Phosphorus pentachloride-induced transformation of (1,2,3-thiadiazol-5-yl) hydrazones of acetophenone

Article abstract of DOI:10.1007/s11172-011-0154-3

Reactions of (4-ethoxycarbonyl-1,2,3-thiadiazol-5-yl)hydrazones of acetophenone with PCl₅ led to transformation of the 1,2,3-thiadiazole moiety involving four atoms of the side chain to give 6-aryl-5H-[1,2,3] triazolo[5,1-b][1,3,4]thiadiazine-3

Full text of DOI:10.1007/s11172-011-0154-3

Russian Chemical Bulletin, International Edition, Vol. 60, No. 5, pp. 981—984, May, 2011
981
Phosphorus pentachlorideꢀinduced transformation of
(1,2,3ꢀthiadiazolꢀ5ꢀyl)hydrazones of acetophenone*
T. A. Kalinina, P. E. Prokhorova, T. V. Glukhareva, and Yu. Yu. Morzherin
aUral Federal University named after the First President of Russia B. N. El´tsin ,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Fax: +7 (343) 375 4135. Eꢀmail: morzherin@mail.ustu.ru
Reactions of (4ꢀethoxycarbonylꢀ1,2,3ꢀthiadiazolꢀ5ꢀyl)hydrazones of acetophenone with
PCl5 led to transformation of the 1,2,3ꢀthiadiazole moiety involving four atoms of the side
chain to give 6ꢀarylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiadiazineꢀ3ꢀcarbonyl chlorides. Reacꢀ
tion of the latter with alcohols and amines gave the corresponding esters and amides.
Key words: 1,2,3ꢀthiadiazoles, 1,2,3ꢀtriazoles, Dimroth rearrangement, [1,2,3]triazoloꢀ
[5,1ꢀb][1,3,4]thiadiazines, hydrazones, phosphorus pentachloride, heterocyclization.
Scheme 1
1,2,3ꢀThiadiazoles are the convenient objects for variꢀ
ous rearrangements,1 e.g., the Dimroth,2—4 the Cornꢀ
forth,5,6 and the L´abbé7,8 rearrangements. Note that
the Dimroth rearrangement of 1,2,3ꢀthiadiazoles into
1,2,3ꢀtriazoles proceeds mainly in the basic media, only
few examples of this rearrangement in the acidic condiꢀ
tions are documented.1 It have previously been shown9
that (1,2,3ꢀthiadiazolyl)hydrazones under the action of
PCl5 underwent transformations to give 1,2,3ꢀtriazole deꢀ
rivatives; the directions of the reaction depended on the
solvent used. The key step of the process is the Dimroth
rearrangement of 1,2,3ꢀthiadiazole ring into 1,2,3ꢀtriꢀ
azole ring.
In continuation of our research on the rearrangements
and transformations of 1,2,3ꢀthiadiazoles, we carried out
the reaction of (4ꢀethoxycarbonylꢀ1,2,3ꢀthiadiazolꢀ5ꢀ
yl)hydrazones of acetophenone 1 with PCl5 in benzene
(Scheme 1). It was found that this reaction furnished 6ꢀ
arylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiadiazineꢀ3ꢀcarbꢀ
onyl chlorides 2.
It should be noted that this transformations is the third
example10,11 of the transformation of 1,2,3ꢀthiadiazole ring
involving four atoms of the side chain. Earlier,11 similar
transformation into 5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]ꢀ
thiadiazines was observed on treatment of acetophenone
(1,2,3ꢀthiadiazolꢀ5ꢀyl)hydrazones with thionyl chloride
with the exception that no conversion of ester group into
acyl chloride one took place, however, the methylene group
of thiadiazine ring was chlorinated.
i. PCl , C6H6; ii. HY.
5
Comꢀ
pound
1a
1b
1c
2a
2b
3a
3b
3c
3d
3e
3f
Ar
Y
Ph
—
—
—
—
—
4ꢀMeC6H4
4ꢀMeOC6H4
Ph
4ꢀMeC6H4
Ph
4ꢀMeC6H4
Ph
4ꢀMeOC6H4
Ph
4ꢀMeC6H4
Ph
OEt
OEt
OCHMe2
OCHMe2
OCH2CHMe2
O(CH2)2CHMe2
NHCHMe2
NH(CH2)2OH
BnNH
BnNH
4ꢀMeOC6H4NH
4ꢀMeOC6H4NH
3g
3h
3i
3j
3k
Ph
Ph
4ꢀMeC6H4
Ph
4ꢀMeC6H4
3l
Treatment of the resulting chlorides 2 with alcohols
afforded triazolothiadiazineꢀ3ꢀcarboxylates 3a—f (see
Scheme 1). Amides 3g—l were synthesized without isolaꢀ
tion of the intermediate chloride 2 by the addition of the
corresponding amines in the reaction mixture.
In summary, one step procedure towards triazolothiaꢀ
diazine chlorides via five successive reactions, namely, the
* Dedicated to academician V. N. Charushin on the occasion of
his 60 birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 957—960, May, 2011.
1066ꢀ5285/11/6005ꢀ981 © 2011 Springer Science+Business Media, Inc.

982
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 5, May, 2011
Kalinina et al.
1
179 °C. H NMR (DMSOꢀd6), δ: 3.89 (s, 3 H, OCH3); 4.22
(s, 2 H, CH2); 7.07 (d, 2 H, ArH, J = 9.2 Hz); 8.07 (d, 2 H, ArH,
J = 8.8 Hz). 13C NMR (DMSOꢀd6), δ: 11.46; 21.34; 56.10;
115.09; 125.36; 128.67; 130.31; 133.58; 155.31; 161.66; 163.25.
MS (EI, 70 eV), m/z (Irel (%)): 308 [M(35Cl)]+ (3), 310 [M(37Cl)]+
(1). Found (%): C, 46.69; H, 2.95; N, 18.14; S, 10.40.
C12H9ClN4O2S. Calculated (%): C, 46.68; H, 2.94; N, 18.15;
S, 10.39.
Dimroth rearrangement, chlorination of the methyl group
of the acetophenone fragment, ring closure involving nuꢀ
cleophilic nitrogen atom of the hydrazine group, and transꢀ
formation of the ester group into chlorocarbonyl moiety,
was suggested. This procedure serves for the significant
increase in the yield of the fused heterocyclic compounds
of the type 2.
Alkyl 6ꢀarylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiadiazineꢀ
3ꢀcarboxylates 3a—f (general procedure). To a suspension of
(1,2,3ꢀthiadiazolꢀ5ꢀyl)hydrazone of acetophenone (1.40 mmol)
in benzene (20 mL), PCl5 (0.58 g, 2.8 mmol) was added and the
mixture was refluxed for 3 h. Then the reaction mixture was
washed with water (3×20 mL). The organic layer was dried with
Na2SO4, the solvent was removed in vacuo. The corresponding
alcohol (10 mL) was added to the residue, and mixture was reꢀ
fluxed for 30 min. After cooling, the precipitate that formed was
filtered off and dried.
Experimental
IR spectra were recorded on a Bruker Alpha spectrometer
1
utilizing attenuated total reflection. H and 13C NMR spectra
were run on a Bruker AVANCE II 400 instrument (400
and 100 MHz, respectively) relative to Me4Si (internal stanꢀ
dard). Electrospray ionization mass spectra were recorded on
a MicrOTOFꢀQ II instrument (Bruker Daltonics) equipped with
sixꢀport lock chamber using direct inlet kd Scientific (flow rate is
180 μL h–1) operating in the positive ion mode, mass range is
50—800 Da. Mass spectrometry was monitored by micrOTOF
control 2.3 patch 1 and HyStar 3.2 (Bruker Daltonics) software.
Nominal mass resolution is m/z 17500. Electron impact mass
spectra were obtained on a Varian MAT 3111A mass spectromeꢀ
ter (70 eV, direct inlet).
Ethyl 6ꢀphenylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiadiazineꢀ
3ꢀcarboxylate (3a). Yield 0.218 g (54%), m.p. 167 °C. IR, ν/cm–1
:
1720 (C=O). 1H NMR (DMSOꢀd6), δ: 1.40 (t, 3 H, OCH2CH3,
J = 7.0 Hz); 4.30 (s, 2 H, CH2); 4.38 (q, 2 H, OCH2CH3, J = 7.2
Hz); 7.55—7.63 (m, 3 H, ArH); 8.10 (d, 2 H, ArH, J = 7.2 Hz).
13C NMR (DMSOꢀd6), δ: 14.64; 21.65; 61.46; 128.32; 129.27;
129.66; 132.80; 133.11; 133.37; 156.08; 160.10. MS (ESI), m/z:
289.0716 [M + H]+; calculated: 289.0754 [M + H]. Found (%):
C, 52.15; H, 4.18; N, 19.44; S, 11.12. C13H12N4O2S. Calculatꢀ
ed (%): C, 52.16; H, 4.20; N, 19.43; S, 11.12.
The starting thiadiazolylhydrazones of acetophenone 1a—c
were synthesized according to the known procedure12. Benzene
(ZAO EKOSꢀ1) was used as purchased.
6ꢀArylꢀ3ꢀchlorocarbonylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]ꢀ
thiadiazines 2 (general procedure). To a suspension of (1,2,3ꢀthiaꢀ
diazolꢀ5ꢀyl)hydrazone of acetophenone 113 (1.40 mmol) in
benzene (20 mL), PCl5 (0.58 g, 2.8 mmol) was added and the
mixture was refluxed for 3 h. Color of the reaction mixture was
changed from yellow to orange. Then the reaction mixture was
washed with water (3×20 mL), organic layer was dried with
Na2SO4, the solvent was removed in vacuo, and the residue was
triturated with EtOH. Brown precipitate that formed was filꢀ
tered off and dried.
Ethyl 6ꢀ(4ꢀmethylphenyl)ꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]ꢀ
thiadiazineꢀ3ꢀcarboxylate (3b). Yield 0.228 g (54%), m.p. 168 °C.
IR, ν/cm–1: 1720 (C=O). 1H NMR (DMSOꢀd6), δ: 1.40 (t, 3 H,
OCH2CH3, J = 7.0 Hz); 4.26 (s, 2 H, CH2); 4.36 (q, 2 H,
OCH2CH3, J = 7.0 Hz); 7.37 (d, 2 H, ArH, J = 8.0 Hz); 7.99
(d, 2 H, ArH, J = 8.0 Hz). 13C NMR (DMSOꢀd6), δ: 14.64;
21.42; 21.68; 61.43; 128.28; 129.27; 130.66; 133.10; 133.80;
143.47; 156.08; 160.08. MS (ESI), m/z: 303.0870 [M + H]+;
calculated: 303.0910 [M + H]. Found (%): C, 55.65; H, 4.68;
N, 18.59; S, 10.62. C14H14N4O2S. Calculated (%): C, 55.61;
H, 4.67; N, 18.53; S, 10.61.
Isopropyl 6ꢀphenylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiaꢀ
diazineꢀ3ꢀcarboxylate (3c). Yield 0.157 g (52%), m.p. 174 °C.
IR, ν/cm–1: 1720 (C=O). 1H NMR (DMSOꢀd6), δ: 1.39 (d, 6 H,
OCH(CH3)2, J = 6.0 Hz); 4.28 (s, 2 H, CH2); 5.16—5.23
(m, 1 H, OCH(CH3)2); 7.55—7.62 (m, 3 H, ArH); 8.10 (d, 2 H,
ArH, J = 7.2 Hz). 13C NMR (DMSOꢀd6), δ: 21.64; 22.19;
69.25; 128.31; 129.12; 129.66; 133.00; 133.10; 133.39; 156.04;
159.61. MS (ESI), m/z: 303.0868 [M + H]+; calculated: 303.0910
[M + H]. Found (%): C, 55.62; H, 4.71; N, 18.51; S, 10.60.
C14H14N4O2S. Calculated (%): C, 55.61; H, 4.67; N, 18.53;
S, 10.61.
6ꢀPhenylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiadiazineꢀ3ꢀ
carbonyl chloride (2a). Yield 0.22 g (56%), m.p. 173 °C. IR,
1
ν/cm–1: 1725 (C=O); 690 (C—Cl). H NMR (DMSOꢀd6), δ:
4.28 (s, 2 H, CH2); 7.55—7.62 (m, 3 H, ArH); 8.09 (d, 2 H,
ArH, J = 6.8 Hz). 13C NMR (DMSOꢀd6), δ: 21.65; 128.28;
128.96; 129.64; 133.04; 133.40; 133.64; 155.86; 161.63. MS (EI,
70 eV), m/z (Irel (%)): 278 [M(35Cl)]+ (7), 280 [M(37Cl)]+ (2).
Found (%): C, 47.42; H, 2.52; N, 20.09; S, 11.53; Cl, 12.70.
C11H7ClN4OS. Calculated (%): C, 47.40; H, 2.53; N, 20.10;
S, 11.50; Cl, 12.65.
6ꢀ(4ꢀMethylphenyl)ꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiaꢀ
diazineꢀ3ꢀcarbonyl chloride (2b). Yield 0.25 g (61%), m.p.
175—176 °C. IR, ν/cm–1: 1725 (C=O); 690 (C—Cl). H NMR
1
(DMSOꢀd6), δ: 2.45 (s, 3 H, CH3); 4.24 (s, 2 H, CH2); 7.36
(d, 2 H, ArH, J = 8.0 Hz); 8.00 (d, 2 H, ArH, J = 8.4 Hz).
13C NMR (DMSOꢀd6), δ: 21.50; 21.58; 128.28; 128.88;
130.23; 130.57; 133.61; 143.45; 155.73; 161.64. MS (ESI), m/z:
293.0211 [M(35Cl) + H]+, 295.0180 [M(37Cl) + H]+; calcuꢀ
lated: 293.0258 [M(35Cl) + H], 295.0229 [M(37Cl) + H].
Found (%): C, 49.13; H, 3.14; N, 19.09; S, 11.00; Cl, 12.03.
C12H9ClN4OS. Calculated (%): C, 49.23; H, 3.10; N, 19.14;
S, 10.95; Cl, 12.11.
Isopropyl 6ꢀ(4ꢀmethoxyphenyl)ꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb]ꢀ
[1,3,4]thiadiazineꢀ3ꢀcarboxylate (3d). Yield 0.183 g (55%), m.p.
1
178—179 °C. IR, ν/cm–1: 1720 (C=O). H NMR (DMSOꢀd6),
δ: 1.39 (d, 6 H, OCH(CH3)2, J = 6.0 Hz); 3.89 (s, 3 H, CH3);
4.22 (s, 2 H, CH2); 5.16—5.22 (m, 1 H, OCH(CH3)2); 7.07
(d, 2 H, ArH, J = 8.8 Hz); 8.07 (d, 2 H, ArH, J = 8.8 Hz).
13C NMR (DMSOꢀd6), δ: 21.33; 22.19; 56.11; 69.18; 115.11;
125.30; 128.90; 130.32; 132.95; 155.48; 159.65; 163.30. MS (ESI),
m/z: 333.0973 [M + H]+; calculated: 333.1016 [M + H].
Found (%): C, 54.22; H, 4.89; N, 16.82; S, 9.68. C15H16N4O3S.
Calculated (%): C, 54.20; H, 4.85; N, 16.86; S, 9.65.
6ꢀ(4ꢀMethoxyphenyl)ꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]ꢀ
thiadiazineꢀ3ꢀcarbonyl chloride (2c). Yield 0.28 g (65%), m.p.

[1,2,3]Triazolo[5,1ꢀb][1,3,4]thiadiazines
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 5, May, 2011
983
Isobutyl 6ꢀphenylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiaꢀ
ν/cm–1: 3330 (NH); 1645 (C=O). 1H NMR (DMSOꢀd6), δ:
4.24 (s, 2 H, CH2); 4.45 (d, 2 H, NHCH2, J = 6.4 Hz); 7.27—
7.34 (m, 5 H, CH2Ph); 7.55—7.62 (m, 3 H, ArH); 8.08 (d, 2 H,
ArH, J = 7.2 Hz); 9.13 (t, 1 H, NH, J = 6.4 Hz). 13C NMR
(DMSOꢀd6), δ: 21.26; 46.73; 127.13; 128.28; 128.79; 129.65;
131.90; 132.80; 133.57; 136.32; 140.77; 143.13; 156.84; 160.27.
MS (ESI), m/z: 350.1011 [M + H]+; calculated: 350.1070
[M + H]. Found (%): C, 61.85; H, 4.35; N, 20.09; S, 9.17.
C18H15N5OS. Calculated (%): C, 61.87; H, 4.33; N, 20.05;
S, 9.18.
diazineꢀ3ꢀcarboxylate (3e). Yield 0.199
g (45%), m.p.
182 °C. IR, ν/cm–1: 1730 (C=O). 1H NMR (DMSOꢀd6), δ: 1.04
(d, 6 H, OCH2CH(CH3)2, J = 6.4 Hz); 2.04—2.11 (m, 1 H,
OCH2CH(CH3)2); 4.10 (d, 2 H, OCH2CH(CH3)2, J = 6.4 Hz);
4.30 (s, 2 H, CH2); 7.55—7.62 (m, 3 H, ArH); 8.10 (d, 2 H, ArH,
J = 7.2 Hz). 13C NMR (DMSOꢀd6), δ: 19.36; 21.72; 27.83;
71.05; 128.31; 129.10; 129.66; 132.77; 133.11; 133.36; 156.07;
160.00. MS (ESI), m/z: 317.1026 [M + H]+; calculated: 317.1067
[M + H]. Found (%): C, 56.92; H, 5.13; N, 17.72; S, 10.20.
C15H16N4O2S. Calculated (%): C, 56.94; H, 5.10; N, 17.71;
S, 10.14.
3ꢀ(NꢀBenzylcarbamoyl)ꢀ6ꢀ(4ꢀmethylphenyl)ꢀ5Hꢀ[1,2,3]triꢀ
azolo[5,1ꢀb][1,3,4]thiadiazine (3j). Yield 0.140 g (55%),
1
Isoamyl 6ꢀ(4ꢀmethylphenyl)ꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]ꢀ
thiadiazineꢀ3ꢀcarboxylate (3f). Yield 0.203 g (42%), m.p.
190 °C. IR, ν/cm–1: 1725 (C=O). 1H NMR (DMSOꢀd6), δ:
0.98 (d, 6 H, OCH2CH2CH(CH3)2, J = 6.4 Hz); 1.65 (q, 2 H,
OCH2CH2CH(CH3)2, J = 6.8 Hz); 1.80—1.86 (m, 1 H,
OCH2CH2CH(CH3)2); 2.45 (s, 3 H, CH3); 4.25 (s, 2 H, CH2);
4.33 (t, 2 H, OCH2CH2CH(CH3)2, J = 6.4 Hz); 7.37 (d, 3 H,
ArH, J = 8.0 Hz); 7.99 (d, 2 H, ArH, J = 8.4 Hz). 13C NMR
(DMSOꢀd6), δ: 21.58; 22.74; 24.98; 34.17; 37.33; 69.46; 128.30;
129.10; 130.25; 130.50; 132.76; 143.54; 155.93; 160.06. MS (ESI),
m/z: 345.1327 [M + H]+; calculated: 345.1380 [M + H].
Found (%): C, 59.30; H, 5.82; N, 16.29; S, 9.28. C17H20N4O2S.
Calculated (%): C, 59.28; H, 5.85; N, 16.27; S, 9.31.
m.p. 213 °C. IR, ν/cm–1: 3330 (NH); 1645 (C=O). H NMR
(DMSOꢀd6), δ: 2.45 (s, 3 H, CH3); 4.19 (s, 2 H, CH2); 4.46
(d, 2 H, NHCH2, J = 6.4 Hz); 7.29—7.37 (m, 7 H, ArH); 7.98
(d, 2 H, ArH, J = 8.0 Hz); 9.07 (t, 1 H, NH, J = 5.6 Hz).
13C NMR (DMSOꢀd6), δ: 21.26; 21.58; 42.43; 126.31; 127.24;
127.81; 128.24; 128.72; 130.23; 130.72; 135.99; 139.97; 143.37;
155.85; 159.77. MS (ESI), m/z: 364.1172 [M + H]+; calculated:
364.1227 [M + H]. Found (%): C, 62.80; H, 4.71; N, 19.22;
S, 8.87. C19H17N5OS. Calculated (%): C, 62.79; H, 4.71;
N, 19.27; S, 8.82.
3ꢀ[Nꢀ(4ꢀMethoxyphenyl)carbamoyl]ꢀ6ꢀphenylꢀ5Hꢀ[1,2,3]ꢀ
triazolo[5,1ꢀb][1,3,4]thiadiazine (3k). Yield 0.089 g (46%),
1
m.p. 211 °C. IR, ν/cm–1: 3370 (NH); 1670 (C=O). H NMR
6ꢀArylꢀ5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiadiazineꢀ3ꢀcarbꢀ
oxamides 3g—l (general procedure). To a suspension of (1,2,3ꢀ
thiadiazolꢀ5ꢀyl)hydrazone of acetophenone (0.2 g, 0.7 mmol) in
benzene (20 mL), PCl5 (0.29 g, 1.4 mmol) was added, the mixꢀ
ture was refluxed for 3 h, and washed with water (20 mL). Then
the corresponding amine (1.4 mmol) was added and reflux was
continued for 2 h, the mixture was washed with water (3×20 mL).
The organic layer was dried with Na2SO4 and the solvent was
removed in vacuo. The product was precipitated with hexane
from chloroform solution. The precipitate that formed was filꢀ
tered off and dried.
3ꢀ(NꢀIsopropylcarbamoyl)ꢀ6ꢀphenylꢀ5Hꢀ[1,2,3]triazoloꢀ
[5,1ꢀb][1,3,4]thiadiazine (3g). Yield 0.091 g (43%), m.p. 205 °C.
IR, ν/cm–1: 3390 (NH); 1650 (C=O). 1H NMR (DMSOꢀd6), δ:
1.22 (d, 6 H, 2 CH3); 4.10—4.14 (m, 1 H, CH); 4.22 (s, 2 H,
CH2); 7.54—7.61 (m, 3 H, ArH); 8.08 (d, 2 H, ArH, J = 8.4 Hz);
8.19 (d, 1 H, NH, J = 8.4 Hz). 13C NMR (DMSOꢀd6), δ: 21.41;
22.67; 104.21; 126.15; 128.23; 129.63; 132.94; 133.61; 136.30;
155.93; 158.79. MS (ESI), m/z: 302.1033 [M + H]+; calculated:
302.1070 [M + H]. Found (%): C, 55.82; H, 5.05; N, 23.23;
S, 10.60. C14H15N5OS. Calculated (%): C, 55.80; H, 5.02;
N, 23.24; S, 10.64.
(DMSOꢀd6), δ: 3.77 (s, 3 H, OCH3); 4.26 (s, 2 H, CH2); 6.84
(d, 2 H, ArH, J = 8.8 Hz); 7.55—7.64 (m, 3 H, ArH); 7.74 (d, 2 H,
ArH, J = 8.8 Hz); 8.10 (d, 2 H, ArH, J = 6.8 Hz); 10.33 (s, 1 H,
NH). 13C NMR (DMSOꢀd6), δ: 21.47; 55.65; 114.21; 122.38;
127.13; 128.28; 128.79; 129.65; 131.90; 132.80; 133.02; 133.57;
136.32; 156.08; 156.15; 158.01. Found (%): C, 59.15; H, 4.13;
N, 19.17; S, 8.77. C18H15N5O2S. Calculated (%): C, 59.16;
H, 4.14; N, 19.17; S, 8.78.
6ꢀ(4ꢀMethylphenyl)ꢀ3ꢀ[Nꢀ(4ꢀmethoxyphenyl)carbamoyl]ꢀ
5Hꢀ[1,2,3]triazolo[5,1ꢀb][1,3,4]thiadiazine (3l). Yield 0.122 g
(48%), m.p. 213—214 °C. IR, ν/cm–1: 3370 (NH); 1670 (C=O).
1H NMR (DMSOꢀd6), δ: 2.45 (s, 3 H, CH3); 3.77 (s, 3 H,
OCH3); 4.23 (s, 2 H, CH2); 6.83 (d, 2 H, ArH, J = 9.2 Hz); 7.37
(d, 2 H, ArH, J = 8.0 Hz); 7.74 (d, 2 H, ArH, J = 9.2 Hz); 8.00
(d, 2 H, ArH, J = 8.4 Hz); 10.31 (s, 1 H, NH). 13C NMR
(DMSOꢀd6), δ: 21.31; 21.58; 55.64; 114.20; 122.36; 127.03;
128.26; 130.24; 130.90; 131.91; 136.30; 143.43; 155.93;
156.14; 158.02. MS (ESI), m/z: 380.1111 [M + H]+; calculated:
380.1176 [M + H]. Found (%): C, 60.16; H, 4.53; N, 18.45;
S, 8.43. C19H17N5O2S. Calculated (%): C, 60.14; H, 4.52;
N, 18.46; S, 8.45.
3ꢀ[Nꢀ(2ꢀHydroxyethyl)carbamoyl]ꢀ6ꢀ(4ꢀmethylphenyl)ꢀ5Hꢀ
[1,2,3]triazolo[5,1ꢀb][1,3,4]thiadiazine (3h). Yield 0.107 g
(48%), m.p. 176 °C. 1H NMR (DMSOꢀd6), δ: 2.45 (s 3 H, CH3);
3.35 (q, 2 H, CH2CH2OH, J = 4.2 Hz); 3.53 (t, 2 H, CH2CH2OH,
J = 5.2 Hz); 4.19 (s, 2 H, CH2); 4.58 (br.s, 1 H, OH); 7.36
(d, 2 H, ArH, J = 8.4 Hz); 7.98 (d, 2 H, ArH, J = 8.4 Hz); 8.27
(t, 1 H, NH, J = 6.4 Hz). 13C (DMSOꢀd6), δ: 21.6; 21.58; 60.11;
99.99; 126.05; 128.23; 130.04; 130.23; 136.07; 143.36; 155.83;
159.79. MS (ESI), m/z: 318.0980 [M + H]+; calculated: 318.1019
[M + H]. Found (%): C, 52.93; H, 4.78; N, 22.09; S, 10.10.
C14H15N5O2S. Calculated (%): C, 52.98; H, 4.76; N, 22.07;
S, 10.10.
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Received February 11, 2011;
in revised form April 12, 2011