Synthesis of novel derivatives of 5-(4,6-dimethyl-2-pyrimidinylsulfanyl) methyl-1,2,4-triazole-3-thione

Article abstract of DOI:10.1080/714040956

Alkylation of 5-(4,6-dimethyl-2-pyrimidinylsulfanyl)methyl-1,2,4-triozole- 3-thione (2) with various alkyl halides, 4-chlorophenacyl bromide, chloroacetic acid, and α-chloroacetanilide afforded S-substituted 1,2,4-triazoles (3-11). 3-Carboxymethylsulfanyl-5-(4,6-dimethyl-2-pyrimidinylsulfanyl)methyl-1, 2,4-triazole (9), in the presence of acetic anhydride, was cyclized to 6-(4,6-dimethyl-2-pyrimidinyl-sulfanyl)methylthiazolo[3,2-b][1,2,4]triazol-3(2H) -one (12). The later condensed with aromatic aldehydes to give 6-(4,6-dimethyl-2-pyrimidinylsulfanyl)methyl-6-[(1-aryl)methylidene]thiazolo[3, 2-b][1,2,4]triazol-3(2H)-ones (13, 14) and under treatment with aniline underwent ring-disclosure reaction to yield 3-(phenylcarbamoyl)methylsulfanyl-5- (4,6-dimethyl-2-pyrimidinylsulfanyl)methyl-1,2,4-triazole (11).

Full text of DOI:10.1080/714040956

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Synthesis of Novel Derivatives of 5-(4,6-Dimethyl-2-
Pyrimidinylsulfanyl)methyl-1,2,4-triazole-3-thione
M. M. Burbuliene a , V. Jakubkiene a , G. Mekuskiene a & P. Vainilavicius a
a Vilnius University, Vilnius, Lithuania
Version of record first published: 18 Jun 2010.
To cite this article: M. M. Burbuliene, V. Jakubkiene, G. Mekuskiene & P. Vainilavicius (2003): Synthesis of Novel Derivatives
of 5-(4,6-Dimethyl-2-Pyrimidinylsulfanyl)methyl-1,2,4-triazole-3-thione, Phosphorus, Sulfur, and Silicon and the Related
Elements, 178:11, 2431-2440
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Phosphorus, Sulfur, and Silicon, 178:2431–2440, 2003
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Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500390235389
SYNTHESIS OF NOVEL DERIVATIVES OF 5-(4,6-
DIMETHYL-2-PYRIMIDINYLSULFANYL)METHYL-1,2,4-
TRIAZOLE-3-THIONE
M. M. Burbuliene, V. Jakubkiene, G. Mekuskiene,
and P. Vainilavicius
Vilnius University, Vilnius, Lithuania
(Received April 2, 2003; accepted June 3, 2003)
Alkylation of 5-(4,6-dimethyl-2-pyrimidinylsulfanyl)methyl-1,2,4-
triazole-3-thione (2) with various alkyl halides, 4-chlorophenacyl
bromide, chloroacetic acid, and α-chloroacetanilide afforded S-substi-
tuted 1,2,4-triazoles (3–11). 3-Carboxymethylsulfanyl-5-(4,6-dimethyl-
2-pyrimidinylsulfanyl)methyl-1,2,4-triazole (9), in the presence of
acetic anhydride, was cyclized to 6-(4,6-dimethyl-2-pyrimidinyl-
sulfanyl)methylthiazolo[3,2-b][1,2,4]triazol-3(2H)-one (12). The later
condensed with aromatic aldehydes to give 6-(4,6-dimethyl-2-pyrimi-
dinylsulfanyl)methyl-6-[(1-aryl)methylidene]thiazolo[3,2-b][1,2,4]tri-
azol-3(2H)-ones (13, 14) and under treatment with aniline underwent
ring-disclosure reaction to yield 3-(phenylcarbamoyl)methylsulfanyl-
5-(4,6-dimethyl-2-pyrimidinylsulfanyl)methyl-1,2,4-triazole (11).
Keywords: Alkylation; cyclization; substituted 1,2,4-triazole-3-thiones;
thiazolo[3,2-b]triazolone
A number of bioactive molecules contain functionalized azole and azine
heterocycles. A 1,2,4-triazole moiety is a key component in the structure
of potential anticancer,1 antimigraine2−4 agents. 1,2,4-Triazole deriva-
tives have been reported to exhibit antimicrobial,5−7 antitubercular,8
serotonergic9 activity, and plant protecting properties.7,10,11 Triazole
ring formation reactions, as well as the rich chemistry of fused or pen-
dant 1,2,4-triazoles, are the subject of research in previous and recent
reports.12−17 Our earlier studies involved synthesis of heterocyclic com-
pounds containing in their structures both the pyrimidine and 1,2,4-
triazole fragments.18−20 In this connection and in continuation of our
The authors thank Dr. E. Udrenaite from the Department of Polymer Chemistry,
Faculty of Chemistry, and Professor V. Gaidelis from the Faculty of Medicine of Vilnius
University for the in vivo evaluation of antiinflammatory activity.
Address correspondence to M. M. Burbuliene, Faculty of Chemistry, Vilnius Univer-
sity, Naugarduko 24, LT-2006 Vilnius, Lithuania. E-mail: milda.burbuliene@chf.vu.lt
2431

2432
M. M. Burbuliene et al.
interest in the synthesis of chemically and biologically important het-
erocycles, we now report on 5-(pyrimidinylsulfanyl)methyl substituted
1,2,4-triazoles.
RESULTS AND DISCUSSION
Triazole 2 was prepared by the condensation reaction of ester 1 with
thiosemicarbazide in the presence of sodium methoxide. While optimiz-
ing this reaction, we found that an excess of thiosemicarbazide and long
reaction times were necessary for high yields of desired product 2. It
was observed that work-up of the reaction mixture with acetic acid in-
stead of hydrochloric acid as well as using low temperatures (∼5◦C)
with the reaction mixture was preferable.
The alkylation of triazole 2 with various alkylating agents was stud-
ied, and 3-alkyl substituted derivatives 3–11 were obtained. These reac-
tions were carried out in methanol/sodium methoxide solution affording
yields of compounds 3–11 from moderate to high (57–94%). Notewor-
thy was the use of triethylamine as a base instead of sodium methoxide,
which did not influence reaction time nor yield of compounds. The yields
varied depending on alkylating agent used. Formation of alkyl deriva-
tives 3–6 was achieved in 1–2 h. Alkylation of 2 with 4-chlorophenacyl
bromide was complete within 0.5 h in high yield of 8 (91%), while the
reaction of 2 with α-chloroacetanilide proceeded in 8 h to give a poor
yield of compound 11 (37%). Acid 9 was synthesized analogously in mod-
erate yield (66%). Acid 9 also was synthesized by a more efficient and
simple method. Thus, triazole 2 reacted with chloroacetic acid in glacial
acetic acid at reflux in the presence of anhydrous sodium acetate to give
an excellent yield (94%) of acid 9. The IR spectra of compounds 3–11
display intensive absorption bands at 1260–1268 cm−1,characteristic
for S-alkylated 1,2,4-triazoles,21 and the absorption for N C S in the
region of 1337 cm−1, characteristic for 1,2,4-triazole-2-thione, was ab-
sent. Treatment of acid 9 with acetic anhydride at reflux induced cycli-
sation to occur and yielded thiazolo[3,2-b]triazolone 12. Moreover, the
same compound 12 was obtained from the triazole 2 in a one-pot, four-
component cycloalkylation reaction, i.e., on heating of the mixture of tri-
azole 2, chloroacetic acid, acetic anhydride, and anhydrous sodium ac-
etate in acetic acid. Cyclisation of acid 9 by the action of acetic anhydride
may occur either at N-2 or at the N-4 atom. The N-2 atom is more likely
involved in the cyclisation reaction because of its greater basicity.22,23
The 1H NMR spectra of compounds 9 and 12 support the structures and
this type of reaction. If cyclization would take place at N-4 atom, one
would expect influence by the carbonyl group on neighbouring protons

Synthesis of Triazoles
2433
SCHEME 1
to be markedly shifted downfield.23,24 Shifts of the CH2S group protons
of acid 9 and the corresponding shift of the CH2S protons of cyclic com-
pound 12 have almost the same values. The IR spectrum of compound 12
displayed an intense absorption band at 1769 cm−1. Absorption in this

2434
M. M. Burbuliene et al.
region is characteristic for ring-fused thiazolotriazolones.25 The methy-
lene groups (C-2) of compound 12 condensed with aromatic aldehydes
to give compounds 13, 14. The latter also were prepared by the reaction
of acid 9 and aromatic aldehyde in the presence of acetic anhydride or
by direct reaction of the mixture of triazole 2, chloroacetic acid, acetic
anhydride, an aromatic aldehyde, and sodium acetate in acetic acid.
1
In the H NMR spectra of compounds 13, 14, characteristic chemical
shifts of CH2S protons are observed in the same region (4.59–4.61 ppm)
as those for compound 12. Moreover, compounds 13, 14 display signals
characteristic of methine protons (8.19–8.26 ppm) and signals of aro-
matic protons (7.21–7.90 ppm). In the IR spectra, due to conjugation of
the C O with double bonds, the absorption bands for the C O group in
compounds 13, 14 are observed at lower frequencies (23–35 cm−1) com-
pared with that of compound 12. Thiazolotriazolone ring of 12 under
treatment with an excess of aniline was easily opened to give anilide 11.
Thus, the said conversion is expedient for the synthesis of compound
9 since the alkylation reaction of triazole 2 with α-chloroacetanilide to
obtain compound 11 was not so successful.
SCHEME 2
The action of concentrated sulfuric acid on compound 8 at 0◦C induced
the thiazolotriazolone ring closure with formation of compound 15. The
shift of CH2S protons of 15 is in the same region as those of thiazolo-
triazoles 12–14. Also a characteristic signal of the vinyl proton occured
at 7.91 ppm in the 1H NMR spectra of 15.
Compounds were preliminary tested for their anti-inflammatory
activity. Several of compounds, i.e., 2, 4, 9, exhibited slight anti-
inflammatory activity induced in rats by bentonite and carrageenin.
EXPERIMENTAL
Melting points were determined in open capillaries and are uncor-
rected. The IR spectra were measured on a Spectrum BX FT-IR (Perkin-
Elmer) in Nujol, 1H-NMR spectra were recorded on a BS-587A (80 MHz,

Synthesis of Triazoles
2435
Tesla) in DMSO-d6 with TMS as an internal standard. Chemical shifts
(δ) are reported in ppm and coupling constants (J) are given in Hz.
The reactions were monitored by TLC on silica gel coated Al plates
(KAVALIER). Elemental analyses were performed at the Microanaly-
sis Laboratory of the Department of Organic Chemistry of Vilnius Uni-
versity. Methyl (4,6-dimethyl-2-pyrimidinylsulfanylmethyl)acetate (1)
was synthesised according literature.26
5-(4,6-Dimethyl-2-pyrimidinylsulfanyl)methyl-1,2,4-
triazole-3-thione (2)
A mixture of ester 1 (10 mmol, 2.12 g), thiosemicarbazide (10 mmol, 0.91
g), and sodium methoxide (10 mmol, 0.23 g of sodium dissolved in 15 ml
CH3OH) was refluxed in CH3OH (30 ml) for 20 h. The solvent was re-
moved in vacuo, and the residue was dissolved in H2O (50 ml), acidified
carefully with acetic acid (at 0–5◦C) to pH 6, filtered, and recrystallized
from isopropanol. Yield 1.67 g (66%), m.p. 216–217◦C. Anal. calcd. for
C9H11N5S2 (253.35): C, 42.67; H, 4.38; N, 27.64. Found: C, 42.82; H,
1
4.49; N, 27.88. H NMR: 2.37 (s, 6H, 2 CH3), 4.35 (s, 2H, CH2S), 6.99
(s, 1H, CH), 13.26 (s, 1H, NH). IR (cm−1): 3086 (NH), 1572, 1532 (C C,
C N), 1337 (N C S).
3-Alkyl Substituted 5-(4,6-dimethyl-2-
pyrimidinylsulfanyl)methyl-1,2,4-triazoles (3–11)
(General Procedure)
To a stirred solution of triazole 2 (5 mmol, 1.27 g) and sodium methoxide
(5 mmol, 0.115 g of sodium dissolved in 10 ml CH3OH) in CH3OH (20
ml) was added dropwise a solution of alkyl halide (5 mmol) in CH3OH
(10 ml). The reaction mixture was refluxed for 1–2 h and filtered off.
The filtrate was concentrated in vacuo, and the residue was filtered and
recrystallized from appropriate solvent.
5-(4,6-Dimethyl-2-pyrimidinylsulfanyl)methyl-3-
propylsulfanyl-1,2,4-triazole (3)
Yield 52%, m.p. 57–58◦C (from hexane). Anal. calcd. for C12H17N5S2
(295.43): C, 48.81; H, 5.76; N, 23.73. Found: C, 49.06; H, 5.53; N, 23.81.
1H NMR: 0.97 (t, J= 4 Hz, 3H, CH3), 1.62 (m, 2H, CH2), 2.35 (s, 6H, 2
CH3), 3.03 (t, J= 4 Hz, 2H, SCH2-3), 4.40 (s, 2H, CH2S-5), 6.98 (s, 1H,
CH), 13.79 (s, 1H, NH). IR (cm−1): 3115 (NH), 1583, 1533 (C C, C N),
1268 (S-alkyl 1,2,4-triazoles).

2436
M. M. Burbuliene et al.
3-Butylsulfanyl-5-(4,6-dimethyl-2-pyrimidinylsulfanyl)
methyl-1,2,4-triazole (4)
Yield 73%, m.p. 70–71◦C (from hexane). Anal. calcd. for C13H19N5S2
(309.46): C, 50.46; H, 6.19; N, 22.63. Found: C, 50.38; H, 6.36; N, 22.84.
1H NMR: 1.29 (t, J= 6 Hz, 3H, CH3), 1.89 (m, 4H, 2 CH2), 2.38 (s, 6H, 2
CH3), 3.07 (t, J= 6 Hz, 2H, SCH2-3), 4.45 (s, 2H, CH2S-5), 6.98 (s, 1H,
CH), 13.78 (s, 1H, NH). IR (cm−1): 3148 (NH), 1584, 1533 (C C, C N),
1266 (S-alkyl 1,2,4-triazoles).
3-Decylsulfanyl-5-(4,6-dimethyl-2-pyrimidinylsulfanyl)
methyl-1,2,4-triazole (5)
Yield 49%, m.p. 36–37◦C (from hexane). Anal. calcd. for C19H31N5S2
(393.62): C, 58.02; H, 7.89; N, 17.81. Found: C, 58.15; H, 7.76; N, 17.89.
1H NMR: 0.86 (t, J= 4 Hz, 3H, CH3), 1.25 (m, 16H, 8 CH2), 2.37 (s, 6H,
2 CH3), 3.07 (t, J= 4 Hz, 2H, SCH2-3), 4.45 (s, 2H, CH2S-5), 6.99 (s, 1H,
CH), 13.20 (s, 1H, NH). IR (cm−1): 3156 (NH), 1586, 1537 (C C, C N),
1267 (S-alkyl 1,2,4-triazoles).
3-Allylsulfanyl-5-(4,6-dimethyl-2-pyrimidinylsulfanyl)
methyl-1,2,4-triazole (6)
Yield 65%, m.p. 64–65◦C (from hexane). Anal. calcd. for C12H15N5S2
(293.42): C, 49.15; H, 5.12; N, 23.89. Found: C, 49.22; H, 5.10; N, 23.70.
1H NMR: 2.41 (s, 6H, 2 CH3), 3.77 (d, J= 4 Hz, 2H, SCH2-3), 4.49 (s,
2H, CH2S-5), 5.15, 5.34 (2s, 2H, CH2), 5.93 (m, 1H, CH), 7.03 (s, 1H,
CH), 13.88 (s, 1H, NH). IR (cm−1): 3082 (NH), 1581, 1532 (C C, C N),
1265 (S-alkyl 1,2,4-triazoles).
3-Benzylsulfanyl-5-(4,6-dimethyl-2-pyrimidinylsulfanyl)
methyl-1,2,4-triazole (7)
Yield 85%, m.p. 91–93◦C (from cyclohexane). Anal. calcd. for
C16H17N5S2 (343.48): C, 55.98; H, 4.96; N, 20.41. Found: C, 55.80; H,
5.02; N, 20.44. 1H NMR: 2.37 (s, 6H, 2 CH3), 4.34 (s, 2H, SCH2-3), 4.48
(s, 2H, CH2S-5), 7.00 (s, 1H, CH), 7.30 (m, 5H, C6H5), 13.86 (s, broad,
1H, NH). IR (cm−1): 3105 (NH), 1582, 1532 (C C, C N), 1260 (S-alkyl
1,2,4-triazoles).
3-[(4-Chlorophenyl)carbonylmethylsulfanyl]-5-(4,6-
dimethyl-2-pyrimidinylsulfanyl)methyl-1,2,4-triazole (8)
Yield 91%, m.p. 104–105◦C (from H2O + CH3OH). Anal. calcd. for
C17H16ClN5OS2 (389.93): C, 50.31; H, 3.95; N, 17.26. Found: C, 49.96;

Synthesis of Triazoles
2437
1
H, 3.95; N, 17.33. H NMR: 2.35 (s, 6H, 2 CH3), 4.43 (s, 2H, CH2S-5),
4.79 (s, 2H, SCH2-3), 6.98 (s, 1H, CH), 7.61 (d, J= 6 Hz, 2H, aromatic),
8.04 (d, J= 6 Hz, 2H, aromatic). IR (cm−1): 3054 (NH), 1683 (CO), 1587,
1532 (C C, C N), 1268 (S-alkyl 1,2,4-triazoles).
3-Carboxymethylsulfanyl-5-(4,6-dimethyl-2-
pyrimidinylsulfanyl)methyl-1,2,4-triazole (9)
Method A
A mixture of triazole 2 (3.8 mmol, 0.95 g), chloroacetic acid (3.8 mmol,
0.36 g), and sodium methoxide (7.6 mmol, 0.175 g of sodium dissolved
in 10 ml CH3OH) in CH3OH (30 ml) was heated at reflux for 2 h. After
the solvent was evaporated, the residue was dissolved in ice-cold water
and acidified with acetic acid. The solid formed was filtered off and
recrystallized from H2O. Yield 0.77 g (66%).
Method B
A mixture of triazole 2 (3.8 mmol, 0.95 g), chloroacetic acid (3.8 mmol,
0.36 g), and sodium acetate (0.49 g, 6 mmol) in acetic acid (30 ml) was
heated at reflux for 2 h. Then the solution was evaporated to dryness,
and the residue was recrystallized from H2O. Yield 0.88 g (75%), m.p.
84–85◦C. Anal. calcd. for C11H13N5O2S2 (311.39): C, 42.43; H, 4.21; N,
22.49. Found: C, 42.25; H, 4.27; N, 22.27. 1H NMR: 2.40 (s, 6H, 2 CH3),
3.93 (s, 2H, SCH2-3), 4.46 (s, 2H, CH2S-5), 6.96 (s, 1H, CH), 14.2 (s,
broad, 1H, NH). IR (cm−1): 3135 (NH); 1694, (CO), 1589, 1537 (C C,
C N), 1269 (S-alkyl 1,2,4-triazoles).
3-Ethoxycarbonylmethylsulfanyl-5-(4,6-dimethyl-2-
pyrimidinylsulfanyl)methyl-1,2,4-triazole (10)
Yield 74%, m.p. 95–96◦C. Anal. calcd. for C12H15N5O2S2 (325.42): C,
1
44.31; H, 4.62; N, 21.54. Found: C, 44.58; H, 4.56; N, 21.47. H NMR:
1.16 (t, J= 6 Hz, 3H, CH3), 2.36 (s, 6H, 2 CH3), 3.97 (s, 2H, SCH2-3),
4.05 (q, J= 6 Hz, 2H, OCH2), 4.45 (s, 2H, CH2S-5), 6.99 (s, 1H, CH),
13.92 (s, broad, 1H, NH). IR (cm−1): 3098 (NH), 1726 (CO), 1590, 1530
(C C, C N), 1265 (S-alkyl 1,2,4-triazoles).
3-(Phenylcarbamoyl)methylsulfanyl-5-(4,6-dimethyl-2-
pyrimidinylsulfanyl)methyl-1,2,4-triazole (11)
Method A
As described in General procedure for compounds 3–11. Reaction
time 8 h. Yield, 37%.

2438
M. M. Burbuliene et al.
Method B
A mixture of compound 12 (1.3 mmol, 0.38 g) and aniline (5.2 mmol,
4.84 g, 4.74 ml) was refluxed in n-propanol (8 ml) for 2 h. After cooling,
the product was filtered off and recrystallized from isopropanol. Yield
0.31 g (65%), m.p. 172–173◦C. Anal. calcd. for C17H18N6OS2 (386.5): C,
1
52.83; H, 4.69; N, 21.74. Found: C, 53.10; H, 4.67; N, 21.81. H NMR:
2.37 (s, 6H, 2 CH3), 4.07 (s, 2H, SCH2-3), 4.48 (s, 2H, CH2S-5), 6.80
(s, 1H, CH), 7.30 (m, 5H, C6H5), 13.90 (s, broad, 1H, NH). IR (cm−1):
3292, 3189 (NH), 1666 (CO), 1585, 1535 (C C, C N), 1264 (S-alkyl
1,2,4-triazoles).
6-(4,6-Dimethyl-2-pyrimidinylsulfanyl)
methylthiazolo[3,2-b][1,2,4]triazol-3(2H)-one (12)
Method A
An acid 9 (1.6 mmol, 0.5 g) was refluxed in acetic anhydride (7 ml) for
2 h, and then the reaction mixture was cooled and poured into ice-water.
The solid was filtered off, dried and recrystallized from benzene. Yield
0.38 g (81%), m.p. 143–145◦C. Anal. calcd. for C11H11N5OS2 (293.37):
C, 42.43; H, 4.21; N, 22.49. Found: C, 41.80; H, 4.47; N, 22.27. 1H NMR:
2.36 (s, 6H, 2 CH3), 4.64 (s, 2H, CH2S-6), 4.52 (s, 2H, CH2-2), 7.00 (s,
1H, CH). IR (cm−1): 1769 (CO), 1576, 1508 (C C, C N), 1265 (S-alkyl
1,2,4-triazoles).
Method B
A mixture of triazole 2 (5 mmol, 1.27 g), chloroacetic acid (8 mmol
0.76 g), sodium acetate (12 mmol, 0.98 g) in acetic acid (10 ml)-acetic
anhydride (15 ml) solution was refluxed for 2 h and worked as above.
Yield 1.12 g (77%).
6-(4,6-Dimethyl-2-pyrimidinylsulfanyl)methyl-2-[(1-aryl)
methylidene]thiazolo[3,2-b] [1,2,4]triazol-3(2H)-ones
(13–14)
Method A
A mixture of triazole 2 (5 mmol, 1.27 g), chloroacetic acid (8 mmol,
0.76 g), sodium acetate (12 mmol, 0.98 g) and an aromatic aldehyde
(8 mmol) in acetic acid ((10 ml)—acetic) anhydride (15 ml) solution was
refluxed for 2 h. When cooled, the precipitate was filtered off, washed
with water and ethanol, and recrystallized from n-butanol.

Synthesis of Triazoles
2439
Method B
A mixture of acid 9 (4 mmol, 1.25 g) and an aromatic aldehyde
(4 mmol) in acetic acid (10 ml)-acetic anhydride (7 ml) solution was
heated at 90◦C for 2 h and decomposed as above.
Method C
A mixture of compound 12 (4 mmol, 1.17 g) and an aromatic aldehyde
(4 mmol) in acetic acid (10 ml) was heated at 95–100◦C for 1 h and
decomposed as above.
6-(4,6-Dimethyl-2-pyrimidinylsulfanyl)methyl-2-[(phenyl)
methylidene]thiazolo[3,2-b][1,2,4]triazol-3(2H)-one (13)
Yield 78%, m.p. 180–182◦C. Anal. calcd. for C18H15N5OS2 (381.48 ): C,
1
56.67; H, 3.96; N, 18.36. Found: C, 56.78; H, 4.27; N, 18.31. H NMR:
2.39 (s, 6H, 2 CH3), 4.61 (s, 2H, CH2S-6), 7.00 (s, 1H, CH pyrimidine),
7.70 (m, 5H, C6H5), 8.26 (s, 1H, CH). IR (cm−1): 1746 (CO), 1588, 1520
(C C, C N), 1268 (S-alkyl 1,2,4-triazoles).
6-(4,6-Dimethyl-2-pyrimidinylsulfanyl)methyl-2-[(4-
methoxyphenyl)methylidene]thiazolo[3,2-b][1,2,4]
triazol-3(2H)-one (14)
Yield 75%, m.p. 202–204◦C. Anal. calcd. for C19H17N5O2S2 (411.51): C,
1
55.46; H, 4.16; N, 17.02. Found: C, 55.66; H, 4.31; N, 17.27. H NMR:
2.43 (s, 6H, 2 CH3), 3.93 (s, 3H, OCH3), 4.59 (s, 2H, CH2S-6), 7.00 (s,
1H, CH pyrimidine), 7.11 (d, J= 6 Hz 2H, aromatic), 7.69 (d, J= 6 Hz
2H, aromatic), 8.19 (s, 1H, CH). IR (cm−1): 1734 (CO), 1585, 1513 (C C,
C N), 1267 (S-alkyl 1,2,4-triazoles).
3-(4-Chlorophenyl)-6-(4,6-dimethyl-2-
pyrimidinylsulfanyl)methylthiazolo[3,2-b][1,2,4]
triazole (15)
Compound 8 (1.48 mmol, 0.6 g) was stirred in conc. H2SO4 (4 ml) at
0◦C for 0.5 h. Then the mixture was diluted with ice-cold water (15 ml)
and neutralized with 15% KOH solution. The precipitate was filtered
off, washed with water and methanol, and recrystallized from benzene.
Yield 75%, m.p. 188–190◦C. Anal. calcd. for C17H14ClN5S2 (387.92): C,
52.64; H, 3.64; N, 18.05. Found: C, 52.96; H, 3.72; N, 18.19. 1H NMR: 2.38
(s, 6H, 2 CH3), 4.65 (s, 2H, CH2S-6), 6.96 (s, 1H, CH pyrimidine), 7.61
(d, J= 6 Hz 2H, aromatic), 7.91 (s, 1H, CH), 8.23 (d, J= 6 Hz 2H, aro-
matic). IR (cm−1): 1584, 1534 (C C, C N), 1267 (S-alkyl 1,2,4-triazoles).

2440
M. M. Burbuliene et al.
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