S1070428016090062
Adams et al. [1] in the pioneering study on the
reaction of N-(arenesulfonyl)- and N-aroyl-1,4-benzo-
quinone diimines with thiols isolated the correspond-
ing 1,4-addition products [1]. Later it was shown that
N-phenyl-1,4-benzoquinone imine reacted with thiols
according to the 1,4- and 6,3-addition schemes [2, 3]
and that 1,4-addition was observed in the reaction of
thiols with the N-tosyl analog [4]. Taking into account
that in all cases reduction products of the correspond-
ing adducts were isolated, it was presumed that the re-
actions followed the nucleophilic addition mechanism.
imines with arenethiols [5–7]. This reaction was also
used for calorimetric determination of thiols in solu-
tion [8–11], but the products were neither isolated nor
identified. Searle [11] showed that the products were
the corresponding N-arylsulfanyl derivatives of
1,4-benzoquinonmone imine. Possible formation of
other products (through introduction of an R-sulfanyl
group into the quinoid ring) and reaction mechanism
were not considered.
The goal of the present work was to reveal all
possible products of the reaction of N-chloro-1,4-ben-
zoquinone imines with arenethiols. The reactions of
quinone imines 1a–1c with arenethiols 2a–2d were
Some N-arylsulfanyl derivatives were obtained
previously by reactions of N-chloro-1,4-benzoquinone
Scheme 1.
R2
R1
R4
N
S
O
O
R1
R2
SH
R3
3a–3f
+
R3
R4
R1
R2
N
Cl
O
1a–1c
2a–2d
N
S
R4
R4
S
R3
4a–4f
1, R1 = Me, R2 = R3 = H (a); R1 = R3 = H, R2 = Me (b); R1 = R3 = Me, R2 = H (c); 2, R4 = H (a), Me (b), Cl (c), O2N (d); 3, 4, R1 =
Me, R2 = R3 = H, R4 = Cl (a); R1 = Me, R2 = R3 = H, R4 = O2N (b); R1 = R3 = R4 = H, R2 = Me (c); R1 = R3 = H, R2 = R4 = Me (d);
R1 = R3 = Me, R2 = R4 = H (e); R1 = R3 = Me, R2 = H, R4 = Cl (f).
1287

KONOVALOVA et al.
1288
Scheme 2.
Me
2a–2d
R
N
S
O
O
Me
2a–2d
3g–3i
Me
Me
Me
R
O
Me
N
N
O
Cl
2a, 2c, 2d
N
Cl
1d
S
R
S
R
S
Me
4g–4i
Me
5a–5c
2a, 2d
2a–2d
R
R
S
Me
S
2a, 2d
O
S
R
O
S
Me
N
N
R
R
S
Cl
Me
Me
6a, 6c
7a, 7c
3, 4, R = H (g), Cl (h), O2N (i); 5–7, R = H (a), Cl (b), O2N (c).
carried out in dioxane in the presence of 10% aqueous
sodium carbonate on cooling. When the reactant ratio
was 1 :1, the reaction mixtures contained quinone
imines 3a–3f as the major products and compounds
4a–4f (Scheme 1) whose fraction did not exceed 20%.
clude that arenethiols react at the quinoid ring only
with N-chloro derivatives 1 and 5 rather than with
N-arylsulfanyl quinone imines 3 and 4; i.e., the second
pathway is operative in the reactions of quinone imines
1 with arenethiols 2.
Quinone imine 1d reacted with equimolar amounts
of arenethiols 2a–2d to give compounds 3g–3i, 4g–4i,
and 5a–5c (Scheme 2). When the reactant ratio was
1:5, the reaction mixtures also contained N-chloro-2,6-
bis(arylsulfanyl) and N,2,6-tris(arylsulfanyl) deriva-
tives 6a, 6c and 7a, 7c which we failed to isolate. They
were identified on the basis of the 1H NMR data. In all
cases, the corresponding diaryl disulfides were detect-
ed in the reaction mixtures.
Thus, quinone imines 1 react with arenethiols 2 to
give products resulting from two competing processes,
nucleophilic substitution of the chlorine atom by aryl-
sulfanyl group and formal substitution of hydrogen in
the quinoid ring by arylsulfanyl group. The mechanism
of the second process remained unclear.
N-Substituted 1,4-benzoquinone imines are capable
of reacting with nucleophiles according to the 1,2-
[12], 1,4- [13, 14], 6,3- [12, 15], 1,6- [16], 6,1-
[12, 16], and even 1,8-addition [17] patterns. Con-
servation of the quinoid structure is possible only in
the case of 1,2-addition–elimination, e.g., as in the
reaction of quinone imines with primary aromatic
amines [5–7]. The quinoid ring of N-substituted
1,4-benzoquinone imines can also be retained in
radical reactions. The formation of radical species in
the reactions of N-arenesulfonyl-1,4-benzoquinone
imines with butan-1-amine and phenylmethanamine in
acetone or chloroform [18], with 4,4′-bipyridine in
It may be presumed that quinone imines 4 (or 7)
are formed along two pathways: (1) initially formed
quinone imine 3 takes up one or two arenethiol mole-
cules 2; (2) the primary product is N-chloroquinone
imine 5 or 6 which reacts with the second (third)
arenethiol molecule 2, yielding quinone imine 4 (7). In
order to shed light on the reaction path, quinone imines
3g–3i and 4g–4i were reacted with 2a–2d (Scheme 2);
however, only the initial compounds were isolated
from the reaction mixtures. Therefore, we can con-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 9 2016

REACTION OF N-CHLORO-1,4-BENZOQUINONE IMINES WITH THIOLS
1289
chloroform [19] and with di- and trialkoxyphosphines
[20] was detected previously by ESR spectroscopy.
with arenethiols. The presence of substituents in
positions 3 and 5 creates steric hindrances to the
nucleophilic substitution of chlorine by an ArS group;
therefore, the probability of the concurrent radical
substitution of hydrogen in positions 2 and 6 by aryl-
sulfanyl group increases, and small amounts of 5 and 6
are formed.
·
O
O
O
S
Ar
N
The radical mechanism with conservation of the
quinoid structure was also proved by studying the
kinetics of the reaction of 1,3-benzothiazole-2-thiol
with N-phenyl-1,4-benzoquinone imine [18, 19] and
N,N′-diphenyl-1,4-benzoquinone diimine [21, 22],
which afforded products of addition of hetarylsulfanyl
radicals to the quinoid carbon atom (Scheme 3). In all
these reactions, bis(1,3-benzothiazol-2-yl) disulfide
was formed.
We presumed that, as in the reactions with 1a–1c,
compounds 5 and 6 should not be formed in the reac-
tions of arenethiols 2 with N-chloro quinone imine 1e
having no substituents in the quinoid ring. In fact,
neither compounds 5 nor 6 were isolated in the reac-
tions of 1e with 2a–2d (Scheme 5). When the reactions
were carried out with equimolar amounts of the re-
actants, the major products were quinone imines 3j–3l,
and compounds 4j–4l and 7d–7f were also formed.
When the 1e-to-2 ratio was 1:5, the reaction mixtures
contained compounds 8a, 8b and 9a, 9b which were
Scheme 3.
X
X
nRH
1
identified by H NMR (we failed to isolate them from
the reaction mixtures).
Ph
Ph
N
N
Rn
Potassium ethyl xanthogenate and hetarenethiols
are sulfur-centered nucleophiles, and the heterocyclic
fragment in the latter may considerably affect the reac-
tion course. Furthermore, new biologically active com-
pounds can be obtained on the basis of heterocyclic
thiols. It is known that 1,3-benzoxazole-2-thiol deriva-
tives exhibit antibacterial and anti-inflammatory activ-
ity [24] and that compounds containing a 1,3-benzo-
thiazol-2-ylsulfanyl group show antibacterial, anti-
fungal [25–27], antihelminthic, anti-inflammatory,
antitumor, antiulcer, anti-Parkinson, hypotensive [28],
and antioxidant [29] activities. On the other hand,
1,4-benzoquinone and 1,4-benzoquinone imine deriva-
tives are insecticides, fungicides, and bactericides
[30, 31], and some compounds exhibit antitumor
activity [32–35] and are antibiotics [36]. Therefore,
a broad spectrum of biological activity may be expect-
ed for quinone imines containing a hetarylsulfanyl sub-
stituent on the nitrogen atom.
N
S
S
R =
X = O, NPh.
Likewise, N,N′-diphenyl-1,4-benzoquinone diimine
reacted with benzenethiol in chlorobenzene by the
radical mechanism. Radical adduct A was formed in
the first step of the radical chain process, and the final
products were C-phenylsulfanyl quinone diimine and
diphenyl disulfide [23] (Scheme 4). These findings led
us to presume that arylsulfanyl group is introduced into
the quinoid ring of N-chloro-1,4-benzoquinone imines
1 via radical substitution of hydrogen. The formation
of the corresponding diaryl disulfides also suggests
radical mechanism of this reaction pathway.
Scheme 4.
·
N
N
·
PhS
Ph
Ph
Quinone imines 1c and 1f–1h reacted with hetero-
cyclic thiols 10a, 10c, and 10d in acetone to give the
corresponding N-hetarylsulfanyl quinone imines 11a–
11j as the only products (Scheme 6). The reactions of
1c and 1f with 1,3-benzoxazole-2-thiol (10b) was very
slow; therefore, it was carried out with the correspond-
ing sodium thiolate in ethanol. Quinone imines 11k
and 11l were obtained by reacting 1c and 1f with
potassium ethyl xanthogenate (10e) in acetone
(Scheme 6). Compounds 11a–11l were isolated as
bright orange crystalline substances whose structure
Ph
Ph
N
N
H
SPh
A
N
Ph
· · ·
Ph
N
SPh
N-Chloro quinone imines 5 and 6 were detected
only in the reactions of 3,5-dimethyl derivative 1d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 9 2016

KONOVALOVA et al.
1290
Scheme 5.
R
N
S
O
O
3j–3l
N
S
R
R
S
4j–4l
O
R
S
SH
+
O
N
S
R
R
N
R
S
Cl
1e
2a–2d
7d–7f
S
R
O
N
S
R
R
S
8a, 8b
R
S
S
R
O
N
S
R
R
S
9a, 9b
3, 4, R = H (j), Me (k), O2N (l); 7, R = H (d), Me (e), O2N (f); 8, 9, R = H (a), Me (b).
1
was determined on the basis of H NMR spectra and
elemental analyses. Thus, the reactions of N-chloro
quinone imines 1c and 1f–1h with heterocyclic thiols
10a, 10c, and 10d and potassium ethyl xanthogenate
(10e) afforded only the corresponding chlorine sub-
stitution products.
EXPERIMENTAL
1
The H NMR spectra were measured on a Varian
VXR-300 spectrometer (300 MHz) relative to tetra-
methylsilane. Silufol UV-254 plates were used for
thin-layer chromatography; samples were applied from
solutions in chloroform, benzene–hexane (10:1) and
ethanol–chloroform (20:1) were used as eluents, and
spots were visualized under UV light.
Analysis of possible biological activity of com-
pounds 11a–11d, 11g, and 11h using PASS (Prediction
of Activity Spectra for Substances) [37] showed a high
probability (0.90–0.94) of antiulcer properties. These
compounds may also exhibit gastric antisecretory and
mucomembranous protector activity with a probability
of 0.90–0.94. It is highly probable (0.97–0.98) that
compounds 11k and 11l are potential inhibitors of hy-
droxylamine reductase, acetylindoxyl oxidase, laccase,
and phenol 2-monooxygenase.
N-Chloro-1,4-benzoquinone imines 1a–1h were syn-
thesized according to the procedure described in [38].
General procedure for the reactions of N-chloro-
1,4-benzoquinone imines 1a–1e with arenethiols 2.
A solution of 0.01 mol of quinone imine 1a–1e in
3 mL of dioxane was quickly added to a solution of
0.01 mol of thiol 2a–2d in 10% aqueous sodium car-
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REACTION OF N-CHLORO-1,4-BENZOQUINONE IMINES WITH THIOLS
1291
Scheme 6.
N
R1
R2
SH
Y
N
O
S
10a–10c
+
HCl
N
Y
R4
R3
11a–11h
N N
R1
O
N
R2
SH
N
H
10d
R1
R2
R4
R3
N
O
S
N
+
HCl
N
N
H
R4
R3
Cl
11i, 11j
1c, 1f–1h
S
R1
R2
EtO
SK
S
O
S
10e
+
KCl
N
EtO
R4
R3
11k, 11l
1, R1 = R4 = Me, R2 = R3 = H (f); R1 = R4 = i-Pr, R2 = R3 = H (g); R1 = R4 = t-Bu, R2 = R3 = H (h); 10, Y = NH (a), O (b), S (c);
11, Y = NH: R1 = R3 = Me, R2 = R4 = H (a); R1 = R4 = Me, R2 = R3 = H (b); R1 = R4 = i-Pr, R2 = R3 = H (c); R1 = R4 = t-Bu,
R2 = R3 = H (d); Y = O, R1 = R3 = Me, R2 = R4 = H (e); R1 = R4 = Me, R2 = R3 = H (f); Y = S, R1 = R3 = Me, R2 = R4 = H (g);
R1 = R4 = Me, R2 = R3 = H (h); R1 = R3 = Me, R2 = R4 = H (i); R1 = R4 = Me, R2 = R3 = H (j); R1 = R3 = Me, R2 = R4 = H (k);
R1 = R4 = Me, R2 = R3 = H (l).
bonate on cooling with an ice bath. After 30 min, the
red crystals were filtered off. If no crystalline product
separated, the mixture was poured onto crushed ice
with stirring. The crude product was dissolved in
a minimum amount of benzene, and the solution was
passed through a column charged with Silicagel 60
(0.04–0.063 mm, ROSS, Belgium) using benzene as
eluent. The isolated fractions were evaporated on
a rotary evaporator. Crystalline or oily products were
subjected to further study.
of thiol 10b and 0.01 mol of sodium hydroxide in
5 mL of ethanol, and the mixture was vigorously
stirred for 30 min. The orange crystals were filtered
off, washed with water, and recrystallized from
propan-2-ol.
The physical constants and spectral parameters of
3a, 3e, 3f [39], 3b, 3c [40], 3g–3i [41], and 3j–3l [42]
were consistent with published data.
3-Methyl-4-{[(4-methylphenyl)sulfanyl]imino}-
cyclohexa-2,5-dien-1-one (3d). Yield 70%, mp 125–
1
127°C. H NMR spectrum (CDCl3), δ, ppm: 2.24 s
Reactions of 1d and 1e with 2a–2d were also
carried out at a ratio of 1:5 using 0.01 mol of 1 and
0.05 mol of 2.
(3H, 3-Me), 2.39 s (3H, Me), 6.38 q (1H, 2-H), 6.47–
6.50 d.d (1H, 6-H, J = 10.2, 2.1 Hz), 7.26 d (2H, 2′-H,
6′-H, J = 8.1 Hz), 7.41 d (1H, 5-H, J = 10.2 Hz), 7.50 d
(2H, 3′-H, 5′-H, J = 8.1 Hz). Found, %: N 5.53, 5.81;
S 12.97, 13.15. C14H13NOS. Calculated, %: N 5.76;
S 13.18.
General procedure for the reactions of N-chloro-
1,4-benzoquinone imines 1c and 1f–1h with thiols
10a–10e. a. A solution of 0.01 mol of quinone imine
1c or 1f–1h in 3 mL of acetone was added to a solution
of 0.01 mol of thiol 10a, 10c, 10d, or 10e in 5 mL of
acetone, and the mixture was vigorously stirred for
30 min. The orange crystals were filtered off and
recrystallized from propan-2-ol.
3,5-Dimethyl-4-[(phenylsulfanyl)imino]cyclo-
hexa-2,5-dien-1-one (3g). Yield 23%, mp 178–179°C
1
[41]. H NMR spectrum (CDCl3), δ, ppm: 2.31 br.s
(3H, 5-Me), 2.51 br.s (3H, 3-Me), 6.37 br.s (2H, 2-H,
6-H), 7.29–7.63 m (5H, Ph). Found, %: N 5.64, 5.92;
S 13.04, 13.28. C14H13NOS. Calculated, %: N 5.76;
S 13.18.
b. A solution of 0.01 mol of quinone imine 1c or 1f
in 3 mL of ethanol was added to a solution of 0.01 mol
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 9 2016

KONOVALOVA et al.
1292
4-{[(4-Chlorophenyl)sulfanyl]imino}-3,5-di-
5-Methyl-2-[(4-methylphenyl)sulfanyl]-4-
{[(4-methylphenyl)sulfanyl]imino}cyclohexa-2,5-
dien-1-one (4d). Yield 7%, mp 87–90°C. H NMR
methylcyclohexa-2,5-dien-1-one (3h). Yield 34%,
1
1
mp 186–187°C [41]. H NMR spectrum (CDCl3), δ,
ppm: 2.28 br.s (3H, 5-Me), 2.51 br.s (3H, 3-Me),
6.37 br.s (2H, 2-H, 6-H), 7.41 d (2H, 2′-H, 6′-H, J =
8.4 Hz), 7.56 d (2H, 3′-H, 5′-H, J = 8.4 Hz). Found, %:
N 4.88, 5.13; S 11.41, 11.59. C14H12ClNOS. Calculat-
ed, %: N 5.04; S 11.54.
spectrum (CDCl3), δ, ppm: 2.21 s (3H, 5-Me), 2.36 s
(3H, Me), 2.44 s (3H, Me), 6.42 q (1H, 6-H), 6.48 br.s
(1H, 3-H), 7.20 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 7.32 d
(2H, 2″-H, 6″-H, J = 8.1 Hz), 7.40 d (2H, 3′-H, 5′-H,
J = 8.4 Hz), 7.46 d (2H, 3″-H, 5″-H, J = 8.1 Hz).
Found, %: N 3.73, 3.91; S 17.32, 17.57. C21H19NOS2.
Calculated, %: N 3.83; S 17.55.
3,5-Dimethyl-4-{[(4-nitrophenyl)sulfanyl]imino}-
cyclohexa-2,5-dien-1-one (3i). Yield 22%, mp 227–
1
228°C [41]. H NMR spectrum (CDCl3), δ, ppm:
3,6-Dimethyl-2-(phenylsulfanyl)-4-[(phenylsul-
fanyl)imino]cyclohexa-2,5-dien-1-one (4e). Yield
5%, mp 65–68°C. 1H NMR spectrum (CDCl3), δ, ppm:
2.08 s (3H, 6-Me), 2.54 s (3H, 3-Me), 6.63 q (1H,
5-H), 7.27–7.63 m (10H, Ph). Found, %: N 3.78, 4.15;
S 18.01, 18.33. C20H17NOS2. Calculated, %: N 3.98;
S 18.24.
2.35 br.s (3H, 5-Me), 2.56 br.s (3H, 3-Me), 6.42 br.s
(2H, 2-H, 6-H), 7.79 d (2H, 2′-H, 6′-H, J = 8.1 Hz),
8.33 d (2H, 3′-H, 5′-H, J = 8.1 Hz). Found, %: N 9.58,
9.75; S 11.07, 11.26. C14H12N2O3S. Calculated, %:
N 9.72; S 11.12.
2-[(4-Chlorophenyl)sulfanyl]-4-{[(4-chloro-
phenyl)sulfanyl]imino}-6-methylcyclohexa-2,5-dien-
2-[(4-Chlorophenyl)sulfanyl]-4-{[(4-chloro-
phenyl)sulfanyl]imino}-3,6-dimethylcyclohexa-2,5-
dien-1-one (4f). Yield 6%, mp 164–166°C. 1H NMR
spectrum (CDCl3), δ, ppm: 2.08 d (3H, 6-Me, J =
1.2 Hz), 2.53 s (3H, 3-Me), 7.18 d (2H, 2′-H, 6′-H, J =
8.4 Hz), 7.19 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.27 d
(1H, 5-H, J = 1.5 Hz), 7.43 d (2H, 2″-H, 6″-H, J =
8.7 Hz), 7.55 d (2H, 3″-H, 5″-H, J = 8.7 Hz). Found,
%: N 3.27, 3.49; S 15.01, 15.22. C20H15Cl2NOS2. Cal-
culated, %: N 3.33; S 15.26.
1
1-one (4a). Yield 4%, mp 134–136°C. H NMR spec-
trum (CDCl3), δ, ppm: E isomer (43%): 2.13 s (3H,
6-Me), 6.29 d (1H, 3-H, J = 2.4 Hz), 6.91 q (1H, 5-H),
7.37 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 7.42 d (2H, 2″-H,
6″-H, J = 8.1 Hz), 7.47 d (2H, 3′-H, 5′-H, J = 8.4 Hz),
7.51 d (2H, 3″-H, 5″-H, J = 8.1 Hz); Z isomer (57%):
2.07 s (3H, 6-Me), 6.49 d (1H, 3-H, J = 2.4 Hz), 7.26 q
(1H, 5-H), 7.36 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 7.42 d
(2H, 2″-H, 6″-H, J = 8.1 Hz), 7.45 d (2H, 3′-H, 5′-H,
J = 8.4 Hz), 7.51 d (2H, 3″-H, 5″-H, J = 8.1 Hz).
F o u n d , % : N 3 . 2 1 , 3 . 4 1 ; S 1 5 . 6 4 , 1 5 . 9 0.
C19H13Cl2NOS2. Calculated, %: N 3.45; S 15.78.
3,5-Dimethyl-2-(phenylsulfanyl)-4-[(phenylsul-
fanyl)imino]cyclohexa-2,5-dien-1-one (4g). Yield
1
6%, mp 110–112°C. H NMR spectrum (CDCl3), δ,
2-Methyl-6-[(4-nitrophenyl)sulfanyl]-4-{[(4-ni-
trophenyl)sulfanyl]imino}cyclohexa-2,5-dien-1-one
ppm: 2.50 br.s (3H, 3-Me), 2.66 br.s (3H, 5-Me), 6.50 s
(1H, 6-H), 7.31–7.63 m (10H, Ph). Found, %: N 3.87,
4.09; S 18.11, 18.38. C20H17NOS2. Calculated, %:
N 3.98; S 18.24.
1
(4b). Yield 20%, mp 246–248°C. H NMR spectrum
(CDCl3), δ, ppm: E isomer (48%): 2.17 s (3H, 2-Me),
6.73 d (1H, 5-H, J = 2.4 Hz), 7.03 q (1H, 3-H), 7.71 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.77 d (2H, 2″-H, 6″-H,
J = 8.1 Hz), 8.27 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 8.37 d
(2H, 3″-H, 5″-H, J = 8.1 Hz); Z isomer (52%): 2.12 s
(3H, 2-Me), 6.64 d (1H, 5-H, J = 2.4 Hz), 7.29 q
(1H, 3-H), 7.65 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.71 d
(2H, 2″-H, 6″-H, J = 8.1 Hz), 8.26 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 8.27 d (2H, 3″-H, 5″-H, J = 8.1 Hz).
Found, %: N 9.63, 9.80; S 14.91, 15.19. C19H13N3O5S2.
Calculated, %: N 9.83; S 15.00.
2-[(4-Chlorophenyl)sulfanyl]-4-{[(4-chloro-
phenyl)sulfanyl]imino}-3,5-dimethylcyclohexa-2,5-
1
dien-1-one (4h). Yield 10%, mp 88–90°C. H NMR
spectrum (CDCl3), δ, ppm: 2.51 br.s (3H, 3-Me),
2.61 br.s (3H, 5-Me), 6.49 q (1H, 6-H), 7.16 d (2H,
2′-H, 6′-H, J = 7.8 Hz), 7.20 d (2H, 3′-H, 5′-H, J =
7.8 Hz), 7.44 d (2H, 2″-H, 6″-H, J = 8.7 Hz), 7.55 d
(2H, 3″-H, 5″-H, J = 8.7 Hz). Found, %: N 3.20, 3.51;
S 15.11, 15.32. C20H15Cl2NOS2. Calculated, %:
N 3.33; S 15.26.
5-Methyl-2-(phenylsulfanyl)-4-[(phenylsulfanyl)-
3,5-Dimethyl-2-[(4-nitrophenyl)sulfanyl]-4-
{[(4-nitrophenyl)sulfanyl]imino}cyclohexa-2,5-dien-
1-one (4i). Yield 12%, mp 81–84°C. H NMR spec-
trum (CDCl3), δ, ppm: 2.51 br.s (3H, 3-Me), 2.67 br.s
(3H, 5-Me), 6.50 q (1H, 6-H), 7.43 d (4H, 2′-H, 6′-H,
J = 8.1 Hz), 8.14 d (4H, 3′-H, 5′-H, J = 8.1 Hz).
imino]cyclohexa-2,5-dien-1-one (4c). Yield 13%,
mp 172–174°C. H NMR spectrum (CDCl3), δ, ppm:
2.27 s (3H, 5-Me), 6.44 q (1H, 6-H), 6.46 br.s (1H,
3-H), 7.34–7.63 m (10H, Ph). Found, %: N 3.94, 4.20;
S 18.78, 18.93. C19H15NOS2. Calculated, %: N 4.15;
S 19.00.
1
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REACTION OF N-CHLORO-1,4-BENZOQUINONE IMINES WITH THIOLS
1293
Found, %: N 9.38, 9.65; S 14.37, 14.62. C20H15N3O5S2.
Calculated, %: N 9.52; S 14.53.
4-(Chloroimino)-2-[(4-chlorophenyl)sulfanyl]-
3,5-dimethylcyclohexa-2,5-dien-1-one (5b). Yield
1
3%, mp 154–156°C. H NMR spectrum (CDCl3), δ,
2-(Phenylsulfanyl)-4-[(phenylsulfanyl)imino]-
ppm: 2.07 s (3H, 3-Me), 2.24 s (3H, 5-Me), 6.61 q
(1H, 6-H), 7.27 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.40 d
(2H, 3′-H, 5′-H, J = 8.1 Hz). Found, %: N 4.37, 4.62;
S 10.03, 10.35. C14H11Cl2NOS. Calculated, %: N 4.49;
S 10.27.
cyclohexa-2,5-dien-1-one (4j). Yield 8%, mp 87–
89°C. H NMR spectrum (CDCl3), δ, ppm: E isomer
1
(55%): 6.52 d (1H, 6-H, J = 9.9 Hz), 7.03–7.06 d.d
(1H, 5-H, J = 3, 9.6 Hz), 7.31–7.64 m (10H, Ph),
7.59 d (1H, 3-H, J = 2.7 Hz); Z isomer (45%): 6.55 d
(1H, 6-H, J = 9.6 Hz), 7.29 d (1H, 3-H, J = 3.1 Hz),
7.31–7.64 m (10H, Ph), 7.39–7.43 d.d (1H, 5-H, J =
2.7, 9.6 Hz). Found, %: N 4.21, 4.38; S 19.72, 19.91.
C18H13NOS2. Calculated, %: N 4.33; S 19.83.
4-(Chloroimino)-3,5-dimethyl-2-[(4-nitrophenyl)-
sulfanyl]cyclohexa-2,5-dien-1-one (5c). Yield 1%,
1
mp 55°C. H NMR spectrum (CDCl3), δ, ppm: 2.11 d
(3H, 3-Me, J = 1.5 Hz), 2.32 s (3H, 5-Me), 6.69 q
(1H, 6-H), 7.43 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 8.14 d
(2H, 3′-H, 5′-H, J = 8.4 Hz). Found, %: N 8.52, 8.75;
S 9.86, 10.11. C14H11ClN2O3S. Calculated, %: N 8.68;
S 9.93.
2-[(4-Methylphenyl)sulfanyl]-4-{[(4-methyl-
phenyl)sulfanyl]imino}cyclohexa-2,5-dien-1-one
1
(4k). Yield 6%, mp 122–128°C. H NMR spectrum
(CDCl3), δ, ppm: E isomer (73%): 2.36 s (3H, Me),
2.44 s (3H, Me), 6.54 d (1H, 6-H, J = 9.9 Hz), 6.55 d
(1H, 3-H, J = 2.4 Hz), 7.00–7.03 d.d (1H, 5-H, J = 2.4,
9.6 Hz), 7.20 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.33 d
(2H, 2″-H, 6″-H, J = 7.8 Hz), 7.42 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 7.46 d (2H, 3″-H, 5″-H, J = 7.8 Hz);
Z isomer (27%): 2.36 s (3H, Me), 2.44 s (3H, Me),
6.32 d (1H, 3-H, J = 2.4 Hz), 6.62 d (1H, 6-H, J =
9.9 Hz), 7.19–7.22 d.d (1H, 5-H, J = 3, 9.6 Hz), 7.20 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.33 d (2H, 2″-H, 6″-H,
J = 7.8 Hz), 7.42 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 7.46 d
(2H, 3″-H, 5″-H, J = 7.8 Hz). Found, %: N 3.85, 4.15;
S 18.07, 18.31. C20H17NOS2. Calculated, %: N 3.99;
S 18.25.
4-(Chloroimino)-3,5-dimethyl-2,6-bis(phenylsul-
1
fanyl)cyclohexa-2,5-dien-1-one (6a). H NMR spec-
trum (CDCl3), δ, ppm: 2.23 s (3H, 5-Me), 2.29 s (3H,
3-Me), 7.17–7.36 m (10H, Ph).
4-(Chloroimino)-3,5-dimethyl-2,6-bis[(4-nitro-
phenyl)sulfanyl]cyclohexa-2,5-dien-1-one (6c).
1H NMR spectrum (CDCl3), δ, ppm: 2.32 s (6H, 3-Me,
5-Me), 7.43 d (4H, 2′-H, 6′-H, J = 8.4 Hz), 8.14 d (4H,
3′-H, 5′-H, J = 8.4 Hz).
3,5-Dimethyl-2,6-bis(phenylsulfanyl)-4-[(phenyl-
sulfanyl)imino]cyclohexa-2,5-dien-1-one (7a).
1H NMR spectrum (CDCl3), δ, ppm: 2.28 s (3H,
5-Me), 2.40 s (3H, 3-Me), 7.10–7.24 m (15H, Ph).
2-[(4-Nitrophenyl)sulfanyl]-4-{[(4-nitrophenyl)-
sulfanyl]imino}cyclohexa-2,5-dien-1-one (4l). Yield
1
3,5-Dimethyl-2,6-bis[(4-nitrophenyl)sulfanyl]-
4-{[(4-nitrophenyl)sulfanyl]imino}-cyclohexa-
2%, mp 150–151°C. H NMR spectrum (CDCl3), δ,
ppm: E isomer (58%): 6.75 d (1H, 6-H, J = 9.3 Hz),
7.06 d (1H, 3-H, J = 2.4 Hz), 7.35–7.39 d.d (1H, 5-H,
J = 2.7, 10.2 Hz), 7.76 d (2H, 2′-H, 6′-H, J = 8.7 Hz),
7.92 d (2H, 2″-H, 6″-H, J = 8.7 Hz), 8.27 d (2H, 3′-H,
5′-H, J = 8.7 Hz), 8.30 d (2H, 3″-H, 5″-H, J = 8.7 Hz);
Z isomer (42%): 6.83 d (1H, 6-H, J = 9.3 Hz), 6.86 d
(1H, 3-H, J = 3 Hz), 7.71–7.74 d.d (1H, 5-H, J = 2.7,
9.6 Hz), 7.76 d (2H, 2′-H, 6′-H, J = 8.7 Hz), 7.92 d
(2H, 2″-H, 6″-H, J = 8.7 Hz), 8.27 d (2H, 3′-H, 5′-H,
J = 8.7 Hz), 8.30 d (2H, 3″-H, 5″-H, J = 8.7 Hz).
Found, %: N 9. 92, 10. 29; S 15. 47, 15. 66.
C18H11N3O5S2. Calculated, %: N 10.16; S 15.51.
1
2,5-dien-1-one (7c). H NMR spectrum (CDCl3), δ,
ppm: 2.28 s (3H, 3-Me), 2.33 s (3H, 5-Me), 7.43 d
(6H, 2′-H, 6′-H, J = 8.1 Hz), 8.14 d (6H, 3′-H, 5′-H,
J = 8.1 Hz).
2,6-Bis(phenylsulfanyl)-4-[(phenylsulfanyl)-
1
imino]cyclohexa-2,5-dien-1-one (7d). H NMR spec-
trum (CDCl3), δ, ppm: 6.30 d (1H, 3-H, J = 2.4 Hz),
6.50 d (1H, 5-H, J = 2.1 Hz), 7.27–7.59 m (15H, Ph).
2,6-Bis[(4-methylphenyl)sulfanyl]-4-{[(4-methyl-
phenyl)sulfanyl]imino}cyclohexa-2,5-dien-1-one
1
(7e). H NMR spectrum (CDCl3), δ, ppm: 2.32 s (3H,
4-(Chloroimino)-3,5-dimethyl-2-(phenylsul-
Me), 2.38 s (3H, Me), 2.43 s (3H, Me), 6.24 d (1H,
3-H, J = 2.4 Hz), 6.51 d (1H, 5-H, J = 2.7 Hz), 7.15 d
(2H, 2′-H, 6′-H, J = 8.4 Hz), 7.22 d (2H, 2″-H, 6″-H,
J = 8.1 Hz), 7.41 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.46 d
(2H, 3″-H, 5″-H, J = 8.1 Hz), 7.52 d (2H, 2′′′-H, 6′′′-H,
J = 8.4 Hz), 7.72 d (2H, 3′′′-H, 5′′′-H, J = 8.4 Hz).
fanyl)cyclohexa-2,5-dien-1-one (5a). Yield 5%,
mp 115–117°C. H NMR spectrum (CDCl3), δ, ppm:
2.06 d (3H, 3-Me, J = 1.5 Hz), 2.21 s (3H, 5-Me),
6.61 q (1H, 6-H), 7.22–7.33 m (5H, Ph). Found, %:
N 4.82, 4.97; S 11.41, 11.68. C14H12ClNOS. Calculat-
ed, %: N 5.04; S 11.54.
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KONOVALOVA et al.
1294
2,6-Bis[(4-nitrophenyl)sulfanyl]-4-{[(4-nitro-
10.31 br.s (1H, NH). Found, %: N 14.68, 14.81;
S 11.23, 11.37. C15H13N3OS. Calculated, %: N 14.83;
S 11.32.
phenyl)sulfanyl]imino}cyclohexa-2,5-dien-1-one
1
(7f). H NMR spectrum (CDCl3), δ, ppm: 7.02 d (1H,
3-H, J = 2.4 Hz), 7.21 d (1H, 5-H, J = 2.7 Hz), 7.76 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.92 d (2H, 2″-H, 6″-H,
J = 8.1 Hz), 7.93 d (2H, 2′′′-H, 6′′′-H, J = 8.4 Hz),
8.27 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 8.30 d (2H, 3″-H,
5″-H, J = 8.1 Hz), 8.38 d (2H, 3′′′-H, 5′′′-H, J = 8.4 Hz).
4-{[(1H-Benzimidazol-2-yl)sulfanyl]imino}-2,6-
di(propan-2-yl)cyclohexa-2,5-dien-1-one (11c). Yield
62%, mp 197–199°C. H NMR spectrum (CDCl3), δ,
ppm: 1.13 d [6H, 2-CH(CH3)2, J = 6.6 Hz], 1.19 d
[6H, 6-CH(CH3)2, J = 6.9 Hz], 3.07–3.21 m [2H,
2-CH(CH3)2, 6-CH(CH3)2], 6.89 q (1H, 3-H), 7.04 q
(1H, 5-H), 7.26–7.28 m (2H, 5′-H, 6′-H), 7.52 br.s (1H,
4′-H), 7.73 br.s (1H, 7′-H), 10.41 br.s (1H, NH).
Found, %: N 12.24, 12.36; S 9.37, 9.52. C19H21N3OS.
Calculated, %: N 12.38; S 9.45.
1
2,5-Bis(phenylsulfanyl)-4-[(phenylsulfanyl)-
1
imino]cyclohexa-2,5-dien-1-one (8a). H NMR spec-
trum (CDCl3), δ, ppm: 5.77 s (1H, 6-H), 6.37 s (1H,
3-H), 7.36–7.61 m (15H, Ph).
2,5-Bis[(4-methylphenyl)sulfanyl]-4-{[(4-methyl-
phenyl)sulfanyl]imino}cyclohexa-2,5-dien-1-one
4-{[(1H-Benzimidazol-2-yl)sulfanyl]imino}-2,6-
di-tert-butylcyclohexa-2,5-dien-1-one (11d). Yield
1
(8b). H NMR spectrum (CDCl3), δ, ppm: 2.35 s (3H,
1
Me), 2.40 s (3H, Me), 2.45 s (3H, Me), 5.73 s (1H,
6-H), 6.39 s (1H, 3-H), 7.22 d (2H, 2′-H, 6′-H, J =
8.4 Hz), 7.25 d (2H, 2″-H, 6″-H, J = 8.7 Hz), 7.32 d
(2H, 2′′′-H, 6′′′-H, J = 7.8 Hz), 7.39 d (2H, 3′-H, 5′-H,
J = 8.4 Hz), 7.44 d (2H, 3′′′-H, 5′′′-H, J = 7.8 Hz),
7.47 d (2H, 3″-H, 5″-H, J = 8.7 Hz).
51%, mp 232–235°C. H NMR spectrum (CDCl3), δ,
ppm: 1.30 s (9H, 6-t-Bu), 1.34 s (9H, 2-t-Bu), 6.94 d
(1H, 3-H, J = 2.7 Hz), 7.10 d (1H, 5-H, J = 2.7 Hz),
7.21–7.29 m (2H, 5′-H, 6′-H), 7.63 br.s (2H, 4′-H,
7′-H), 10.34 br.s (1H, NH). Found, %: N 11.39, 11.55;
S 8.57, 8.70. C21H25N3OS. Calculated, %: N 11.43;
S 8.72.
2,3,6-Tris(phenylsulfanyl)-4-[(phenylsulfanyl)-
1
imino]cyclohexa-2,5-dien-1-one (9a). H NMR spec-
4-{[(1,3-Benzoxazol-2-yl)sulfanyl]imino}-2,5-di-
trum (CDCl3), δ, ppm: 7.27 s (1H, 5-H), 7.38–7.60 m
(20H, Ph).
methylcyclohexa-2,5-dien-1-one (11e). Yield 30%,
1
mp 150–153°C. H NMR spectrum (CDCl3), δ, ppm:
2.06 s (3H, 5-Me), 2.15 s (3H, 2-Me), 6.52 s (1H,
6-H), 7.12 s (1H, 3-H), 7.35–7.38 m (2H, 5′-H, 6′-H),
7.58–7.61 m (1H, 4′-H), 7.74–7.77 m (1H, 7′-H).
Found, %: N 9.79, 9.94; S 11.07, 11.42. C15H12N2O2S.
Calculated, %: N 9.85; S 11.28.
2, 3, 6-Tris[(4-methy lphenyl)sulfanyl]-
4-{[(4-methylphenyl)sulfanyl]imino}cyclohexa-2,5-
dien-1-one (9b). H NMR spectrum (CDCl3), δ, ppm:
2.32 s (3H, Me), 2.38 s (3H, Me), 2.42 s (6H, Me),
7.15 s (1H, 5-H), 7.22 d (4H, 2′-H, 6′-H, J = 8.1 Hz),
7.25 d (2H, 2″-H, 6″-H, J = 9 Hz), 7.32 d (2H, 2′′′-H,
6′′′-H, J = 7.8 Hz), 7.39 d (4H, 3′-H, 5′-H, J = 8.1 Hz),
7.44 d (2H, 3′′′-H, 5′′′-H, J = 7.8 Hz), 7.47 d (2H,
3″-H, 5″-H, J = 9 Hz).
1
4-{[(1,3-Benzoxazol-2-yl)sulfanyl]imino}-2,6-di-
methylcyclohexa-2,5-dien-1-one (11f). Yield 40%,
1
mp 155–156°C. H NMR spectrum (CDCl3), δ, ppm:
2.05 d (3H, 6-Me, J = 0.6 Hz), 2.13 d (3H, 2-Me, J =
1.5 Hz), 7.12 q (1H, 3-H), 7.16 q (1H, 5-H), 7.35–
7.38 m (2H, 5′-H, 6′-H), 7.58–7.61 m (1H, 4′-H), 7.74–
7.77 m (1H, 7′-H). Found, %: N 9.73, 9.91; S 11.12,
11.41. C15H12N2O2S. Calculated, %: N 9.85; S 11.28.
4-{[(1H-Benzimidazol-2-yl)sulfanyl]imino}-2,5-
dimethylcyclohexa-2,5-dien-1-one (11a). Yield 93%,
1
mp 178–181°C. H NMR spectrum (CDCl3), δ, ppm:
2.10 d (3H, 5-Me, J = 1.2 Hz), 2.31 s (3H, 2-Me),
6.42 s (1H, 6-H), 7.16 q (1H, 3-H), 7.25–7.31 m (2H,
5′-H, 6′-H), 7.51 br.s (1H, 4′-H), 7.72 br.s (1H, 7′-H),
9.91 br.s (1H, NH). Found, %: N 14.72, 14.95;
S 11.16, 11.43. C15H13N3OS. Calculated, %: N 14.83;
S 11.32.
4-{[(1,3-Benzothiazol-2-yl)sulfanyl]imino}-2,5-
dimethylcyclohexa-2,5-dien-1-one (11g). Yield 42%,
1
mp 192–195°C. H NMR spectrum (CDCl3), δ, ppm:
2.08 s (3H, 5-Me), 2.32 s (3H, 2-Me), 6.41 s (1H,
6-H), 7.05 s (1H, 3-H), 7.35 t (1H, 5′-H), 7.46 t (1H,
6′-H), 7.87 d (1H, 4′-H, J = 8.1 Hz), 7.92 d (1H, 7′-H,
J = 7.8 Hz). Found, %: N 9.21, 9.37; S 21.19, 21.40.
C15H12N2OS2. Calculated, %: N 9.33; S 21.35.
4-{[(1H-Benzimidazol-2-yl)sulfanyl]imino}-2,6-
dimethylcyclohexa-2,5-dien-1-one (11b). Yield 90%,
1
mp 175–179°C. H NMR spectrum (CDCl3), δ, ppm:
2.04 d (3H, 6-Me, J = 1.5 Hz), 2.12 d (3H, 2-Me, J =
1.5 Hz), 6.96 q (1H, 3-H), 7.16 q (1H, 5-H), 7.24–
7.30 m (2H, 5′-H, 6′-H), 7.61 br.s (2H, 4′-H, 7′-H),
4-{[(1,3-Benzothiazol-2-yl)sulfanyl]imino}-2,6-
dimethylcyclohexa-2,5-dien-1-one (11h). Yield 40%,
1
mp 148–152°C. H NMR spectrum (CDCl3), δ, ppm:
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REACTION OF N-CHLORO-1,4-BENZOQUINONE IMINES WITH THIOLS
1295
7. Pollak, R., Riesz, E., and Riesz, J., Monatsh. Chem.,
1931, vol. 58, p. 170.
8. Fearon, W.R., Biochem. J., 1944, vol. 38, p. 399.
2.06 d (3H, 6-Me, J = 1.5 Hz), 2.11 d (3H, 2-Me, J =
1.2 Hz), 7.02 q (1H, 3-H), 7.10 q (1H, 5-H), 7.35 t
(1H, 5′-H), 7.46 t (1H, 6′-H), 7.87 d (1H, 4′-H, J =
7.5 Hz), 7.92 d (1H, 7′-H, J = 7.8 Hz). Found, %:
N 9.18, 9.49; S 21.22, 21.52. C15H12N2OS2. Calculat-
ed, %: N 9.33; S 21.35.
9. McAllister, R.A., J. Pharm. Pharmacol., 1951, vol. 3,
p. 506.
10. McAllister, R.A. and Howells, K.W., J. Pharm.
Pharmacol., 1952, vol. 4, p. 259.
11. Searle, C.E., J. Appl. Chem., 1955, vol. 5, p. 313.
12. Avdeenko, A.P., Evgrafova, N.I., Tolmachev, A.A.,
Pirozhenko, V.V., and Gol’dfarb, E.I., Zh. Obshch.
Khim., 1992, vol. 62, p. 815.
13. Burmistrov, K.S. and Burmistrova, A.K., Russ. J. Org.
Chem., 1998, vol. 34, p. 856.
2,5-Dimethyl-4-{[(4H-1,2,4-triazol-3-yl)sulfanyl]-
imino}cyclohexa-2,5-dien-1-one (11i). Yield 42%,
1
mp 192–195°C. H NMR spectrum (CDCl3), δ, ppm:
2.08 s (3H, 5-Me), 2.22 s (3H, 2-Me), 6.72 s (1H,
6-H), 7.11 s (1H, 3-H), 8.57 (1H, 3′-H), 9.97 br.s (1H,
NH). Found, %: N 23.76, 23.95; S 13.52, 13.71.
C10H10N4OS. Calculated, %: N 23.91; S 13.69.
14. Avdeenko, A.P., Pirozhenko, V.V., Konovalova, S.A.,
Roman’kov, D.A., Palamarchuk, G.V., and Shish-
kin, O.V., Russ. J. Org. Chem., 2009, vol. 45, p. 408.
2,6-Dimethyl-4-{[(4H-1,2,4-triazol-3-yl)sulfanyl]-
imino}cyclohexa-2,5-dien-1-one (11j). Yield 78%,
1
15. Burmistrov, K.S. and Toropin, N.V., Zh. Org. Khim.,
mp 187–190°C. H NMR spectrum (CDCl3), δ, ppm:
1985, vol. 21, p. 1544.
2.18 s (6H, 2-Me, 6-Me), 6.93 s (2H, 3-H, 5-H), 8.58 s
(1H, 3′-H), 10.12 br.s (1H, NH). Found, %: N 23.82,
24.07; S 13.48, 13.65. C10H10N4OS. Calculated, %:
N 23.91; S 13.69.
16. Avdeenko, A.P., Konovalova, S.A., Roman’kov, D.A.,
Burmistrov, K.S., Nichvoloda, V.M., Shishkin, O.V.,
Zubatyuk, R.I., and Palamarchuk, G.V., Russ. J. Org.
Chem., 2009, vol. 45, p. 48.
4-{[(Ethoxycarbonothioyl)sulfanyl]imino}-2,5-
17. Burmistrov, K.S., Murashevich, B.V., and Toropin, N.V.,
dimethylcyclohexa-2,5-dien-1-one (11k). Yield 41%,
mp 130–132°C. H NMR spectrum (CDCl3), δ, ppm:
Russ. J. Org. Chem., 2011, vol. 47, p. 140.
18. Titov, E.A., Vopr. Khim. Khim. Tekhnol., 1973, no. 30,
1
1.53 t (3H, CH3CH2), 2.03 s (3H, 5-Me), 2.22 s (3H,
2-Me), 4.79–4.86 q (2H, CH3CH2), 6.42 s (1H, 6-H),
6.98 s (1H, 3-H). Found, %: N 5.33, 5.56; S 24.91,
25.18. C11H13NO2S2. Calculated, %: N 5.49; S 25.11.
p. 43.
19. Titov, E.A. and Podobuev, G.A., Khim. Tekhnol.
Respublik. Mezhved. Nauch.-Tekh. Sb., 1971, no. 24,
p. 16.
20. Avdeenko, A.P. and Koshechko, V.G., Zh. Obshch.
Khim., 1974, vol. 44, p. 1459.
21. Gadomska, A.V., Gadomsky, S.Ya., and Varlamov, V.T.,
Russ. Chem. Bull., Int. Ed., 2013, vol. 62, no. 7, p. 1558.
22. Varlamov, V.T., Gadomsky, S.Ya., and Gadomska, A.V.,
4-{[(Ethoxycarbonothioyl)sulfanyl]imino}-2,6-di-
methylcyclohexa-2,5-dien-1-one (11l). Yield 58%,
1
mp 134–136°C. H NMR spectrum (CDCl3), δ, ppm:
1.54 t (3H, CH3CH2), 2.06 s (6H, 2-Me, 6-Me), 4.83–
4.91 q (2H, CH3CH2), 7.04 br.s (2H, 3-H, 5-H). Found,
%: N 5.36, 5.50; S 25.14, 25.22. C11H13NO2S2. Calcu-
lated, %: N 5.49; S 25.11.
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23. Varlamov, V.T. and Gadomska, A.V., Russ. J. Phys.
Chem. A, 2015, vol. 89, p. 616.
24. Srivastava, S.K., Jain, A., and Srivastava, S.D., J. Indian
Chem. Soc., 2006, vol. 83, p. 1118.
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