α-Thioureidoalkylation of urea heteroanalogs

Article abstract of DOI:10.1007/s11172-009-0266-1

α-Thioureidoalkylation of urea heteroanalogs such as thiosemicarbazide, amino-guanidine, sulfamide, and sulfonamides with 4,5-dihydroxyimidazolidine-2-thiones has been studied. Previously unknown 4,5-bis[thiosemicarbazido(guanidinoamino)]imidazolidine-2-thiones, 5,7-dialkylperhydroimidazo[4,5- e][1,2,4]triazine-3,6-dithiones, 4,6-diethyl-5(3H)-thioxotetrahydro-1 H-imidazo[4,5- c][1,2,5]thiadiazole 2,2-dioxide, and 1,3-dialkyl-4-[guanidinoimino(arylsulfonylimino)]imidazolidine- 2-thiones have been synthesized.

Full text of DOI:10.1007/s11172-009-0266-1

Russian Chemical Bulletin, International Edition, Vol. 58, No. 9, pp. 1945—1954, September, 2009
1945
αꢀThioureidoalkylation of urea heteroanalogs
G. A. Gazieva,a Yu. V. Nelyubina,b A. N. Kravchenko,a A. S. Sigachev,a
I. V. Glukhov,b M. I. Struchkova,a K. A. Lyssenko,b and N. N. Makhovaa
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: gaz@server.ioc.ac.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5508. Eꢀmail: kostya@xrlab.ineos.ac.ru
αꢀThioureidoalkylation of urea heteroanalogs such as thiosemicarbazide, aminoꢀ
guanidine, sulfamide, and sulfonamides with 4,5ꢀdihydroxyimidazolidineꢀ2ꢀthiones has been
studied. Previously unknown 4,5ꢀbis[thiosemicarbazido(guanidinoamino)]imidazolidineꢀ
2ꢀthiones, 5,7ꢀdialkylperhydroimidazo[4,5ꢀe][1,2,4]triazineꢀ3,6ꢀdithiones, 4,6ꢀdiethylꢀ
5(3H)ꢀthioxotetrahydroꢀ1Hꢀimidazo[4,5ꢀc][1,2,5]thiadiazole 2,2ꢀdioxide, and 1,3ꢀdialkylꢀ
4ꢀ[guanidinoimino(arylsulfonylimino)]imidazolidineꢀ2ꢀthiones have been synthesized.
Key words: αꢀthioureidoalkylation, thiosemicarbazide, aminoguanidine, sulfamide,
4,5ꢀdihydroxyimidazolidineꢀ2ꢀthiones, 4,5ꢀbis[thiosemicarbazido(guanidinoamino)]imidazolꢀ
idineꢀ2ꢀthiones, 5,7ꢀdialkylperhydroimidazo[4,5ꢀe][1,2,4]triazineꢀ3,6ꢀdithiones, 4,6ꢀdiethylꢀ
5(3H)ꢀthioxotetrahydroꢀ1Hꢀimidazo[4,5ꢀc][1,2,5]thiadiazole 2,2ꢀdioxide, 1,3ꢀdialkylꢀ
4ꢀ[guanidinoimino(arylsulfonylimino)]imidazolidineꢀ2ꢀthiones.
αꢀUreidoalkylation of ureas and their analogs with
4,5ꢀdihydroxyimidazolidinꢀ2ꢀones have been carefully
studied in our laboratories.1—5 αꢀUreidoalkylation of
thiosemicarbazide, aminoguanidine, and sulfamides yielded
5,7ꢀdialkylꢀ3ꢀthioxoperhydroimidazo[4,5ꢀe][1,2,4]triꢀ
azinꢀ6ꢀones (1),2 4,5ꢀbis(thiosemicarbazido)ꢀ and 4,5ꢀbisꢀ
(guanidinoamino)imidazolidinꢀ2ꢀones (2, 3),2 4ꢀ(guaniꢀ
dinoamino)ꢀ and 4ꢀ(sulfonylimino)imidazolidinꢀ2ꢀones
(4—6),2—4 and 5(3H)ꢀthioxotetrahydroꢀ1Hꢀimidazo[4,5ꢀc]ꢀ
[1,2,5]thiadiazole 2,2ꢀdioxides (7).5
Only few examples of the synthesis of glycoluril
heteroanalogs by condensation of ureas with 4,5ꢀdihydroxyꢀ
imidazolidineꢀ2ꢀthiones (DHIT) have been published.6,7
The present work is devoted to αꢀthioureidoalkylation
of urea heteroanalogs (thiosemicarbazide, aminoguaniꢀ
dine, sulfamide, and sulfonamides) with DHIT 8a—c and
development of the synthetic methods towards novel
imidazolidineꢀ2ꢀthione derivatives.
Thioureidoalkylation of thiosemicarbazide with DHIT
8a—c under conditions described previously2 for the synꢀ
thesis of compounds 2 (water, pH 2, 80 °C, DHIT : thioꢀ
semicarbazide = 1 : 2) resulted in 4,5ꢀbis(thiosemiꢀ
carbazido)imidazolidineꢀ2ꢀthiones 9a—c in 70—75%
X = S (2), NH2+Cl– (3)
yields and perhydroimidazo[4,5ꢀe][1,2,4]triazineꢀ3,6ꢀdiꢀ
thiones 10a—c (Scheme 1). Imidazotriazines 10b,c were
isolated in 5—15% yields. Together with signals of the
main product 9a, the signals that were attributed to comꢀ
pound 10a (4.94 and 5.25 (both d, each 1 H, CH—CH,
J = 8.5 Hz); 5.69 (br.s, 1 H, NH); 7.29 (br.s, 2 H, 2 NH);
8.87 (br.s, 1 H, NH); 9.42 (br.s, 1 H, NH)) have been
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1884—1892, September, 2009.
1066ꢀ5285/09/5809ꢀ1945 © 2009 Springer Science+Business Media, Inc.

1946
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009
Gazieva et al.
Scheme 1
8—13: R = H (a), Me (b), Et (c)
15, 16: R = Me (a), Et (b)
18: R´ = Me, R = H (a), Me (b); R´ = Et; R = H (c), Me (d)

αꢀThioureidoalkylation of urea heteroanalogs
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009 1947
1
observed in the H NMR spectrum of the reaction mixꢀ
4,5ꢀbis(guanidinoamino)imidazolidineꢀ2ꢀthione dihydroꢀ
chloride 13a in 80—83% yield (Scheme 1). The reaction
of 1,3ꢀdimethylꢀsubstituted DHIT 8b with aminoguaniꢀ
dine in water or methanol resulted in compound 13b in
59—62% and 52—55% yields, respectively. DHIT 8b
gave also compound 12b in the yield of about 35%. The
reaction of imidazolidinethione 8c in water furnished an
unknown compound. Its 1H NMR spectrum exhibited
multiplets at δ 1.12, 3.70, and 3.91, a singlet at δ 4.55, and
broadened singlets at δ 7.40 and 10.83 with 6 : 2 : 2 : 2 : 4 : 1
integral intensity ratio. According to the published data
for compound 4,2 the structure of this novel compound
was assigned as 4ꢀguanidinoiminoꢀ1,3ꢀdiethylimidazolꢀ
idineꢀ2ꢀthione hydrochloride (14). Besides, 2ꢀthiohydanꢀ
toin 12c also formed as the reaction product.
The compositions and structures of compounds 13a,b
were confirmed by the data from 1H and 13C NMR specꢀ
troscopy and elemental analysis and, in the case of 13b,
Xꢀray diffraction analysis. An additional interest in salt
13b (Fig. 1) is due to the fact that in the crystallization
of the racemate of its oxygen analog, 1,3ꢀdimethylꢀ
4,5ꢀbis(guanidinoamino)imidazolidinꢀ2ꢀone hydrochloꢀ
ride (3, R = Me),13 spontaneous separation (space group
P61) was observed. It is known that the spontaneous sepaꢀ
ration occurs provided the crystal of the corresponding
compound contained homochiral molecule associates14
formed preferably by strong hydrogen bonds.5 Indeed,
in compound 3 (R = Me) dications associated in homoꢀ
chiral chains16 by N—H...O hydrogen bonds (N...O
2.792(8)—2.806(8) Å). The anions and the water molꢀ
ecules formed the threeꢀdimensional Hꢀbonded backbone
by crossꢀlinking the mentioned homochiral aggregates.
ture concentrated to dryness. However, the isolation of
triazine 10a in the individual state failed.
OꢀMethylation of DHIT 8a occurred under condiꢀ
tions that were optimal for the formation of the bicyclic
compounds 1 (DHIT : thiosemicarbazide = 1 : 1, refluxing
in methanol in the presence of catalytic amounts of HCl,
portionwise addition of thiosemicarbazide)2 to furnish the
corresponding ether 11 in 60—65% yields. Significant
amount of DHIT 8a—c is converted to 2ꢀthioxoimidazolꢀ
idinꢀ4ꢀones 12a—c (up to 20% of 12a and 70% of 12b,c).
From the reaction mixtures, compounds 9b,c (in 10—30%
yields) and nonconsumed thiosemicarbazide were also
isolated. Portionwise addition of thiosemicarbazide to
DHIT 8a with water or MeCN as solvents resulted in
compound 9a in 62—65% or 57—59% (in respect of
thiosemicarbazide), respectively.
1
The H NMR spectra of 4,5ꢀdisubstituted derivatives
9a—c exhibited the signals for the CH—CH protons in
the range of δ 4.09—4.41. The signals of imidazolidine
fragments were observed in their typical shift ranges (sinꢀ
glets at δ ~7.40 (N—H), singlets at δ ~2.96 (N—Me), and
multiplets in the range of δ 0.92—0.96 and 3.15—3.95
(NEt)). The broadened signals in the range of δ 5.53—8.78
with the intensity ratio 1 : 1 : 1 : 1 were also observed.
Taking in the account the published data on the chemical
shifts of 4,5ꢀdi(thiosemicabazido)imidazolidinꢀ2ꢀones,2
these signals could be attributed to the hydrazine NHꢀ
protons (δ 5.67—6.22 and 8.28—8.78) or the amide NH2ꢀ
protons (δ 7.52—7.92) in the thiosemicarbazide moiety.
The amide NH2ꢀprotons appeared as two singlet signals.
The 1H NMR spectra of the bicyclic compounds 10b,c
contained singlet signals for the Nꢀmethyl groups at
δ 2.94 and 2.97, multiplets for Nꢀethyl groups in the range
of δ 1.03—1.12 and 3.25—3.75, the signals for the bridgꢀ
ing methine protons (δ 4.90—5.25, AB system), and
the signals of three NHꢀgroups (δ 5.8—5.9, 8.9—9.0,
and 9.5—9.6).
S(1)
C(16)
C(2)
N(1)
N(3)
The formation of dimethyl ether 11 has been observed
previously in the reaction of DHIT 8a with ureas in methaꢀ
nol in the presence of HCl. This reaction resulted in a
significant decrease in the yields of the target tetrahydroꢀ
imidazo[4,5ꢀd]imidazoleꢀ2,5ꢀdiones. Ether 11 was obꢀ
tained by refluxing compound 8a in methanol for 30 min
in the presence of an ionꢀexchange resin as a catalyst in
80% yield.6 In the present paper, the similar result
was obtained with the use of HCl instead of the ionꢀ
exchange resin.
C(5)
C(17)
N(12)
C(4)
N(14)
N(7)
N(11)
C(13)
N(9)
N(6)
N(15)
C(8)
N(10)
Cl(2)
O(1W)
2ꢀThioxoimidazolidinꢀ4ꢀones 12a—c have previously
been synthesized from amino acid derivatives and thioꢀ
urea8 or alkyl isothiocyanates9,10 and their structures were
confirmed by the data from IR9,11,12 (12a—c) and NMR
spectroscopy8,9 (12a,b).
Cl(1)
Fig. 1. General view of the formula unit of compound 13b
with the presentation of atoms as ellipsoids of thermal vibrations
(p = 50%).
The αꢀthioureidoalkylation of aminoguanidine with
unsubstituted DHIT 8a proceeded only in water to give

1948
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009
Gazieva et al.
Therefore, it was of interest to find whether this cationꢀ
cation pattern remained on going from the C=O group to
the C=S group that forms the hydrogen bonds that differ
from those with the carbonyl group in the number and
strength.17,18
crystal of 4,5ꢀdihydroxyimidazolidineꢀ2ꢀthione19 is
–0.30 e. For comparison, for the oxo analog the partial
charge on the oxygen atom in the C=O group is –0.82 e;
hence it formed stronger hydrogen bonds, which is in
good agreement with the published data.7,18 The correꢀ
sponding value for the water in the crystal of piperidineꢀ
2ꢀcarboxylic acid tetrahydrate20 is –1.4 e; the charge on
the chlorine atom is –0.78 e according to the calculations
of the close ion pair of guanidinium chloride (N…Cl
3.256—3.357 Å).21 Therefore, the possibility of the sponꢀ
taneous separation of salt 3 (R = Me) and the lack of this
property in the case of 13b, is due mainly to the electroꢀ
static reasons. It should be noted that the thiocarbonyl
group in the crystal of compound 13b interacts with the
guanidine (NH)C(8)(NH2)2 fragment of the neighboring
dication in a C=S...πꢀtype (S...C 3.446(3) Å) with the
formation of chiral chains. In turn, dications of the neighꢀ
boring associate bonded to the first one by stronger
hydrogen bonds N—H...Cl and N—H...O exhibited
opposite chirality. As a result, salt 13b crystallized in a
centrosymmetric space group without spontaneous
separation.
It is only compounds 8b,c that react with sulfamide.
The condensation was carried out in water at pH 1—6
and at 60—80 °C. The highest yields (33—36%) of
N,N´ꢀbis(1,3ꢀdialkylꢀ2ꢀthioxoimidazolidinꢀ4ꢀylidene)ꢀ
sulfamides 15a,b (see Scheme 1) were obtained by refluxꢀ
ing the reaction mixture in methanol in the presence of
HCl for 1 h. Reduction of the reaction time to 30 min
allowed isolation and identification of Nꢀ(1,3ꢀdialkylꢀ
2ꢀthioxoimidazolidinꢀ4ꢀylidene)sulfamides 16a,b. Under
the described conditions, along with the compounds
16a,b, diimines 15a,b were formed as minor products in
5—10% yields. Recrystallization from methanol resulted
in partial conversion of compounds 16a,b into 15a,b and
sulfamide.
Analysis of the geometry of dication 13b indicated
that replacement of the oxygen atom by the sulfur atom
resulted in the insignificant lengthening of the C(2)—N
bonds (the difference did not exceed 0.03 Å) and in the
change in the heterocycle conformation from the flatꢀ
tened twist to the envelope (mean deviation of the C(5)
atom is 0.24 Å). Similar results have previously been obꢀ
served in 4,5ꢀdihydroxyimidazolidineꢀ2ꢀthione and its
oxo analog.19 The difference in the bond lengths of
aminoguanidine fragments for compounds 13b and 3
(R = Me) is on average 0.005 Å. Although the replaceꢀ
ment of the C=O group by the thiocarbonyl group in
compound 13b does not affect the dication geometry, this
compound crystallized as a racemate (space group Pbca),
which is obviously due to the influence of the environꢀ
ment. The study of the package of compounds 13b and 3
(R = Me) in the crystal shows that these compounds are
hydrates. Salt 13b contained one molecule of the solvatꢀ
ing water per dication, while the molecule of compound 3
(R = Me) crystallized with two molecules of the solvating
water. This difference results in a change in the nature of
bonding in hydrochloride sublattice. In the crystal of comꢀ
pound 3 (R = Me), the chloride anions and the water
molecules form a nonplanar fourꢀmembered ring (O...Cl
3.049(7)—3.232(7) Å), while in the crystal of the thioꢀ
analog they formed only half of the ring Cl(H2O)Cl (O...Cl
3.177(3)—3.286(3) Å). On the one hand, it could be
assumed that this difference is responsible for a different
type of the supramolecular organization, hence for the
lack of spontaneous separation in the case of the salt 13b.
Thus in the crystal of 13b no cationꢀcation hydrogen bonds
are present, instead the dication formed nine bonds
with the chloride anions (N…Cl 3.217(2)—3.387(2) Å)
and three bonds with the water molecules (N...O
2.835(3)—3.190(3) Å); the thiocarbonyl group is not
involved in these interactions. On the other hand, in
compound 3 (R = Me) the number of the N—H...Cl
bonds (N...Cl 3.279(7)—3.423(7) Å) reduced to 6, whereas
the number of the N—H...O bonds (N…O 2.882(7)—
2.943(7) Å) increased only by one (four in total), which is
due to the cationꢀcation bonding. Consequently, the difꢀ
ference in the number of the solvating water molecules in
compounds 3 (R = Me) and 13b is not the main reason
for the lack of the cationꢀcation hydrogen bonds in the
molecule of the thiocarbonyl derivative. The latter feature
is obviously due to the fact that the oxygen atoms and
the chlorine anions are stronger proton acceptors than the
sulfur atom of the thiocarbonyl group, which followed
from the electronegativity values of the corresponding
elements. Thus the charge on the sulfur atom in the
Scheme 2
15,15´: R1 = Me (a), Et (b); R2
=
16,16´: R1 = Me (a), Et (b); R2 = NH2
18,18´: R1 = Me (a, b), Et (c, d); R2 = Ph (a, c), C6H4Meꢀp (b, d)

αꢀThioureidoalkylation of urea heteroanalogs
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009 1949
Table 1. Yields and physicochemical properties of compounds synthesized
Comꢀ
pound
Yield
(%)
M.p./°С
Found
Calculated
Molecular
formula
(%)
C
H
N
S
Cl
—
9a
73—75
72—74
70—72
5—10
243—245
(decomp.)
197—199
(decomp.)
220—222
(decomp.)
206—208
(decomp.)
238—240
21.45
21.42
27.28
27.26
32.16
32.13
33.19
33.16
39.19
39.16
37.04
37.02
48.78
4.35
4.31
5.33
5.23
6.02
5.99
5.12
5.10
6.20
6.16
6.25
6.21
7.07
39.91
39.96
36.31
36.33
33.31
33.30
32.22
32.23
28.52
28.54
17.25
17.27
16.26
34.23
34.30
31.13
31.18
28.53
28.58
29.43
29.51
26.09
26.13
19.73
19.76
18.55
C5H12N8S3
C7H16N8S3
C9H20N8S3
C6H11N5S2
C8H15N5S2
C5H10N2O2S
C7H12N2OS
9b
9с
—
10b
10c
11
5—15
—
—
—
(decomp.)
185—186
82—84
(ref.6: 80)
69—71
(ref.6: 183—184)
77—79
12c
(ref.12: 79.2)
217—219
(decomp.)
195—197
(decomp.)
197—199
(decomp.)
239—241
(decomp.)
232—234
(decomp.)
193—195
(decomp.)
138—140
48.81
18.83
18.81
22.98
23.02
35.99
36.29
34.44
34.47
41.55
41.56
27.07
27.02
33.55
33.59
33.61
33.59
46.66
46.63
48.51
48.47
50.13
50.14
51.65
51.67
7.02
5.07
5.05
6.08
6.07
6.47
6.47
4.61
4.63
5.94
5.98
4.47
4.53
5.60
5.64
5.62
5.64
4.59
4.62
5.11
5.08
5.48
5.50
5.90
5.88
16.26
43.91
43.88
38.37
38.34
31.84
31.74
24.15
24.12
20.79
20.77
25.15
25.21
22.36
22.38
22.35
22.38
14.85
14.83
14.11
14.13
13.51
13.49
12.89
12.91
18.61
9.99
13a
13b
14
80—83
59—62
35—38
30—33
33—36
32—34
19—21
21—23
42—45
44—46
26—28
35—38
22.24
22.21
19.36
19.41
13.28
13.39
—
C5H16Cl2N10S
10.04
8.76
C7H20Cl2N10S•
•H2O
8.78
11.86
12.11
27.56
27.60
23.73
23.77
28.82
28.85
25.57
25.61
25.56
25.61
22.58
22.63
21.52
21.56
20.56
20.59
19.66
19.70
C8H17ClN6S
15a
15b
16a
16b
17
C10H16N6O2S3
C14H24N6O2S3
C5H10N4O2S2
C7H14N4O2S2
C7H14N4O2S2
C11H13N3O2S2
C12H15N3O2S2
C13H17N3O2S2
C14H19N3O2S2
—
—
—
—
199—201
(decomp.)
121—123
18a
18b
18c
18d
185—187
147—149
170—172
—
—
—
The reaction of DHIT 8c with sulfamide in methanol
at pH 4—5 resulted in compound 15b and a product,
whose elemental analysis coincides with that of compound
16b. The mass spectrum of this unknown compound
revealed a molecular ion with m/z 250, which also coinꢀ
cided with that for compound 16b. However, the melting
points and the 1H NMR spectra of this product and
compound 16b differ, they correspond to the bicyclic
product 17. No reaction of sulfamide with compound 8b
was observed under conditions mentioned.
The condensation of DHIT 8b,c with sulfonamides
under conditions analogous to those used for the synthesis
of derivatives 5 (see Ref. 3) furnished 4ꢀarylsulfonylꢀ
iminoꢀ1,3ꢀdiethylimidazolidineꢀ2ꢀthiones 18a—d (see
Scheme 1).
The data from the 1H NMR spectra of compounds 15,
16, and 18 in DMSOꢀd6 revealed the iminoꢀenamino
tautomerism (Scheme 2). The most characteristic signals
of compounds 15, 16 and 18 in the imine forms are the
singlet signals for the ring CH2 groups, while signals for

1950
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009
Gazieva et al.
Table 2. Mass spectral and 13C NMR spectral data of compounds synthesized
Compound MS, m/z (I (%))
Solvent
13C NMR, δ
9b
217 [M – H2NNH –
C(S)NH2]+ (25)
DMSOꢀd6
31.8 (CH3); 76.0 (CH); 182.2 (C=S); 182.9 (C=S)
9c
245 [M – H2NNH –
C(S)NH2]+ (27)
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
11.2 (CH3); 37.3 (CH2); 72.5 (CH); 180.3 (C=S);
183.0 (C=S)
10b
10c
—
30.9 (CH3); 31.2 (CH3); 65.7 (CH); 72.7 (CH);
181.2 (C=S); 183.4 (C=S)
245 [M]+ (40)
12.4 (CH3); 13.1 (CH3); 38.3 (CH2); 38.7 (CH2);
64.4 (CH); 71.7 (CH);180.2 (C=S); 185.9 (C=S)
11
162 [M]+ (58)
—
DMSOꢀd6
DMSOꢀd6
53.9 (OCH3); 91.2 (CH); 183.5 (C=S)
12c
11.8 (CH3); 12.9 (CH3); 36.0 (NCH2); 41.1 (NCH2);
51.4 (CH2); 170.1 (C=S); 180.1 (C=S)
13a
13b
15a
15b
—
DMSOꢀd6
DMSOꢀd6
—
75.1 (CH); 159.0 (C=N); 182.3 (C=S)
—
32.0 (CH3); 76.1 (CH); 159.5 (C=N); 182.7 (C=S)
—
348 [M]+ (17)
404 [M]+ (8)
CDCl3
12.1 (CH3); 12.3 (CH3); 39.2 (NCH2); 42.2 (NCH2);
52.6 (CH2); 165.8 (C=N); 180.0 (C=S)
16a
16b
222 [M]+ (56)
250 [M]+ (5)
—
CDCl3
11.6 (CH3); 11.7 (CH3); 38.5 (NCH2); 41.6 (NCH2);
51.8 (CH2); 164.5 (C=N); 179.7 (C=S)
17
250 [M]+ (38)
283 [M]+ (45)
—
—
18a
CDCl3
30.6 (NCH3); 34.2 (NCH3); 55.1 (CH2); 126.6 (CH(Ph));
128.9 (CH(Ph)); 132.8 (C(Ph)); 140.7 (C(Ph));
165.0 (C=N); 180.8 (C=S)
21.6 (CH3); 30.7 (NCH3); 34.2 (NCH3); 55.0 (CH2);
126.4 (CH(Ph)); 126.8 (CH(Ph)); 129.6 (C(Ph));
143.9 (C(Ph)); 164.7 (C=N); 180.1 (C=S)
12.0 (CH3); 12.1 (CH3); 39.1 (NCH2); 42.1 (NCH2);
52.6 (CH2); 126.6 (CH(Ph)); 128.9 (CH(Ph));
132.8 (CH(Ph)); 141.0 (C(Ph)); 164.6 (C=N); 179.6 (C=S)
12.1 (CH3), 12.2 (CH3), 21.6 (CH3), 39.1 (NCH2),
42.1 (NCH2), 52.6 (CH2), 126.7 (CH(Ph)); 129.6 (CH(Ph));
138.1 (C(Ph)); 143.8 (C(Ph)); 164.4 (C=N); 179.7 (C=S)
18b
18c
18d
297 [M]+ (52)
311 [M]+ (8)
325 [M]+ (100)
CDCl3
CDCl3
CDCl3
the CH and NH protons are characteristic of enamines
15´, 16´, and 18´. In the spectra of derivatives 15 and 16,
the singlet signals for the imine CH2 protons were obꢀ
served in the range of δ 4.76—4.81, the CH and NH
protons of enamines 15´ and 16´ were found in the range
of δ 7.03—7.23 and 9.16—10.08, respectively. The signals
for the methyl and ethyl groups of the tautomers appeared
approximately in the same regions.
In the DMSOꢀd6 and acetonitrileꢀd3 solutions, comꢀ
pounds 18a—d exist in equilibrium with 4ꢀarylsulfonylꢀ
aminoꢀ1,3ꢀdiethylꢀ2,3ꢀdihydroꢀ1Hꢀimidazoleꢀ2ꢀthiones
18´a—d. The singlet signals for the ring CH2 groups of
compounds 18 appeared in the range of δ 4.76—4.96, the
CH and NH protons of the enamine 18´ exhibited signals
in the range of δ 6.63—6.77 and 10.23—10.34, respecꢀ
tively. The signals for the methyl and ethyl groups of the
tautomers appeared approximately in the same regions,
while the signals for enamine aromatic protons shifted
to the higher fields compared with the imine form. The
ratios of the imineꢀenamine tautomeric forms 18a—d and
18´a—d in DMSOꢀd6 were estimated as approximately
1 : 3, 1 : 4, 1 : 5, and 1 : 6, respectively; the tautomer ratio
for 18d in acetonitrile was 10 : 1. With the use of the LS/MS
technique, the ratio of 18d and 18´d in acetonitrile—
water mixture in the presence of trifluoroacetic acid was
estimated as 1 : 1. The chromatogram revealed two peaks
with approximately equal intensities and with TR 1.58 and
1.92 min; for each of them, molecular ions with m/z 326
[M + H]+ were present in the mass spectra.
No tautomeric equilibrium was observed in chloroꢀ
1
form. The H NMR spectra in CDCl3 exhibited signals
of only the imine forms of compounds 15, 16, and 18.
Due to the low solubility, the 13C NMR spectra were
recorded not for all compounds.
The mass spectra of compounds 18a—d revealed
intensive peaks of the corresponding molecular ions.
Crystals of compound 18d for the Xꢀray diffraction study
were obtained by crystallization from methanol (Fig. 2).

αꢀThioureidoalkylation of urea heteroanalogs
Table 3. 1H NMR of compounds synthesized
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009 1951
Compound
Solvent
δ (J/Hz)
4.41 (d, 2 H, CHCH, J = 5.6); 5.77 (d, 2 H, 2 NH, J = 5.6); 7.39 (br.s, 2 H, 2 NH);
9a
DMSOꢀd6
7.90 (br.s, 4 H, 2 NH2); 8.42 (s, 2 H, 2 NH)
9b
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
2.96 (s, 6 H, NMe); 4.09 (s, 2 H, CHCH); 6.22 (s, 2 H, 2 NH); 7.77, 7.92 (both br.s,
2 H each, NH2); 8.78 (s, 2 H, 2 NH)
9c
0.94 (t, 6 H, Me, J = 7.0); 3.23 (m, 2 H, NCH2); 3.90 (m, 2 H, NCH2); 4.28 (s, 2 H,
CHCH); 6.14 (s, 2 H, 2 NH); 7.63, 7.85 (both br.s, 2 H each, NH2); 8.61 (s, 2 H, 2 NH)
2.94, 2.97 (both s, 3 H, NMe); 4.91 (dd, 1 H, CH, 3J = 9.3, 3J = 2.5); 5.12 (dd, 1 H,
CH, 3J = 9.3, 3J = 2.4); 5.89 (s, 1 H, NH); 8.98 (s, 1 H, NH); 9.52 (br.s, 1 H, NH)
1.08 (m, 6 H, Me); 3.38 (m, 2 H, NCH2); 3.64 (m, 2 H, NCH2); 4.96 (dd, 1 H, CH,
J = 9.3, J = 2.6); 5.21 (dd, 1 H, CH, J = 9.3, J = 2.0); 5.85 (d, 1 H, NH, J = 2.0);
8.94 (s, 1 H, NH); 9.52 (br.s, 1 H, NH)
10b
10c
11
12c
13a
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
3.24 (s, 6 H, OMe); 4.69 (s, 2 H, CH); 9.38 (s, 2 H, NH)
1.09—1.18 (m, 6 Н, Me); 3.67—3.77 (m, 4 H, NCH2); 4.23 (s, 2 H, CH2)
4.43 (d, 2 H, CHCH, J = 3.7); 6.15 (d, 2 H, 2 NH, J = 3.7); 7.21 (br.s, 8 H, 2 NH3
+
,
2 NH); 8.64 (s, 2 H, 2 NH); 9.09 (s, 2 H, 2 NH)
3.03 (s, 6 H, NMe); 4.27 (s, 2 H, CHCH); 6.56 (s, 2 H, 2 NH); 7.28 (br.s, 8 H, 2 NH3
2 NH); 9.18 (s, 2 H, 2 NH)
+
13b
14
DMSOꢀd6
DMSOꢀd6
,
1.12 (m, 6 H, Me); 3.70 (m, 2 H, NCH2); 3.91 (m, 2 H, NCH2); 4.55 (s, 2 H, CH2);
7.39 (br.s, 4 H, NH2+NH2+); 10.83 (br.s, 1 H, NH)
15a
15a
15a´
15b
15b+15b´
15b
15b´
16a
16a
16a´
16b
16b+16b´*
16b
CDCl3
3.37 (s, 6 H, NMe); 3.42 (s, 6 H, NСН3); 4.81 (s, 4 H, CH2)
3.23 (s, 6 Н, NMe); 3.25 (s, 6 Н, NMe); 4.81 (s, 4 Н, CH2)
3.38 (s, 6 Н, NMe); 3.48 (s, 6 Н, NMe); 7.04 (s, 2 Н, CH); 9.92 (s, 2 Н, NH)
1.28 (m, 12 H, Me); 3.87, 4.05 (both m, 4 H each, NСН2); 4.77 (s, 4 H, CH2)
1.03—1.28 (m, 12 Н, Me); 3.67—4.04 (m, 8 Н, 2 NCH2)
DMSOꢀd6
DMSOꢀd6
CDCl3
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
CDCl3
DMSOꢀd6
ДМСОꢀd6
CDCl3
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
4.78 (s, 4 Н, CH2)
7.23 (s, 2 Н, CH); 10.08 (s, 2 Н, NH)
3.36 (s, 3 H, NMe); 3.40 (s, 3 H, NСН3); 4.72 (s, 4 H, CH2); 5.09 (s, 2 H, NH2)
3.22 (s, 3 Н, NMe); 3.23 (s, 3 Н, NMe); 4.78 (s, 2 Н, CH2); 7.14 (s, 2 Н, NH2);
3.36 (s, 3 Н, NMe); 3.47 (s, 3 Н, NMe); 7.03 (s, 1 Н, CH); 9.19 (s, 1 Н, NH)
1.26 (m, 6 H, Me); 3.85, 4.02 (both m, 2 H each, NСН2); 4.67 (s, 2 H, 2 CH2); 4.93 (s, 2 H, NH2)
1.04—1.27 (m, 6 Н, Me); 3.67—4.01 (m, 4 Н, 2 NCH2)
4.76 (s, 2 Н, CH2); 7.13 (s, 2 Н, NH2)
7.04 (s, 1 Н, CH), 9.16 (s, 1 Н, NH)
1.09 (t, 6 Н, 2 CH3, J = 7.0); 3.31 (m, 2 Н, NCH2); 3.75 (m, 2 H, NCH2); 5.57 (s, 2 Н, CHCH);
8.05 (s, 2 Н, 2 NH)
16b´
17
18a
CDCl3
3.35 (s, 6 H, NMe); 4.82 (s, 2 H, CH2); 7.57 (m, 2 H, Ph); 7.95 (d, 2 H, Ar, J = 6.8)
18a+18a´*
18a
18a´
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
7.65 (m, 3 Н, HAr)
3.19 (s, 3 Н, NMe); 3.24 (s, 3 Н, NMe); 4.96 (s, 2 Н, CH2); 7.92 (d, 2 Н, HAr, J = 7.3)
3.16 (s, 3 Н, NMe); 3.35 (s, 3 Н, NMe); 6.77 (s, 1 Н, CH); 7.78 (d, 2 H, HAr, J = 7.3);
10.34 (s, 1 Н, NH)
18b
CDCl3
2.44 (s, 3 H, Me); 3.55 (s, 6 H, NСН3); 4.80 (s, 2 H, CH2); 7.33 (d, 2 H, Ar, J = 8.3);
7.84 (d, 2 H, Ar, J = 8.3)
18b+18b´*
18b
18b´
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
3.39 (s, 3 Н, NMe); 7.42 (m, 2 Н, HAr)
2.39 (s, 3 Н, Ме); 3.24 (s, 3 Н, NMe); 4.95 (s, 2 Н, CH2); 7.80 (d, 2 Н, HAr, J = 8.1)
2.41 (s, 3 Н, Ме); 3.17 (s, 3 Н, NMe); 6.78 (s, 1 Н, CH); 7.66 (d, 2 H, HAr, J = 8.1);
10.27 (s, 1 Н, NH)
18c
CDCl3
1.20, 1.29 (both t, 3 H each, Me, J = 7.3); 3.86, 4.01 (both m, 2 H each, NСН2); 4.78 (s, 2 H, CH2);
7.58 (m, 3 H, Ph); 7.96 (d, 2 H, Ph, J = 6.9)
18c+18c´*
18c
18c´
DMSOꢀd6
DMSOꢀd6
DMSOꢀd6
CDCl3
1.03—1.18 (m, 6 Н, 2 Ме); 3.73—3.94 (m, 4 Н, 2 NCH2); 7.65 (m, 3 Н, HAr
4.96 (s, 2 Н, CH2); 7.93 (d, 2 Н, HAr, J = 6.8)
6.64 (s, 1 Н, CH); 7.78 (d, 2 Н, HAr, J = 6.3); 10.29 (s, 1 Н, NH)
1.20, 1.29 (both t, 3 H each, Me, J = 7.2); 2.45 (s, 3 H, Me); 3.86, 4.00 (both m, 2 H each, NСН2);
4.76 (s, 2 H, 2 CH2); 7.34 (d, 2 H, Ar, J = 8.2); 7.84 (d, 2 H, Ar, J = 8.2)
)
18d
18d+18d´*
18d
DMSOꢀd6
1.00—1.20 (m, 6 Н, 2 Ме); 3.71—3.92 (m, 4 Н, 2 NCH2); 7.40 (m, 2 Н, HAr)
2.37 (s, 3 Н, Ме), 4.93 (s, 2 Н, CH2); 7.79 (d, 2 Н, HAr, J = 8.3)
18d´
2.39 (s, 3 Н, Ме); 6.63 (s, 1 Н, CH); 7.64 (d, 2 Н, HAr, J = 8.6); 10.23 (s, 1 Н, NH)
* The signals for the protons of the tautomers coincide.

1952
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009
Gazieva et al.
glyoxal and glyoxal trimer dihydrate were used as purchased
(Acros). The 1H and 13C NMR spectra were recorded on a
Bruker AMꢀ250 at 250.0 and 75.5 MHz, respectively. The
chemical shifts are given in the δ scale relative to tetramethylꢀ
silane (internal standard). The mass spectra were run on a Kratos
MSꢀ30 (70 eV) mass spectrometer. Melting points were deterꢀ
mined on a GALLENKAMP (Sanyo) apparatus.
Analysis of compound 18d was carried out on a 1100 LS/MSD
(Agilent Technologies) chromatoꢀmass spectrometer equipped
with an ELSD PLꢀELSꢀ1000 mass detector. The column used
was Onyx monolithic C18, 50Ѕ4.6 mm, the flow rate was
3.75 mL min–1, the acetonitrile—water mixture (5 : 95) conꢀ
taining 0.1% of trifluoroacetic acid was used as eluent.
Xꢀray diffraction analysis of the compounds 13b and 18d were
performed on a Smart 1000 CCD threeꢀcircle diffractometer
at 120 K (λMoꢀKα, graphite monochromator, ωꢀscan mode).
The structures was solved by the direct method and refined by
the full matrix leastꢀsquare method in anisotropic approximation
for nonhydrogen atoms (isotropic for hydrogen atoms). The
coordinates of hydrogen atoms were geometrically calculated.
All computations were carried out using SHELXTL PLUS 5.0
program package.22 The principal crystallographic data and
refinement parameters are given in Table 4.
4,5ꢀBis(thiosemicarbazido)imidazolidineꢀ2ꢀthiones 9a—c and
5,7ꢀdialkylperhydroimidazo[4,5ꢀe][1,2,4]triazineꢀ3,6ꢀdithiones
10b,c. To a solution of DHIT 8a—c (0.005 mmol) in H2O (5 mL),
catalytic amount of conc. HCl (2 drops, pH 1) was added
followed by solid thiosemicarbazide (0.91 g, 0.01 mol). The
reaction mixture was heated with stirring at 80 °C for 1 h.
The precipitates that formed (9a—c) were filtered off, washed
with hot methanol—water mixture (1 : 1). The filtrate was kept
in refrigerator for 12—15 h. The precipitate that formed was
filtered off and recrystallized from methanol to give 10b
(or 10c).
Physicochemical properties of 2ꢀthiohydantoins 12a—c that
were prepared by reaction of DHIT 8a—c with thiosemicarbazide
under conditions used for the synthesis of compound 1,2
coincided with the literature data.8—12 Physicochemical data,
the 1H and 13C NMR spectral data, and elemental analyses of
compounds 12c are given in Tables 1—3.
4,5ꢀDimethoxyimidazolidineꢀ2ꢀthione (11). To a solution of
DHIT 8a (0.0.67 g, 005 mol) in methanol (4 mL), catalytic
amount of conc. HCl (1 drop) was added and the mixture was
refluxed for 30 min. After cooling, the precipitate of compound
11 was filtered off.
4,5ꢀBis(guanidinoamino)imidazolidineꢀ2ꢀthione dihydroꢀ
chlorides 13a,b and 4ꢀguanidinoiminoꢀ1,3ꢀdiethylimidazolidineꢀ
2ꢀthione hydrochloride (14). To a solution of DHIT 8a—c
(0.01 mol) in water (10 mL), conc. HCl (0.1 mL) was added
followed by the addition of aminoguanidine hydrochloride
(2.21 g, 0.02 mol). The reaction mixture was heated at 80 °C for
0.5 h for 8c and 1 h for 8a,b, then the mixture was cooled and
kept in the refrigerator for 16 h. The precipitates of the salts 13a,
12b, and 14 were filtered off and recrystallized from methanol.
After isolation of compound 12b, the mother liquor was conꢀ
centrated in vacuo, the resulted precipitate was recrystallized
from methanol to give compound 13b.
C(10)
N(6)
C(4)
C(9)
O(1)
N(3)
C(12)
S(1)
C(2)
C(11)
S(2)
C(13)
C(16)
C(15)
C(5)
C(8)
C(14)
N(1)
C(17)
O(2)
C(7)
Fig. 2. General view of compound 18d with the presentation of
atoms as ellipsoids of thermal vibrations (p = 30%). Only one
component is shown for the disordered atoms.
In the crystal of compound 18d, the tolyl substituent
and one of the ethyl groups are disordered over two posiꢀ
tions with equal population. The structure of 18d closely
resembled that of the oxo derivative, 1,3ꢀdimethylꢀ4ꢀ
(phenylsulfonylimino)imidazolidinꢀ2ꢀone.4 According to
the data from the Xꢀray diffraction analysis, the imidazolꢀ
idine ring of compound 18d is nearly planar, the N(1),
C(2), N(3), C(4), and C(5) atoms are coplanar to within
0.007 Å. Bond length analysis of the ring bonds in the
crystal of 18d indicated that the replacement of the oxyꢀ
gen atom by the sulfur atom led to significant redistribuꢀ
tion of the bond lengths. Thus C(2)—N(1) and C(2)—N(3)
(1.324(4) and 1.391(4) Å, respectively) are shorter by
0.021 and 0.023 Å, respectively, as compared with the
oxo derivative, while lengths of the other bonds of the
fiveꢀmembered ring changed insignificantly. This can
be explained by lower electronꢀwithdrawing character of
the sulfur atom compared with the oxygen atom and
by the formation of a more stable conjugation system in
the ring. These features partially manifested themselves
in the greater planarity of the ring of the compound 18d
compared with the previously studied oxo derivatives.
In summary, in the present work the αꢀthioureidoꢀ
alkylation of the urea heteroanalogs, viz., thiosemicarbꢀ
azide, aminoguanidine, sulfamide and sulfonamides with
4,5ꢀdihydroxyꢀ1,3ꢀdimethylꢀ and ꢀ1,3ꢀdiethylimidazolꢀ
idineꢀ2ꢀthiones under conditions of acid catalysis were
studied. The reaction conditions and structural factors
that favor formation of 4,5ꢀbis(thiosemicarbazido)ꢀ and
4,5ꢀbis(guanidinoimino)imidazolidineꢀ2ꢀthiones, 5,7ꢀdiꢀ
alkylperhydroimidazo[4,5ꢀe][1,2,4]triazineꢀ3,6ꢀdithiones,
1,3ꢀdialkylꢀ4ꢀ(guanidinoimino)ꢀ and 1,3ꢀdialkylꢀ4ꢀ(arylꢀ
sulfonylimino)imidazolidineꢀ2ꢀthiones, N,N´ꢀbis(1,3ꢀ
dialkylꢀ2ꢀthioxoimidazolidinꢀ4ꢀylidene)sulfamides or
4,6ꢀdiethylꢀ5(3H)ꢀthioxotetrahydroꢀ1Hꢀimidazo[4,5ꢀc]ꢀ
[1,2,5]thizdiazole 2,2ꢀdioxide were found.
Experimental
1,3ꢀDialkylꢀ4,5ꢀbis(guanidinoamino)imidazolidineꢀ2ꢀthione
dihydrochlorides 13b,c. To a solution of DHIT (0.005 mol)
in methanol (10 mL), aminoguanidine hydrochloride (1.11 g,
0.01 mol) and catalytic amount of conc. HCl (1 drop) were
Commercially available thiourea, dimethyl and diethylꢀ
thioureas, thiosemicarbazide, aminoguanidine hydrochloride,
sulfamide, and benzeneꢀ and toluenesulfonamides, 40% aqueous

αꢀThioureidoalkylation of urea heteroanalogs
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009 1953
Table 4. The principal crystallographic data and refinement parameters of crystal
Parameter
14b
20d
Molecular formula
Molecular weight
Crystal system
Space group
C7H22Cl2N10OS
365.31
Orthorhombic
Pbca
C14H19N3O2S2
325.44
Monoclinic
P2(1)/c
4 (1)
Z (Z´)
8 (1)
a/Å
b/Å
c/Å
10.0919(4)
17.0325(9)
19.228(1)
—
3305.1(3)
1.468
5.2803(10)
14.586(3)
20.444(4)
93.317(4)
1572.0(5)
1.375
β/deg
V/Å3
dcalc/g cmꢀ3
μ/mm–1
0.535
0.346
F(000)
1536
688
2θmax/deg
58
54
Number of measured reflections
34670
16223
Rint
0.033
0.099
Number of independent reflections
Number of refined parameters
Number of reflections with I > 2σ(I)
R1 (I > 2σ(I))
4389
192
3575
0.047
3429
196
2260
0.056
wR2
0.116
0.128
GOOF
1.003
1.008
Residual electron density
/e•Åꢀ3, ρmax/ρ
0.654/–0.358
0.480/–0.600
min
added. The mixture was refluxed for 1 h, the solvent was removed
in vacuo, the resulting precipitates were recrystallized from
methanol to give compounds 13b,c.
N,N´ꢀBis(1,3ꢀdialkylꢀ2ꢀthioxoimidazolidinꢀ4ꢀylidene)ꢀ
sulfamides 15a,b. To a solution of DHIT 8b,c (0.005 mol) in
methanol (5mL), sulfamide (0.24 g, 0.0025 mol) and catalytic
amount of conc. HCl (1 drop) were added. The reaction mixture
was stirred and refluxed for 1 h and then concentrated in vacuo
until the precipitate formed. The crystals were filtered off and
washed with acetone to give compounds 15a,b.
Nꢀ(1,3ꢀDialkylꢀ2ꢀthioxoimidazolidinꢀ4ꢀylidene)sulfamides
16a,b. To a solution of DHIT 8b,c (0.005 mol) in methanol
(5mL), sulfamide (0.48 g, 0.005 mol) and catalytic amount of
conc. HCl (1 drop) were added. The reaction mixture was stirred
and refluxed for 30 min. The precipitate that formed upon
cooling was filtered off to give compounds 15a and 15b in the
yields of 0.14 g and 0.11 g, respectively. After 16 h, an additional
crop of sulfamides 16a and 16b was obtained in the yields of
0.36 g and 0.33 g, respectively.
4,6ꢀDiethylꢀ5(3H)ꢀthioxotetrahydroꢀ1Hꢀimidazo[4,5ꢀc]ꢀ
[1,2,5]thiadiazole 2,2ꢀdioxide (17). A solution of DHIT 8c
(0.95 g, 0.005 mol) and sulfamide (0.48 g, 0.005 mol) in methanol
(5 mL) was stirred and refluxed for 1 h. After cooling, a
precipitate that formed was filtered off and washed with acetone
to furnish compound 17 in the yield of 0.29 g. The solvent was
removed in vacuo, the residue was triturated with ethyl acetate
until white powder was formed. The precipitate was filtered off,
washed with small amount of cold methanol to give compound
15b (0.12 g).
amount of conc. HCl (2 drops) was added. The reaction mixture
was refluxed for 30 min. The mixture was cooled, the resulting
precipitate was filtered off, washed with hot water and acetone
to give compound 18a (or 18b—d).
The yields and physicochemical characteristics of comꢀ
pounds 9—18 are given in Tables 1—3.
This work was financially supported by Russian
Academy of Sciences (Program “Biomolecular and
Medicinal Chemistry” (OCh 10) of the Division of Chemꢀ
istry and Materials Science) and by the Council on Grants
at the President of the Russian Federation (Program for
the State Support of Leading Scientific Schools, Grant
NShꢀ3019.2008.3).
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1,3ꢀDialkylꢀ4ꢀ(arylsulfonylimino)imidazolidinꢀ2ꢀthiones
18a—d. To a solution of DHIT 8b,c (0.005 mol) and benzene or
pꢀtoluenesulfonamide (0.005 mol) in methanol (5 mL), catalytic

1954
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 9, September, 2009
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Received February 12, 2009;
in revised form June 4, 2009