Synthesis of [1,2,3]triazolo[1,5-a]pyrazinium-3-olates

Article abstract of DOI:10.1007/s10593-014-1558-4

4-Carbamoyl-3-cyanomethyl-1,2,3-triazolium-5-olates were shown to cyclize when treated with sodium ethoxide giving zwitterionic 6-amino-4-oxo-4,5-dihydro-2H-1,2,3-triazolo[1,5-a]pyrazinium-3-olates. In contrast to 4-carbamoyl-3-cyanomethyl-1,2,3-triazolium-5-olates, 4-carbamoyl-3-phenacyl-1,2,3-tri-azolium-5-olates cyclized only by the action of phosphoric acid.

Full text of DOI:10.1007/s10593-014-1558-4

Chemistry of Heterocyclic Compounds, Vol. 50, No. 7, October, 2014 (Russian Original Vol. 50, No. 7, July, 2014)
SYNTHESIS OF [1,2,3]TRIAZOLO[1,5-a]PYRAZINIUM-3-OLATES*
Yu. I. Nein1 and Yu. Yu. Morzherin1**
4-Carbamoyl-3-cyanomethyl-1,2,3-triazolium-5-olates were shown to cyclize when treated with sodium
ethoxide giving zwitterionic 6-amino-4-oxo-4,5-dihydro-2Н-1,2,3-triazolo[1,5-а]pyrazinium-3-olates.
In contrast to 4-carbamoyl-3-cyanomethyl-1,2,3-triazolium-5-olates, 4-carbamoyl-3-phenacyl-1,2,3-tri-
azolium-5-olates cyclized only by the action of phosphoric acid.
Keywords: condensed ring systems, mesoionic heterocycles, 1,2,3-triazoles, cyclization.
Mesoionic heterocycles are known to possess a broad range of biological activity [1], such as antitumor
[2-4], antimicrobial [5, 6], antipyretic, and other effects [7, 8]. Some condensed mesoionic 1,2,3-triazolium-
5-olates have been shown to act as immunosuppressants [9]. Previously we have shown [10-12] that alkylation
of 1-aryl- and 1-arylmethyleneamino-1,2,3-triazol-5-olate sodium salts with alkyl halides leads to the zwitter-
ionic 3-alkyl-1,2,3-triazol-3-ium-5-olate and [1,2,3]triazolo[1,5-а]pyrazinium-3-olate. In a continuation of our
research in the field of mesoionic heterocycles [13-16], in this work we present the synthesis of new
[1,2,3]triazolo[1,5-a]pyrazinium-3-olate derivatives.
The geometry of 3-phenacyl- and 3-cyanomethyl derivatives of triazolium-5-olates 1а-с [10-12]
indicates a possible interaction of carboxamide group nitrogen atom at position 4 of the triazole ring with keto
or cyano groups, forming a condensed zwitterionic triazolopyrazine. Indeed, refluxing of 3-cyanomethyl
derivatives 1a-c with sodium ethoxide for 5 h resulted in good yields (up to 80%) of the individual bicyclic
compounds 2a-c.
The obtained compounds were identified by IR and NMR spectroscopy, mass spectrometry, as well as
elemental analysis data. For example, the cyano group absorption band at 2110 cm-1 was absent in the IR spectra
1
of final products 2a-c, while it was observed in the spectra of compounds 1a-c. The Н NMR spectrum of
H2N
Ar
O
N
NHAr
O
6
5
4
O
7
N+
N
N8+
EtONa
h
EtOH
3a
N
N1
3
2
N
N
O
a Ar = Ph,
b Ar = 4-MeC6H4,
Ar
Ar
2a–c
1a–c
c Ar = 4-MeOC6H4
_______
*Dedicated to Academician O. N. Chupakhin on the occasion of his 80th birthday.
**To whom correspondence should be addressed, e-mail: yu.yu.morzherin@urfu.ru.
1Ural Federal University named after the First President of Russia B. N. Yeltsin, 19 Mira St., Yekaterinburg
620002, Russia.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1107-1113, July, 2014. Original
article submitted April 30, 2014.
0009-3122/14/5007-1021©2014 Springer Science+Business Media New York
1021

compound 2c showed an insignificant upfield shift of aryl proton signals by 0.10 ppm compared to the starting
compounds. Also absent was the amide group proton signal at 10.14 ppm characteristic of alkylated 1,2,3-tri-
azoles, while a signal characteristic for NH2 group was observed at 6.81 ppm. A methyne group signal was
found at 8.03 ppm instead of methylеne group signals at 6.12 ppm.
It should be noted that this method failed to convert compounds 3a-c having a cyanoethyl substituent at
the ring position 3 into the respective condensed seven-membered heterocycles. Refluxing with sodium
ethoxide or with phosphoric acid led to dealkylation of 3-substituted triazoles 3a-c with the formation of
5-hydroxy-1,2,3-triazole derivatives 4a-c.
H2N
N
Ar
Ar
HN
O
N
N
H
N
O
O
EtONa or H3PO4
Ar
N+
N
N+
OH

N
N N
O
O
N
N
a Ar = Ph,
Ar
b Ar = 4-MeC6H4,
Ar
3a–c
Ar
4a–c
c Ar = 4-MeOC6H4
Unlike the cyanomethyl derivatives 1a-c, the 3-phenacyltriazoles 5a-f did not cyclize under analogous
conditions into the respective triazolopyrazines, and the starting triazoles were isolated in these experiments.
Cyclic products also could not be obtained upon reflux of phenacyl derivatives 5a-f in toluene, even when
dehydrating agents were used, such as phosphorus oxide and 3Å or 4Å molecular sieves.
The synthesis of triazolopyrazines 2d-i was achieved by using phosphoric acid as cyclizing agent,
which led to the condensation of carbonyl and amide fragments within the molecule.
Ar1
N
Ar2
Ar2
O
Ar1
O
O
5a, 2d Ar1 = Ar2 = Ph;
N
H
H3PO4
N+
N+
5b, 2e Ar1 = Ph, Ar2 = 4-MeC6H4;
h
5c, 2f Ar1 = Ph, Ar2 = 4-MeOC6H4;
5d, 2g Ar1 = 4-MeC6H4, Ar2 = 4-MeOC6H4;
5e, 2h Ar1 = 4-MeC6H4, Ar2 = 4-ClC6H4;
5f, 2i Ar1 = Ar2 = 4-MeOC6H4
O
N
N
O
N
N
Ar1
2d–i
Ar1
5a–f
The structure of bicyclic compounds obtained from 3-carbonyl-1,2,3-triazolium-5-olate derivatives 5a-f
was proved by IR and NMR spectroscopy, as well as mass spectrometry. For example, the IR spectra of final
products 2d-i lacked the keto group absorption band at 1700 cm-1. Instead of the methylene group two-proton
1
singlet at 5.6-6.5 ppm, Н NMR spectra contained an aromatic proton signal in the region of 7.21-8.19 ppm, and
also there was no amide proton signal in the region of 9-10 ppm.
Thus, we have developed a method for the preparation of zwitterionic 1,2,3-triazolopyrazines by the
cyclization of 3-cyanomethyl- and 4-carbamoyl-3-phenacyl-1,2,3-triazolium-5-olates. The selection of cycli-
zation agent was shown to depend on the substituent properties at the triazole ring position 3.
EXPERIMENTAL
1
IR spectra were recorded on a Bruker Alpha spectrometer (ZnSe ATR accessory). Н and 13С NMR
spectra were acquired on a Вruker Avance II spectrometer (400 and 100 MHz, respectively) in DMSO-d6–CCl4
with TMS as internal standard at the Laboratory of Complex Investigation and Expert Evaluation of
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Organic Materials, Collective Access Center of the Ural Federal University. 13С NMR spectra were acquired
without suppression of С–Н coupling. Mass spectra were recorded on a МАТ11 instrument (EI, 70 eV).
Elemental analysis was performed on a РЕ 2400 Series II CHNS-analyzer. Melting points were determined on a
Stuart SMP3 apparatus. The reaction progress and the individuality of the synthesized compounds were
controlled by TLC on Silufol UV-254 plates in 1:2 ethyl acetate–hexane system (visualization under UV light).
Compounds 1b,с, 5a,c,f were synthesized by a published method [11], the triazole 1a and
triazolopyrazinolate 2а were obtained according to another reference [16].
Preparation of [1,2,3]Triazolo[1,5-a]pyrazinium-3-olates 2a-c (General Method). A solution of
1-aryl-3-cyanomethyl-1Н-1,2,3-triazolium-5-olate 1а-с (0.6 mmol) and sodium ethoxide, prepared from sodium
metal (0.014 g, 0.6 mmol) in ethanol (25 ml), was refluxed for 5 h, cooled to room temperature, the precipitate
formed was filtered off and recrystallized from ethanol.
6-Amino-4-oxo-2,5-diphenyl-4,5-dihydro-2Н-[1,2,3]triazolo[1,5-а]pyrazinium-3-olate (2a). Yield
0.15 g (80%). Mp 280-281°С (mp 280°С [16]). IR spectrum, ν, cm-1: 3370, 3358, 3180 (NH), 2920 (CH), 1640
(CO). Found, %: C 64.01; H 4.18; N 21.61. C17H13N5O2. Calculated, %: C 63.94; Н 4.10; N 21.93.
6-Amino-2,5-bis(4-methylphenyl)-4-oxo-4,5-dihydro-2Н-1,2,3-triazolo[1,5-а]pyrazinium-3-olate (2b).
Yield 0.16 g (78%). Mp 154-155°C. IR spectrum, ν, cm-1: 3400 (NH), 2950 (CH), 1630 (CO). 1H NMR spectrum,
δ, ppm (J, Hz): 2.32 (3H, s, CH3); 2.36 (3H, s, CH3); 5.23 (2H, br. s, NH2); 6.88 (2H, d, J = 8.0, H Ar); 7.16
(2H, d, J = 8.4, H Ar); 7.36 (2H, d, J = 8.0, H Ar); 7.65 (2H, d, J = 8.4, H Ar); 8.06 (1H, s, H-7). Mass
spectrum, m/z (Irel, %): 347 [M]+ (10), 91 [C6H5CH2]+ (100). Found, %: C 65.52; H 5.04; N 20.02. C19H17N5O2.
Calculated, %: C 65.69; H 4.93; N 20.16.
6-Amino-2,5-bis(4-methoxyphenyl)-4-oxo-4,5-dihydro-2Н-1,2,3-triazolo[1,5-а]pyrazinium-3-olate (2c).
Yield 0.19 g (82%). Mp 280-281°C. IR spectrum, ν, cm-1: 3390 (NH), 2930 (CH), 1630 (CO). 1H NMR spectrum,
δ, ppm (J, Hz): 3.71 (3H, s, OCH3); 3.78 (3H, s, OCH3); 6.81 (2H, s, NH); 6.83 (2H, d, J = 9.2, H Ar); 7.02 (2H,
d, J = 9.2, H Ar); 7.37 (2H, d, J = 9.2, H Ar); 7.87 (2H, d, J = 9.2, H Ar); 8.54 (1H, s, H-7). Mass spectrum, m/z
(Irel, %): 379 [M]+ (7), 107 [C6H4OCH3]+ (100). Found, %: C 60.02; H 4.61; N 18.13. C19H17N5O4. Calculated,
%: C 60.15; H 4.52; N 18.46.
Preparation of [1,2,3]Triazolo[1,5-a]pyrazinium-3-olates 2d-i (General Method). A solution of 1-aryl-
4-(arylcarbamoyl)-3-phenacyl-1Н-1,2,3-triazolium-5-olate 5a-f (0.6 mmol) in phosphoric acid (7 ml) was refluxed
for 5 h, then cooled to room temperature. A precipitate formed upon the addition of distilled water (50 ml). The
precipitate was filtered off, washed with distilled water, crystallized from ethanol, and dried.
4-Oxo-2,5,6-triphenyl-4,5-dihydro-2Н-[1,2,3]triazolo[1,5-а]pyrazinium-3-olate (2d). Yield 0.20 g
1
(87%). Mp 125-126°C. IR spectrum, ν, cm-1: 2920 (CH), 1620 (CO). H NMR spectrum, δ, ppm (J, Hz):
7.20-7.31 (10H, m, H Ph); 7.47 (1H, t, J = 5.4, H Ph); 7.60 (2H, t, J = 5.3, H Ph); 7.94 (1H, s, H-7); 7.97 (2H, d,
J = 7.3, H Ph). Mass spectrum, m/z (Irel, %): 380 [M]+ (7), 77 [C6H5]+ (100). Found, %: C 72.48; H 4.41;
N 14.34. C23H16N4O2. Calculated, %: C 72.62; H 4.24: N 14.73.
6-(4-Methylphenyl)-4-oxo-2,5-diphenyl-4,5-dihydro-2Н-[1,2,3]triazolo[1,5-а]pyrazinium-3-olate (2e).
1
Yield 0.20 g (86%). Mp 137-138°C. IR spectrum, ν, cm-1: 2950, 2920 (CH), 1625 (CO). H NMR spectrum, δ,
ppm (J, Hz): 2.21 (3H, s, CH3); 7.05 (2H, d, J = 8.0, H Ar); 7.15-7.29 (7H, m, H Ar); 7.46 (1H, t, J = 7.9,
H Ar); 7.60 (2H, t, J = 8.2, H Ar); 7.88 (1H, s, H-7); 7.98 (2H, d, J = 7.6, H Ar). Mass spectrum, m/z (Irel, %):
394 [M]+ (10), 91 [C6H5CH2]+ (100). Found, %: C 73.04; H 4.80; N 14.02. C24H18N4O2. Calculated, %: C 73.08;
H 4.60; N 14.20.
6-(4-Methoxyphenyl)-4-oxo-2,5-diphenyl-4,5-dihydro-2Н-[1,2,3]triazolo[1,5-а]pyrazinium-3-olate (2f).
1
Yield 0.22 g (90%). Mp 100-101°C. IR spectrum, ν, cm-1: 2980, 2930 (CH), 1620 (CO). H NMR spectrum, δ,
ppm (J, Hz): 3.69 (3H, s, OCH3); 6.79 (2H, d, J = 6.8, H Ar); 7.18-7.31 (7H, m, H Ar); 7.46 (1H, t, J = 6.1,
H Ar); 7.60 (2H, t, J = 6.0, H Ar); 7.87 (1H, s, H-7); 7.97 (2H, d, J = 7.7, H Ar). Mass spectrum, m/z (Irel, %):
410 [M]+ (23), 77 [C6H5]+ (100). Found, %: C 70.03; H 4.64; N 13.31. C24H18N4O3. Calculated, %: C 70.23;
H 4.42; N 13.65.
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6-(4-Methoxyphenyl)-2,5-bis(4-methylphenyl)-4-oxo-4,5-dihydro-2Н-[1,2,3]triazolo[1,5-а]pyrazin-
ium-3-olate (2g). Yield 0.11 g (41%). Mp 100-101°C. IR spectrum, ν, cm-1: 3000, 2950, 2930 (CH), 1620 (CO).
1H NMR spectrum, δ, ppm (J, Hz): 1.90 (3H, s, CH3); 2.41 (3H, s, CH3); 3.70 (3H, s, OCH3); 6.72 (2H, d,
J = 8.9, H Ar); 7.18 (2H, d, J = 7.3, H Ar); 7.19 (2H, d, J = 8.9, H Ar); 7.21 (1H, s, H-7); 7.41 (2H, d, J = 7.3,
H Ar); 7.50 (2H, d, J = 6.8, H Ar); 8.00 (2H, d, J = 7.3, H Ar). Mass spectrum, m/z (Irel, %): 438 [M]+ (33), 91
[C6H5CH2]+ (100). Found, %: C 71.22; H 5.30; N 12.28. C26H22N4O3. Calculated, %: C 71.22; H 5.06; N 12.78.
6-(4-Chlorophenyl)-2,5-bis(4-methylphenyl)-4-oxo-4,5-dihydro-2Н-[1,2,3]triazolo[1,5-а]pyrazinium-
3-olate (2h). Yield 0.08 g (29%). Mp 178-179°C. IR spectrum, ν, cm-1: 2980, 2950 (CH), 1630 (CO), 740 (C–Cl).
1H NMR spectrum, δ, ppm (J, Hz): 2.24 (3H, s, CH3); 2.38 (3H, s, CH3); 7.08-7.14 (4H, m, H Ar); 7.29-7.37 (4H,
m, H Ar); 7.39 (2H, d, J = 8.3, H Ar); 7.81 (2H, d, J = 8.4, H Ar); 7.93 (1H, s, H-7). Mass spectrum, m/z (Irel, %):
444 [M (37Cl)]+ (8), 442 [M (35Cl)]+ (23), 91 [C6H5CH2]+ (100). Found, %: C 67.79; H 4.31; N 12.72.
C25H19ClN4O2. Calculated, %: C 67.80; H 4.32; N 12.67 .
2,5,6-Tris(4-methoxyphenyl)-4-oxo-4,5-dihydro-2Н-[1,2,3]triazolo[1,5-а]pyrazinium-3-olate (2i).
1
Yield 0.15 g (52%). Mp 210-211°C. IR spectrum, ν, cm-1: 2950, 2930 (CH), 1620 (CO). H NMR spectrum, δ,
ppm (J, Hz): 3.71 (3H, s, OCH3); 3.72 (3H, s, OCH3); 3.82 (3H, s, CH3); 7.08-6.51 (8H, m, H Ar); 7.13 (2H, d,
J = 8.5, H Ar); 7.85 (2H, d, J = 8.9, H Ar); 8.19 (1H, s, H-7). Mass spectrum, m/z (Irel, %): 470 [M]+ (21), 107
[C6H4OCH3]+ (100). Found, %: C 66.22; H 4.89; N 11.52. C26H22N4O5. Calculated, %: C 66.37; H 4.71;
N 11.91.
Preparation of 1,4-Disubstituted 3-(2-Cyanoethyl)-1,2,3-triazolium-5-olates 3a-c (General Method).
A suspension of the respective sodium 1-aryl-4-(arylcarbamoyl)-1Н-1,2,3-triazole-5-olate [11] (1.0 mmol) in
DMF (1 ml) was treated with 1-iodopropionitrile (0.35 ml, 0.72 g, 4.0 mmol) and maintained at 50-60°C for
72 h. The addition of water (50 ml) gave a precipitate that was filtered off and crystallized from ethanol.
3-(2-Cyanoethyl)-1-phenyl-4-(phenylcarbamoyl)-1Н-1,2,3-triazolium-5-olate (3a). Yield 0.13 g
(39%). Mp 155-156°C. IR spectrum, ν, cm-1: 3410 (NH), 2985, 2950, 2930 (CH), 2250 (CN), 1680 (CO).
1H NMR spectrum, , ppm (J, Hz): 3.31 (2H, t, J = 6.5, CH2); 5.08 (2H, t, J = 6.5, CH2); 7.10 (1H, t, J = 7.5,
H Ar); 7.48-7.66 (5H, m, H Ar); 8.01 (2H, dd, J = 2.1, J = 7.0, H Ar); 7.34 (2H, t, J = 7.3, H Ar); 10.37 (1H, s,
NH). Mass spectrum, m/z (Irel, %): 333 [M]+ (42), 77 [C6H5]+ (100). Found, %: C 64.52; H 4.88; N 20.85.
C18H15N5O2. Calculated, %: C 64.86; H 4.54; N 21.02.
3-(2-Cyanoethyl)-1-(4-methylphenyl)-4-[(4-methylphenyl)carbamoyl]-1Н-1,2,3-triazolium-5-olate (3b).
Yield 0.30 g (94%). Mp 151-152°C. IR spectrum, ν, cm-1: 3410 (NH), 2990, 2940 (CH), 2220 (CN), 1680 (CO).
1H NMR spectrum, , ppm, (J, Hz): 2.31 (3H, s, CH3); 2.42 (3H, s, CH3); 3.28 (2H, t, J = 6.4, CH2); 5.05 (2H, t,
J = 6.4, CH2); 7.12 (2H, d, J = 8.2, H Ar); 7.37 (2H, d, J = 8.2, H Ar); 7.51 (2H, d, J = 8.2, H Ar); 7.85 (2H, d,
J = 8.2, H Ar); 10.30 (1Н, s, NH). Mass spectrum, m/z (Irel, %): 361 [M]+ (79), 91 [C6H5CH2]+ (100). Found, %:
C 66.32; H 5.68; N 19.08. C20H19N5O2. Calculated, %: C 66.47; H 5.30; N 19.39.
3-(2-Cyanoethyl)-1-(4-methoxyphenyl)-4-[(4-methoxyphenyl)carbamoyl]-1Н-1,2,3-triazolium-5-olate
(3c). Yield 0.25 g (63%). Mp 179-180°C. IR spectrum, ν, cm-1: 3400 (NH), 2990, 2950 (CH), 2250 (CN), 1690
(CO). 1H NMR spectrum, , ppm (J, Hz): 3.29 (2H, t, J = 6.3, CH2); 3.76 (3H, s, OCH3); 3.85 (3H, s, OCH3);
5.04 (2H, t, J = 6.3, CH2); 7.03 (2H, dd, J = 9.2, J = 2.1, H Ar); 7.11 (2H, dd, J = 9.2, J = 2.1, H Ar); 7.62 (2H,
d, J = 9.0, H Ar); 7.77 (2H, d, J = 9.0, H Ar); 10.26 (1Н, s, NH). Mass spectrum, m/z (Irel, %): 393 [M]+ (13).
Found, %: C 60.93; H 5.01; N 17.50. C20H19N5O4. Calculated, %: C 61.06; H 4.87; N 17.80.
Preparation of 1-Aryl-5-hydroxy-1,2,3-triazole-4-carboxamides 4a-c (General Method). А. Tosyl
azide (1.97 g, 0.01 mol) was added with stirring to a solution of the appropriate malonodiamide (0.01 mol) in
sodium ethoxide, prepared from sodium metal (0.23 g, 0.01 mol) in ethanol (50 ml). After 2 h, the white
precipitate was filtered off, dissolved in cold water (10 ml), and precipitated by cooling and acidification with
hydrochloric acid to рН 1. The precipitate formed was filtered off and dried over P2O5 in vacuum.
B. A solution of 1-aryl-3-(2-cyanoethyl)-1Н-1,2,3-triazolium-5-olate 3а-с (1.0 mmol) and sodium
ethoxide, prepared from sodium metal (23 mg, 1 mmol) in ethanol (25 ml), was refluxed for 5 h, cooled to room
temperature. The precipitate formed was filtered off and recrystallized from ethanol.
1024

C. A solution of 1-aryl-3-cyanoethyl-1Н-1,2,3-triazolium-5-olate 3а-с (1.0 mmol) in phosphoric acid
(10 ml) was refluxed for 5 h, then cooled to room temperature. A precipitate formed after the addition of distilled
water (100 ml). The precipitate was filtered off, washed with distilled water, crystallized from ethanol, and dried.
5-Hydroxy-N,1-diphenyl-1Н-1,2,3-triazole-4-carboxamide (4a). Yield 2.42 g (86, method А), 252 mg
(90, method B), 155 mg (55%, method C). Mp 165-166°C. IR spectrum, ν, cm-1: 3430-3490 (OH), 3380 (NH),
1
3120, 3050, 2950 (CH), 1690 (CO). H NMR spectrum, , ppm (J, Hz): 6.96 (1H, t, J = 7.0, H Ar); 7.29-7.33
(4H, m, H Ar); 7.64 (2H, dd, J = 7.5, J = 1.2, H Ar); 7.70 (1H, dd, J = 4.8, J = 1.7, H Ar); 8.07 (2H, dd, J = 7.5,
J = 1.2, H Ar); 10.67 (1H, s, NH); 11.20 (1Н, br. s, OH). Mass spectrum, m/z (Irel, %): 280 [M]+ (33), 252 (100).
Found, %: C 63.98; H 4.61; N 19.77. C15H12N4O2. Calculated, %: C 64.28; H 4.32; N 19.99.
5-Hydroxy-N,1-bis(4-methylphenyl)-1Н-1,2,3-triazole-4-carboxamide (4b). Yield 2.40 g (78,
method А), 265 mg (86%, method B), 201 mg (65%, method C). Mp 187-188°C. IR spectrum, ν, cm-1:
1
3480-3520 (OH), 3390 (NH), 3120, 3050, 2950, 2920 (CH), 1695 (CO). H NMR spectrum, , ppm (J, Hz):
2.25 (3H, s, CH3); 2.35 (3H, s, CH3); 7.10 (2H, d, J = 8.3, H Ar); 7.36 (2H, d, J = 8.3, H Ar); 7.65 (2H, d,
J = 8.5, H Ar); 7.65 (2H, d, J = 8.5, H Ar); 10.12 (1H, s, NH); 11.45 (1Н, br. s, OH). Mass spectrum, m/z
(Irel, %): 308 [M]+ (25), 280 (100). Found, %: C 66.12; H 5.38; N 18.06. C17H16N4O2. Calculated, %: C 66.22;
H 5.23; N 18.17.
5-Hydroxy-N,1-bis(4-methoxyphenyl)-1Н-1,2,3-triazole-4-carboxamide (4c). Yield 2.70 g (77,
method А), 289 mg (98%, method B), 245 mg (72%, method C). Mp 158-159°C. IR spectrum, ν, cm-1:
3420-3490 (OH), 3380 (NH), 3050, 2950, 2940 (CH), 1690 (CO). 1H NMR spectrum, , ppm (J, Hz): 3.75 (3H,
s, OCH3), 3.85 (3H, s, OCH3), 6.89 (2H, d, J = 9.1, H Ar), 7.02 (2H, d, J = 9.1, H Ar), 7.60 (2H, d, J = 9.1,
H Ar), 7.90 (2H, d, J = 9.1, H Ar), 10.30 (1H, s, NH), 11.05 (1Н, br. s, OH). Mass spectrum, m/z (Irel, %): 340
[M]+ (55), 312 (100). Found, %: C 59.85; H 4.93; N 16.26. C17H16N4O4. Calculated, %: C 59.99; H 4.74;
N 16.46.
3-(p-Methylphenacyl)-1-phenyl-4-(phenylcarbamoyl)-1Н-1,2,3-triazolium-5-olate (5b) was obtained
analogously to compound 3a by using p-methylphenacyl bromide. Yield 0.30 g (73%). Mp 137-138°C.
IR spectrum, ν, cm-1: 3310 (NH), 2950, 2930 (CH), 1700 (CO). 1H NMR spectrum, , ppm (J, Hz): 2.47 (3H, s,
CH3); 6.37 (2H, s, CH2); 7.03 (1H, t, J = 7.3, H Ar); 7.40 (2H, d, J = 7.5, H Ar); 7.54-7.60 (5H, m, H Ar); 7.21
(2H, t, J = 8.2, H Ar); 7.97-8.08 (4H, m, H Ar); 10.27 (1H, s, NH). Mass spectrum, m/z (Irel, %): 412 [M]+ (37),
77 (100) [Ph]+. Found, %: C 69.75; H 5.01; N 13.23. C24H20N4O3. Calculated, %: C 69.89; H 4.89; N 13.58.
3-(p-Methoxyphenacyl)-1-(4-methylphenyl)-4-[(4-methylphenyl)carbamoyl]-1Н-1,2,3-triazolium-
5-olate (5d) was obtained analogously to compound 3b by using p-methoxyphenacyl bromide. Yield 0.38 g
1
(83%). Mp 184-185°C. IR spectrum, ν, cm-1: 3380 (NH), 2950, 2920 (CH), 1700 (CO). H NMR spectrum, ,
ppm (J, Hz): 2.31 (3H, s, CH3); 2.42 (3H, s, CH3); 3.90 (3H, s, OCH3); 6.35 (2H, s, CH2); 7.04 (2H, d, J = 7.3,
H Ar); 7.10 (2H, d, J = 7.3, H Ar); 7.39 (2H, d, J = 7.3, H Ar); 7.75 (2H, d, J = 7.3, H Ar); 7.90 (2H, d, J = 8.2,
H Ar); 8.03 (2H, d, J = 8.2, H Ar);10.25 (1H, s, NH). Mass spectrum, m/z (Irel,%): 456 (30) [M]+, 91 (100)
[C6H5CH2]+. Found, %: C 68.30; H 5.41; N 11.96. C26H24N4O4. Calculated, %: C 68.41; H 5.30; N 12.27.
3-(p-Chlorophenacyl)-1-(4-methylphenyl)-4-[(4-methylphenyl)carbamoyl]-1Н-1,2,3-triazolium-5-olate
(5e) was obtained analogously to compound 3b by using p-chlorophenacyl bromide. Yield 0.25 g (54%).
1
Mp 168-169°C. IR spectrum, ν, cm-1: 3370 (NH), 2930, 2920 (CH), 1710 (CO). H NMR spectrum, , ppm (J,
Hz): 2.27 (3H, s, CH3); 2.42 (3H, s, CH3); 6.31 (2H, s, CH2); 7.07 (2H, d, J = 8.2, H Ar); 7.40 (2H, d, J = 8.5,
H Ar); 7.62 (2H, d, J = 8.2, H Ar); 7.86 (2H, d, J = 8.2, H Ar); 7.90 (2H, d, J = 8.2, H Ar); 8.12 (2H, d, J = 8.2,
H Ar); 10.19 (1H, s, NH). Mass spectrum, m/z (Irel,%): 462 (15) [M (37Cl)]+, 460 [M (35Cl)]+ (44), 91 (100)
[C6H5CH2]+. Found, %: C 65.03; H 4.82; N 12.01. C25H21ClN4O3. Calculated, %: C 65.15; H 4.59; N 12.16.
This work received support from the Russian Foundation for Basic Research (grant 13-03-00137).
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