Heterocyclic thiones and their analogs in 1,3-dipolar cycloaddition: VII. Reaction of 4-methyl-1,3-thiazole-2(3H)-thiones with nitrile imines

Article abstract of DOI:10.1134/S1070428007100193

Reactions of 4-methyl-1,3-thiazole-2(3H)-thiones with various C,N-disubstituted nitrile imines occurred by the common [3+2]-cycloaddition scheme leading to the formation in general of stable spiro compounds. In reactions of o-nitrophenylnitrile imines acy

Full text of DOI:10.1134/S1070428007100193

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 10, pp. 1516−1525. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © E.V. Budarina, T.S. Dolgushina, M.L. Petrov, N.N. Labeish, A.A. Kol’tsov, V.K. Bel’skii, 2007, published in Zhurnal Organicheskoi
Khimii, 2007, Vol. 43, No. 10, pp. 1521−1529.
Heterocyclic Thiones and Their Analogs in 1,3-Dipolar
Cycloaddition: VII.* Reaction
of 4-Methyl-1,3-thiazole-2(3H)-thiones with Nitrile Imines
E. V. Budarinaa, T. S. Dolgushinaa, M. L. Petrova, N. N. Labeisha,
A. A. Kol’tsova, and V. K. Bel’skiib
aSt. Petersburg State Technological Institute, St. Petersburg, Russia
e-mail: tdolgushina@itcwin.com
bState Scientific Center Karpov Research Physicochemical Institute, Moscow, Russia
Received October 26, 2005; final version May 2, 2007
Abstract—Reactions of 4-methyl-1,3-thiazole-2(3H)-thiones with various C,N-disubstituted nitrile imines occurred
by the common [3+2]-cycloaddition scheme leading to the formation in general of stable spiro compounds. In
reactions of o-nitrophenylnitrile imines acyclic compounds were the main products.
DOI: 10.1134/S1070428007100193
Reactions of versatile cyclic thiocarbonyl compounds
with nitrile imines resulted in substituted thiadiazoles of
spiro structure [2–4]. The decomposition and further
transformations of spiro compounds are known for nitrile
imines addition at the exocyclic C=S bond in the 1,3,4-
oxathiadiazole-2(3H)-thiones and benzothiazole-2-thione
[5–9].
cycloaddition scheme leading to the formation in the
majority of cases of stable spiro compounds III.
Compounds obtained are solid crystalline substances.
In the 1H NMR spectra of compounds IIIa–IIIr appear
signals characteristic of substituents at the carbon and
nitrogen atoms of nitrile imine, and also the signals of
the substituents of the 1,3-thiazoline ring.
In the 13C NMR spectra of compounds IIIa–IIIr the
signals of spiro carbon atoms linked to four hetero atoms
are observed at δ 109–118 ppm. In the region δ 144–
147 ppm signals appeared belonging to the carbon in
the position 2 of thiadiazole ring, and C7 and C8 atoms
of the thiazole ring give rise to signals in the region δ
113–117 and 135–141 ppm respectively. The other
signals in the 13C NMR spectra are also consistent with
1,3-Dipolar cycloaddition of nitrile imines to 1,3-
thiazole-2(3H)-thiones was not studied before. We
recently reported on reactions of 4-methyl-1,3-thiazole-
2(3H)-thiones with some nitrile imines [10]. Here we
consider in detail the reactions of these compounds with
various C,N-disubstituted nitrile imines generated in situ
by treating with triethylamine corresponding hydrazonoyl
chlorides. The reactions occurred by the common [3+2]-
Scheme 1.
Ar
N
R1
R1
S
S
_
N
+
+ R3 C N N Ar
S
N
R2
S
R3
N
R2
Me
Me
II
_
IIIa IIIn
I
R1 = MeOC(O) (a, d, f, g), EtOC(O) (b, c, l–r), Ac (e, h–j); R2 = Me (a, b), Bn (d, e), Ph (f–r); R3= Ac (c, d, f, i, n, o),
R3 = MeOC(O) (b, e, h, l, m), EtOC(O) (a, g, j, k, p, q, r); Ar = C6H4Br-p (a, e), C6H4Me-p (b, d, j, l, q), C6H4NO2-p (c,
f), C6H4Cl-p (g), Ph (h, i, m, n, p), C6H4OMe-p (k), C6H4Me-o (o), C6H4Cl-o (r).
*For Communication VI, see [1].
1516

HETEROCYCLIC THIONES AND THEIR ANALOGS IN 1,3-DIPOLAR CYCLOADDITION: VII.
C12
1517
C11
C13
C10
C5
C8
C9
C2
N1
S2
O1
C1
O2
C4
C3
C6
C22
C20
S1
C15
N2
N3
C14
C7
O3
C19
C21
C16
C18
C17
C23
Fig. 1. Structure of the molecule of 7-acetyl-8-methyl-1-(4-methylphenyl)-9-phenyl-3-ethoxycarbonyl-4,6-dithia-1,2,9-
triazaspiro[4.4]nona-2,7-diene (IIIj) according to X-ray diffraction study.
the assumed structure of compounds obtained. The
formation of substituted 4,6-dithia-1,2,9-triazaspiro-
[4.4]nona-2,7-dienes IIIa–IIIr was also confirmed by
their mass spectra. The mass spectra of these compounds
contained the peaks of the corresponding molecular ions.
The main fragmentation direction of the molecular ions
was a recyclic decomposition of the thiadiazole ring with
ejection of the nitrile imine ion. Further fragmentation
was complicated.
Table 1. Bond lengths d (Å) and bond angles ω (deg) in the
molecule of 7-acetyl-8-methyl-1-(4-methylphenyl)-9-phenyl-
3-ethoxycarbonyl-4,6-dithia-1,2,9-triazaspiro[4.4]nona-2,7-
diene (IIIj)
Bond
S1–C3
S1–C1
S2–C4
S2–C1
O1–C6
O2–C20
O3–C20
O3–C21
N1–C2
N1–C8
N1-C1
N2-N3
N2–C14
N2–C1
N3–C4
C2–C3
C2–C5
C3–C6
C4–C20
C6–C7
C21–C22
d
Angle
N3N2C14
N3N2C1
C14N2C1
C4N3N2
N2C1N1
N2C1S2
N1C1S2
N2C1S1
N1C1S1
S2C1S1
C3C2N1
C3C2C5
N1C2C5
C2C3C6
C2C3S1
C6C3S1
N3C4C20
N3C4S2
C20C4S2
O1C6C3
O1C6C7
ω
1.782(5)
1.843(4)
1.721(5)
1.842(4)
1.230(6)
1.194(6)
1.306(7)
1.683(11)
1.388(5)
1.442(5)
1.459(5)
1.362(5)
1.433(5)
1.455(5)
1.282(5)
1.341(6)
1.496(6)
1.457(7)
1.489(6)
1.476(8)
1.187(12)
116.2(3)
118.4(3)
125.2(3)
111.7(3)
112.4(3)
102.4(3)
114.5(3)
116.1(3)
103.8(3)
107.9(2)
114.4(4)
127.3(4)
118.3(4)
128.5(5)
111.9(3)
119.5(4)
123.3(5)
117.0(3)
119.6(4)
121.7(5)
119.8(6)
The structure of spiro compounds obtained was
confirmed by X-ray diffraction study of crystals of
7-acetyl-8-methyl-1-(4-methylphenyl)-9-phenyl-3-
ethoxycarbonyl-4,6-dithia-1,2,9-triazaspiro[4.4]nona-
2,7-diene (IIIj) (Fig. 1, Table 1) (everywhere in describ-
ing the results of X-ray diffraction analysis the numbering
of atoms is the same as on the figure). The X-ray diffrac-
tion analysis showed that the thiazole (S1C1N1C2C3) and
thiadiazole (S2C4N3N2C1) rings are planar, the maximum
deviations of atoms from the planes S1C1N1C2C3 and
S2C4N3N2C1 amount to0.0344 and 0.0048 Å respectively.
The angle between these planes is 86.2 deg.Aconjugation
of the acetyl group with the thiazole ring is possible in
the molecule for they are located virtually in the same
plane,the angle between these planes is 2.1 deg.
The substitutents in the benzene ring of nitrile imine
do not affect as a rule the structure of the reaction
products, but when a benzene ring attached to nitrile
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

BUDARINA et al.
1518
Table 1. (Contd.).
We presume that the reaction can take two routes.
Angle
C3S1C1
C4S2C1
C20O3C21
C2N1C8
C2N1C1
C8N1C1
ω
C3C6C7
C15C14N2
C19C14N2
O2C20O3
O2C20C4
O3C20C4
C22C21O3
118.5(6)
123.0(4)
118.8(4)
126.4(5)
119.7(6)
113.8(5)
93.0(9)
In the first case the arising spiro compound A proves
to be unstable and suffers further transformations.
Evidently the decomposition starts by the rupture of the
C–S bond in the thiadiazole ring; as a result forms
a bipolar ion B. The stabilization of the bipolar ion occurs
by a migration of ortho-nitrophenyl moiety to the sulfur
atom.
92.1(2)
90.4(2)
119.8(5)
122.9(3)
117.3(3)
119.7(3)
The second route begins with an electrophilic attack
on the sulfur atom leading to a bipolar ion C, then the
negatively charged nitrogen attacks the positively
charged carbon with a simultaneous cleavage of the C–
S bond and the formation of bipolar ion B. In the third
stage a nucleophilic attack occurs on the most electro-
philic atom of the aromatic ring. The rupture of the C–N
bond is facilitated by the positive charge on the
contiguous carbon atom.
imine nitrogen contains a nitro group in the ortho
position, the reaction takes an uncommon route providing
acyclic compounds VI as main products. Usually the
ortho-nitro substituted nitrile imines react with the
exocyclic C=S bond giving stable spiro compounds [11].
It is known from the literature that in some events the
ortho-substituents in the benzene ring of the nitrile imine
hamper the cycloaddition to the double bond. For
instance, in the reaction of benzothiazole-2(3H)-thione
with C-ethoxycarbonyl-N-arylnitrile imines with a ortho-
substituent in the benzene ring products of nucleophilic
substitution of chlorine in the hydrazonoyl chloride of
the thiol form of initial reagent were obtained [8].
The crucial importance for the change in the reaction
route is the presence of a nitro group just in the ortho-
position. The presence of other substituents, even donor
ones, in the ortho-nitro substituted benzene ring of nitrile
imine does not affect the reaction direction. At the para-
position of the nitro group the C–S bond does not suffer
R4
O2N
R4
_
+
R3 C N N
R4
NO2
R1
IV
V
R1
_
S
NO
S
S
N
S
+
S
N
R1
+
N N
R3
N
R2
N
R2
R3
S
Me
Me
N
R2
Me
A
B
R4
R4
NO2
_N
R1
R1
S
S
R3
S
N
NO2
+
N N
N
R2
S
R3
N
R2
Me
Me
_
VIа VIh
C
R1 = Ac (a, d, e), EtOC(O) (b, c, g, h), MeOC(O) (f); R2 = Me (a–c), Ph (d–h); R3 = Me (b), Ac (g), MeOC(O) (c, d),
EtOC(O) (a, e, f, h); R4 = OMe (a), NO2 (b), H (c–h).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

HETEROCYCLIC THIONES AND THEIR ANALOGS IN 1,3-DIPOLAR CYCLOADDITION: VII.
1519
Fig. 2. Structure of the of 1-[acetyl(2-nitrophenylsulfanyl)methylene]-2-[4-methyl-3-phenyl-5-ethoxycarbonyl-1,3-thiazole-
2(3H)-ylidene]hydrazine (VIg) according to X-ray diffraction analysis.
rupture, and a stable spiro compound is obtained. It is
presumable that the field effect of the nitro group causes
the loosening of bonds at the spiro center, and the
cleavage of the C–S bond in the thiadiazole ring favors
just the migration of the ortho-nitro substituted ring but
not the methyl or phenyl group.
from the plane was 0.0122 Å). It is presumable that the
ethoxycarbonyl group is involved into the conjugation
with the thiazole ring, for the angle between their planes
is 7.1 deg, and the conjugtion of phenyl and thiazole
rings is lacking since the angle between their planes
is 76.9 deg. A conjugation might also exist between the
thiazole ring and the thiohydrazine chain because
the molecule is virtually planar (maximum deviation
of atoms from the plane of 2-thiahydrazothiazole is
0.0122 Å).
1
The structure of products was established from H
13
and C NMR and mass spectra and was confirmed by
X-ray diffraction analysis. 1H NMR spectra of isolated
compounds VIa–VIh are in agreement with the assumed
structures. In the 13C NMR spectra of these compounds
lacked the signal characteristic of the spiro carbon of
3,4,7,8,9-substituted-4,6-dithia-1,2,9-triazaspiro[4.4]-
nona-2,7-dienes, but appeared a signal in the region 170–
172 ppm from the carbon in the acyclic chain attached
to sulfur and nitrogen. The other signals are also
consistent with the assumed structure. In the mass spectra
of compounds VId–VIh the peaks of their molecular ions
appeared; subsequent fragmentaion of the molecular ions
occurred with the rupture of the C–S bond and ejection
of the thiophenyl fragment. Further fragmentation was
complicated like that with compounds IIIa–IIIr.
EXPERIMENTAL
1H (500 MHz) and 13C (125 MHz) NMR spectra were
registered on a spectrometer Bruker AM-500 from 1–
5% solutions of compounds in DMSO-d6 or CDCl3. Mass
spectra were recorded on a Kratos MS-890 instrument,
vaporizer temperature 120°C, ion source temperature
200°C, ionizing energy 70 eV. Reaction progress was
monitored by TLC on Silufol UV-254 plates, develop-
ment under UV irradiation.
X-ray diffraction study of crystals of spiro compound
IIIj was carried out on an automatic diffractometer
CAD-4 (MoK-radiation, β-filter, θ/2θ-scanning, 2.28 ≤
θ ≤ 24.97 deg). Crystals orthorhombic. C23H23N3O3S2.
a 16.006(3) Å, α 90 deg, b 7.869(2) Å, β 90 deg,
c 17.852(4) Å, γ 90 deg, V 2248.5(9) Å3; space group
Pna2(1), Z 4, dcalc 1.394 g/cm3. The structure was solved
The structure of hydrazines obtained was confirmed
by X-ray diffraction analysis on crystals of 1-[acetyl(2-
nitrophenylsulfanyl)methylene]-2-[4-methyl-3-phenyl-5-
ethoxycarbonyl-1,3-thiazol-2(3H)-ylidene]hydrazine
(VIg) (Fig. 2, Table 2).
The X-ray diffraction analysis showed that the
thiazole ring is planar (the maximum deviation of atoms
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

BUDARINA et al.
1520
Table 2. Bond lengths d (Å) and bond angles ω (deg) in the
molecule of 1-[acetyl(2-nitrophenylsulfanyl)methylene]-2-[4-
methyl-3-phenyl-5-ethoxycarbonyl-1,3-thiazole-2(3H)-
ylidene]hydrazine (VIg)
C22H20N4O5S2. a 9.102(2) Å, α 65.98(3) deg., b 10.945(2)
Å, β 88.92(3) deg, c 12.914(3) Å, γ 76.13(3) deg,
V 1136.3(4) Å3; space group P-1, Z 2, dcalc 1.416 g/cm3.
The structure was solved by the direct method [2940
reflections with I > 2σ (I)] in a full-matrix approximation,
anisotropic for atoms O, N, C, S and isotropic for
hydrogen, till R 0.0327, RW 0.0876 (no correction for
extinction was introduced). The crystallographic
coordinates of nonhydrogen and hydro-gen atoms and
their equivalent temperature factors are available from
the authors.
Bond
S1–C1
S1–C3
S2–C17
S2–C14
O1–C4
O1–C5
O2–C4
O3–C15
O4–N4
O5–N4
d
Angle
O5N4O4
O5N4C18
O4N4C18
N2C1N1
N2C1S1
N1C1S1
C3C2N1
C3C2C7
N1C2C7
C2C3C4
ω
1.738(2)
1.761(2)
1.758(2)
1.771(2)
1.333(3)
1.460(3)
1.206(2)
1.208(2)
1.235(3)
1.217(3)
123.1(3)
119.0(2)
117.8(3)
120.10(17)
129.51(15)
110.38(13)
112.31(16)
129.08(18)
118.60(18)
127.04(18)
Initial 1,3-thiazole-2-thiones were synthesized by
a reaction of ammonium salts of N-phenyl-, N-benzyl,
and N-methyldithiocarbamic acids with methyl and ethyl
α-chloroacetoacetates or with 3-chloroacetylacetone
[12]. Nitrile imines were generated in situ by treating
with triethylamine appropriate hydrazonoyl chlorides II
and IV [13].
N1–C1
N1–C2
N1–C8
N2–C1
1.372(2)
1.393(2)
1.445(2)
1.298(2)
C2C3S1
C4C3S1
O2C4O1
O2C4C3
112.26(14)
120.56(15)
124.60(18)
125.24(19)
Reaction of 4-methyl-1,3-thiazole-2-thione with
hydrazonoyl chlorides. To a mixture of 4 mmol of
1,3-thiazole-2-thione (I) or V and 4 mmol of an appropriate
hydrazonoyl chloride II or IV in 15–20 ml of dichloro-
methane was added 20 ml of 2-propanol and 1 ml
(7 mmol) of triethylamine. The reaction mixture was left
overnight at room temperature. Then the solution was
concentrated, the separated precipitate was filtered off,
washed with 50% 2-propanol, and recrystallized from
acetone or acetonitrile.
N2–N3
N3–C14
N4–C18
C2–C3
1.379(2)
1.290(2)
1.459(4)
1.343(3)
1.491(3)
1.471(3)
1.472(4)
1.502(3)
1.497(3)
ω
O1C4C3
O1C5C6
C9C8C13
C9C8N1
110.14(17)
108.7(2)
121.2(2)
119.80(18)
119.0(2)
C2–C7
C13C8N1
N3C14C15
N3C14S2
C15C14S2
O3C15C16
O3C15C14
C16C15C14
C22C17C18
C22C17S2
C18C17S2
C19C18C17
C19C18N4
C17C18N4
C3–C4
C5–C6
C14–C15
C15–C16
Angle
C1S1C3
C17S2C14
C4O1C5
C1N1C2
C1N1C8
C2N1C8
C1N2N3
C14N3N2
117.06(17)
119.53(15)
122.40(14)
122.2(2)
1-(4-Bromophenyl)-8,9-dimethyl-7-methoxy-
carbonyl-3-ethoxycarbonyl-4,6-dithia-1,2,9-triaza-
spiro[4.4]nona-2,7-diene (IIIa). Yield 74%, mp 144–
146°C (from acetone). 1H NMR spectrum, δ, ppm: 1.36 t
[3H, CH3CH2OC(O)], 2.37 s (3H, CH3), 2.87 s (3H, CH3N),
3.66 s [3H, CH3OC(O)], 4.32 q [2H, CH3CH2OC(O)],
7.15–7.46 m (4Harom). 13C NMR spectrum, δ, ppm: 13.00
[CH3CH2OC(O)], 13.91 (CH3), 29.71 (CH3N), 51.04
[CH3OC(O)], 61.99 [CH3CH2OC(O)], 116.63 (C5),
117.31 (C7), 139.05 (C8), 146.93 (C2), 159.15
[CH3OC(O)], 162.44 [CH3CH2OC(O)], 120.28, 131.75,
134.11 (Ar). Mass spectrum, m/z (Irel, %): 472 (10) [M]+,
203 (100) [C7H9NO2S2]+. Found, %: C 43.51; H 4.01; N
8.73. C17H18BrN3O4S2. Calculated, %: C 43.23; H 3.84;
N 8.90. M 472.38.
120.81(19)
117.01(19)
116.8(2)
90.19(10)
102.56(10)
117.65(18)
114.77(16)
120.37(15)
124.81(15)
111.96(16)
113.03(16)
120.07(17)
123.11(19)
121.6(3)
117.5(3)
120.8(2)
by the direct method [2343 reflections with I > 2σ (I)] in
a full-matrix approximation, anisotropic for atoms O, N,
C, S and isotropic for hydrogen, till R 0.0344, RW 0.08
(no correction for extinction was introduced).
8,9-Dimethyl-1-(4-methylphenyl)-3-methoxy-
carbonyl-7-ethoxycarbonyl-4,6-dithia-1,2,9-triaza-
spiro[4.4]nona-2,7-diene (IIIb). Yield 80%, mp 115–
117°C (from a mixture acetone−acetonitrile).1H NMR
spectrum, δ, ppm: 1.24 t [3H, CH3CH2OC(O)], 2.31 s
X-ray diffraction study of crystals of substituted
hydrazine VIg was carried out on an automatic
diffractometer CAD-4 (MoK-radiation, β-filter, θ/2θ-
scanning, 1.73 ≤ θ ≤ 24.97 deg). Crystals triclinic.
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HETEROCYCLIC THIONES AND THEIR ANALOGS IN 1,3-DIPOLAR CYCLOADDITION: VII.
1521
(3H, CH3), 2.34 s (3H, C6H4CH3-p), 2.87 s (3H, CH3N),
3.85 C [3H, CH3OC(O)], 4.11 q [2H, CH3CH2OC(O)],
7.05–7.25 m (4Harom). 13C NMR spectrum, δ, ppm: 12.89
[CH3CH2OC(O)], 13.87 (CH3), 20.26 (C6H4CH3-p),
29.35 (CH3N), 52.42 [CH3OC(O)], 59.76
[CH3CH2OC(O)], 117.58 (C5), 118.70 (C7), 137.25 (C8),
145.29 (C2), 160.24 [CH3OC(O)], 162.78
[CH3CH2OC(O)], 129.11, 132.16, 133.86 (Ar). Mass
spectrum, m/z (Irel, %): 407 (25) [M]+, 217 (30)
[C8H11NO2S2]+. Found, %: C 53.13; H 5.00; N 10.25.
C18H21N3O4S2. Calculated, %: C 53.05; H 5.19; N 10.31.
M 407.51.
[CH3C(O)], 47.40 (C6H5CH2N), 52.86 [CH3OC(O)],
108.50 (C5), 115.51 (C7), 138.92 (C8), 145.60 (C2),
159.56 [CH3OC(O)], 188.26 [CH3C(O)], 117.08, 121.26,
126.22, 127.16, 128.39, 131.74, 133.51, 136.11 (Ar).
Mass spectrum, m/z (Irel, %): 518 (20) [M]+, 263 (30)
[C13H13NOS2]+. Found, %: C 50.73; H 4.11; N 8.02.
C22H20BrN3O3S2. Calculated, %: C 50.97; H 3.89; N
8.10. M 518.46.
3-Acetyl-8-methyl-7-methoxycarbonyl-1-(4-
nitrophenyl)-9-phenyl-4,6-dithia-1,2,9-triaza-
spiro[4.4]nona-2,7-diene (IIIf). Yield 78%, mp 168–
1
170°C (from acetonitrile). H NMR spectrum, δ, ppm:
2.05 s (3H, CH3), 2.29 s [3H, CH3C(O)], 3.73 s [3H,
CH3OC(O)], 6.65–8.33 m (9Harom). 13C NMR spectrum,
δ, ppm: 14.31 (CH3), 24.38 [CH3C(O)], 51.22
[CH3OC(O)], 114.35 (C5), 117.99 (C7), 145.67 (C8),
146.93 (C2), 163.01 [CH3OC(O)], 190.73 [CH3C(O)],
125.26, 129.70, 130.02, 135.74, 143.53, 145.14 (Ar).
Mass spectrum, m/z (Irel, %): 471 (100) [M]+, 266 (30)
[C12H12NO2S2]+. Found, %: C 53.43; H 4.03; N 11.70.
C21H18N4O5S2. Calculated, %: C 53.61; H 3.86; N 11.91.
M 470.53.
3-Acetyl-8,9-dimethyl-1-(4-nitrophenyl)-7-ethoxy-
carbonyl-4,6-dithia-1,2,9-triazaspiro[4.4]-nona-2,7-
diene (IIIc). Yield 93%, mp 160–162°C (from aceto-
1
nitrile). H NMR spectrum, δ, ppm: 1.26 t [3H,
CH3CH2OC(O)], 2.37 s (3H, CH3), 2.54 s [3H,
CH3C(O)], 2.60 s (3H, CH3N), 4.28 q [2H,
CH3CH2OC(O)], 7.35–8.21 m (4Harom). 13C NMR
spectrum, δ, ppm: 12.89 [CH3CH2OC(O)], 13.85 (CH3),
24.80 [CH3C(O)], 29.29 (CH3N), 69.14
[CH3CH2OC(O)], 116.42 (C5), 116.62 (C7), 145.07 (C8),
145.48 (C2), 162.45 [CH3CH2OC(O)], 190.73
[CH3C(O)], 124.53, 142.70 144.58 (Ar). Mass spectrum,
m/z (Irel, %): 422 (15) [M]+, 217 (100) [C8H11NO2S2]+.
Found, %: C 48.56; H 4.31; N 12.97. C17H18N4O5S2.
Calculated, %: C 48.33; H 4.29; N 13.26. M 422.48.
8-Methyl-7-methoxycarbonyl-9-phenyl-1-(4-
chlorophenyl)-3-ethoxycarbonyl-4,6-dithia-1,2,9-
triazaspiro[4.4]nona-2,7-diene (IIIg). Yield 89%, mp
1
173–174°C (from acetonitrile). H NMR spectrum, δ,
ppm: 1.27 t [3H, CH3CH2OC(O)], 2.05 sC (3H, CH3),
3.37 sC [3H, CH3OC(O)], 4.18 q [2H, CH3CH2OC(O)],
7.29–7.41 m (9Harom). 13C NMR spectrum, δ, ppm 13.78
[CH3CH2OC(O)], 14.48 (CH3), 51.31 [CH3OC(O)],
61.90 [CH3CH2OC(O)], 114.23 (C5), 119.18 (C7), 138.57
(C8), 145.93 (C2), 158.77 [CH3OC(O)], 162.48
[CH3CH2OC(O)], 128.18, 128.97, 129.26, 129.52,
130.48, 133.64, 135.10 (Ar). Mass spectrum, m/z (Irel,
%): 490 (100) [M]+, 265 (40) [C12H11NO2 S2]+. Found,
%: C 54.11; H 3.91; N 8.91. C22H20ClN3O4S2. Calculated,
%: C 53.93; H 4.11; N 8.58. M 490.00.
3-Acetyl-9-benzyl-8-methyl-1-(4-methylphenyl)-7-
methoxycarbonyl-4,6-dithia-1,2,9-triazaspiro-
[4.4]nona-2,7-diene (IIId). Yield 83%, mp 138–140°C
1
(from acetonitrile). H NMR spectrum, δ, ppm: 2.13 s
(3H, CH3), 2.35 s [3H, CH3C(O)], 2.50 s (3H, C6H4CH3-
p), 3.64 s [3H, CH3OC(O)], 4.58 s (2H, C6H5CH2N),
7.15–7.31 m (9Harom). 13C NMR spectrum, δ, ppm: 13.48
(CH3), 20.38 (C6H4CH3-p), 24.80 [CH3C(O)], 47.13
(C6H5CH2N), 51.15 [CH3OC(O)], 116.18 (C5), 120.61
(C7), 141.36 (C8), 147.29 (C2), 162.48 [CH3OC(O)],
190.87 [CH3C(O)], 126.13, 127.11, 128.42, 129.44,
134.94, 136.51, 137.19 (Ar). Mass spectrum, m/z (Irel,
%): 453 (5) [M]+, 279 (25) [C13H13NO2 S2]+. Found, %:
C 61.35; H 5.95; N 8.91. C23H23N3O3S2. Calculated, %:
C 60.90; H 5.11; N 9.26. M 453.59.
7-Acetyl-8-methyl-3-methoxycarbonyl-1,9-
diphenyl-4,6-dithia-1,2,9-triazaspiro[4.4]nona-2,7-
diene (IIIh). Yield 74%, mp 161–163°C (from aceto-
1
nitrile). H NMR spectrum, δ, ppm: 2.05 s (3H, CH3),
2.25 s [3H, CH3C(O)], 3.75 s [3H, CH3OC(O)], 7.18–
7.45 m (10Harom). 13C NMR spectrum, δ, m.d: 15.58
(CH3), 29.58 [CH3C(O)], 52.81 [CH3OC(O)], 109.63
(C5), 113.24 (C7), 137.74 (C8), 144.36 (C2), 159.41
[CH3OC(O)], 188.82 [CH3C(O)], 117.82, 123.99, 129.16,
129.34, 129.64, 132.51, 135.27 (Ar). Mass spectrum,
m/z (Irel, %): 425 (30) [M]+, 316 (45) [C15H14N3O3S]+,
249 (70) [C12H11NOS2]+, 250 (15) [C12H12NOS2]+.
Found, %: C 59.47; H 4.44; N 9.79. C21H19N3O3S2.
7-Acetyl-9-benzyl-1-(4-bromophenyl)-8-methyl-3-
methoxycarbonyl-4,6-dithia-1,2,9-triazaspiro-
[4.4]nona-2,7-diene (IIIe). Yield 98%, mp 114–116°C
1
(from acetonitrile). H NMR spectrum, δ, ppm: 2.18 s
[3H, CH3C(O)], 2.20 s (3H, CH3), 3.82 s [3H,
CH3OC(O)], 4.59 s (2H, C6H5CH2N), 7.16–7.46 m
(9Harom). 13C NMR spectrum, δ, ppm: 14.51 (CH3), 29.57
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

BUDARINA et al.
1522
Calculated, %: C 59.28; H 4.50; N 9.87. M 425.53.
spectrum, δ, ppm: 1.30 t [3H, CH3CH2OC(O)], 2.05 s
(3H, CH3C6H4), 2.25 s (3H, CH3), 3.82 s [3H,
CH3OC(O)], 4.17 q [2H, CH3CH2OC(O)], 6.92–7.43 m
(9H, Ar). 13C NMR spectrum, δ, ppm: 14.15
[CH3CH2OC(O)], 14.48 (CH3), 20.25 (CH3C6H4), 52.65
[CH3OC(O)], 59.96 [CH3CH2OC(O)], 114.34 (C5),
117.81 (C7), 137.42 (C8), 145.55 (C2), 159.45
[CH3OC(O)], 162.21 [CH3CH2OC(O)], 129.23, 129.44,
129.54, 131.30, 131.20, 133.20, 135.27 (Ar). Mass
spectrum, m/z (Irel, %): 469 (40) [M]+, 346 (70)
[C16H16N3O4S]+, 279 (60) [C13H13NO2S2]+, 190 (10)
[C10H10N2O2]+. Found, %: C 59.20; H 4.60; N 8.94.
C23H23N3O4S2. Calculated, %: C 58.83; H 4.94; N 8.95.
M 469.59.
3,7-Diacetyl-8-methyl-1,9-diphenyl-4,6-dithia-
1,2,9-triazaspiro[4.4]nona-2,7-diene (IIIi). Yield 71%,
mp 155–157°C (from acetonitrile). 1H NMR spectrum,
δ, ppm: 2.05 s (3H, CH3), 2.24 s, 2.35 s [6H, CH3C(O)],
7.2–7.45 m (10Harom). 13C NMR spectrum, δ, ppm: 15.51
(CH3), 24.55, 29.54 [CH3C(O)], 109.50 (C5), 112.96 (C7),
141.66 (C8), 144.29 (C2), 188.57, 190.17 [CH3C(O)],
117.99, 124.15, 129.09, 129.19, 129.50, 131.68, 135.27,
139.65 (Ar). Mass spectrum, m/z (Irel, %): 409 (5) [M]+,
250 (15) [C12H12NOS2]+. Found, %: C 61.88; H 5.02;
N 10.24. C21H19N3O2S2. Calculated, %: C 61.59; H 4.68;
N 10.26. M 409.53.
7-Acetyl-8-methyl-1-(4-methylphenyl)-9-phenyl-3-
ethoxycarbonyl-4,6-dithia-1,2,9-triazaspiro-
[4.4]nona-2,7-diene (IIIj). Yield 75%, mp 170–172°C
(from acetone). 1H NMR spectrum, δ, ppm: 1.25 t [3H,
CH3CH2OC(O)], 2.05 (3H, C6H4CH3-p), 2.25 s (3H, CH3),
2.35 s [3H, CH3C(O)], 4.20 q [2H, CH3CH2OC(O)], 7.1–
7.45 m (9Harom). 13C NMR spectrum, δ, ppm: 13.81
[CH3CH2OC(O)], 15.51 (CH3), 20.25 (C6H4CH3-p),
29.54 [CH3C(O)], 61.72 [CH3CH2OC(O)], 109.33 (C5),
113.30 (C7), 137.42 (C8), 144.12 (C2), 158.97
[CH3CH2OC(O)], 188.56 [CH3C(O)], 117.89, 129.24,
129.50, 132.24, 133.15, 135.35 (Ar). Mass spectrum, m/
z (Irel, %): 453 (30) [M]+, 249 (30) [C12H11NOS2]+, 250
(10) [C12H12NOS2]+, 204 (5) [C11H12N2O2]+. Found, %:
C 60.57; H 5.11; N 9.51. C23H23N3O3S2. Calculated, %:
C 60.90; H 5.11; N 9.26. M 453.59.
8-Methyl-3-methoxycarbonyl-1,9-diphenyl-7-
ethoxycarbonyl-4,6-dithia-1,2,9-triazaspiro[4.4]-
nona-2,7-diene (IIIm). Yield 70%, mp 144–145°C (from
1
acetonitrile). H NMR spectrum, δ, ppm: 1.20 t [3H,
CH3CH2OC(O)], 2.05 s (3H, CH3), 3.70 s [3H,
CH3OC(O)], 4.15 q [2H, CH3CH2OC(O)], 7.05–7.45 m
(10Harom). 13C NMR spectrum, δ, ppm: 14.17
[CH3CH2OC(O)], 14.51 (CH3), 52.79 [CH3OC(O)],
60.06 [CH3CH2OC(O)], 114.35 (C5), 117.80 (C7), 139.79
(C8), 145.79 (C2), 159.45 [CH3OC(O)], 162.26
[CH3CH2OC(O)], 124.01, 129.16, 129.27, 129.51,
130.41, 132.64, 135.22 (Ar). Mass spectrum, m/z (Irel,
%): 455 (62) [M]+, 346 (74) [C16H16N3O4S]+, 279 (100)
[C13H13NO2S2]+, 280 (20) [C13H14NO2S2]+. Found, %:
C 57.99; H 4.66; N 9.11. C22H21N3O4S2. Calculated, %:
C 58.00; H 4.65; N 9.22. M 455.56.
7-Acetyl-8-methyl-1-(4-methoxyphenyl)-9-phenyl-
3-ethoxycarbonyl-4,6-dithia-1,2,9-triazaspiro-
[4.4]nona-2,7-diene (IIIk). Yield 96%, mp 181–182°C
3-Acetyl-8-methyl-1,9-diphenyl-7-ethoxycarbonyl-
4,6-dithia-1,2,9-triazaspiro[4.4]nona-2,7-diene (IIIn).
Yield 90%, mp 136.5–138°C (from acetonitrile).
1H NMR spectrum, δ, ppm: 1.28 t [3H, CH3CH2OC(O)],
2.05 s (3H, C6H5CH3), 2.35 s (3H, CH3), 3.73 s [3H,
CH3OC(O)], 4.20 q [2H, CH3CH2OC(O)], 7.10–7.41 m
(9Harom). 13C NMR spectrum, δ, ppm: 14.17
[CH3CH2OC(O)], 14.53 (CH3), 24.60 [CH3C(O)], 60.05
[CH3CH2OC(O)], 113.95 (C5), 118.01 (C7), 141.79 (C8),
145.86 (C2), 162.25 [CH3CH2OC(O)], 190.49
[CH3C(O)], 124.26, 129.20, 129.47, 135.20, 139.68 (Ar).
Mass spectrum, m/z (Irel, %): 279 (32) [C13H13NO2S2]+,
280 (5) [C13H14NO2S2]+. Found, %: C 60.49; H 4.58;
N 9.37. C22H21N3O3S2. Calculated, %: C 60.12; H 4.82;
N 9.56. M 439.56.
1
(from acetonitrile). H NMR spectrum, δ, ppm: 1.25 t
[3H, CH3CH2OC(O)], 2.05 s (3H, CH3), 2.25 s [3H,
CH3C(O)], 3.82 s (3H, C6H4OCH3-p) 4.17 q [2H,
CH3CH2OC(O)], 6.92–7.43 m (9Harom). 13C NMR
spectrum, δ, ppm: 12.91 [CH3CH2OC(O)], 13.81 (CH3),
29.57 [CH3C(O)], 51.14 (C6H4OCH3), 61.63
[CH3CH2OC(O)], 109.26 (C5), 113.48 (C7), 135.47 (C8),
144.02 (C2), 159.01 [CH3CH2OC(O)], 188.51
[CH3C(O)], 114.23, 119.78, 129.23, 129.44, 130.30,
131.70, 133.07, 156.18 (Ar). Mass spectrum, m/z (Irel,
%): 470 (100) [M]+, 338 (32) [C19H18N2O2S]+. Found,
%: C 59.01; H 4.93; N 8.85. C23H23N3O4S2. Calculated,
%: C 58.83; H 4.94; N 8.95. M 469.59.
3-Acetyl-8-methyl-1-(2-methylphenyl)-9-phenyl-7-
ethoxycarbonyl-4,6-dithia-1,2,9-triazaspiro-
[4.4]nona-2,7-diene (IIIo). Yield 88%, mp 152–154°C
8-Methyl-1-(4-methylphenyl)-3-methoxycarbonyl-
9-phenyl-7-ethoxycarbonyl-4,6-dithia-1,2,9-triaza-
spiro[4.4]nona-2,7-diene (IIIl). Yield 64%, mp 165–
167°C (from a mixture 2-PrOH−acetonitrile). 1H NMR
1
(from acetonitrile). H NMR spectrum, δ, ppm: 1.19 t
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HETEROCYCLIC THIONES AND THEIR ANALOGS IN 1,3-DIPOLAR CYCLOADDITION: VII.
1523
[3H, CH3CH2OC(O)], 2.08 s (3H, C6H5CH3), 2.17 s (3H,
CH3), 2.23 s [3H, CH3C(O)], 4.05 q [2H,
CH3CH2OC(O)], 7.29–7.51 m (9H, Ar). 13C NMR
spectrum, δ, m.d: 14.14 [CH3CH2OC(O)], 14.93 (CH3),
18.85 (CH3C6H4), 24.51 [CH3C(O)], 59.83
[CH3CH2OC(O)], 113.75 (C5), 124.91 (C7), 140.06 (C8),
145.38 (C2), 162.06 [CH3CH2OC(O)], 190.18
[CH3C(O)], 126.70, 128.17, 129.02, 129.24, 129.79,
131.64, 136.54, 138.67 (Ar). Mass spectrum, m/z (Irel,
%): 454 (100) [M]+, 280 (75) [C13H14NO2S2]+. Found,
%: C 61.15; H 5.22; N 9.01. C23H23N3O3S2. Calculated,
%: C 60.90; H 5.11; N 9.26. M 453.59.
(CH3), 59.89, 61.74 [CH3CH2OC(O)], 115.32 (C5),
126.81 (C7), 137.42 (C8), 144.61 (C2), 159.55, 162.72
[CH3CH2OC(O)], 127.71, 128.65, 129.08, 129.44,
130.60, 134.10, 134.38, 136.74 (Ar). Mass spectrum,
m/z (Irel, %): 504 (50) [M]+, 280 (100) [C13H14NO2S2]+.
Found, %: C 54.64; H 4.67; N 8.30. C23H22ClN3O4S2.
Calculated, %: C 54.81; H 4.40; N 8.34. M 504.03.
2-[5-Acetyl-3,4-dimethyl-1,3-thiazol-2(3H)-
ylidene]-1-[4-methoxy-2-nitrophenylsulfanyl-
(ethoxycarbonyl)methylene]hydrazine (VIa). Yield
1
84%, mp 161–161.5°C (from acetonitrile). H NMR
spectrum, δ, ppm: 1.10 t [3H, CH3CH2OC(O)], 2.32 s
(3H, CH3), 2.58 s [3H, CH3C(O)], 3.24 s (3H, CH3N),
3.82 s (3H, OCH3) 4.04 q [2H, CH3CH2OC(O)], 6.90–
7.50 m (3Harom). 13C NMR spectrum, δ, ppm: 13.15
[CH3CH2OC(O)], 13.64 (CH3), 29.88 [CH3C(O)], 31.81
(CH3N), 55.78 (OCH3), 61.84 [CH3CH2OC(O)], 109.54
(C5), 145.07 (C4), 151.01 (C2), 159.12 [CH3OC(O)],
161.69 [CH3CH2OC(O)], 169.87 (N=C–S), 189.10
[CH3C(O)], 114.65, 119.31, 120.29, 135.38, 145.41 (Ar).
Found, %: C 48.07; H 4.70; N 12.29. C18H20N4O6S2.
Calculated, %: C 47.78; H 4.46; N 12.38. M 452.51.
8-Methyl-1,9-diphenyl-3,7-bis(ethoxycarbonyl)-
4,6-dithia-1,2,9-triazaspiro[4.4]nona-2,7-diene (IIIp).
Yield 53%, mp 134–135°C (from acetonitrile). 1H NMR
spectrum, δ, ppm: 1.25 d.t [6H, CH3CH2OC(O)], 2.05 s
(3H, CH3), 4.15 d.q [4H, CH3CH2OC(O)], 7.10–7.45 m
(10Harom). 13C NMR spectrum, δ, ppm: 13.80, 14.15
[CH3CH2OC(O)], 14.48 (CH3), 59.98, 61.81
[CH3CH2OC(O)], 114.28 (C5), 117.78 (C7), 139.84 (C8),
145.60 (C2), 158.95, 162.19 [CH3CH2OC(O)], 123.90,
129.02, 129.20, 129.43, 130.29, 132.88, 135.27 (Ar).
Mass spectrum, m/z (Irel, %): 469 (20) [M]+, 360 (25)
[C17H18N3O4S]+, 279 (48) [C13H13NO2S2]+, 278 (30)
[C13H12NO2S2]+. Haθdε-νO, %: C 58.57; H 4.63; N 8.65.
C23H23N3O4S2. Calculated, %: C 58.83; H 4.94; N 8.95.
M 469.59.
2-[3,4-Dimethyl-5-ethoxycarbonyl-1,3-thiazol-
2(3H)-ylidene]-1,2,4-dinitrophenylsulfanyl-(methyl)-
methylene]hydrazine (VIb). Yield 78%, mp 188–189°C
1
(from acetonitrile). H NMR spectrum, δ, ppm: 1.36 t
[3H, CH3CH2OC(O)], 2.18 s (3H, CH3) 2.30 s (3H,
CH3C=N), 3.25 s (3H, CH3N), 4.22 q [2H,
CH3CH2OC(O)], 7.31–8.80 m (3Harom). 13C NMR
spectrum, δ, ppm: 12.56 [CH3CH2OC(O)], 14.07 (CH3),
23.21 (CH3C=N), 31.27 (CH3N), 60.66
[CH3CH2OC(O)], 103.76 (C5), 146.09 (C4), 149.70 (C2),
161.58 [CH3CH2OC(O)], 166.90 (N=C–S), 120.02,
125.63, 136.04, 138.54, 146.28, 147.38 (Ar). Found, %:
C 43.49; H 4.21; N 15.55. C16H17N5O6S2. Calculated,
%: C 43.73; H 3.90; N 15.94. M 439.471.
8-Methyl-1-(4-methylphenyl)-9-phenyl-3,7-
bis(ethoxycarbonyl)-4,6-dithia-1,2,9-triazaspiro-
[4.4]nona-2,7-diene (IIIq). Yield 98%, mp 147–148.5°C
(from acetonitrile). 1H NMR spectrum, δ, ppm: 1.28 d.t
[6H, CH3CH2OC(O)], 2.03 s (3H, CH3), 2.37 s (3H,
CH3C6H4), 4.17 d.q [4H, CH3CH2OC(O)], 7.20–7.41 m
(9H, Ar). 13C NMR spectrum, δ, ppm: 13.81, 14.17
[CH3CH2OC(O)], 14.51 (CH3), 60.01, 61.83
[CH3CH2OC(O)], 114.31 (C5), 117.88 (C7), 137.45 (C8),
145.67 (C2), 159.05, 162.26 [CH3CH2OC(O)], 129.24,
129.46, 129.59, 132.40, 133.27, 135.30 (Ar). Mass
spectrum, m/z (Irel, %): 484 (100) [M]+, 280 (10)
[C13H14NO2S2]+, 205 (5) [C11H13N2O2]+. Found, %:
C 60.00; H 5.15; N 8.49. C24H25N3O4S2. Calculated, %:
C 59.61; H 5.21; N 8.69. M 483.61.
2-[3,4-Dimethyl-5-ethoxycarbonyl-1,3-thiazol-
2(3H)-ylidene]-1-[methoxycarbonyl(2-nitrophenyl-
sulfanyl)methylene]hydrazine (VIc). Yield 84%, mp
1
175–176°C (from acetonitrile). H NMR spectrum, δ,
ppm: 1.25 t [3H, CH3CH2OC(O)], 2.58 s (3H, CH3),
3.26 s (3H, CH3N), 3.36 s [3H, CH3OC(O)], 4.24 q [2H,
CH3CH2OC(O)], 7.24–8.08 m (4Harom). 13C NMR spec-
trum, δ, ppm: 12.53 [CH3CH2OC(O)], 14.02 (CH3), 31.83
(CH3N), 52.72 [CH3OC(O)], 60.97 [CH3CH2OC(O)],
106.55 (C5), 146.15 (C4), 148.51 (C2), 161.18
[CH3OC(O)], 162.74 [CH3CH2OC(O)], 171.91 (N=C–S),
125.01, 126.70, 131.88, 132.40, 132.45, 140.83 (Ar).
8-Methyl-1-phenyl-4-(4-chlorophenyl)-3,7-
bis(ethoxycarbonyl)-4,6-dithia-1,2,9-triazaspiro-
[4.4]nona-2,7-diene (IIIr). Yield 74%, mp 149–150°C
(from acetonitrile). 1H NMR spectrum, δ, ppm: 1.20 d.t
[6H, CH3CH2OC(O)], 2.07 s (3H, CH3), 4.04 q, 4.14 q
[4H, CH3CH2OC(O)], 7.41–7.65 m (9H, Ar). 13C NMR
spectrum, δ, ppm: 13.74, 13.95 [CH3CH2OC(O)], 14.92
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

BUDARINA et al.
1524
Found, %: C 45.87; H 4.43; N 12.46. C17H18N4O6S2.
Calculated, %: C 46.57; H 4.14; N 12.78. M 438.48.
ylidene]hydrazine (VIg). Yield 70%, mp 153–155°C
(from acetonitrile). H NMR spectrum, δ, ppm: 1.36 t
1
[3H, CH3CH2OC(O)], 2.23 s (3H, CH3), 2.52 s [3H,
CH3C(O)], 4.31 q [2H, CH3CH2OC(O)], 7.04–7.94 m
(9Harom). 13C NMR spectrum, δ, ppm: 13.76
[CH3CH2OC(O)], 14.12 (CH3), 26.12 [CH3C(O)], 61.17
[CH3CH2OC(O)], 106.25 (C5), 146.51 (C4), 147.45 (C2),
160.81 [CH3CH2OC(O)], 172.38 (N=C–S), 193.79
[CH3C(O)], 125.40, 126.84, 127.68, 129.41, 130.65,
131.81, 133.02,134.86, 146.93 (Ar). Mass spectrum,
m/z (Irel, %): 484 (10) [M]+, 330 (10) [C16H16N3O3S]+,
288 (100) [C14H14N3O2S]+. Found, %: C 54.99; H 4.41;
N 11.58. C22H20N4O5S2. Calculated, %: C 54.53; H 4.16;
N 11.56. M 484.56.
2-[5-Acetyl-4-methyl-3-phenyl-1,3-thiazol-2(3H)-
ylidene]-1-[methoxycarbonyl(2-nitrophenyl-
sulfanyl)methylene]hydrazine (VId). Yield 96%, mp
1
187–188°C (from acetonitrile). H NMR spectrum, δ,
ppm: 2.25 s (3H, CH3), 2.45 s [3H, CH3C(O)], 3.69 s
[3H, CH3OC(O)], 7.12–8.01 m (9H, Ar). 13C NMR
spectrum, δ, ppm: 14.39 (CH3), 29.39 [CH3C(O)], 52.41
[CH3OC(O)], 117.36 (C5), 141.44 (C4), 147.69 (C2),
162.06 [CH3OC(O)], 171.45 (N=C–S), 188.63
[CH3C(O)], 125.25, 127.38, 127.70, 129.33, 130.05,
132.11, 132.89, 135.04, 145.01 (Ar). Mass spectrum,
m/z (Irel, %): 471 (100) [M]+, 316 (35) [C15H14N3O3S]+.
Found, %: C 53.37; H 3.88; N 11.67. C21H18N4O5S2.
Calculated, %: C 53.61; H 3.86; N 11.91. M 470.53.
2-[4-Methyl-3-phenyl-5-ethoxycarbonyl-1,3-
thiazol-2(3H)-ylidene]-1-[(2-nitrophenylsulfanyl)-
ethoxycarbonylmethylene]hydrazine (VIh). Yield
2-[5-Acetyl-4-methyl-3-phenyl-1,3-thiazol-2(3H)-
ylidene]-1-[(2-nitrophenylsulfanyl)ethoxycarbonyl-
methylene]hydrazine (VIe). Yield 98%, mp 167–
167.5°C (from acetonitrile). 1H NMR spectrum, δ, ppm:
1.10 t [3H, CH3CH2OC(O)], 2.25 s (3H, CH3), 2.46 s
[3H, CH3C(O)], 4.04 q [2H, CH3CH2OC(O)], 7.19–
8.01 m (9H, Ar). 13C NMR spectrum, δ, ppm: 13.56
[CH3CH2OC(O)], 14.63 (CH3), 26.58 [CH3C(O)], 61.76
[CH3CH2OC(O)], 117.32 (C5), 142.89 (C4), 148.50 (C2),
161.34 [CH3CH2OC(O)], 171.28 (N=C–S), 189.25
[CH3C(O)], 125.45, 127.98, 128.32, 129.04, 129.56,
132.97, 133.43, 135.18, 145.51 (Ar). Mass spectrum,
m/z (Irel, %): 485 (100) [M]+, 330 (10) [C16H16N3O3S]+.
Found, %: C 54.72; H 4.41; N 11.43. C22H20N4O5S2.
Calculated, %: C 54.53; H 4.16; N 11.56. M 484.56.
1
92%, mp 163–164°C (from acetonitrile). H NMR
spectrum, δ, ppm: 1.14, 1.36 d.t [6H, CH3CH2OC(O)],
2.26 s (3H, CH3), 4.06, 4.28 d.q [4H, CH3CH2OC(O)],
7.18–7.99 m (9Harom). 13C NMR spectrum, δ, ppm: 13.56
[CH3CH2OC(O)], 14.05 (CH3), 60.62, 61.29
[CH3CH2OC(O)], 105.80 (C5), 146.45 (C4), 148.14 (C2),
160.54, 161.23 [CH3CH2OC(O)], 171.33 (N=C–S),
125.02, 127.39, 127.64, 129.21, 129.29, 130.06, 132.50,
132.61, 135.07, 142.38 (Ar). Mass spectrum, m/z (Irel,
%): 515 (100) [M]+, 360 (50) [C17H18N3O4S]+, 288 (25)
[C14H14N3O2S]+. Found, %: C 53.91; H 4.67; N 10.70.
C23H22N4O6S2. Calculated, %: C 53.69; H 4.31; N 10.89.
M 514.58.
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grants
nos. 00-03-32578 and 03-03-32919).
2-[4-Methyl-5-methoxycarbonyl-3-phenyl-1,3-
thiazol-2(3H)-ylidene]-1-[(2-nitrophenylsulfanyl)-
ethoxycarbonylmethylene]hydrazine (VIf). Yield
1
87%, mp 215–216°C (from acetonitrile). H NMR
REFERENCES
spectrum, δ, ppm: 1.1 t [3H, CH3CH2OC(O)], 2.24 s (3H,
CH3), 3.82 s [3H, CH3OC(O)], 4.04 q [2H,
CH3CH2OC(O)], 7.21–8.01 m (9Harom). 13C NMR
spectrum, δ, ppm: 13.55 [CH3CH2OC(O)], 13.76 (CH3),
52.25 [CH3OC(O)], 61.75 [CH3CH2OC(O)], 105.07 (C5),
142.69 (C4), 148.49 (C2), 161.32 [CH3CH2OC(O),
CH3OC(O)], 171.59 (N=C–S), 125.43, 127.94, 128.31,
129.09, 129.50, 132.95, 133.43, 135.13, 147.45 (Ar).
Mass spectrum, m/z (Irel, %): 501 (100) [M]+, 346 (20)
[C16H16N3O4S]+, 247 (15) [C12H11N2O2S]+. Found, %:
C 52.58; H 4.11; N 10.97. C22H20N4O6S2. Calculated,
%: C 52.79; H 4.03; N 11.19. M 500.56.
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