Reaction of N-sulfonyl-1,4-benzoquinone imines with sodium azide

Article abstract of DOI:10.1134/S1070428016010048

Depending on the conditions and the order of addition of the reactants, reactions of N-sulfonyl-1,4-benzoquinone imines with sodium azide afforded N-(3-azido-4-hydroxyphenyl)alkane(arene)sulfonamides, N-(3-azido-4-oxocyclohexa-2,5-dienylidene)alkane(arene

Full text of DOI:10.1134/S1070428016010048

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 1, pp. 15–24. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © S.A. Konovalova, A.P. Avdeenko, S.V. Shelyazhenko, V.V. Pirozhenko, O.N. Mikhailichenko, A.L. Yusina, 2016, published in
Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 1, pp. 23–32.
Reaction of N-Sulfonyl-1,4-benzoquinone Imines
with Sodium Azide
S. A. Konovalovaa, A. P. Avdeenkoa, S. V. Shelyazhenkob, V. V. Pirozhenkob,
O. N. Mikhailichenkoa, and A. L. Yusinaa
a Donbass State Engineering Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
b Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 5, Kiev, 02660 Ukraine
Received October 30, 2015
Abstract—Depending on the conditions and the order of addition of the reactants, reactions of N-sulfonyl-1,4-
benzoquinone imines with sodium azide afforded N-(3-azido-4-hydroxyphenyl)alkane(arene)sulfonamides,
N-(3-azido-4-oxocyclohexa-2,5-dienylidene)alkane(arene)sulfonamides, and N-(3,5-diazido-4-hydroxyphenyl)-
alkanesulfonamides. Quantum chemical calculations showed that the reactions begin with addition of azide ion
to the quinone imine.
DOI: 10.1134/S1070428016010048
We previously synthesized new N-alkyl(trifluoro-
methyl)sulfonyl derivatives of 1,4-benzoquinone imine
[1] and studied their reactivity toward potassium thio-
cyanate [1] and sodium arenesulfinates [2]. In the
present work we examined reactions of these com-
pounds with sodium azide.
tions, namely in acetic acid at room temperature and in
a chloroform–acetic acid mixture at room temperature
and on cooling under argon with different reactant
ratios. The reactions of 1a and 2a with sodium azide in
acetic acid at room temperature gave only the corre-
sponding 2,6-diazidophenols 3 and 4 regardless of the
reactant ratio (1:1, 1:2, or 1:4). The reaction rate
increased as the amount of sodium azide increased, but
the yields of 3 and 4 did not change (40 and 45%,
respectively). The oxidation of sulfonamide 3 with
silver oxide in chloroform afforded quinone imine 5
(Scheme 1).
Sodium azide is a moderately hard nucleophile; it
occupies an intermediate position between arenesul-
finic acids and hydrogen chloride [3]. The addition of
sodium azide to N-substituted 1,4-quinone imines gen-
erally proceeded in a way similar to the addition of
HCl, i.e., according to the 1,4-addition path [4–10],
while no reaction was observed with 2,6-dimethyl-1,4-
benzoquinone imine derivatives; this indicated that no
other reaction paths were operative [8].
We previously obtained N-diazidophenyl sulfon-
amides only by stepwise addition of two molecules of
sodium azide with intermediate oxidation of the
primary addition products [8]. Therefore, we presumed
that quinone imines 1a and 2a react with sodium azide
via initial formation of 1,4-addition products 6a and 7a
which are oxidized during the process to quinone
imines 8a and 9a; addition of the second sodium azide
molecule to 8a and 9a yields sulfonamides 3 and 4.
Both initial quinone imine and atmospheric oxygen
can act as oxidant. To check this possibility, the reac-
tions of 1a and 2a with sodium azide were carried out
in a mixture of acetic acid with chloroform at –10°C
under argon to avoid oxidation of intermediate com-
pounds 6a and 7a with atmospheric oxygen. The
It was found that the addition products in boiling
acetic acid may undergo intramolecular oxidation/re-
duction with formation of N-(3-amino-4-oxocyclo-
hexa-2,5-dienylidene)arenesulfonamides [5, 6, 8, 10],
but the mechanism of this process was not studied.
Analogous transformations of 1,4-benzo- [11, 12] and
1,4-naphthoquinones [11] were also observed in
chloroform in an inert atmosphere.
The reactions of N-methyl(trifluoromethyl)sul-
fonyl-1,4-benzoquinone imines 1a–1g and 2a–2g with
sodium azide were carried out under different condi-
15

KONOVALOVA et al.
16
Scheme 1.
N3
N3
OH
N3
O
Ag2O, CHCl3
Alk = Me
AlkSO2
MeSO2
N
H
N
N3
3, 4
5
R1
R1
R1
R2
N
O
R2
OH
N3
R2
O
NaN3
∆
AlkSO2
AlkSO2
AlkSO2
R4
N
N
NH2
H
R3
1a–1g, 2a–2g
R3
R3
10c–10e, 11c–11e
6a–6f, 7a, 7c–7f
[O]
R1
R2
N
O
AlkSO2
N3
R3
8b–8f, 9b–9f
1, 3, 6, 8, 10, Alk = Me; 2, 4, 7, 9, 11, Alk = CF3; 1, 2, R1 = R2 = R3 = R4 = H (a); R1 = R3 = Me, R2 = R4 = H (b); R1 = i-Pr, R2 = R4 =
H, R3 = Me (c); R1 = Me, R2 = R4 = H, R3 = i-Pr (d); R1 = R2 = Me, R3 = R4 = H (e); R1 = R4 = H, R2 = R3 = Me (f); R1 = R4 = Me,
R2 = R3 = H (g); 6–11, R2 = H, R1 = R3 = H (a), Me (b); R1 = i-Pr, R3 = Me (c); R1 = Me, R3 = i-Pr (d); R1 = R2 = Me, R3 = H (e);
R1 = H, R2 = R3 = Me (f).
1
resulting mixtures were analyzed by H NMR. The
1H NMR spectra contained signals assignable to sul-
fonamides 12a and 13a and compounds 3 and 4 at
a ratio of 1:1 (Scheme 2). In the 19F NMR spectrum of
a mixture of 4 and 13a we observed two signals at
δF –76.04 and –76.75 ppm. These findings indicated
with certainty that initial quinonimines 1a and 2a act
as oxidants in the intermediate step. This is also sup-
ported by the yields of 3 and 4 (40–45%).
a solution of 1a or 2a; therefore, quinone imines 1a
and 2a were present in excess in the reaction mixture
and were able to oxidize sulfonamides 6a and 7a. In
order to suppress the redox reaction, the order of
addition of the reactants was changed, and a solution
of 1a or 2a was slowly added dropwise to a solution of
sodium azide in acetic acid, so that constant excess of
sodium azide was maintained in the reaction mixture.
As a result, we isolated sulfonamides 6a and 7a.
The reactions of 1a and 2a with sodium azide were
carried out by adding a solution of sodium azide to
According to our previous data [1, 2], in no case
the addition product formed in reactions of quinone
Scheme 2.
R1
R2
OH
R4
NaN3
1a–1d, 2a–2d
1a–1d, 2a–2d
6a–6d, 7a–7d
8a–8d, 9a–9d
+
AlkSO2
N
H
R3
12a–12d, 13a–13d
NaN3
8a–8d, 9a–9d
3, 4
12, Alk = Me; 13, Alk = CF3; R1 = R2 = R3 = R4 = H (a); R1 = R3 = Me, R2 = R4 = H (b); R1 = i-Pr, R2 = R4 = H, R3 = Me (c);
R1 = Me, R2 = R4 = H, R3 = i-Pr (d).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

REACTION OF N-SULFONYL-1,4-BENZOQUINONE IMINES WITH SODIUM AZIDE
17
imines 1 and 2 with potassium thiocyanate and sodium
sulfinates was oxidized with the initial quinone imine
[1, 2]. A probable reason is that the electron-with-
drawing sulfonyl and isothiocyanato groups hinder
oxidation of the addition products by increasing the
redox potential of the corresponding quinone imines
[13]. The azido group exerts a positive or weakly
negative mesomeric effect (σm = 0.37, σp = –0.08) due
to p–π or π–π conjugation with the aromatic ring,
respectively [14]. Therefore, the redox potential of
quinone imines 8a and 9a is lower than that of initial
quinone imines 1a and 2a, and the latter are capable of
oxidizing 6a and 7a.
tives 10e and 11e (Scheme 1). The transformation of
6e was complete in a few second, whereas 2–3 days
were required for the transformation of 7e. Numerous
attempts to isolate quinone imine 10e in the pure state
were unsuccessful, and it was identified by 1H NMR in
a mixture with 6e.
Quinone imines 1g and 2g with methyl groups in
the ortho positions with respect to the carbonyl group
reacted with sodium azide to produce mixtures of
hydrolysis and reduction products, which confirmed
our previous conclusion implying completely regio-
selective 1,4-addition of azide ion [8].
The structure of all isolated compounds was con-
1
firmed by their IR, H and 19F NMR spectra, and
In the reaction of 1b with sodium azide we obtained
a mixture of sulfonamide 6b and quinone imine 8b,
whereas only quinone imine 9b was isolated in the
reaction of sodium azide with quinone imine 2b
(Scheme 1). Compound 9b was formed in 30 min after
the reaction started. The reaction mixture darkened on
further stirring, and the isolated product was 6-azido-
2,5-dimethyl-1,4-benzoquinone which was formed as
a result of hydrolysis. By reactions of 1c, 1d, 2c, and
2d with sodium azide we obtained mixtures 6c/8c,
6d/8d, 7c/9c, and 7d/9d, respectively (Scheme 1). We
succeeded in separating these mixtures by repeated
recrystallization from aqueous acetic acid or hexane–
benzene (2:1) or by column chromatography on silica
gel with benzene as eluent. Compounds 8b–8d, 9c, and
9d were also synthesized independently by oxidation of
6b–6d, 7c, and 7d, respectively, with freshly prepared
silver oxide in chloroform or methylene chloride.
elemental analyses. Protons in the MeSO2 group reso-
1
nated in the H NMR spectra at δ 2.88–2.96 (6b–6f),
3.21–3.29 (8b–8f), and 3.01–3.20 ppm (10c–10e). The
NH2 signal appeared in the spectra of 10c–10e and
11c–11e as a broadened singlet at δ 5.06–5.98 ppm.
The 19F NMR spectra of 7b–7f, 9b–9e, and 11c–11e
contained a singlet due to trifluoromethyl group in the
regions δF –76.04 to –76.85, –79.12 to –79.22, and
–79.76 to –81.18 ppm, respectively. Compounds 3–9
displayed in the IR spectrum an absorption band at
2110–2180 cm–1 corresponding to stretching vibrations
of the azido group, and NH stretching band was
observed at 3420–3465 cm–1 in the IR spectra of 10c–
10e and 11c–11e.
In order to compare the reactivities of N-arylsul-
fonyl and N-methyl(trifluoromethyl)sulfonyl deriva-
tives, we also studied for the first time reactions of
NaN3 with compounds 14a and 14b (Scheme 3). Like
quinone imines 1b, 1e, 2b, and 2e, compound 14a
reacted with sodium azide to give a mixture of azides
15a and 16a. From quinone imine 14b we obtained
sulfonamide 15b which was stable on storage; com-
pound 15b was readily oxidized to 16b with sodium
dichromate in acetic acid. Thus, replacement of the
methyl (trifluoromethyl) group on the sulfur atom by
aryl did not affect the reaction course to an appreciable
extent.
The reactions of 1b–1d and 2b–2d with sodium
azide under argon resulted in the formation of mixtures
of products. Apart from already isolated compounds
6b–6d, 8b–8d and 7b–7d, 9b–9d, these mixtures con-
tained N-(2,5-dialkyl-4-hydroxyphenyl) sulfonamides
12b–12d and 13b–13d. These data suggest inter-
mediate oxidation of 6b–6d and 7b–7d with initial
quinone imines 1b–1d and 2b–2d to 8b–8d and 9b–9d
(Scheme 2).
Heating of 6c, 6d, 7c, and 7d in both acetic acid
and benzene afforded intramolecular oxidation/reduc-
tion products, quinone imines 10c, 10d, 11c, and 11d
(Scheme 1), which is consistent with the data of [8].
Our results showed that the first reaction step is
1,4-addition of the nucleophile. Depending on the
redox potential of the quinone imine and reaction con-
ditions, next follow oxidation of the addition product
with the initial quinone imine and addition of the
second nucleophile molecule. However, on the basis of
the experimental data it was impossible to determine
whether the 1,4-addition step begins with protonation
of the nitrogen atom or addition of azide ion. The
Quinone imines 1e, 1f, 2e, and 2f reacted with
sodium azide to give only sulfonamides 6e, 6f, 7e, and
7f. Compounds 6e and 7e on heating in polar and
nonpolar organic solvents, as well as under irradiation,
underwent intramolecular oxidation/reduction with
elimination of nitrogen and formation of amino deriva-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

KONOVALOVA et al.
18
Scheme 3.
R1
R1
R2
OH
N3
R2
N
O
∆
4-YC6H4SO2
4-YC6H4SO2
N
H
NH2
R3
R3
R1
R2
N
O
15a, 15b
17a, 17b
NaN3
[O]
4-YC6H4SO2
R1
R3
14a, 14b
R2
O
4-YC6H4SO2
N
N3
R3
16a, 16b
Y = R2 = H, R1 = R3 = Me (a); Y = R1 = R2 = Me, R3 = H (b).
mechanism proposed in [11] for the reaction of
1,4-naphthoquinone with sodium azide involved initial
addition of azide ion to the quinone and subsequent
aromatization of the ring. On the other hand, we previ-
ously found [15] that nucleophilic addition reactions of
N-substituted 1,4-benzoquinone imines, in particular
hydrohalogenation reactions, are initiated by protona-
tion of the nitrogen atom with subsequent addition of
halide ion (nucleophile).
We made an attempt to shed light on this problem
by resorting to quantum chemical calculations. The
geometric parameters of initial quinone imines 1a, 2a,
and 18 (having no substituents in the quinoid ring) and
possible transition states A–C (Scheme 4) were op-
timized at the DFT B3LYP/6-31+G(d) level of theory.
Here, transition state C is common for both reaction
paths. The calculations showed that the change in
the energy of the system in going to transition state
A [–1342.602714 (1a), –1640.298900 (2a),
–1534.355226 a.u. (18)] is considerably larger than
that corresponding to the formation of transition state
B [–1342.846841 (1a), –1640.590947 (2a),
–1534.596125 a.u. (18)]. The energy difference be-
tween transition states A and B is 640.96 (1a), 766.77
(2a), and 632.48 kJ/mol (18), and the energy of the
system upon formation of transition state C
[– 1 3 4 2 . 8 1 2 0 5 1 ( 1 a ) , – 1 6 4 0 . 5 2 5 5 2 1 ( 2 a ),
–1534.554440 a.u. (18)] is considerably lower than the
Scheme 4.
O
O
O
N3
O
N
O
OH
NH
H
NH
O
NH
NH
N3
XSO2
XSO2
XSO2
O
N3
H+ + N3
A
NH
H
H
XSO2
XSO2
XSO2
H+
N3
N3
1a, 2a, 18
C
6a, 7a, 19
N
N
XSO2
XSO2
B
1a, 6a, X = Me; 2a, 7a, X = CF3; 18, 19, X = Ph.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

REACTION OF N-SULFONYL-1,4-BENZOQUINONE IMINES WITH SODIUM AZIDE
19
energy for transition state A [the energy difference
between A and C is 549.61 (1a), 595.00 (2a), and
523.04 kJ/mol (18)] and somewhat higher than for
transition state B [the energy difference between B and
C is 91.34 (1a), 171.78 (2a), and 109.44 kJ/mol (18)].
These data suggest that the reactions of quinone imines
with sodium azide involve initial addition of azide ion
with formation of transition state B, which is followed
by protonation of the nitrogen atom to form transition
state C, and intramolecular proton transfer in the latter
yields final product 6a, 7a, or 19 (Scheme 4).
merization of the latter yields final p-quinone imine
10c–10e, 11c–11e, 17a, or 17b.
It is known that ortho- and para-quinoid structures
can be converted into each other; however, the para-
quinoid structure is energetically more favorable than
ortho-quinoid, which follows from their redox poten-
tials [16, 17]. For example, the redox potential of
1,4-benzoquinone is Eo = 0.699 V against 0.792 V for
1,2-benzoquinone [16]. Presumably, compounds 10c–
10e, 11c–11e, 17a, or 17b in solution give rise to
a small amount of ortho-quinoid structure H. This
follows from the color change of a solution of
N-[3-(benzenesulfonyl)-4-oxocyclohexa-2,5-dienyli-
dene]benzenesulfonamide after addition of an alkali
solution. This compound changes its color due to
formation of mesomeric ion, and this property under-
lies the use of analogous quinone imines as acid–base
indicators [18].
As shown above, heating of sulfonamides 6c–6e,
7c–7e, 15a, and 15b in boiling acetic acid or benzene
leads to the formation of quinone imines 10c–10e,
11c–11e, 17a, and 17b as a result of intramolecular
oxidation/reduction. Couladouros et al. [11] proposed
a mechanism for the formation of 2-azidonaphthalene-
1,4-diol from sodium azide and 1,4-naphthoquinone
with participation of acetic acid proton. It was also
noted that intramolecular oxidation/reduction of analo-
gous adduct derived from NaN3 and 1,4-benzoquinone
follows a similar scheme, though the reaction was
carried out in an aprotic solvent under argon [11, 12].
In fact, addition of alkali to a solution of 10c–10e,
11c–11e, 17a, or 17b in alcohol changed the color
from pink or violet to deep dark blue. This confirms
the presence in their solutions of mesomeric ion I as
intermediate species in the tautomeric transformation
of para- (10c–10e, 11c–e, 17a, b) and ortho-quinoid
structures (H) (Scheme 6) and provides an additional
support to the mechanism of intramolecular oxidation/
reduction involving structure H (Scheme 5).
Taking into account that intramolecular oxidation/
reduction of 6c–6e, 7c–7e, 15a, and 15b occurred in
both acetic acid and aprotic solvent, we proposed
a reaction mechanism shown in Scheme 5. Compounds
6c–6e, 7c–7e, 15a, and 15b may be represented by
canonical structures D and E. Proton transfer from the
hydroxy group to the negatively charged nitrogen atom
of the azido group in E gives intermediate resonance
structures F and G which lose nitrogen molecule with
formation of o-quinone imine H, and prototropic tauto-
In summary, we have studied the reactivity of
N-sulfonyl-1,4-benzoquinone imines toward sodium
azide. 2,5-Dialkyl-substituted N-(3-amino-4-oxocyclo-
hexa-2,5-dienylidene) sulfonamides and N-(3,5-di-
azido-4-hydroxyphenyl)alkanesulfonamides have been
isolated as the reaction products for the first time. This
Scheme 5.
OH
OH
O–
O
H
H
N
N
N
N
N
N
N
N
R
N
R
N
R
N
R
N
NH
NH
NH
NH
XSO2
XSO2
XSO2
XSO2
D
E
F
G
6c–6e, 7c–7e, 15a, 15b
O
NH
R
10c–10e, 11c–11e, 17a, 17b
–N2
NH
XSO2
H
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

KONOVALOVA et al.
20
Scheme 6.
O
N
O
O
N
NH2
NH
NH
NaOH
R
R
R
H
H+
N
XSO2
XSO2
XSO2
10c–10e, 11c–11e, 17a, 17b
I
may be rationalized by the ability of the corresponding
monoazido-substituted sulfonamides to readily under-
go oxidation with the initial quinone imine and take up
the second HN3 molecule provided that the ortho
position with respect to the carbonyl group is free. The
product composition and structure depend on the reac-
tion conditions and order of addition of the reactants.
A probable reaction mechanism has been proposed on
the basis of the experimental data and quantum
chemical calculations.
1.15 d (6H, CHMe2, J = 6.9 Hz), 2.12 s (2-Me), 2.97–
3.09 m (1H, CHMe2), 3.29 s (3H, CH3SO2), 6.55 q
(1H, 3-H), 7.65 s (1H, 6-H). Found, %: N 5.70, 5.75;
S 13.28, 13.33. C11H15NO3S. Calculated, %: N 5.80;
S 13.29.
N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-
enylidene)methanesulfonamide (1d). Yield 92%,
1
mp 88–89°C. H NMR spectrum (CDCl3), δ, ppm:
1.17 d (6H, CHMe2, J = 6.9 Hz), 2.08 d (5-Me, J =
1.8 Hz), 3.13–3.23 m (1H, CHMe2), 3.30 s (3H,
CH3SO2), 6.52 s (1H, 3-H), 7.73 q (1H, 6-H). Found,
%: N 5.80, 5.88; S 13.25, 13.37. C11H15NO3S. Cal-
culated, %: N 5.80; S 13.29.
EXPERIMENTAL
The IR spectra were recorded on a Bruker Vertex-
70 spectrometer from samples pressed with KBr (3, 4,
6a–6f, 7a, 7c–7f, 12c, 12d, 13c, 13d, 15a, 15b) or
dissolved in chloroform (1c, 1d, 2c, 2d, 5, 8b–8f, 9b–
9e, 10c–10e, 11c–11e, 16a, 16b, 17a, 17b). The
1H NMR spectra were recorded on a Varian VXR-300
instrument at 300 MHz using tetramethylsilane as
standard. The 19F NMR spectra were measured on
a Varian Gemini-200 spectrometer at 188.14 MHz
relative to trichloro(fluoro)methane. The purity of the
initial quinone imines and isolated compounds was
checked by TLC on Silufol UV-254 plates; samples
were applied from solutions in chloroform, acetone, or
THF; plates were eluted with ethanol–chloroform
(1 :10), benzene–hexane (10 :1), or hexane–ethyl
acetate (1:2); spots were visualized under UV light.
N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-
enylidene)trifluoromethanesulfonamide (2c). Yield
87%, mp 34–36°C. H NMR spectrum (CDCl3), δ,
ppm: 1.16 d (6H, CHMe2, J = 6.9 Hz), 2.14 d (2-Me,
J = 1.8 Hz), 3.00–3.17 m (1H, CHMe2), 6.62 q (1H,
3-H), 7.36 d (1H, 6-H, J = 1.2 Hz). 19F NMR spectrum
(CFCl3): δF –79.08 ppm, s. Found, %: N 4.68, 4.72;
S 10.80, 10.88. C11H12F3NO3S. Calculated, %: N 4.74;
S 10.86.
1
N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-
enylidene)trifluoromethanesulfonamide (2d). Yield
1
95%, mp 56–57°C. H NMR spectrum (CDCl3), δ,
ppm: 1.19 d (6H, CHMe2, J = 6.9 Hz), 2.13 d (5-Me,
J = 1.8 Hz), 3.04–3.17 m (1H, CHMe2), 6.59 d (1H,
2-H, J = 1.2 Hz), 7.47 q (1H, 5-H). 19F NMR spectrum
(CFCl3): δF –79.15 ppm, s. Found, %: N 4.65, 4.70;
S 10.82, 10.90. C11H12F3NO3S. Calculated, %: N 4.74;
S 10.86.
Quantum-chemical calculations were performed
using Firefly QC software [19] which is based in part
on the GAMESS code [20]. Transition states were
localized by standard structure optimization procedure.
Reaction of quinone imines 1a–1g, 2a–2g, 14a,
and 14 b with sodium azide (general procedures).
a. Sodium azide, 4 mmol, was added in one portion to
a solution of 2 mmol of quinone imine 1a–1g, 14a, or
14b in 20 mL of glacial acetic acid. The solution
turned red and then became colorless. When the mix-
ture bleached, it was poured onto ice, and the precip-
itate was filtered off, washed with water, and recrys-
tallized from acetic acid or benzene–hexane (1:2) or
purified by column chromatography on silica gel.
Compounds 1c, 1d, 2c, and 2d were synthesized
according to the procedures described in [1]. Com-
pounds 1a, 1b, 1e–1g, 2a, 2b, 2e–2g, 12a, 12b, 13a,
13b [1], 14a [21], and 14b [22] were reported
previously.
N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-
enylidene)methanesulfonamide (1c). Yield 90%,
1
mp 79–81°C. H NMR spectrum (CDCl3), δ, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

REACTION OF N-SULFONYL-1,4-BENZOQUINONE IMINES WITH SODIUM AZIDE
21
b. A solution of 4 mmol of sodium azide in 10 mL
of glacial acetic acid was added dropwise to a solution
of 2 mmol of quinone imine 1a–1g or 2a–2g in 10 mL
of chloroform or methylene chloride at room tempera-
ture or on cooling to –10°C, and the mixture was
purged with argon. The mixture turned red and then
bleached. When the reaction was complete, the mix-
ture was evaporated under reduced pressure, and the
residue was poured onto ice. The precipitate was
filtered off, washed with water, and purified by recrys-
tallization from acetic acid or benzene–hexane (1:2) or
by column chromatography on silica gel.
N-(3-Azido-4-hydroxy-2,5-dimethylphenyl)-
methanesulfonamide (6b). Yield 69%, mp 105–
107°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.13 s
(3H, 2-Me), 2.17 s (3H, 5-Me), 2.90 s (3H, CH3SO2),
6.85 s (1H, 6-H), 8.88 s (1H, NH), 9.35 s (1H, OH).
Found, %: N 21.75, 21.80; S 12.42, 12.49.
C9H12N4O3S. Calculated, %: N 21.86; S 12.51.
1
N-(3-Azido-4-hydroxy-5-isopropyl-2-methyl-
phenyl)methanesulfonamide (6c). Yield 21%,
1
mp 115–117°C. H NMR spectrum (DMSO-d6), δ,
ppm: 1.14 d (6H, CHMe2, J = 6 Hz), 2.15 s (2-Me),
2.90 s (3H, CH3SO2), 3.19–3.30 m (1H, CHMe2),
6.89 s (1H, 6-H), 8.89 s (1H, NH), 9.26 s (1H, OH).
Found, %: N 19.67, 19.72; S 11.29, 11.35.
C11H16N4O3S. Calculated, %: N 19.70; S 11.28.
c. A solution of 2 mmol of quinone imine 1a or 2a
was added dropwise under vigorous stirring over
a period of 30 min to a solution of 4 mmol of sodium
azide in 10 mL of glacial acetic acid maintained at
room temperature. The solution immediately turned
colorless and was stirred for 1 h and evaporated under
reduced pressure. The residue was poured onto ice, the
precipitate was extracted with diethyl ether, the extract
was dried over magnesium sulfate and evaporated,
and the residue was recrystallized from benzene–
hexane (1:2).
N-(3-Azido-4-hydroxy-2-isopropyl-5-methyl-
phenyl)methanesulfonamide (6d). Yield 32%,
1
mp 144–145°C. H NMR spectrum (DMSO-d6), δ,
ppm: 1.27 d (6H, CHMe2, J = 3.6 Hz), 2.17 s (5-Me),
2.93 s (3H, CH3SO2), 3.45–3.57 m (1H, CHMe2),
6.86 s (1H, 6-H), 8.87 s (1H, NH), 9.39 s (1H, OH).
Found, %: N 19.64, 19.68; S 11.24, 11.30.
C11H16N4O3S. Calculated, %: N 19.70; S 11.28.
N-(5-Azido-4-hydroxy-2,3-dimethylphenyl)-
methanesulfonamide (6e). Yield 71%, mp 155–
157°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.04 s
(3H, 3-Me), 2.15 s (3H, 2-Me), 2.95 s (3H, CH3SO2),
6.72 s (1H, 6-H), 8.57 s (1H, NH), 8.82 s (1H, OH).
Found, %: N 21.83, 21.90; S 12.48, 12.53.
C9H12N4O3S. Calculated, %: N 21.86; S 12.51.
N-(3,5-Diazido-4-hydroxyphenyl)methanesulfon-
amide (3). Yield 43%, mp 134–136°C. 1H NMR spec-
trum (DMSO-d6), δ, ppm: 2.94 s (3H, CH3SO2), 6.69 s
(2H, 2-H, 6-H), 9.20 br.s (1H, NH), 9.61 br.s (1H,
OH). Found, %: N 36.25, 36.30; S 11.85, 11.93.
C7H7N7O3S. Calculated, %: N 36.42; S 11.91.
1
N-(3,5-Diazido-4-hydroxyphenyl)trifluoro-
methanesulfonamide (4). Yield 45%, mp 119–121°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 6.72 s (2H,
2-H, 6-H), 8.96 br.s (1H, NH), 10.15 br.s (1H, OH).
19F NMR spectrum (CFCl3): δF –75.63 ppm, s. Found,
%: N 30.25, 30.40; S 9.85, 9.93. C7H4F3N7O3S. Calcu-
lated, %: N 30.34; S 9.92.
N-(3-Azido-4-hydroxy-2,6-dimethylphenyl)-
methanesulfonamide (6f). Yield 58%, mp 139–
140°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.16 s
(3H, 6-Me), 2.22 s (3H, 2-Me), 2.96 s (3H, CH3SO2),
6.61 s (1H, 5-H), 8.72 s (1H, NH), 9.29 s (1H, OH).
Found, %: N 21.81, 21.85; S 12.50, 12.54.
C9H12N4O3S. Calculated, %: N 21.86; S 12.51.
1
N-(3,5-Diazido-4-oxocyclohexa-2,5-dienylidene)-
methanesulfonamide (5). Yield 90%, mp 113–114°C.
1H NMR spectrum (CDCl3), δ, ppm: 3.21 s (3H,
MeSO2), 6.41 s (1H, 3-H), 7.32 s (1H, 5-H). Found, %:
N 36.55, 36.70; S 11.95, 12.15. C7H5N7O3S. Calculat-
ed, %: N 36.69; S 12.00.
N-(3-Azido-4-hydroxyphenyl)trifluoromethane-
sulfonamide (7a). Yield 87%, mp 110–112°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 6.77 s (1H,
5-H), 6.90 s (2H, 2-H, 6-H), 10.43 s (1H, NH),
11.59 br.s (1H, OH). 19F NMR spectrum (CFCl3):
δF –75.56 ppm, s. Found, %: N 19.75, 19.80; S 11.30,
11.33. C7H5F3N4O3S. Calculated, %: N 19.85; S 11.36.
N-(3-Azido-4-hydroxyphenyl)methanesulfon-
1
amide (6a). Yield 75%, mp 130–132°C. H NMR
N-(3-Azido-4-hydroxy-5-isopropyl-2-methyl-
phenyl)trifluoromethanesulfonamide (7c). Yield
spectrum (DMSO-d6), δ, ppm: 2.88 s (3H, CH3SO2),
6.79 d (1H, 2-H, J = 1.8 Hz), 6.83 d (1H, 5-H, J =
6.9 Hz), 6.88 d.d (1H, 6-H), 9.34 s (1H, NH), 10.04 s
(1H, OH). Found, %: N 24.15, 24.25; S 13.98, 14.12.
C7H8N4O3S. Calculated, %: N 24.55; S 14.05.
1
29%, mp 123–124°C. H NMR spectrum (DMSO-d6),
δ, ppm: 1.21 d (6H, CHMe2, J = 6.6 Hz), 2.38 s (3H,
2-Me), 3.11–3.22 m (1H, CHMe2), 5.75 s (1H, NH),
6.53 s (1H, OH), 6.99 s (1H, 6-H). 19F NMR spectrum
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

KONOVALOVA et al.
22
(CFCl3): δF –76.04 ppm, s. Found, %: N 16.50, 16.55;
S 9.40, 9.47. C11H13F3N4O3S. Calculated, %: N 16.56;
S 9.48.
N-(5-Azido-2,3-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)-4-methylbenzenesulfonamide (16b).
Yield 55%, mp 122–124°C. 1H NMR spectrum (CDCl3),
δ, ppm: 2.05 s (3H, 3-Me), 2.07 s (3H, 2-Me), 2.46 s
(3H, 4′-Me), 7.54 s (1H, 6-H), 7.35–7.87 d.d (4H,
C6H4, J = 8.1 Hz). Found, %: N 16.85, 17.00; S 9.61,
9.69. C15H14N4O3S. Calculated, %: N 16.96; S 9.71.
N-(3-Azido-4-hydroxy-2-isopropyl-5-methyl-
phenyl)trifluoromethanesulfonamide (7d). Yield
1
39%, mp 118–120°C. H NMR spectrum (DMSO-d6),
δ, ppm: 1.37 d (6H, CHMe2, J = 6.9 Hz), 2.22 s (3H,
5-Me), 3.29–3.43 m (1H, CHMe2), 6.72 s (1H, NH),
6.93 s (1H, 6-H), 7.06 s (1H, OH). 19F NMR spectrum
(CFCl3): δF –76.29 ppm, s. Found, %: N 16.45, 16.51;
S 9.44, 9.49. C11H13F3N4O3S. Calculated, %: N 16.56;
S 9.48.
Oxidation of compounds 3, 6b–6f, 7a, 7c–7e, 15a,
and 15b (general procedures). a. Silver oxide, 0.26 g
(1.1 mmol), was added under stirring to a suspension
of 1 mmol of compound 3, 6b–6f, or 7c–7e in 20 mL
of anhydrous chloroform or methylene chloride. The
mixture was stirred for 24 h, the precipitate of silver
was filtered off, the filtrate was evaporated under
reduced pressure, and the red–orange precipitate was
recrystallized from benzene–hexane or chloroform–
hexane.
N-(5-Azido-4-hydroxy-2,3-dimethylphenyl)tri-
fluoromethanesulfonamide (7e). Yield 57%, mp 120–
1
122°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.20 s
(3H, 3-Me), 2.26 s (3H, 2-Me), 5.50 s (1H, NH), 6.48 s
(1H, OH), 6.95 s (1H, 6-H). 19F NMR spectrum
(CFCl3): δF –76.42 ppm, s. Found, %: N 18.00, 18.10;
S 10.28, 10.36. C9H9F3N4O3S. Calculated, %: N 18.06;
S 10.34.
b. A suspension of 1 mmol of compound 15a or 15b
in 2 mL of acetic acid was heated under stirring until
complete dissolution and was then cooled under con-
tinuous stirring to 15–18°C. Sodium dichromate,
0.21 g (1 mmol), was added in one portion, and the
mixture was vigorously stirred for 1 h so that the tem-
perature did not exceed 35°C. The mixture was cooled
to 15°C, and the precipitate was filtered off and
washed with acetic acid and ethanol.
N-(3-Azido-4-hydroxy-2,6-dimethylphenyl)tri-
fluoromethanesulfonamide (7f). Yield 29%, mp 125–
1
127°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.33 s
(3H, 2-Me), 2.37 s (3H, 6-Me), 5.49 s (1H, NH), 6.13 s
(1H, OH), 6.65 s (1H, 5-H). 19F NMR spectrum
(CFCl3): δF –76.85 ppm, s. Found, %: N 17.99, 18.01;
S 10.30, 10.38. C9H9F3N4O3S. Calculated, %: N 18.06;
S 10.34.
N-(3-Azido-2,5-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)methanesulfonamide (8b). Yield 53%,
1
mp 131–132°C. H NMR spectrum (CDCl3), δ, ppm:
N-(3-Azido-4-hydroxy-2,5-dimethylphenyl)ben-
zenesulfonamide (15a). Yield 42%, mp 178–180°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.87 s (3H,
2-Me), 2.06 s (3H, 5-Me), 6.45 s (1H, 6-H), 7.31–
7.60 m (5H, Ph), 9.05 s (1H, NH), 9.25 s (1H, OH).
Found, %: N 17.35, 17.55; S 10.02, 10.15.
C14H14N4O3S. Calculated, %: N 17.60; S 10.07.
2.02 s (3H, 2-Me), 2.09 s (3H, 3-Me), 3.26 s (3H,
CH3SO2), 7.71 s (1H, 6-H). Found, %: N 21.95,
21.99; S 12.57, 12.59. C9H10N4O3S. Calculated, %:
N 22.03; S 12.61.
N-(3-Azido-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dienylidene)methanesulfonamide (8c).
1H NMR spectrum (CDCl3), δ, ppm: 1.10 d (6H,
CHMe2, J = 6.9 Hz), 1.96 s (3H, 2-Me), 2.92–3.05 m
(1H, CHMe2), 3.21 s (3H, CH3SO2), 7.60 s (1H, 6-H).
N-(5-Azido-4-hydroxy-2,3-dimethylphenyl)-
4-methylbenzenesulfonamide (15b). Yield 80%,
1
mp 156–158°C. H NMR spectrum (DMSO-d6), δ,
ppm: 1.91 s (3H, 3-Me), 2.02 s (3H, 2-Me), 2.37 s (3H,
4′-Me), 6.17 s (1H, 6-H), 7.35–7.50 d.d (4H, C6H4, J =
7.8 Hz), 9.00 s (1H, NH), 9.31 s (1H, OH). Found, %:
N 16.54, 16.65; S 9.52, 9.63. C15H16N4O3S. Calcu-
lated, %: N 16.86; S 9.65.
N-(3-Azido-2-isopropyl-5-methyl-4-oxocyclo-
hexa-2,5-dienylidene)methanesulfonamide (8d).
1
Yield 76%, mp 83–85°C. H NMR spectrum (CDCl3),
δ, ppm: 1.23 d (6H, CHMe2, J = 7 Hz), 2.04 s (3H,
5-Me), 3.19–3.30 m (1H, CHMe2), 3.24 s (3H,
CH3SO2), 7.69 s (1H, 6-H). Found, %: N 19.79, 19.81;
S 11.29, 11.32. C11H14N4O3S. Calculated, %: N 19.85;
S 11.36.
N-(3-Azido-2,5-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)benzenesulfonamide (16a). Yield 65%,
1
mp 105–107°C. H NMR spectrum (CDCl3), δ, ppm:
1.94 s (3H, 2-Me), 2.13 d (3H, 5-Me, J = 1.8 Hz),
7.54–8.01 m (5H, Ph), 7.95 q (1H, 6-H). Found, %:
N 17.73, 17.78; S 10.05, 10.14. C14H12N4O3S. Calcu-
lated, %: N 17.71; S 10.14.
N-(5-Azido-2,3-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)methanesulfonamide (8e). Yield 77%,
mp 112–114°C. H NMR spectrum (CDCl3), δ, ppm:
1
2.10 s (3H, 3-Me), 2.14 s (3H, 2-Me), 3.26 s (3H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

REACTION OF N-SULFONYL-1,4-BENZOQUINONE IMINES WITH SODIUM AZIDE
23
CH3SO2), 7.29 s (1H, 6-H). Found, %: N 22.01, 22.07;
S 12.59, 12.65. C9H10N4O3S. Calculated, %: N 22.03;
S 12.61.
δ, ppm: 1.15 d (6H, CHMe2, J = 6.9 Hz), 1.86 s (3H,
2-Me), 2.90–3.02 m (1H, CHMe2), 3.18 s (3H,
CH3SO2), 5.06 br.s (2H, NH2), 7.61 s (1H, 6-H).
Found, %: N 10.89, 10.95; S 12.49, 12.52.
C11H14N4O3S. Calculated, %: N 10.93; S 12.51.
N-(3-Azido-2,6-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)methanesulfonamide (8f). Yield 61%,
1
mp 102–105°C. H NMR spectrum (CDCl3), δ, ppm:
N-(3-Amino-2-isopropyl-5-methyl-4-oxocyclo-
2.27 s (3H, 6-Me), 2.30 s (3H, 2-Me), 3.29 s (3H,
CH3SO2), 6.50 s (1H, 5-H). Found, %: N 21.98, 22.01;
S 12.60, 12.66. C9H10N4O3S. Calculated, %: N 22.03;
S 12.61.
hexa-2,5-dienylidene)methanesulfonamide (10d).
Yield 77%, mp 118–120°C. H NMR spectrum
1
(CDCl3), δ, ppm: 1.24 d (6H, CHMe2, J = 6.9 Hz),
2.00 s (3H, 5-Me), 3.20–3.31 m (1H, CHMe2), 3.20 s
(3H, CH3SO2), 5.15 br.s (2H, NH2), 7.64 s (1H, 6-H).
Found, %: N 10.91, 10.97; S 12.45, 12.49.
C11H14N4O3S. Calculated, %: N 10.93; S 12.51.
N-(3-Azido-2,5-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)trifluoromethanesulfonamide (9b). Yield
1
35%, mp 115–117°C. H NMR spectrum (CDCl3), δ,
ppm: 2.05 s (3H, 2-Me), 2.16 d (3H, 5-Me, J =
1.5 Hz), 7.45 q (1H, 6-H). 19F NMR spectrum (CFCl3):
δF –79.13 ppm, s. Found, %: N 18.10, 18.15; S 10.38,
10.44. C9H7F3N4O3S. Calculated, %: N 18.18; S 10.40.
N-(5-Amino-2,3-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)methanesulfonamide (10e). 1H NMR spec-
trum (CDCl3), δ, ppm: 2.20 s (3H, 3-Me), 2.32 s (3H,
2-Me), 3.01 s (3H, CH3SO2), 5.98 br.s (2H, NH2),
6.93 s (1H, 6-H).
N-(3-Azido-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dienylidene)trifluoromethanesulfonamide
(9c). Yield 71%, mp 85–86°C. H NMR spectrum
N-(3-Amino-5-isopropyl-2-methyl-4-oxocyclo-
1
hexa-2,5-dienylidene)trifluoromethanesulfonamide
1
(CDCl3), δ, ppm: 1.18 d (6H, CHMe2, J = 6.6 Hz),
2.04 s (3H, 2-Me), 3.01–3.17 m (1H, CHMe2), 7.36 s
(1H, 6-H). 19F NMR spectrum (CFCl3): δF –79.12 ppm,
s. Found, %: N 16.55, 16.60; S 9.48, 9.55.
C11H11F3N4O3S. Calculated, %: N 16.66; S 9.53.
(11c). Yield 78%, mp 164–165°C. H NMR spectrum
(CDCl3), δ, ppm: 1.16 d (6H, CHMe2, J = 6.9 Hz),
1.91 s (3H, 2-Me), 2.92–3.06 m (1H, CHMe2),
5.36 br.s (2H, NH2), 7.34 s (1H, 6-H). 19F NMR spec-
trum (CFCl3): δF –81.18 ppm, s. Found, %: N 9.01,
9.07; S 10.30, 10.40. C11H13F3N2O3S. Calculated, %:
N 9.03; S 10.33.
N-(3-Azido-2-isopropyl-5-methyl-4-oxocyclo-
hexa-2,5-dienylidene)trifluoromethanesulfonamide
1
(9d). Yield 82%, mp 105–107°C. H NMR spectrum
N-(3-Amino-2-isopropyl-5-methyl-4-oxocyclo-
(CDCl3), δ, ppm: 1.26 d (6H, CHMe2, J = 7 Hz), 2.14 s
(3H, 5-Me), 3.27–3.46 m (1H, CHMe2), 7.43 s (1H,
6-H). 19F NMR spectrum (CFCl3): δF –79.22 ppm, s.
F o u n d , % : N 1 6 . 4 5 , 1 6 . 5 1 ; S 9 . 4 8 , 9 . 5 5.
C11H11F3N4O3S. Calculated, %: N 16.66; S 9.53.
hexa-2,5-dienylidene)trifluoromethanesulfonamide
(11d). Yield 55%, mp 106–107°C. H NMR spectrum
1
(CDCl3), δ, ppm: 1.26 d (6H, CHMe2, J = 6.9 Hz),
2.05 s (3H, 5-Me), 2.92–3.10 m (1H, CHMe2),
5.58 br.s (2H, NH2), 7.37 s (1H, 6-H). 19F NMR spec-
trum (CFCl3): δF –79.76 ppm, s. Found, %: N 8.97,
9.02; S 10.28, 10.35. C11H13F3N2O3S. Calculated, %:
N 9.03; S 10.33.
N-(5-Azido-2,3-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)trifluoromethanesulfonamide (9e). Yield
1
68%, mp 78–81°C. H NMR spectrum (CDCl3), δ,
ppm: 2.14 s (3H, 3-Me), 2.16 s (3H, 2-Me), 6.99 s (1H,
6-H). 19F NMR spectrum (CFCl3): δF –79.18 ppm, s.
Found, %: N 18.11, 18.17; S 10.35, 10.41.
C9H7F3N4O3S. Calculated, %: N 18.18; S 10.40.
N-(5-Amino-2,3-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)trifluoromethanesulfonamide (11e). Yield
58%, mp 180–182°C. H NMR spectrum (CDCl3), δ,
ppm: 2.05 s (3H, 3-Me), 2.13 s (3H, 2-Me), 5.73 br.s
(2H, NH2), 6.45 s (1H, 6-H). 19F NMR spectrum
(CFCl3): δF –79.87 ppm, s. Found, %: N 9.85, 9.95;
S 11.30, 11.38. C9H9F3N2O3S. Calculated, %: N 9.93;
S 11.36.
1
Intramolecular oxidation/reduction of com-
pounds 6c–6e, 7c–7e, 15a, and 15b (general proce-
dure). Compound 6c–6e, 7c–7e, 15a, or 15b was
heated for 10–15 min in boiling glacial acetic acid, and
the solution turned dark red or violet. The mixture was
cooled and diluted with water, and the dark precipitate
was recrystallized from benzene–hexane.
N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-
enylidene)methanesulfonamide (12c). Yield 64%,
1
mp 140–142°C. H NMR spectrum (CDCl3), δ, ppm:
N-(3-Amino-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dienylidene)methanesulfonamide (10c).
Yield 85%, mp 99–101°C. 1H NMR spectrum (CDCl3),
1.11 d (6H, CHMe2), 2.18 s (3H, 2-Me), 2.88 s (3H,
MeSO2), 3.03–3.16 m (1H, CHMe2), 6.38 s (1H, 3-H),
6.43 s (1H, 6-H) 8.68 s (1H, NH), 9.31 s (1H, OH).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016

KONOVALOVA et al.
24
2. Avdeenko, A.P., Konovalova, S.A., Mikhailichen-
ko, O.N., Shelyazhenko, S.V., Pirozhenko, V.V., and
Yagupol’skii, L.M., Russ. J. Org. Chem., 2012, vol. 48,
p. 221.
3. Toropin, N.V. and Burmistrov, K.S., Zh. Org. Khim.,
1991, vol. 27, p. 376.
4. Adams, R. and Moje, W., J. Am. Chem. Soc., 1952,
vol. 74, p. 5560.
5. Adams, R. and Blomstrom, D.C., J. Am. Chem. Soc.,
1953, vol. 75, p. 3405.
6. Adams, R. and Reifschneider, W., Bull. Soc. Chim. Fr.,
Found, %: N 5.71, 5.78; S 13.20, 13.26. C11H15NO3S.
Calculated, %: N 5.76; S 13.18.
N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-
enylidene)methanesulfonamide (12d). Yield 58%,
1
mp 130–131°C. H NMR spectrum (CDCl3), δ, ppm:
1.09 d (6H, CHMe2), 2.07 s (3H, 5-Me), 2.91 s (3H,
MeSO2), 3.28–3.65 m (1H, CHMe2), 6.71 s (1H, 3-H),
6.92 s (1H, 6-H), 8.68 s (1H, NH), 9.30 s (1H, OH).
Found, %: N 5.77, 5.83; S 13.20, 13.24. C11H15NO3S.
Calculated, %: N 5.76; S 13.18.
N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-
enylidene)trifluoromethanesulfonamide (13c). Yield
83%, mp 95–97°C. H NMR spectrum (CDCl3), δ,
1958, vol. 25, p. 23.
7. Rajappa, S. and Shenoy, S.J., Tetrahedron, 1986,
1
vol. 42, p. 5739.
ppm: 1.12 d (6H, CHMe2), 2.18 s (3H, 2-Me), 3.01–
3.17 m (1H, CHMe2), 6.66 s (1H, 3-H), 6.88 s (1H,
6-H), 9.53 s (1H, NH), 10.94 s (1H, OH). 19F NMR
spectrum (CFCl3): δF –76.83 ppm, s. Found, %:
N 4.65, 4.70; S 10.64, 10.71. C11H14F3NO3S. Calculat-
ed, %: N 4.71; S 10.79.
8. Avdeenko, A.P., Menafova, Yu.V., and Zhukova, S.A.,
Russ. J. Org. Chem., 1998, vol. 34, p. 210.
9. Avdeenko, A.P. and Marchenko, I.L., Russ. J. Org.
Chem., 2006, vol. 42, p. 873.
10. Avdeenko, A.P. and Menafova, Yu.V., Russ. J. Org.
Chem., 2006, vol. 42, p. 403.
11. Couladouros, E.A., Plyta, Z.F., and Haroutounian, S.A.,
J. Org. Chem., 1997, vol. 62, p. 6.
12. Moore, H.W., Shelden, H.R., and Shellhamer, D.F.,
J. Org. Chem., 1969, vol. 34, p. 1999.
13. Burmistrov, K.S., Cand. Sci. (Chem.) Dissertation,
N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-
enylidene)trifluoromethanesulfonamide (13d). Yield
80%, mp 115–116°C. H NMR spectrum (CDCl3), δ,
ppm: 1.02 d (6H, CHMe2), 2.06 s (3H, 5-Me), 3.01–
3.25 m (1H, CHMe2), 6.73 s (1H, 3-H), 6.85 s (1H,
6-H), 9.53 s (1H, NH), 10.78 br.s (1H, OH). 19F NMR
spectrum (CFCl3): δF –75.82 ppm, s. Found, %:
N 4.70, 4.74; S 10.69, 10.77. C11H14F3NO3S. Calculat-
ed, %: N 4.71; S 10.79.
1
Dnepropetrovsk, 1990.
14. Khimicheskaya entsiklopediya (Chemical Encyclo-
pedia), Knunyants, I.L., Ed., Moscow: Sovetskaya
Entsiklopediya, 1988, vol. 1, p. 48.
15. Avdeenko, A.P., Konovalova, S.A., Ludchenko, O.N.,
Ledeneva, O.P., and Vakulenko, A.V., Russ. J. Org.
Chem., 2011, vol. 47, p. 214.
16. Fieser, L.F. and Fieser, M., Advanced Organic
Chemistry, New York: Reinhold, 1962. Translated under
the title Organicheskaya khimiya, Moscow: Mir, 1966,
vol. 2, p. 403.
N-(3-Amino-2,5-dimethyl-4-oxocyclohexa-2,5-di-
enylidene)benzenesulfonamide (17a). Yield 74%,
1
mp 203–204°C. H NMR spectrum (CDCl3), δ, ppm:
1.82 s (3H, 2-Me), 2.13 d (3H, 5-Me, J = 1.8 Hz),
4.93 br.s (2H, NH2), 7.46–8.05 m (5H, Ph), 7.91 q (1H,
6-H). Found, %: N 9.57, 9.62; S 10.96, 11.03.
C14H14N2O3S. Calculated, %: N 9.65; S 11.04.
17. Titov, E.A., Avdeenko, A.P., and Rudchenko, V.F.,
Zh. Org. Khim., 1972, vol. 8, p. 2546.
N-(5-Amino-2,3-dimethyl-4-oxocyclohexa-2,5-di-
18. Avdeenko, A.P., Surmii, A.M., Yurchenko, E.I.,
Kremlev, M.M., and Bezverkhii, N.P., Vopr. Khim.
Khim. Tekhnol., 1981, no. 64, p. 23.
enylidene)-4-methylbenzenesulfonamide (17b).
Yield 70%, mp 188–190°C. H NMR spectrum
1
(CDCl3), δ, ppm: 2.00 s (3H, 3-Me), 2.05 s (3H,
2-Me), 2.44 s (3H, 4′-Me), 5.48 br.s (2H, NH2), 6.91 s
(1H, 6-H), 7.32–7.88 d.d (4H, C6H4, J = 8.1 Hz).
Found, %: N 9.10, 9.17; S 10.51, 10.60. C15H16N2O3S.
Calculated, %: N 9.20; S 10.54.
19. Granovsky, A.A., Firefly, version 7.1.G. www http://
classic.chem.msu.su/gran/firefly/index.html
20. Schmidt, M.W., Baldridge, K.K., Boatz, J.A.,
Elbert, S.T., Gordon, M.S., Jensen, J.J., Koseki, S.,
Matsunaga, N., Nguyen, K.A., Su, S., Windus, T.L.,
Dupuis, M., and Montgomery, J.A., Jr., J. Comput.
Chem., 1993, vol. 14, p. 1347.
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21. Avdeenko, A.P. and Konovalova, S.A., Russ. J. Org.
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22. Avdeenko, A.P., Konovalova, S.A., and Ludchen-
1. Avdeenko, A.P., Konovalova, S.A., Mikhailichen-
ko, O.N., Shelyazhenko, S.V., Pirozhenko, V.V., and
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 1 2016