Alkylation of sodium 4-acetyl-1-phenyl-1,2,3-triazol-5-olate with α-bromoacetophenones was shown to occur at position 3 of the heterocycle, with the formation of 1,2,3-triazol-3-ium-5-olates. Intramolecular crotonic condensation of the latter led to the formation of 1,2,3-triazolo[1,5-а]pyridin-8-ium-3-olates.
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Mesoionic 1,2,3-triazolium-5-olates, in particular their fused analogs, represent a little known class of heterocyclic compounds.1 At the same time, these compounds have been characterized with regard to various biological effects: herbicidal,2 , 3 antitumor,4 and other types of activity.5 , 6 There are two main approaches to the synthesis of fused mesoionic 1,2,3-triazolium-5-olates: intramolecular acylation of triazenes, obtained by azo coupling of cyclic α-amino acids with aromatic and heterocyclic diazonium salts,1 , 2 , 7 – 10 or intramolecular condensation of mesoionic 1,2,3-triazoles, containing suitable substituents at the ring positions 3 and 4.6 , 11 – 13
We used the second approach for the synthesis of a new heterocyclic system, 1,2,3-triazolo[1,5-а]pyridin-8-ium-3-olates. The reaction of sodium 4-acetyl-1-phenyl-1H-1,2,3-triazol-5-olate14 (1) with α-bromoacetophenones allowed us to synthesize the 1,2,3-triazol-3-ium-5-olates 2a–e (Scheme 1). The X-ray structural analysis data for compound 2а (Fig. 1) confirmed that the alkylation had occurred at position 3 of the triazole ring.
Scheme 1
Molecular structure of compound 2a with atoms represented by thermal vibration ellipsoids of 50% probability.
Triazolium-5-olates 2a–e underwent intramolecular crotonic condensation in the presence of NaOH in aqueous alcohol solution, giving the triazolopyridiniumolate sodium salts 3a–e. Acidification of aqueous suspension of the latter gave the triazolopyridiniumolates 4a–e.
It should be noted that triazolopyridiniumolates 4a–e, in particular their sodium salts 3a–e, rapidly decomposed in DMSO or DMF solutions.
Thus, in this work we propose a convenient method for the synthesis of 4-hydroxy-1,2,3-triazolo[1,5-а]pyridin-8-ium-3-olates and their sodium salts.
IR spectra were recorded on a Bruker Alpha spectrometer (ATR, ZnSe). 1Н and 13С NMR spectra were obtained on a Вruker Avance II spectrometer (400 and 100 MHz, respectively) in DMF-d 7 (the 13С NMR spectrum of compound 3а) and in DMSO-d 6 (the rest of the NMR spectra), with TMS as internal standard. Mass spectra were recorded on a Shimadzu GCMS-QP-2010 Plus GC-MS instrument (EI ionization, 70 eV). Elemental analysis was performed on a РЕ 2400 Series II CHNS-analyzer. Melting points were determined on a Stuart SMP3 apparatus and were reported uncorrected. The reaction progress and the individuality of the synthesized compounds were monitored by TLC on Silufol UV-254 plates, eluent 1:9 EtOH–CHCl3, visualization under UV light.
4-Acetyl-3-(2-aryl-2-oxoethyl)-1-phenyl-1 Н -1,2,3-triazol-3-ium-5-olates 2а–e (General method). The corresponding α-bromoacetophenone (2.2 mmol) was added to a solution of sodium 4-acetyl-1-phenyl-1H-1,2,3-triazol-5-olate (1) (500 mg, 2.2 mmol) in anhydrous MeCN (15 ml). The mixture was refluxed for 20 h, cooled; the solvent was removed under vacuum, the obtained residue was recrystallized from a 3:1 mixture of H2O–EtOH.
4-Acetyl-3-(2-oxo-2-phenylethyl)-1-phenyl-1 H -1,2,3-triazol-3-ium-5-olate (2a). Yield 460 mg (65%), sand colored powder, mp 115–117°C. IR spectrum, ν, cm–1: 687, 767, 1142, 1231, 1318, 1342, 1359, 1394, 1410, 1460, 1638, 1674 (С=О), 1705 (С=О), 2919–3036 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 2.44 (3Н, s, CH3); 6.35 (2H, s, CH2); 7.53 (1H, ddd, J = 7.5, J = 7.4, J = 1.9, Н Ph); 7.61–7.66 (4Н, m, Н Ph); 7.78 (1H, ddd, J = 7.4, J = 7.7, J = 1.2, Н Ph); 7.95 (2H, br. d, J = 7.4, Н Ph); 8.09 (2H, br. d, J = 7.2, Н Ph). 13C NMR spectrum, δ, ppm: 27.8 (СН3); 61.1 (СН2); 116.6, 121.9, 128.8, 129.3, 129.5, 130.0, 134.5, 134.9, 135.1 (C Ar); 156.8 (C-5 triazole); 185.9 (C=О); 190.7 (C=О). Mass spectrum, m/z (I rel, %): 322 [М+H]+ (4), 321 [М]+ (16), 146 (16), 119 (12), 105 (75), 91 (15), 77 (100), 51 (23), 43 (45). Found, %: С 67.14; H 4.47; N 12.96. C18H15N3O3. Calculated, %: С 67.28; H 4.71; N 13.08.
4-Acetyl-3-[2-(4-methylphenyl)-2-oxoethyl]-1-phenyl-1 H -1,2,3-triazol-3-ium-5-olate (2b). Yield 500 mg (68%), light-yellow powder, mp 134–135°C. IR spectrum, ν, cm–1: 665, 756, 971, 1136, 1229, 1309, 1402, 1457, 1593, 1639, 1673 (С=О), 1699 (С=О), 2925–3087 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 2.43 (3Н, s, CH3); 2.44 (3Н, s, CH3); 6.30 (2H, s, CH2); 7.44 (2H, d, J = 8.0, НAr); 7.52 (1H, dd, J = 7.4, J = 7.5, Н Ph); 7.63 (2H, dd, J = 7.5, J = 8.1, Н Ph); 7.94–7.99 (4H, m, Н Ar, H). 13C NMR spectrum, δ, ppm: 21.8 (СН3); 27.9 (СН3); 61.0 (СН2); 116.7, 121.9, 128.9, 129.2, 130.0 (2C), 132.0, 135.1, 145.5 (C Ar); 156.8 (C-5 triazole); 185.9 (C=О); 190.1 (C=О). Mass spectrum, m/z (I rel, %): 336 [М+H]+ (3), 335 [М]+ (15), 160 (7), 133 (7), 119 (100), 105 (18), 91 (29), 77 (60), 65 (12), 51 (13), 43 (34). Found, %: С 67.96; H 5.17; N 12.44. C19H17N3O3. Calculated, %: С 68.05; H 5.11; N 12.53.
4-Acetyl-3-[2-(4-methoxyphenyl)-2-oxoethyl]-1-phenyl-1 H -1,2,3-triazol-3-ium-5-olate (2с). Yield 479 mg (62%), yellow-brown crystals, mp 164–165°C. IR spectrum, ν, cm–1: 762, 832, 964, 1025, 1174, 1234, 1394, 1460, 1573, 1597, 1644, 1674 (С=О), 1693 (С=О), 2915–3085 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 2.41 (3Н, s, CH3); 3.87 (3Н, s, OCH3); 6.25 (2H, s, CH2); 7.12 (2H, d, J = 8.9, Н Ar); 7.49 (1H, dd, J = 7.5, J = 7.4, НPh); 7.60 (2H, dd, J = 7.5, J = 8.1, Н Ph); 7.93 (2H, d, J = 7.5, Н Ph); 8.03 (2H, d, J = 8.9, Н Ar). 13C NMR spectrum, δ, ppm: 27.8 (СН3); 56.2 (OСН3); 60.8 (СН2); 114.8, 116.7, 121.8, 127.3, 129.2, 130.0, 131.2, 135.1, 156.8 (C Ar); 164.6 ( C-5 triazole); 185.9 (C=О); 188.9 (C=О). Mass spectrum, m/z (I rel, %): 352 [М+H]+ (2), 351 [М]+ (11), 136 (9), 135 (100), 121 (12), 107 (6), 92 (7), 78 (6), 77 (50), 51 (9), 43 (21). Found, %: С 64.58; H 5.05; N 12.11. C19H17N3O4. Calculated, %: С 64.95; H 4.88; N 11.96.
4-Acetyl-3-[2-(4-ethoxyphenyl)-2-oxoethyl]-1-phenyl-1 H -1,2,3-triazol-3-ium-5-olate (2d). Yield 485 mg (60%), light-yellow powder, mp 169–170°C. IR spectrum, ν, cm–1: 602, 667, 761, 838, 968, 1139, 1173, 1237, 1392, 1459, 1560, 1573, 1644, 1672 (С=О), 1695 (С=О), 2887–3176 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 1.38 (3Н, t, J = 7.0, OCH2CH 3); 2.43 (3Н, s, COCH3); 4.18 (2Н, q, J = 7.0, OCH 2CH3); 6.28 (2H, s, CH 2COAr); 7.13 (2H, d, J = 8.9, Н Ar); 7.52 (1H, dd, J = 7.4, J = 7.4, Н Ph); 7.63 (2H, dd, J = 7.4, J = 7.6, Н Ph); 7.94 (2H, d, J = 7.6, НPh); 8.04 (2H, d, J = 8.9, Н Ar). 13C NMR spectrum, δ, ppm: 14.9 (СН3); 27.8 (СН3); 60.8 (СН2); 64.3 (OСН2); 115.1, 116.7, 121.9, 127.1, 129.2, 130.0, 131.2, 135.1, 156.8 (C Ar); 163.9 (C-5 triazole); 185.9 (C=О); 188.9 (C=О). Mass spectrum, m/z (I rel, %): 366 [М+H]+ (3), 365 [М]+ (14), 150 (10), 149 (100), 135 (5), 121 (42), 107 (14), 93 (11), 77 (51), 65 (11), 51 (9), 43 (27). Found, %: С 65.70; H 5.13; N 11.42. C20H19N3O4. Calculated, %: С 65.74; H 5.24; N 11.50.
4-Acetyl-3-[2-(4-chlorophenyl)-2-oxoethyl]-1-phenyl-1 H -1,2,3-triazol-3-ium-5-olate (2e). Yield 564 mg (72%), yellow crystals, mp 128–129°C. IR spectrum, ν, cm–1: 759, 833, 1095, 1139, 1228, 1354, 1391, 1401, 1460, 1632, 1680 (С=О), 1701 (С=О), 2951–3066 (СН). 1Н NMR spectrum, δ, ppm (J, Hz): 2.44 (3Н, s, CH3); 6.31 (2H, s, CH2); 7.53 (1H, dd, J = 7.4, J = 7.5, Н Ph); 7.63 (2H, dd, J = 7.0, J = 8.1, Н Ph); 7.71 (2H, d, J = 8.6, Н Ar); 7.95 (2H, d, J = 7.7, Н Ph); 8.10 (2H, d, J = 8.6, Н Ar). 13C NMR spectrum, δ, ppm: 27.8 (СН3); 61.0 (СН2); 116.5, 121.9, 129.3, 129.6, 130.1, 130.7, 133.3, 135.0, 139.8, 156.8 (C Ar); 185.9 (C=О); 189.9 (C=О). Mass spectrum, m/z (I rel,%): 358 [М(37Cl)+H]+ (3), 357 [М(37Cl)]+ (12), 356 [М (35Cl)+H]+ (8), 355 [М(35Cl)]+ (35), 182 (5), 180 (15), 141 (20), 139 (64), 125 (10), 113 (5), 111 (16), 105 (22), 77 (100), 51 (14), 43 (50). Found, %: С 60.35; H 3.86; N 11.64. C18H14ClN3O3. Calculated, %: С 60.77; H 3.97; N 11.81.
Sodium 2,6-diaryl-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3,4-bis(olates) 3а–e (General method). A solution of compound 2а–e (1.2 mmol) in EtOH (15 ml) was treated with NaOH (70 mg, 1.8 mmol) dissolved in minimum amount of Н2О. The reaction mixture was heated at 50°С for 2 h, resulting in the formation of a precipitate. The mixture was then cooled to room temperature, the precipitate was filtered off, washed with water, and dried.
Sodium 2,6-diphenyl-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3,4-bis(olate) (3а). Yield 330 mg (84%), yellow powder, mp >320°C. IR spectrum, ν, cm–1: 690, 744, 830, 927, 1167, 1231, 1360, 1408, 1488, 1526, 1587, 1632, 3062–3600 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 6.02 (1H, s, H-5); 7.23 (1H, dd, J = 7.4, J = 7.4, Н Ph); 7.31–7.44 (5Н, m, Н Ph); 7.49 (1H, s, H-7); 7.57 (2H, d, J = 7.2, Н Ph); 8.13 (2H, d, J = 8.3, Н Ph). 13C NMR spectrum, δ, ppm: 102.9; 118.3; 120.2; 126.0; 127.1; 128.2; 129.0 (2С); 137.7; 139.0; 139.5; 154.4; 162.5; 166.6. Found, %: С 66.24; H 3.68; N 13.02. C18H12N3NaO2. Calculated, %: С 66.46; H 3.72; N 12.92.
Sodium 6-(4-methylphenyl)-2-phenyl-2 H -1,2,3-triazolo-[1,5- а ]pyridin-8-ium-3,4-bis(olate) (3b). Yield 370 mg (92%), yellow powder, mp >320°C. IR spectrum, ν, cm–1: 690, 753, 820, 927, 1169, 1234, 1313, 1359, 1399, 1417, 1489, 1538, 1587, 1633, 3209–3496 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 2.35 (3Н, s, СН3); 5.89 (1H, s, H-5); 7.25 (2H, d, J = 7.9, Н Ph); 7.30 (1Н, dd, J = 7.4, J = 7.4, Н Ph); 7.48–7.58 (5Н, m, H-7, Н Ar, H Ph); 8.12 (2H, d, J = 8.7, Н Ar). Found, %: С 66.97; H 4.28; N 12.49. C19H14N3NaO2. Calculated, %: С 67.25; H 4.16; N 12.38.
Sodium 6-(4-methoxyphenyl)-2-phenyl-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3,4-bis(olate) (3c). Yield 337 mg (79%), yellow powder, mp >320°C. IR spectrum, ν, cm–1: 752, 826, 929, 1049, 1227, 1252, 1290, 1398, 1426, 1489, 1516, 1627, 3106–3350 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 3.80 (3Н, s, OСН3); 5.87 (1H, s, H-5); 6.99 (2H, d, J = 8.7, Н Ar); 7.29 (1Н, dd, J = 7.4, J = 7.4, НPh); 7.50 (2Н, dd, J = 7.4, J = 7.8, H Ph); 7.53 (1Н, s, H-7); 7.59 (2H, d, J = 8.7, Н Ar); 8.12 (2H, d, J = 7.8, Н Ph). 13C NMR spectrum, δ, ppm: 55.1 (OСН3); 99.5; 104.0; 114.1; 117.6; 119.6; 125.6; 127.7; 128.9; 130.5; 136.8; 138.4; 153.7; 159.3; 167.2. Found, %: С 63.95; H 3.80; N 11.68. C19H14N3NaO3. Calculated, %: С 64.23; H 3.97; N 11.83.
Sodium 6-(4-ethoxyphenyl)-2-phenyl-2 H -1,2,3-triazolo-[1,5- а ]pyridin-8-ium-3,4-bis(olate) (3d). Yield 375 mg (85%), bright-yellow powder, mp >320°C. IR spectrum, ν, cm-1: 752, 825, 926, 1048, 1226, 1253, 1359, 1398, 1426, 1488, 1515, 1587, 1608, 1633, 3228–3385 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 1.35 (3Н, t, J = 6.9, OCH2CH 3); 4.06 (2Н, q, J = 6.9, OCH 2CH3); 5.93 (1H, s, H-5); 6.96 (2H, d, J = 8.6, Н Ar); 7.29 (1Н, dd, J = 7.3, J = 7.3, Н Ph); 7.51 (2Н, dd, J = 7.3, J = 7.9, Н Ph); 7.54 (1Н, s, H-7); 7.57 (2H, d, J = 8.6, Н Ar); 8.12 (2H, d, J = 7.9, Н Ph). 13C NMR spectrum, δ, ppm: 15.1 (СН3); 63.7 (СН2); 100.9; 104.5; 115.2; 118.1; 120.2; 126.1; 128.2; 129.3; 130.9; 137.4; 139.0; 154.2; 159.1; 167.6. Found, %: С 64.94; H 4.80; N 11.15. C20H16N3NaO3. Calculated, %: С 65.04; H 4.37; N 11.38.
Sodium 6-(4-chlorophenyl)-2-phenyl-2 H -1,2,3-triazolo-[1,5- а ]pyridin-8-ium-3,4-bis(olate) (3e). Yield 392 mg (91%), dark-yellow powder, mp >320°C. IR spectrum, ν, cm–1: 754, 816, 927, 1359, 1393, 1416, 1489, 1537, 1586, 1633, 3022–3472 (СН). 1H NMR spectrum, δ, ppm (J, Hz): 5.98 (1H, br. s, H-5); 7.30 (1Н, dd, J = 7.2, J = 7.3, НPh); 7.45–7.51 (4Н, m, H Ar); 7.65 (1Н, s, H-7); 7.68 (2H, d, J = 7.2, Н Ph); 8.09 (2H, d, J = 7.7, Н Ph). 13C NMR spectrum, δ, ppm: 99.5; 114.7; 120.2; 126.7; 128.6; 128.7; 129.0; 129.1; 133.5; 135.2; 135.3; 136.0; 139.0; 136.2. Found, %: С 60.18; H 3.20; N 11.46. C18H11ClN3NaO2. Calculated, %: С 60.10; H 3.08; N 11.68.
2,6-Diaryl-4-hydroxy-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3-olates 4а–e (General method). A suspension of salt 3a–e (0.74 mmol) in Н2О (20 ml) was acidified with 1 N HCl to рН 1–3. The reaction mixture was maintained at room temperature for 1 h, the precipitate was filtered off, washed with water, and dried.
4-Hydroxy-2,6-diphenyl-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3-olate (4а). Yield 185 mg (82%), yellow powder, mp 240–242°C. IR spectrum, ν, cm–1: 689, 751, 831, 924, 1157, 1315, 1364, 1414, 1489, 1550, 1593, 1643, 2546–3062 (СН, OH). 1H NMR spectrum, δ, ppm (J, Hz): 6.52 (1H, d, J = 1.0, H-5); 7.38 (1H, dd, J = 7.4, J = 7.4, Н Ph); 7.45–7.58 (5Н, m, Н Ph); 7.72 (2H, d, J = 6.9, Н Ph); 8.08 (2H, d, J = 7.6, Н Ph); 8.42 (1H, d, J = 1.0, H-7); 11.31 (1Н, br. s, ОН). 13C NMR spectrum, δ, ppm: 100.0; 101.4; 112.9; 113.6; 120.9; 127.4; 129.6; 129.7 (2С); 136.1; 136.7; 137.1; 151.5; 154.2. Mass spectrum, m/z (I rel, %): 304 [М+H]+ (5), 303 [М]+ (24), 198 (52), 170 (44), 142 (22), 140 (8), 116 (22), 115 (100), 105 (8), 89 (6), 77 (84), 63 (5), 51 (30). Found, %: С 70.99; H 4.31; N 13.47. C18H13N3O2. Calculated, %: С 71.28; H 4.32; N 13.85.
4-Hydroxy-6-(4-methylphenyl)-2-phenyl-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3-olate (4b). Yield 209 mg (89%), sand colored powder, mp 252–253°C. IR spectrum, ν, cm–1: 688, 755, 790, 830, 1155, 1174, 1231, 1248, 1309, 1406, 1426, 1489, 1519, 1555, 1606, 1633, 2623–3062 (СН, OH). 1H NMR spectrum, δ, ppm (J, Hz): 2.37 (3Н, s, СН3); 6.52 (1H, d, J = 0.7, H-5); 7.33 (2H, d, J = 8.0, Н Ar); 7.39 (1Н, dd, J = 7.4, J = 7.4, НPh); 7.56 (2Н, dd, J = 8.2, J = 7.7, Н Ph); 7.61 (2H, d, J = 8.1, Н Ar); 8.09 (2H, d, J = 7.7, Н Ph); 8.39 (1H, d, J = 0.7, H-7); 11.28 (1Н, br. s, ОН). 13C NMR spectrum, δ, ppm: 21.2 (СН3); 101.4; 112.5; 113.5; 120.8; 127.2; 127.4; 129.6; 130.2; 133.2; 136.7; 137.0; 139.2; 151.5; 154.1. Mass spectrum, m/z (I rel, %): 319 [М+2H]+ (1), 318 [М+H]+ (10), 317 [М]+ (44), 212 (91), 184 (59), 156 (34), 140 (10), 129 (98), 115 (20), 105 (7), 91 (6), 77 (100), 65 (6), 51 (30). Found, %: С 71.87; H 4.40; N 13.12. C19H15N3O2. Calculated, %: С 71.91; H 4.76; N 13.24.
4-Hydroxy-6-(4-methoxyphenyl)-2-phenyl-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3-olate (4c). Yield 190 mg (77%), yellow powder, mp 247–248°C. IR spectrum, ν, cm–1: 754, 925, 1120, 1405, 1427,1490, 1520, 1555, 1635, 2649–3061 (СН, OH). 1H NMR spectrum, δ, ppm (J, Hz): 3.81 (3Н, s, OСН3); 6.50 (1H, d, J = 1.0, H-5); 7.07 (2H, d, J = 8.8, Н Ar); 7.38 (1Н, dd, J = 7.4, J = 7.4, Н Ph); 7.55 (2Н, dd, J = 8.3, J = 7.6, Н Ph); 7.61 (2H, d, J = 8.7, Н Ar); 8.08 (2H, d, J = 7.6, Н Ph); 8.37 (1H, d, J = 1.0, H-7); 11.23 (1Н, br. s, ОН). 13C NMR spectrum, δ, ppm: 55.8 (OСН3); 101.4; 101.2; 112.1; 113.4; 115.1; 120.8; 127.3; 128.2; 128.7; 129.7; 136.7; 151.5; 154.7; 160.6. Mass spectrum, m/z (I rel, %): 334 [М+H]+ (4), 333 [М]+ (21), 288 (48), 200 (30), 185 (8), 172 (12), 169 (4), 157 (4), 146 (11), 145 (36), 140 (6), 131 (10), 115 (15), 102 (13), 77 (100), 63 (5), 51 (33). Found, %: С 68.38; H 4.22; N 12.39. C19H15N3O3. Calculated, %: С 68.46; H 4.54; N 12.61.
6-(4-Ethoxyphenyl)-4-hydroxy-2-phenyl-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3-olate (4d). Yield 188 mg (73%), dark-yellow powder, mp 250–251°C. IR spectrum, ν, cm–1: 753, 823, 922, 1044, 1153, 1180, 1228, 1252, 1406, 1487, 1518, 1556, 1606, 1625, 2631–3044 (СН, OH). 1H NMR spectrum, δ, ppm (J, Hz): 1.36 (3Н, t, J = 6.9, OСН2СН 3); 4.09 (2Н, q, J = 6.9, OСН 2СН3); 6.49 (1H, s, H-5); 7.05 (2H, d, J = 8.6, Н Ar); 7.38 (1Н, dd, J = 7.4, J = 7.4, Н Ph); 7.56 (2Н, dd, J = 7.4, J = 7.8, Н Ph); 7.65 (2H, d, J = 8.6, Н Ar); 8.09 (2H, d, J = 7.8, Н Ph); 8.39 (1H, s, H-7); 10.00–12.00 (1Н, br. s, ОН). 13C NMR spectrum, δ, ppm: 15.1 (СН3); 63.7 (СН2); 100.0; 101.3; 111.6; 115.5; 120.7; 127.3; 128.1; 128.6; 129.6; 136.7; 136.8; 140.2; 151.6; 159.8. Mass spectrum, m/z (I rel, %): 349 [М+2H]+ (2), 348 [М+H]+ (11), 347 [М]+ (45), 243 (16), 242 (100), 215 (7), 214 (49), 186 (22), 159 (16), 158 (28), 140 (6), 132 (18), 131 (58), 130 (10), 115 (6), 105 (8), 103 (22), 102 (9), 78 (8), 77 (98), 76 (5), 51 (22). Found, %: С 68.69; H 4.64; N 11.89. C20H17N3O3. Calculated, %: С 69.15; H 4.93; N 12.10.
6-(4-Chlorophenyl)-4-hydroxy-2-phenyl-2 H -1,2,3-triazolo[1,5- а ]pyridin-8-ium-3-olate (4e). Yield 192 mg (77%), sand colored powder, mp 252–253°C. IR spectrum, ν, cm–1: 754, 830, 925, 1092, 1161, 1316, 1391, 1427, 1489, 1545, 1594, 1636, 2650–3069 (СН, OH). 1H NMR spectrum, δ, ppm (J, Hz): 6.53 (1H, s, H-5); 7.39 (1H, dd, J = 7.3, J = 7.4, Н Ar); 7.53–7.59 (4Н, m, Н Ar); 7.74 (2H, d, J = 8.3, Н Ar); 8.08 (2H, d, J = 8.0, Н Ar); 8.44 (2H, d, J = 0.7, H-7); 10.00–12.50 (1Н, br. s, ОН). 13C NMR spectrum, δ, ppm: 101.2; 113.0; 113.7; 120.9; 120.7; 127.4; 129.2; 129.6; 129.7; 134.4; 135.0; 135.8; 136.6; 151.5; 154.3. Mass spectrum, m/z (I rel,%): 339 [М(37Cl)]+ (9), 338 [М(35Cl) +H]+ (7), 337 [М(35Cl)]+ (32), 234 (26), 232 (75), 206 (149), 204 (45), 176 (14), 169 (12), 151 (9), 149 (40), 140 (25), 114 (11), 105 (9), 78 (10), 77 (100), 63 (6), 52 (11), 51 (37), 50 (10), 39 (29). Found, %: С 63.87; H 3.66; N 12.28. C18H12ClN3O2. Calculated, %: С 64.01; H 3.58; N 12.44.
X-Ray structural analysis of compound 2а was performed on an Xcalibur S automated four-circle X-ray diffractometer by using the standard procedure (МоKα radiation, graphite monochromator, ω/2θ-scanning). A yellow prismatic crystal with dimensions of 0.4×0.3×0.25 mm was used for the analysis of compound 2a (C18H15N3O3, M 321.33). The crystal at 295(2) K was rhombic; space group P212121; unit cell parameters: a 8.0484(12), b 8.1876(8), c 23.784(3) A; Z 4; d calc 1.362 g/cm3; μ 0.095 mm–1. A total of 8547 reflections were collected in the range of 2.63 < θ < 26.37°, of which 3064 were independent (R int 0.0688), including 1812 reflections with I > 2σ(I). No correction for absorption was used. The structure was solved and refined with the SHELX15 software suite by using anisotropic approximation for non-hydrogen atoms. The hydrogen atoms were placed at calculated positions and were included in the refinement according to the "rider" model in isotropic approximation with dependent thermal parameters. The final structural refinement parameters: R 1 0.0414, wR 2 0.0761 (by reflections with I > 2σ(I)), R 1 0.0784, wR 2 0.0811 (by all reflections) with the robustness parameter S 1.001. The maximum/minimum residual electron density peaks were 0.131/–0.195 ēÅ–3. The atomic coordinates and temperature factors were deposited at the Cambridge Crystallographic Data Center (deposit CCDC 1030491).
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The results were obtained within the framework of the State Assignment for sscientific activity No. 4.560.2014-K from the the Ministry of Education and Science of the Russian Federation and with support from the Russian Foundation for Basic Research (grant 13-03-00137).
The authors are grateful to the Laboratory of Complex Investigations and Expert Evaluation of Organic Materials, Collective Use Center of the Ural Federal University, for acquiring NMR spectra of the obtained compounds.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2015, 51(2), 199–202
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Khazhieva, I.S., Demkin, P.M., Nein, J.I. et al. Synthesis of 1,2,3-Triazolo[1,5-а]Pyridin-8-Ium-3-Olates. Chem Heterocycl Comp 51, 199–202 (2015). https://doi.org/10.1007/s10593-015-1681-x
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DOI: https://doi.org/10.1007/s10593-015-1681-x