Reactions of N-alkenyl Thioureas with p-alkoxyphenyltellurium Trichlorides

Article abstract of DOI:10.1002/jhet.3281

N-Аlkenyl thioureas, under the action of aryltellurium trichlorides, form the addition products N-{2-chloro-3-[dichloro(4-alkoxyphenyl)-tellanyl]propyl} thioureas or the intramolecular cyclization products 5-{dichloro(4-alkoxyphenyl)-telluromethyl}-2-phenylamino-4,5-dihydro-1,3-thiazole hydrochlorides. The reaction route depends on the nature of the substituent in the thiourea. The Fukui function reactivity indexes identify the electrophilic/nucleophilic centers and explain the possible cyclization reaction in the case of phenyl substituted thioureas. In the case of other substituents, the calculated values of partial atomic charges clearly predict that the addition reaction is more possible.

Full text of DOI:10.1002/jhet.3281

Month 2018 Reactions of N-alkenyl Thioureas with p-alkoxyphenyltellurium Trichlorides
*
Mykola Kut, Maksym Fizer, Mikhajlo Onysko,
and Vasil Lendel
Organic Synthesis Laboratory, Uzhhorod National University, Uzhhorod 88000, Ukraine
*E-mail: muonysko@gmail.com
Received April 27, 2018
DOI 10.1002/jhet.3281
Published online 00 Month 2018 in Wiley Online Library (wileyonlinelibrary.com).
N-Аlkenyl thioureas, under the action of aryltellurium trichlorides, form the addition products
N-{2-chloro-3-[dichloro(4-alkoxyphenyl)-tellanyl]propyl} thioureas or the intramolecular cyclization prod-
ucts 5-{dichloro(4-alkoxyphenyl)-telluromethyl}-2-phenylamino-4,5-dihydro-1,3-thiazole hydrochlorides.
The reaction route depends on the nature of the substituent in the thiourea. The Fukui function reactivity in-
dexes identify the electrophilic/nucleophilic centers and explain the possible cyclization reaction in the case
of phenyl substituted thioureas. In the case of other substituents, the calculated values of partial atomic
charges clearly predict that the addition reaction is more possible.
J. Heterocyclic Chem., 00, 00 (2018).
INTRODUCTION
addition and cyclization products [6–10]. We have
determined that only products 6–11 are formed via the
action of p-alkoxyphenyltellurium trichlorides on thioureas
Reportedly, aryltellurium trihalides are quite promising
electrophilic reagents [1–5]; however, the reactions
of aryltellurium trihalides with acyclic unsaturated
thioureas have not yet been investigated. Reactions of
N-alkenyl thioureas with electrophilic reagents can lead
to the formation of addition products or heterocyclic
systems. Thus, when N-allyl-N0-arylthiourea reacts with
halogens or arylselenenyl chloride, then the thiazoline
or thiazolidine cycles are formed [6–10]. Furthermore,
N-β-bromoallyl-N0-phenylthiourea can be cyclized to
thiazole via the action of potassium carbonate [11].
Taking into account all the aforementioned facts, the
purpose of this work was to study the regioselectivity
of the reaction of electrophilic aryltellurium trichlorides
with N-alkenyl thioureas.
1
1–3 in chloroform, which was proven by the data of H
NMR and 13C NMR spectra. However, under the same
conditions, the thioureas 4 and 5 are cyclized via the
nucleophilic sulfur atom, and the telluro-containing
products 12–14 with thiazoline cycle are formed. In the
case of thiazolines 12–14, the signal of the central
carbon atom in isothiourea moiety in the 13C NMR spectra
is shifted to a stronger region in comparison with a carbon
of thiourea fragment. This shifting of signals confirms
the participation of the S-nucleophilic center in
heterocyclization. Therefore, the ability of thioureas to
cyclization, under the action of aryltellurium trichlorides, is
influenced by the nature of the substituent in the thioureas.
The presence of the electron withdrawing phenyl ring at N0
atom causes the cyclization, whereas the addition reaction
takes place in the case of the methyl substituent or
hydrogen atom.
RESULTS AND DISCUSSION
The unequivocal proof of the addition of the electrophile
to the terminal carbon is the data of homo- and
heteronuclear correlations (Fig. 1).
Computational study. In the computational study, we
were focused on the investigation of the possible reaction
mechanism between 4-methoxyphenyltellurium trichloride
and N-alkenyl substituted thioureas: N-allylthiourea
(1), N-methallylthiourea (2), N-allyl-N0-phenylthiourea
(4), N-allyl-N0-methylthiourea (15). Despite the fact that
Experimental study.
Unsaturated thioureas 1–5 were
synthesized from ammonia, methylamine, or aniline and
corresponding alkenyl isothiocyanate in ethanol [12,13].
The reaction of thioureas 1–5 with p-alkoxyphenyltellurium
trichlorides was carried out in chloroform at room
temperature (Scheme 1). Thioureas 1–5 contain several
reaction centers, and this is why the action of
electrophilic reagents can lead to the formation of both
© 2018 Wiley Periodicals, Inc.

M. Kut, M. Fizer, M. Onysko, and V. Lendel
Vol 000
Scheme 1. Interaction of p-alkoxyphenyltellurium trichlorides with N-alkenyl thioureas.
Figure 1. Nuclear Overhauser effect spectroscopy (NOESY) and heteronuclear multiple bond correlation (HMBC) for thioureas 6 and 7.
N-allyl-N0-methylthiourea (15) was not investigated
experimentally, it is a convenient object for theoretical
investigation of the electronic influence of substituents,
so it was included in the studied raw of thioureas.
The main stages of our quantum chemical investigation
were devoted to (a) the determination of the most stable
conformer of the flexible molecules of substituted
thioureas 1, 2, 4, and 15; (b) modeling of the geometry of
the telluronium cation that plays crucial role in the
reaction route; (c) finding of the most reactive sites in
the intermediate telluronium cation by analysis of
partial atomic charges and condensed Fukui function
(CFF) indexes [14]; and (d) explanation of special
behavior of N-allyl-N0-phenylthiourea (4) through the
analysis of reactivity descriptors and binding energy in
telluronium cation.
find the most stable conformer in chloroform solution, we
have studied four possible conformers of N-allyl-N0-
phenylthiourea (4) (Fig. 2). According to the Hartree–
Fock calculations, the conformation b is the most stable
one, and it is the predominant form of 4 in the
chloroform solution. For consistency, in all our next
The substituted thioureas 1, 2, 4, and 15 can exist in a
few conformations due to the presence of flexible alkenyl
fragment and the possible rotation of amino group around
N–C (S) bond. The conformation of allyl group was
taken from X-ray data [15]. The reciprocal position of
substituents in thiourea is usually opposite [16]. Finding
of the most stable conformer can play a crucial role in the
investigation of reactivity [17]. This is why, in order to
Figure 2. Considered conformers of 4. The relative difference in the
Gibbs free energy is shown along with the corresponding partition of each
conformer calculated according to Boltzmann distribution. The values of
the Gibbs free energy are given in kcal/mol.
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Month 2018
Reactions of N-alkenyl Thioureas with p-alkoxyphenyltellurium Trichlorides
computations, we have used this structure for all thioureas
1, 2, 4, and 15.
and to understand and predict the mechanism of the
chloride attack, we considered partial atomic charges as
the reactivity and selectivity descriptors. Thus, in the case
of the cation of thiourea 2, the partial charge of C3 atom
is 0.065eꢀ, whereas the partial charge of C4 atom is
ꢀ0.029eꢀ. A similar picture, but with slightly lower
values for C3 atom, can be seen for cations of thioureas
1, 4, and 15. Thus, in the case of telluronium cation of 1,
the partial charges of C3/C4 atoms are 0.014/ꢀ0.023eꢀ,
respectively. For thioureas 4 and 15, the partial charges
of the C3 atom are 0.009eꢀ and 0.010eꢀ, respectively,
whereas the partial charge of C4 in the case of 4 is
ꢀ0.027eꢀ and ꢀ0.026eꢀ in the case of 15. These values
clearly testify that in all the aforementioned cases, the
attack of the chloride anion selectively takes place to the
C3 carbon with the formation of the Markovnikov
addition product.
To understand the specific behavior of thiourea 4, we
have to consider additional computed data. The energy of
dissociation, according to Figure 4, is the lowest in the
case of thiourea 4 (ꢀ20.1 kcal/mol), and taking into
account that Te–C bonding is the same for the cases of
thioureas 1, 4, and 15, this means that the Te–S bond is
the weakest in the cation of thiourea 4. Moreover, the
partial atomic charge on sulfur is the highest in the case
of the cation of 4, with the value ꢀ0.224eꢀ, while in the
cases of 1/2/15 the sulfur charge is ꢀ0.232/ꢀ0.252/
ꢀ0.234eꢀ, respectively. As mentioned earlier, the partial
charge of the C3 atom is the lowest in the case of 4, and
it will be slightly less attractable to the chloride anion.
Considering all three points together, it is expected that
the cation of 4 can behave differently.
In non-polar solvents, according to literature data [18],
4-methoxyphenyltellurium trichloride interacts with a
double bond through the formation of telluronium cation.
On the next stage, the chloride anion attacks the cation
from the opposite site to tellurium atom. Moreover, it is
known that tellurium (IV) halide compounds readily react
with thiocarbonyl group [19,20], and this is why, it is
reasonable to suggest that 4-methoxyphenyltellurium will
react with thioureas 1, 2, 4, and 15 with the formation of
Te–S bond and next coordination of Te atom to the
double bond. The similar complex is described in the
literature [20], where the tellurium atom coordinates to
the aromatic ring to form the intermolecular interactions
in the crystal. We have suggested that the elimination of
chlorine atom, which is opposite to the sulfur atom, will
take place on the next stage with the formation of
telluronium cation (Fig. 3). The fact that aryltellurium
dihalide fragment contains the halogen atoms opposite
to each other [18,21,22] clearly confirms that the
aforementioned chlorine atom detaches from the tellurium
atom during the telluronium formation.
During the attack of the tricyclic telluronium cation, the
chloride anion can attach to carbon C3 or C4 and form the
product of the Markovnikov or anti-Markovnikov addition,
respectively. This reaction belongs to the ionic reactions,
Typically, good results in explanation and prediction of
reactivity can be obtained by a combination of a few
different approaches [23,24]. This is why we have
calculated the CFF, which is a local reactivity and
selectivity descriptor. Table 1 presents the values of
CFFꢀ (electrophilic attack) and CFF+ (nucleophilic
attack). It is clear that the sulfur atom (CFFꢀ = 0.253) is
the most reactive nucleophilic site in the telluronium
cation of thiourea 4. On the other hand, the most
electrophilic site is the S-TeCl+2 system, which is quite
expected as the chloride anion eliminated from this group
can be attracted back with the formation of starting
materials (reverse reaction). Moreover, the C3 atom
(CFF+ = 0.068) is an additional electrophilic center. So
Figure 3. Proposed structure of the intermediate telluronium cation.
Figure 4. Dissociation energy (kcal/mol) of the telluronium cations.
Journal of Heterocyclic Chemistry
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M. Kut, M. Fizer, M. Onysko, and V. Lendel
Vol 000
Table 1
Condensed Fukui function indexes for telluronium cation in the case of thiourea 4.
Atom
CFFꢀ
CFF+
Atom
CFFꢀ
CFF+
Atom
CFFꢀ
CFF+
Atom
CFFꢀ
CFF+
N1
C2
C3
C4
N5
S6
0.016
0.018
0.047
0.053
0.028
0.253
0.008
0.011
0.068
0.048
0.015
0.076
Cl7
Te8
Cl9
C10
C18
C19
0.059
0.056
0.051
0.015
0.014
0.007
0.108
0.091
0.103
0.015
0.054
0.019
C20
C21
C22
C23
O26
C29
0.022
0.019
0.017
0.014
0.022
0.006
0.025
0.022
0.023
0.024
0.016
0.006
C33
C34
C35
C36
C37
C38
0.001
0.006
0.009
0.012
0.008
0.005
ꢀ0.001
0.003
0.005
0.006
0.004
0.001
CFFꢀ and CFF+ correspond to electrophilic and nucleophilic attack, respectively. Hydrogens are omitted for clarity. Highest values are shown in bold.
CFF, condensed Fukui function.
taking into account (a) the electrophilic character of C3 and
its relatively low partial charge, (b) nucleophilic character
of sulfur and its relatively high partial charge, and (c)
relatively low Te–S bond energy, we can conclude that
the attack of C3 by the chloride anion is less plausible
than the attack by the sulfur atom due to the easy
breaking of the Te–S bond.
General procedures for synthesis of thioureas 1–5. To
the stirred solution of allyl (methallyl) isothiocyanate
(0.03 mol) in ethanol (15 mL), an ethanol solution of the
corresponding amine (ammonia, methylamine, and
aniline) (0.04 mol) was added dropwise. The reaction
mixture was stirred for 4 h. The formed precipitate was
filtered and washed with cold ethanol and crystallized
from ethanol.
N-Prop-2-en-1-ylthiourea (1). Yield 73%; white powder
1
(ethanol); mp 71–72°C (mp 73–73.5°C [27]). H NMR
CONCLUSION
(400 MHz, DMSO-d6) δ (ppm) 7.65 (br s, 1H), 7.00 (br
s, 2H), 5.86–5.78 (m, 1H), 5.14 (d, 1H, J = 12 Hz), 5.06
(d, 1H, J = 8 Hz), 4.09–3.98 (m, 2H). 13C NMR
(100 MHz, DMSO-d6) δ (ppm) 183.8, 135.6, 115.9, 46.9.
Anal. Calcd for C4H8N2S: С, 41.35; Н, 6.94; N, 24.11; S,
27.60. Found: С, 41.26; Н, 6.85; N, 23.93; S, 27.43.
Consequently, the reaction of N-alkenyl thioureas with
electrophilic reagents can lead to the formation of
addition products or to the heterocyclic systems. The
presence of phenyl substituent at N0 atom causes the
cyclization reaction with formation of thiazoline cycle.
The Fukui function indexes calculated for the case of
electrophilic/nucleophilic attack explain the possibility of
cyclization reaction in the case of phenyl substituted
thioureas. In other cases, the calculated values of partial
atomic charges clearly testify the formation of the
Markovnikov addition products.
N-(2-Methylprop-2-en-1-yl)thiourea (2).
Yield 70%;
white powder (ethanol); mp 89–90°C (mp 92–94°C [28]).
1H NMR (400 MHz, DMSO-d6) δ (ppm) 7.84 (br s, 1H),
6.69 (br s, 2H), 4.77 (s, 2H), 3.97 (s, 2H), 1.66 (s, 3H).
13C NMR (100 MHz, DMSO-d6) δ (ppm) 184.0, 142.9,
110.5, 49.9, 20.8. Anal. Calcd for C5H10N2S: С, 46.12;
Н, 7.74; N, 21.51; S, 24.63. Found: С, 45.94; Н, 7.61; N,
21.43; S, 24.54.
N-Methyl-N0-(2-methylprop-2-en-1-yl)thiourea (3). Yield
78%; white powder (ethanol); mp 64–65°C. 1H NMR
(400 MHz, DMSO-d6) δ (ppm) 7.55 (br s, 1H), 7.35 (br
s, 1H), 4.76 (s, 2H), 3.34 (s, 2H), 2.82 (d, 3H, J = 8 Hz),
1.66 (s, 3H). 13C NMR (100 MHz, DMSO-d6) δ (ppm)
183.1, 142.4, 109.5, 48.8, 30.8, 20.2. Anal. Calcd for
C6H12N2S: С, 49.96; Н, 8.39; N, 19.42; S, 22.23. Found:
С, 49.82; Н, 8.28; N, 19.31; S, 22.11.
EXPERIMENTAL SECTION
1H NMR (400 MHz) and 13C NMR (100 MHz) spectra
were recorded on Varian Mercury-400 instruments. The
chemical shift values (δ) are given in parts per million
(ppm) downfield from TMS as internal standard and are
referred to the residual peak of the deuterated solvent used
(CD3)2SO. The melting points were determined on Stuart
SMP30 instrument. Elemental analyses were performed on
Elementar Vario MICRO cube analyzer. All reagents were
obtained from commercial suppliers and used without any
further purification. Dry solvents were prepared according
to the standard methods. The p-alkoxyphenyltellurium
trichlorides were obtained according to the procedure [25].
The methallyl isothiocyanate was obtained according to
the procedure [26].
N-Phenyl-N0-prop-2-en-1-ylthiourea (4).
Yield 81%;
white powder (ethanol); mp 97–98°C (mp 98–99°C [29]).
1H NMR (400 MHz, DMSO-d6) δ (ppm) 9.53 (br s, 1H),
7.82 (br s, 1H), 7.42 (d, 2H, J = 7.8 Hz), 7.32 (t, 2H,
J = 7.7 Hz), 7.11 (t, 1H, J = 7.1 Hz), 5.93–5.82 (m, 1H),
5.19 (d, 1H, J = 7.2 Hz), 5.11 (d, 1H, J = 10.2 Hz),
4.15–4.12 (m, 2H). 13C NMR (100 MHz, DMSO-d6) δ
(ppm) 181.1, 139.7, 135.3, 129.1, 124.7, 124.3, 116.2,
46.6. Anal. Calcd for C10H12N2S: С, 62.46; Н, 6.29; N,
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Reactions of N-alkenyl Thioureas with p-alkoxyphenyltellurium Trichlorides
14.57; S, 16.68. Found: С, 62.33; Н, 6.14; N, 14.41; S,
J = 8.0 Hz), 7.11 (d, 2H, J = 8.0 Hz), 4.25 (d, 1H,
J = 8.0 Hz), 4.20 (d, 1H, J = 8.0 Hz), 4.14–4.06 (m, 3H),
3.85 (d, 1H, J = 8.0 Hz), 1.85 (s, 3H), 1.33 (t, 3H,
J = 8.9 Hz). 13C NMR (100 MHz, DMSO-d6) δ (ppm)
171.2, 160.5, 135.3, 124.9, 115.2, 63.5, 59.3, 59.1, 56.1,
24.5, 14.5. Anal. Calcd for C13H19Cl3N2OSTe: С, 32.17;
Н, 3.95; N, 5.77; S, 6.61. Found: С, 32.02; Н, 3.82; N,
16.49.
N-(2-Methylprop-2-en-1-yl)-N0-phenylthiourea (5). Yield
78%; white powder (ethanol); mp 74–75°C (mp 79–80°C
1
[29]). H NMR (400 MHz, DMSO-d6) δ (ppm) 9.55 (br
s, 1H), 7.80 (br s, 1H), 7.44 (d, 2H, J = 7.6 Hz), 7.32 (t,
2H, J = 7.8 Hz), 7.11 (t, 1H, J = 7.2 Hz), 4.82 (s, 2H),
4.09 (s, 2H), 1.71 (s, 3H). 13C NMR (100 MHz,
DMSO-d6) δ (ppm) 181.4, 142.6, 139.8, 129.2, 124.7,
123.5, 110.7, 49.5, 20.9. Anal. Calcd for C11H14N2S: С,
64.04; Н, 6.84; N, 13.58; S, 15.54. Found: С, 63.87; Н,
6.74; N, 13.41; S, 15.41.
General procedures for synthesis of aryltellurium
trihalides 6–14. To the stirred solution of thiourea 1–5
(0.001 mol) in dry chloroform (15 mL), a solution of p-
methoxy (ethoxy) phenyltellurium trichloride (0.001 mol)
in dry chloroform (25 mL) was added dropwise. The
reaction mixture was stirred for 8 h. The formed
5.63; S, 6.53.
N-{2-Chloro-3-[dichloro(4-methoxyphenyl)-tellanyl]-2-
methylpropyl}-N0-methylthiourea (10).
Yield 62%;
white powder; mp 158–159°C. 1H NMR (400 MHz,
DMSO-d6) δ (ppm) 10.25 (br s, 2H) 8.05 (d, 2H,
J = 8.0 Hz), 7.14 (d, 2H, J = 8.8 Hz), 4.30 (d, 1H,
J = 9.6 Hz), 4.21 (d, 1H, J = 8.0 Hz), 4.13 (d, 1H,
J = 8.0 Hz), 3.90 (d, 1H, J = 8.0 Hz), 3.83 (s, 3H), 2.97 (s,
3H), 1.87 (s, 3H). 13C NMR (100 MHz, DMSO-d6) δ
(ppm) 168.6, 161.2, 135.3, 125.1, 114.2, 113.3, 59.4, 56.0,
55.5, 31.2, 17.2. Anal. Calcd for C13H19Cl3N2OSTe: С,
32.17; Н, 3.95; N, 5.77; S, 6.61. Found: С, 32.00; Н, 3.81;
precipitate was filtered and washed with chloroform.
N-{2-Chloro-3-[dichloro(4-methoxyphenyl)-tellanyl]propyl}
N, 5.60; S, 6.52.
thiourea (6).
Yield 58%; white powder; mp 186–
N-{2-Chloro-3-[dichloro(4-ethoxyphenyl)-tellanyl]-2-
methylpropyl}-N0-methylthiourea (11).
Yield 60%; white
1
188°C. H NMR (400 MHz, DMSO-d6) δ (ppm) 10.04
(br s, 1H), 9.57 (br s, 2H), 8.03 (d, J 8 Hz, 2H), 7.10
(d, 2H, J = 8.0 Hz), 4.71–4.62 (m, 1H), 3.96 (d, 2H,
J = 8.0 Hz), 3.88 (t, 2H, J = 9.6 Hz), 3.81 (s, 3H).
13C NMR (100 MHz, DMSO-d6) δ (ppm) 171.8,
161.7, 135.9, 125.9, 115.4, 55.9, 54.4, 49.2, 46.0.
Anal. Calcd for C11H15Cl3N2OSTe: С, 28.89; Н, 3.31;
N, 6.13; S, 7.01. Found: С, 28.72; Н, 3.22; N, 6.07;
1
powder; mp 181–182°C. H NMR (400 MHz, DMSO-d6)
δ (ppm) 10.25 (br s, 2H) 8.05 (d, 2H, J = 8.0 Hz), 7.14
(d, 2H, J = 8.8 Hz), 4.30 (d, 1H, J = 8.0 Hz), 4.21 (d, 1H,
J = 8.0 Hz), 4.14–4.07 (m, 3H), 3.89 (d, 1H, J = 8.0 Hz),
2.97 (s, 3H), 1.86 (s, 3H), 1.34 (t, 3H, J = 8.0 Hz). 13C
NMR (100 MHz, DMSO-d6) δ (ppm) 168.6, 160.5,
135.3, 124.9, 115.2, 113.7, 63.6, 59.2, 55.9, 31.3, 27.7,
14.5. Anal. Calcd for C14H21Cl3N2OSTe: С, 33.67; Н,
4.24; N, 5.61; S, 6.42. Found: С, 33.54; Н, 4.11; N, 5.49;
S, 6.87.
N-{2-Chloro-3-[dichloro(4-ethoxyphenyl)-tellanyl]propyl}
thiourea (7).
Yield 56%; white powder; mp 168–
S, 6.33.
1
169°C. H NMR (400 MHz, DMSO-d6) δ (ppm) 10.05
(br s, 1H), 9.61 (br s, 2H), 8.02 (d, 2H, J = 8.0 Hz),
7.08 (d, 2H, J = 8.0 Hz), 4.71–4.62 (m, 1H), 4.09 (q,
2H, J = 8.0 Hz), 3.96 (d, 2H, J = 4 Hz), 3.86 (d, 1H,
J = 8.0 Hz), 3.82 (d, 1H, J = 5.6 Hz), 1.33 (t, 3H,
J = 8.0 Hz). 13C NMR (100 MHz, DMSO-d6) δ (ppm)
171.3, 160.5, 135.4, 125.1, 115.2, 63.5, 53.9, 48.8,
45.5, 14.5. Anal. Calcd for C12H17Cl3N2OSTe: С,
30.58; Н, 3.64; N, 5.94; S, 6.80. Found: С, 30.42; Н,
5-{Dichloro(4-methoxyphenyl)-telluromethyl}-2-
phenylamino-4,5-dihydro-1,3-thiazol hydrochloride (12).
Yield 62%; white powder; mp 185–186°C. 1H NMR
(400 MHz, DMSO-d6) δ (ppm) 11.45 (br s, 1H), 8.05
(d, 2H, J = 8.7 Hz), 7.49–7.46 (m, 2H), 7.39–7.35 (m,
3H), 7.10 (d, 2H, J = 8.7 Hz), 4.75–4.66 (m, 1H), 4.07
(d, 2H, J = 8.0 Hz), 4.00 (dd, 1H, J = 8.0, 6.6 Hz), 3.89
(dd, 1H, J = 8.0, 6.6 Hz), 3.82 (s, 3H). 13C NMR
(100 MHz, DMSO-d6) δ (ppm) 161.6, 137.5, 135.9,
130.1, 127.9, 126.0, 124.1, 115.3, 113.9, 56.0, 55.5,
49.1, 46.1. Anal. Calcd for C17H18Cl2N2OSTe•HCl: С,
38.28; Н, 3.59; N, 5.25; S, 6.01. Found: С, 38.14; Н,
3.51; N, 5.83; S, 6.69.
N-{2-Chloro-3-[dichloro(4-methoxyphenyl)-tellanyl]-2-
methylpropyl} thiourea (8). Yield 58%; white powder; mp
127–128°C. 1H NMR (400 MHz, DMSO-d6) δ (ppm) 10.13
(br s, 1H), 9.71 (br s, 2H), 8.04 (d, 2H, J = 8.0 Hz), 7.11 (d,
2H, J = 8.0 Hz), 4.25 (d, 1H, J = 8.0 Hz), 4.20 (d, 1H,
J = 8.0 Hz), 4.13 (d, 1H, J = 8.0 Hz), 3.86 (d, 1H,
J = 8.0 Hz), 3.83 (s, 3H), 1.87 (s, 3H). Anal. Calcd for
C12H17Cl3N2OSTe: С, 30.58; Н, 3.64; N, 5.94; S, 6.80.
Found: С, 30.41; Н, 3.52; N, 5.85; S, 6.70.
3.41; N, 5.13; S, 5.89.
5-{Dichloro(4-ethoxyphenyl)-telluromethyl}-2-phenylamino-
4,5-dihydro-1,3-thiazol hydrochloride (13).
Yield 65%;
white powder; mp 177–178°C. 1H NMR (400 MHz,
DMSO-d6) δ (ppm) 11.47 (br s, 1H), 8.06 (d, 2H,
J = 8.7 Hz), 7.48–7.45 (m, 2H), 7.39–7.35 (m, 3H), 7.12
(d, 2H, J = 8.7 Hz), 4.74–4.66 (m, 1H), 4.12–4,03 (m,
4H), 4.00 (dd, 1H, J = 6.8 Hz, J = 6.4 Hz), 3.88 (dd, 1H,
J = 5.6 Hz, J = 5.2 Hz), 1.34 (t, 3H, J = 8.0 Hz). 13C
NMR (100 MHz, DMSO-d6) δ (ppm) 160.4, 136.8, 135.5,
129.7, 127.5, 125.4, 123.6, 115.2, 113.7, 63.5, 54.9, 48.7,
N-{2-Chloro-3-[dichloro(4-ethoxyphenyl)-tellanyl]-2-
methylpropyl} thiourea (9).
Yield 60%; white powder;
mp 139–140°C. 1H NMR (400 MHz, DMSO-d6): δ
(ppm) 10.13 (br s, 1H), 9.71 (br s, 2H), 8.04 (d, 2H,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

M. Kut, M. Fizer, M. Onysko, and V. Lendel
Vol 000
REFERENCES AND NOTES
45.5, 14.5. Anal. Calcd for C18H20Cl2N2OSTe•HCl: С,
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3.71; N, 5.03; S, 5.71.
5-{Dichloro(4-methoxyphenyl)-telluromethyl}-5-methyl-2-
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Yield 58%; white powder; mp 129–130°C. 1H NMR
(400 MHz, DMSO-d6) δ (ppm) 11.57 (br s, 1H) 8.06 (d,
2H, J = 8.7 Hz), 7.45–7.42 (m, 2H), 7.30–7.26 (m, 3H),
7.14 (d, 2H, J = 8.8 Hz), 4.36 (d, 1H J = 9.6 Hz), 4.21
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5.86. Found: С, 39.32; Н, 3.73; N, 5.00; S, 5.72.
Computational methods.
All starting geometries
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2018
Reactions of N-alkenyl Thioureas with p-alkoxyphenyltellurium Trichlorides
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet