Synthesis of 5-alkyl-1,3,5-triazinan-2-ones and 5-alkyl-1,3,5-triazinane-2- thiones using Cu- and Sm-containing catalysts

Article abstract of DOI:10.1134/S1070428013060171

Efficient procedures have been developed for the synthesis of 5-alkyl-1,3,5-triazinan-2-ones and 5-alkyl-1,3,5-triazinane-2-thiones by reaction of urea (thiourea) with primary alkylamines and N,N,N′,N′- tetramethylmethylenediamine and by reaction of prima

Full text of DOI:10.1134/S1070428013060171

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 6, pp. 904–908. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © R.R. Khairullina, A.R. Geniyatova, A.G. Ibragimov, U.M. Dzhemilev, 2013, published in Zhurnal Organicheskoi Khimii, 2013,
Vol. 49, No. 6, pp. 918–922.
Synthesis of 5-Alkyl-1,3,5-triazinan-2-ones and 5-Alkyl-1,3,5-tri-
azinane-2-thiones Using Cu- and Sm-Containing Catalysts
R. R. Khairullina, A. R. Geniyatova, A. G. Ibragimov, and U. M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received October 17, 2012
Abstract—Efficient procedures have been developed for the synthesis of 5-alkyl-1,3,5-triazinan-2-ones and
5-alkyl-1,3,5-triazinane-2-thiones by reaction of urea (thiourea) with primary alkylamines and N,N,N′,N′-tetra-
methylmethylenediamine and by reaction of primary amines with N,N′-bis(dimethylaminomethyl)urea(thio-
urea) in the presence of Cu- and Sm-containing catalysts.
DOI: 10.1134/S1070428013060171
Interest in compounds of the 1,3,5-triazinane series
originates from their potential applications as pesti-
cides [1] and bioprotective agents for fuels and lubri-
cants [2]. Substituted 1,3,5-triazinane-2-thiones and
1,3,5-triazinan-2-ones exhibit antiviral and antibacte-
rial activity [3] and are also promising as intermediate
products in the synthesis of antitumor alkaloids [4, 5].
With a view to develop a new efficient procedure
for the synthesis of potentially practically important
5-alkyl-1,3,5-triazinan-2-ones and 5-alkyl-1,3,5-triazi-
nane-2-thiones [3–5] we examined the reaction of urea,
thiourea, and N-allylthiourea with primary alkylamines
(Alk = i-Pr, Bu, Pr, t-Bu, cyclohexyl, 2-hydroxyethyl)
and N,N,N′,N′-tetramethylmethylenediamine, catalyzed
by transition and rare-earth metal salts and complexes.
N,N,N′,N′-Tetramethylmethylenediamine was selected
as aminomethylating agent, taking into account its
efficiency in C–N bond-forming reactions with pri-
mary and secondary amines [10–13]. We presumed
that geminal diamines can be used in intermolecular
aminomethylation of ureas (thioureas) and primary
amines for the synthesis of 1,3,5-triazinan-2-ones and
1,3,5-triazinane-2-thiones.
One of the most popular procedures for the synthe-
sis of 5-substituted 1,3,5-triazinan-2-ones and 1,3,5-tri-
azinane-2-thiones is based on classical Mannich
aminomethylation of ureas (thioureas) with primary
amines and formaldehyde [6–8]; a modification of this
procedure, thermal condensation of primary amines
with bis(hydroxymethyl)urea preliminarily prepared
from formaldehyde and urea, is also known [6, 9].
These methods are characterized by some limitations
related to the use of aqueous formaldehyde [6–8],
elevated reaction temperature (90–100°C), and low
selectivity [9].
Urea reacted with N,N,N′,N′-tetramethylmethylene-
diamine and cyclohexylamine to give 5-cyclohexyl-
1,3,5-triazinan-2-one (Ia) [molar ratio C6H11NH2–
Scheme 1.
X
R
H
X
Me
Me
[Cu]
N
N
N
N
+
+ R'NH2
R
–2Me2NH
N
NH2
Me
Me
N
H
R'
Ia–Ic, IIa–IIf, IIIa, IIIb
[Cu] = CuCl2·2H2O; I, X = O, R = H; II, X = S, R = H; III, X = S, R = CH2=CHCH2;
R′ = cyclo-C6H11 (a), t-Bu (b), HO(CH2)2 (c), i-Pr (d), Bu (e), Pr (f).
904

SYNTHESIS OF 5-ALKYL-1,3,5-TRIAZINAN-2-ONES
905
Me2NCH2NMe2–urea–catalyst 10:20:10:0.5, 80°C,
CHCl3–EtOH (3 :1), 8 h] in 44 (CuCl2 ·2H2O), 32
(SmCl3·6H2O), 29 [Sm(NO3)3·6H2O], and 27% yield
(FeCl3·6H2O). In the absence of a catalyst the yield of
Ia did not exceed 10%. Using CuCl2·2H2O as catalyst
under the above conditions, by reactions of urea (thio-
ureas) with N,N,N′,N′-tetramethylmethylenediamine
and alkylamines we obtained triazinan-2-ones and tri-
azinane-2-thiones Ia–Ic, IIa–IIf, IIIa, and IIIb in 24–
46% yield (Scheme 1).
aminomethyl)urea (IV) was formed in no more than
30% yield. To improve the yield of IV, various cata-
lysts based on metal halides and complexes were tested
[SmCl3·6H2O, ZnCl2·2H2O, Sm(NO3)3·6H2O, YbF3,
EuCl3 ·6H2O, CuCl2 ·2 H2O, FeCl3 ·6 H2O, CoCl2,
MnCl2 ·2 H2O, Cp2ZrCl2, Cp2TiCl2, PdCl2], and the
effects of temperature, reaction time, and solvent
nature on the yield of IV were studied. Among the
above catalysts, the most active were SmCl3 ·6H2O
and Sm(NO3)3·6H2O: they ensured formation of IV in
98 and 97% yield, respectively (Scheme 2). When the
reaction was carried out in C6H14–EtOH or DMF–
EtOH, the yield of IV decreased to 60% against 98%
in CHCl3–EtOH or EtOAc–EtOH.
The structure of compounds I–III was proved by
1
their H and 13C NMR (including 2D), IR, and mass
1
spectra. The 13C and H NMR spectra of I–III con-
tained signals from methylene carbon atoms and
protons at δC 57.18–63.39 and δ 3.99–4.30 ppm. In the
2D HMBC spectra of these compounds we observed
cross peaks corresponding to interactions of C2 with
4-H and 6-H.
The structure of compounds IV and V was proved
by spectral data. The NCH2N fragment in IV and V
was represented by the following signals in the 1H and
13C NMR spectra: δC 63.56, δ 4.34–4.44 (IV),
δC 68.00, δ 3.65 ppm (V). The MALDI TOF mass
spectra contained the molecular ion peaks [M + K]+
with m/z 213.554 (IV) and 229.354 (V).
Presumably, the reaction involves initial amino-
methylation of urea (thiourea) with N,N,N′,N′-tetra-
methylmethylenediamine to produce N,N′-bis[(dimeth-
ylamino)methyl]urea(thiourea) IV or V, and the latter
reacts with primary alkylamines, yielding 1,3,5-triazi-
nan-2-ones or -thiones. In order to verify this assump-
tion we synthesized N,N′-bis[(dimethylamino)methyl]-
urea (IV) and N,N′-bis[(dimethylamino)methyl]thio-
urea (V) by aminomethylation of urea and thiourea
with N,N,N′,N′-tetramethylmethylenediamine by anal-
ogy with catalytic aminomethylation of compounds
having labile hydrogen atoms (terminal acetylenes and
thiols) with geminal diamines; these reactions were
reported to afford propargylamines [14, 15] or amino
sulfides [16, 17].
Compounds IV and V reacted with primary alkyl-
amines to give the corresponding 1,3,5-triazinan-2-
ones and 1,3,5-triazinane-2-thiones Ia–Ic and IIa–IId
(Scheme 2). The reactions were carried under the con-
ditions optimized for the reaction with cyclohexyl-
amine [amine–IV–SmCl3 ·6 H2O ratio 10:10:0.5,
EtOH, 80°C, 8 h]. The yield of 5-cyclohexyl-1,3,5-tri-
azinan-2-one (Ia) was ~39%, and the yields of the
other compounds I and II ranged from 23 to 41%. If
no catalyst was added, the yield of I and II did not
exceed 5%.
Taking into account published data [18–21], the
aminomethylation of primary amines with N,N′-bis-
[(dimethylamino)methyl]urea(thiourea) is likely to
begin with coordination of molecule IV or V to the
In the model aminomethylation of urea with
N,N,N′,N′-tetramethylmethylenediamine in the absence
of a catalyst (EtOH, 20°C, 1.5 h) N,N′-bis(dimethyl-
Scheme 2.
X
X
Me
Me
Me
Me
SmCl3·6H2O
N
N
N
N
N
N
+
2
H
H
–Me2NH
H2N
NH2
Me
Me
Me
Me
IV, V
X
H
H
N
N
R'NH2, SmCl3·6H2O
–2Me2NH
N
R'
Ia–Ic, IIa–IId
I, IV, X = O; II, V, X = S; R′ = cyclo-C6H11 (a), t-Bu (b), HO(CH2)2 (c); i-Pr (d).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

KHAIRULLINA et al.
906
Scheme 3.
X
X
X
H
H
Me
Catalyst
R'NH2
Me
Me
Me
Me
CH2
N
R'
··
N
N
N
N
N
N
N
N
N
N
N
Me
H
H
H
H
H
H
Me
Me
Me
Cat
Me
Me
··
N
Cat
Me
X
X
X
H
R'
Me
N
N
H
N
HN
NH
H
··
N
N
N
N
–Me2NH
–Cat, –Me2NH
CH2
Me
H
Me
H
H
N
Cat
R'
· ·
R'
N
Cat
Me
central metal ion of the catalyst. The subsequent
nucleophilic addition of alkylamine molecule to the
carbocation thus formed generates new C–N bonds
and leads to the formation of 1,3,5-triazinane ring
(Scheme 3).
ylmethylenediamine. A mixture of 10 mmol of alkyl-
amine, 20 mmol of N,N,N′,N′-tetramethylmethylenedi-
amine, and 0.5 mmol of CuCl2·2H2O was stirred for
5 min. Urea, 10 mmol, was then added, and the mix-
ture was heated to 80°C and stirred for 8 h at that
temperature. The product was isolated by column
chromatography on silica gel.
We can conclude that the aminomethylation of
primary alkylamines with N,N′-bis[(dimethylamino)-
methyl]urea(thiourea) in the presence of Sm-contain-
ing catalyst ensures successful selective synthesis of
5-alkyl-1,3,5-triazinan-2-ones and 5-alkyl-1,3,5-tri-
azinane-2-thiones.
b. Aminomethylation of alkylamines with N,N′-bis-
[dimethylaminomethyl]urea(thiourea). A mixture of
10 mmol of N,N′-bis[(dimethylamino)methyl]urea
(thiourea), 3 ml of ethanol, 0.5 mmol of SmCl3·6H2O,
and 10 mmol of alkylamine was stirred for 8 h at 80°C.
The product was isolated by column chromatography
on silica gel.
EXPERIMENTAL
The progress of reactions was monitored by TLC
5-Cyclohexyl-1,3,5-triazinan-2-one (Ia). Yield
44% (a), 39% (b); colorless crystals, mp 204–205°C
(205°C [6]), Rf 0.63 (ethanol–acetone, 1:1). H NMR
1
on Sorbfil plates. The H and 13C NMR spectra were
1
recorded on a Bruker Avance-400 spectrometer at
400.13 and 100.62 MHz, respectively, using DMSO-d6
as solvent and reference (δ 2.50, δC 39.50 ppm). The
IR spectra were measured on a Bruker Vertex 70v
spectrometer from samples dispersed in mineral oil.
The mass spectra were obtained on a Bruker Autoflex
III MALDI TOF spectrometer (Germany) using α-cy-
ano-4-hydroxycinnamic acid and 2,5-dihydroxyben-
zoic acid as matrices; samples were prepared by the
dried drop technique in chloroform (1:10). The ele-
mental compositions were determined on a Carlo Erba
1106 analyzer, and the melting points were measured
on an PHMK 80/2617 melting point apparatus. Indivi-
dual substances were isolated by column chromatog-
raphy on KSK silica gel (50–160 μm).
spectrum, δ, ppm: 1.17 m (5H, 8-H, 9-H, 10-H, 11-H,
12-H), 1.55 s (1H, 10-H), 1.70 s (2H, 9-H, 11-H),
1.89 br.s (2H, 8-H, 12-H), 2.54 br.s (1H, 7-H), 4.28 s
(4H, 4-H, 6-H), 6.21 s (2H, NH). 13C NMR spectrum,
δC, ppm: 25.08 (C9, C11), 25.96 (C10), 31.05 (C8, C12),
54.20 (C7), 58.48 (C4, C6), 155.69 (C2). Mass spec-
trum: m/z 184.444 (Irel 100%) [M + H]+. Calculated:
M 183.251.
5-tert-Butyl-1,3,5-triazinan-2-one (Ib). Yield 37%
(a), 34% (b); colorless crystals, mp 182–184°C (181–
1
182°C [22]), Rf 0.66 (ethanol–acetone, 1:1). H NMR
spectrum, δ, ppm: 1.12 s (9H, t-Bu), 4.10 s (4H, 4-H,
6-H), 6.23 br.s (2H, NH). 13C NMR spectrum, δC, ppm:
28.71 [C(CH3)3], 53.50 [C(CH3)3], 57.18 (C4, C6),
156.12 (C2). Mass spectrum: m/z 158.446 (Irel 100%)
[M + H]+. Calculated: M 157.214.
5-Alkyl-1,3,5-triazinan-2-ones Ia–Ic and 5-alkyl-
1,3,5-triazinane-2-thiones IIa–IIf, IIIa, and IIIb
(general procedures). a. Three-component condensa-
tion of alkylamine with urea and N,N,N′,N′-tetrameth-
5-(2-Hydroxyethyl)-1,3,5-triazinan-2-one (Ic).
Yield 25% (a), 23% (b); colorless crystals, mp 173–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

SYNTHESIS OF 5-ALKYL-1,3,5-TRIAZINAN-2-ONES
907
176°C (176–177°C [6]), Rf 0.45 (ethanol–acetone,
1:1). H NMR spectrum, δ, ppm: 2.65 t (2H, 5-CH2),
(acetone). IR spectrum, ν cm–1: 3188, 2854–2925,
1609, 1556, 1456, 1391, 1301, 1206, 992, 666.
1H NMR spectrum, δ, ppm: 0.85 m (3H, CH3), 1.26 m
(2H, CH3CH2), 1.37 m (2H, 5-CH2CH2), 2.47 m (2H,
5-CH2), 3.99 s (4H, 4-H, 6-H), 7.06 br.s (2H, NH).
13C NMR spectrum, δC, ppm: 14.20 (CH3), 20.32
(CH3CH2), 29.64 (5-CH2CH2), 49.85 (5-CH2), 61.32
(C4, C6), 175.57 (C2). Mass spectrum: m/z 174.342
(Irel 100%) [M + H]+. Calculated: M 173.280.
1
3.50 br.s (2H, CH2OH), 4.00 s (4H, 4-H, 6-H),
4.78 br.s (1H, OH), 6.23 s (2H, NH). 13C NMR spec-
trum, δC, ppm: 52.34 (5-CH2), 59.95 (CH2OH), 61.87
(C4, C6), 155.74 (C2). Mass spectrum: m/z 146.404
(Irel 100%) [M + H]+. Calculated: M 145.160.
5-Cyclohexyl-1,3,5-triazinane-2-thione (IIa).
Yield 46% (a), 41% (b); colorless crystals, mp 172–
174°C (172–176°C [6]), Rf 0.76 (ethanol–acetone,
5-Propyl-1,3,5-triazinane-2-thione (IIf). Yield
24%, colorless crystals, mp 135–137°C, Rf 0.61
(acetone). IR spectrum, ν, cm–1: 3187, 2854–2925,
1609, 1556, 1376, 1301, 1239, 1063, 955, 667.
1H NMR spectrum, δ, ppm: 0.83 t (3H, CH3), 1.41 q
(2H, CH3CH2, J = 6.8 Hz), 2.44 t (2H, 5-CH2), 3.99 s
(4H, 4-H, 6-H), 7.88 br.s (2H, NH). 13C NMR spec-
trum, δC, ppm: 11.96 (CH3), 20.79 (CH3CH2), 52.08
(5-CH2), 61.33 (C4, C6), 175.55 (C2). Mass spectrum:
m/z 160.405 (Irel 100%) [M + H]+. Found, %: C 45.24;
H 8.02; N 26.33; S 20.41. C6H13N3S. Calculated, %:
C 45.25; H 8.25; N 26.36; S 20.14. M 159.254.
1
1:1). H NMR spectrum, δ, ppm: 1.15 m (5H, 8-H,
9-H, 10-H, 11-H, 12-H), 1.53 s (1H, 10-H), 1.70 s (2H,
9-H, 11-H), 1.85 br.s (2H, 8-H, 12-H), 2.45 br.s (1H,
7-H), 4.09 s (4H, 4-H, 6-H), 7.94 s (2H, NH).
13C NMR spectrum, δC, ppm: 25.01 (C9, C11), 25.89
(C10), 30.88 (C8, C12), 55.22 (C7), 58.62 (C4, C6),
176.56 (C2). Found, %: C 54.17; H 8.86; N 20.99;
S 15.98. C9H17N3S. Calculated, %: C 54.23; H 8.60;
N 21.08; S 16.09.
5-tert-Butyl-1,3,5-triazinane-2-thione (IIb). Yield
35% (a), 28% (b); colorless crystals, mp 169–172°C
(175–177°C [7]), Rf 0.79 (ethanol–acetone, 1:1).
1H NMR spectrum, δ, ppm: 1.10 s (9H, t-Bu), 4.11 s
(4H, 4-H, 6-H), 7.98 br.s (2H, NH). 13C NMR spec-
trum, δC, ppm: 28.44 [C(CH3)3], 53.71 [C(CH3)3],
57.19 (C4, C6), 176.78 (C2). Mass spectrum: m/z
174.380 (Irel 100%) [M + H]+. Calculated: M 173.280.
1-Allyl-5-cyclohexyl-1,3,5-triazinane-2-thione
(IIIa). Yield 43%, colorless crystals, mp 107–110°C,
Rf 0.33 (ethyl acetate–hexane, 2:1). IR spectrum, ν,
cm–1: 3243, 2780–2958, 1641, 1520, 1463, 1303, 1212,
1
1113, 993, 645. H NMR spectrum, δ, ppm: 1.11 m
(5H, 8-H, 9-H, 10-H, 11-H, 12-H), 1.53 s (1H, 10-H),
1.67 s (2H, 9-H, 11-H), 1.83 br.s (2H, 8-H, 12-H),
2.43 br.s (1H, 7-H), 4.11 s (2H, 4-H), 4.22 s (2H, 6-H),
4.27 s (2H, 1-CH2), 5.18 m (2H, =CH2), 5.77 m (1H,
CH=), 7.91 s (1H, NH). 13C NMR spectrum, δC, ppm:
24.92 (C9, C11), 25.74 (C10), 30.80 (C8, C12), 52.20
(1-CH2), 55.63 (C7), 58.27 (C4), 63.39 (C6), 118.18
(=CH2), 133.45 (=CH), 177.11 (C2). Mass spectrum:
m/z 240.435 (Irel 100%) [M + H]+. Found, %: C 60.12;
H 8.91; N 17.54; S 13.43. C12H21N3S. Calculated, %:
C 60.21; H 8.84; N 17.55; S 13.40. M 239.381.
5-(2-Hydroxyethyl)-1,3,5-triazinane-2-thione
(IIc). Yield 29% (a), 25% (b); colorless crystals,
mp 160–162°C (162°C [6]), Rf 0.71 (ethanol–acetone,
1
1:1). H NMR spectrum, δ, ppm: 2.59 t (2H, 5-CH2),
3.51 m (2H, CH2OH), 4.00 s (4H, 4-H, 6-H), 4.57 br.s
(1H, OH), 8.00 s (2H, NH). 13C NMR spectrum, δC,
ppm: 53.04 (5-CH2), 60.01 (CH2OH), 62.12 (C4, C6),
175.89 (C2). Mass spectrum: m/z 162.416 (Irel 100%)
[M + H]+. Calculated: M 161.226.
5-Isopropyl-1,3,5-triazinane-2-thione (IId). Yield
25% (a), 23% (b); colorless crystals, mp 153–155°C,
Rf 0.74 (ethanol–acetone, 1:1). IR spectrum, ν, cm–1:
3205, 2854–2924, 1555, 1539, 1384, 1302, 1203,
1038, 721, 666. 1H NMR spectrum, δ, ppm: 1.02 s and
1.04 s (3H each, CH3), 2.78 m (1H, 5-CH), 4.08 s (4H,
4-H, 6-H), 7.88 br.s (2H, NH). 13C NMR spectrum, δC,
ppm: 21.23 (CH3), 47.49 (5-CH), 59.08 (C4, C6),
176.19 (C2). Mass spectrum: m/z 160.360 (Irel 100%)
[M + H]+. Found, %: C 45.22; H 8.04; N 26.40;
S 20.34. C6H13N3S. Calculated, %: C 45.25; H 8.25;
N 26.38; S 20.12. M 159.254.
1-Allyl-5-tert-butyl-1,3,5-triazinane-2-thione
(IIIb). Yield 32%, colorless crystals, mp 65–68°C,
Rf 0.38 (ethyl acetate–hexane, 2:1). IR spectrum, ν,
cm–1: 3204, 2866–3004, 1695, 1638, 1538, 1310, 1217,
1
1137, 996, 648. H NMR spectrum, δ, ppm: 1.17 s
(9H, t-Bu), 4.30 m (4H, 4-H, 6-H), 4.41 d (2H, 1-CH2,
J = 6 Hz), 5.26 m (2H, =CH2), 5.91 m (1H, =CH),
7.25 br.s (1H, NH). 13C NMR spectrum, δC, ppm:
28.42 [C(CH3)3], 53.22 (1-CH2), 54.47 [C(CH3)3],
57.21 (C4), 61.68 (C6), 118.60 (=CH2), 132.60 (=CH),
177.76 (C2). Mass spectrum: m/z 212.377 (Irel 100%)
[M – H]+. Found, %: C 56.23; H 9.07; N 19.64;
S 15.06. C10H19N3S. Calculated, %: C 56.30; H 8.98;
N 19.70; S 15.02. M 213.344.
5-Butyl-1,3,5-triazinane-2-thione (IIe). Yield
25%, colorless crystals, mp 166–170°C, Rf 0.64
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KHAIRULLINA et al.
908
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Ibragimov, A.G., Russ. J. Org. Chem., 2011, vol. 47,
p. 161.
16. Khairullina, R.R., Akmanov, B.F., Tyumkina, T.V.,
Kunakova, R.V., and Ibragimov, A.G., Russ. J. Org.
Chem., 2012, vol. 48, p. 175.
17. Khairullina, R.R., Akmanov, B.F., Kunakova, R.V., and
Ibragimov, A.G., Russ. J. Org. Chem., 2012, vol. 48,
p. 902.
N,N′-Bis[(dimethylamino)methyl]urea (IV) [23].
Yield 99%, viscous resinous material, nD20 = 1.4770,
1
Rf 0.33 (ethanol–acetone, 1:1). H NMR spectrum, δ,
ppm: 2.67 br.s (12H, CH3), 4.34 br.s and 4.44 br.s (2H
each, CH2), 8.16 br.s (2H, NH). 13C NMR spectrum,
δC, ppm: 41.79 (CH3), 63.56 (CH2), 159.83 (C=O).
Mass spectrum: m/z 213.554 (Irel 100%) [M + K]+.
Found, %: C 48.53; H 10.24; N 31.98. C7H18N4O. Cal-
culated, %: C 48.25; H 10.42; N 32.15. M 174.244.
N,N'-Bis[(dimethylamino)methyl]thiourea (V).
Yield 99%, colorless amorphous substance, mp 77–
80°C, Rf 0.46 (ethanol–acetone, 1:1). IR spectrum, ν,
cm–1: 3437, 2923–2853, 1619, 1463, 1383, 1095–1072,
1
845–738. H NMR spectrum, δ, ppm: 2.26 br.s (12H,
CH3), 3.65 br.s (4H, CH2), 8.58 br.s (2H, NH).
13C NMR spectrum, δC, ppm: 41.81 (CH3), 68.00
(CH2), 184.89 (C=S). Mass spectrum: m/z 229.354
(Irel 100%) [M + K]+. Found, %: C 44.02; H 9.76;
N 29.49; S 16.73. C7H18N4S. Calculated, %: C 44.18;
H 9.53; N 29.44; S 16.85. M 190.311.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 11-03-00101-a, 11-03-97011-r_Povolzh’e_a).
18. Tramontini, M. and Angiolini, L., Tetrahedron, 1990,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013