5-Amino-N-(2,2-dimethoxyethyl)-1Н-1,2,3-triazole-4-carboxamides in formic acid were subjected to intramolecular cyclization to 5-hydroxy[1,2,3]triazolo[4,5-е][1,4]diazepines, which were converted by treatment with S-nucleophiles to 5-thio-functionalized derivatives.
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Heterocyclic systems containing [1,4]diazepine ring fused with azole ring are of importance due to their synthetic utility and potential biological activity.1,2 Currently the most thoroughly studied examples of such compounds are [1,4]diazepine derivatives fused with pyrazole and imidazole rings. The pharmacological significance of pyrazolo[1,4]diazepines is obvious from their use as active substances in the anxiolytic drug zolazepam3,4,5 and the antidepressant zometapine.6,7 Besides that, selective phosphodiesterase inhibitors8 and oxytocin receptor antagonists9 have been identified in pyrazolo[1,4]diazepine series.
From the viewpoint of medicinal chemistry, imidazo[1,4]diazepines are no less valuable, especially the adenosine receptor antagonists10 and inhibitors of the metalloenzyme guanase – the natural product azepinomycin11 (I) (Fig. 1) and its synthetic analogs.12,13,14,15,16 It has been recently shown17 that some derivatives of isoazepinomycin (II) (5-hydroxy-4,5,6,7-tetrahydroimidazo[4,5-е][1,4]diazepin-8-ol), which is a positional isomer of azepinomycin, can be used as guanase inhibitors. The authors of that study proposed that the inhibitory activity of these compounds was substantially affected by the hydrophobic cleft between the imidazole and diazepine ring nitrogen atoms. It could be expected that the structural changes in azole ring could also influence the inhibition of guanase – an enzyme catalyzing the hydrolytic deamination of guanine to xanthine.18,19
The molecular structures of azepinomycin (I) and isoazepinomycin (II).
Taking all of this into account, it was considered worthwhile to develop a convenient method for the synthesis of isoelectronic isoazepinomycin analogs – derivatives of triazolo[4,5-е][1,4]diazepine. It should be noted that only a single literature source20 describes the synthesis of tetrahydro[1,2,3]triazolo[4,5-е][1,4]diazepin-8-ol derivatives by cyclization of 5-amino-N-(2-chloroethyl)-1H-1,2,3-triazole-4-carboxamides in the presence of NaH.
The method previously proposed by our group21 and by other authors17 for the formation of hydroxydiazepine ring starting from 5-amino-N-(2,2-dialkoxyethyl)-1Н-pyrazole-(imidazole)-4-carboxamides was found to be also suitable for the preparation of new triazolo[1,4]diazepine derivatives. The key starting materials for this reaction were 5-amino-N-(2,2-dimethoxyethyl)-1Н-1,2,3-triazole-4-carboxamides 3a–l, which were synthesized by us earlier using anionic cyclization of azides 1a–l with 2-cyano-N-(2,2-dimethoxyethyl)acetamide (Scheme 1). This method was found to be generally applicable and could use alkyl-, aryl-, and hetaryl azides as starting materials for triazole ring formation under mild conditions in the presence of t-BuOK as base, giving compounds 3a–l in 79–94% yields (Table 1). The obtained N-functionalized aminotriazolecarboxamides 3a–l readily underwent intramolecular cyclization in formic acid at room temperature, forming 5-hydroxy-substituted triazolo[4,5-е][1,4]diazepines 4a–l in nearly quantitative yields (Scheme 1, Table 1).
Scheme 1
IR spectra of compounds 4a–l featured a set of absorption bands corresponding to the stretching vibrations of C=O (1627–1636 cm–1), N–H (3247–3312 cm–1), and O–H bonds (3247–3312 cm–1). 1Н NMR spectra contained the expected signals for substituents R, as well as multiplets of the 6-CH2 protons at 2.98–3.38 ppm, 5-CH protons at 4.86–5.18 ppm, and the signals of NH protons: doublets at 7.26–8.01 ppm and multiplets at 7.13–7.66 ppm. 1H NMR spectra of compounds 4a–l did not show any changes after maintaining the samples in DMSO-d6 solution for a week. This observation indicated that, in contrast to 7-hydroxypyrazolo[1,4]diazepines,21 the more electron-withdrawing 1,2,3-triazole ring did not facilitate the elimination of water molecule from O,N-ketene acetal moiety in compounds 4 and establishment of equilibrium with the azomethine form. At the same time, a process of this type can easily proceed in acidic medium, which was used by us for selective functionalization of position 5 in triazolodiazepines with sulfur-containing groups.
We found that diazepines 4a,e–i,l in the presence of S-nucleophilic reagents 5a–g in formic acid at room temperature (method I) were readily converted to 5-sulfanyl-substituted triazolodiazepines 6a–i in 91–98% yields (Scheme 2, Table 2). Studying this transformation in more detail in the case of compounds 6a–c,h showed that they can be also obtained in a one-pot process from amides 3a,e,i and sulfur-containing nucleophiles 5a,d,e,g under analogous conditions, without isolation of 5-hydroxytriazolodiazepine intermediates (method II) (Scheme 2, Table 2). Most probably, an acid-catalyzed formation of the cyclic iminium intermediate А occurred in both cases, and the reagents containing HS group added to this intermediate. It should be noted that alcohols as weaker nucleophiles were not effective in such reactions. Thus, LC-MS analysis indicated that the reactions with alcohols under analogous conditions did not produce more than 12–15% of 5-alkoxy derivatives.
Scheme 2
Thus, our study has shown that intramolecular cyclization of 5-amino-N-(2,2-dimethoxyethyl)-1Н-1,2,3triazole-4-carboxamides in formic acid provides a convenient method for the synthesis of isoelectronic analogs of isoazepinomycin – 5-hydroxy[1,2,3]triazolo[4,5-е][1,4]diazepines, which are promising targets for synthetic and medicinal chemistry research.
Experimental
IR spectra were recorded on a Bruker Vertex 70 spectrometer for samples in the form of KBr pellets. 1Н NMR spectra were acquired in pulsed FT mode on Varian VXR-400 (400 MHz) and 13С NMR spectra on Bruker Avance DRX-500 (125 MHz) spectrometers. The solvents were CDCl3 (1Н and 13С NMR spectra of compounds 3a–d,f–h,k, 13С NMR spectrum of compound 3е) and DMSO-d6 (1Н and 13С NMR spectra of the rest of the compounds). The solvent signals were used as internal standards (CDCl3: 7.26 ppm for 1Н nuclei, 77.0 ppm for 13С nuclei; DMSO-d6: 2.49 ppm for 1Н nuclei, 39.5 ppm for 13С nuclei). Mass spectra were recorded on an Agilent LC/MSD SL instrument; the column was Zorbax SB-C18, 4.6 × 15 mm, 1.8 μm (PN 82(c)75-932); solvent DMSO, electrospray ionization at atmospheric pressure. Elemental analysis was performed on a PerkinElmer CHN Analyzer 2400 instrument. Melting points were determined on a Kofler bench and were not corrected.
Synthesis of compounds 3a–l (General method). A solution of cyanoacetamide 2 (1.89 g, 11 mmol) and t-BuOK (1.23 g, 11 mmol) in MeOH (20 ml) was treated by adding a MeOH solution (10 ml) of alkyl azide 1a–d, obtained from 14 mmol of the respective alkyl halide according to a literature procedure22 or aryl azide 1g–l that was obtained from the respective arylamine according to another published procedure.23 The mixture was stirred at room temperature for 1 h, then refluxed for 0.5 h. The reaction mixture was evaporated, the residue was treated with water (20 ml), the obtained precipitate was filtered off, washed with water (10 ml), dried, and recrystallized from МеОН.
5-Amino- N -(2,2-dimethoxyethyl)-1-isobutyl-1 Н -1,2,3-triazole-4-carboxamide (3а). Yield 2.35 g (79%), white powder, mp 162–163°С. IR spectrum, ν, cm–1: 1646 (С=О), 3311, 3455 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 0.91 (6H, d, J = 6.4, CH(CH3)2); 2.16–2.23 (1H, m, CH2CHMe2); 3.37 (6H, s, 2OCH3); 3.52 (2H, d, J = 5.4, CH2CH(OMe)2); 3.88 (2H, d, J = 7.2, CH2CHMe2); 4.42 (1H, t, J = 5.2, CH2CH(OMe)2); 5.18 (2H, s, NH2); 7.01 (1H, br. s, NH). 13C NMR spectrum, δ, ppm: 19.9 (2С); 28.5; 40.1; 53.2; 54.3 (2С); 102.8; 122.9; 143.7; 162.7. Mass spectrum, m/z (Irel, %): 270 [М–Н]– (100). Found, %: C 48.61; H 7.96; N 25.94. С11H21N5O3. Calculated, %: C 48.70; H 7.80; N 25.81.
5-Amino-1-benzyl- N -(2,2-dimethoxyethyl)-1 Н -1,2,3-triazole-4-carboxamide (3b). Yield 2.85 g (85%), white powder, mp 144–145°С. IR spectrum, ν, cm–1: 1647 (С=О), 3295, 3369 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.39 (6H, s, 2OCH3); 3.53 (2H, t, J = 5.4, CH2CH(OMe)2); 4.43 (1H, t, J = 5.2, CH2CH(OMe)2); 4.80 (2H, s, NH2); 5.36 (2H, s, CH2Ph); 6.98 (1H, t, J = 5.4, NH); 7.18–7.38 (5H, m, H Ph). 13C NMR spectrum, δ, ppm: 39.8; 49.1; 53.9 (2С); 102.2; 124.1 (2С); 128.7; 130.4 (2С); 139.4; 143.3; 147.1; 161.8. Mass spectrum, m/z (Irel, %): 304 [М–Н]– (97). Found, %: C 54.92; H 6.19; N 23.11. С14H19N5O3. Calculated, %: C 55.07; H 6.27; N 22.94.
5-Amino- N -(2,2-dimethoxyethyl)-1-(4-methoxybenzyl)1 Н -1,2,3-triazole-4-carboxamide (3c). Yield 2.85 g (89%), white powder, mp 136–137°С. IR spectrum, ν, cm–1: 1644 (С=О), 3283, 3394 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.43 (6H, s, 2OCH3); 3.59 (2H, t, J = 5.4, CH2CH(OMe)2); 3.85 (3H, s, ArOCH3); 4.47 (1H, t, J = 5.2, CH2CH(OMe)2); 5.27 (2H, s, NH2); 5.30 (2H, s, CH2Ar); 6.88 (2H, d, J = 8.4, H Ar); 7.05 (1H, t, J = 5.2, NH); 7.18 (2H, d, J = 8.4, H Ar). 13C NMR spectrum, δ, ppm: 40.3; 47.8; 54.3 (2С); 55.9; 102.8; 115.2 (2С); 122.9; 130.1 (2С); 134.7; 143.7; 162.7; 163.8. Mass spectrum, m/z (Irel, %): 335 [М–Н]– (100). Found, %: C 53.80; H 6.46; N 21.07. С15H21N5O4. Calculated, %: C 53.72; H 6.31; N 20.88.
5-Amino-1-(3-chlorobenzyl)- N -(2,2-dimethoxyethyl)1 Н -1,2,3-triazole-4-carboxamide (3d). Yield 3.13 g (84%), beige powder, mp 129–130°С. IR spectrum, ν, cm–1: 1645 (С=О), 3278, 3389 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.40 (6H, s, 2OCH3); 3.53 (2H, t, J = 5.4, CH2CH(OMe)2); 4.44 (1H, t, J = 5.2, CH2CH(OMe)2); 5.01 (2H, s, NH2); 5.32 (2H, s, CH2Ar); 7.00–7.07 (2H, m, NH, H Ar); 7.18 (1H, s, H Ar); 7.25–7.30 (2H, m, H Ar). 13C NMR spectrum, δ, ppm: 40.2; 49.4; 54.3 (2С); 102.7; 123.5; 125.3; 127.3; 128.9; 130.5; 135.2; 135.6; 143.9; 162.6. Mass spectrum, m/z (Irel, %): 338 [М–Н]– (100). Found, %: C 49.61; H 5.27; N 20.38. С14H18ClN5O3. Calculated, %: C 49.49; H 5.34; N 20.61.
5-Amino- N -(2,2-dimethoxyethyl)-1-phenyl-1 Н -1,2,3triazole-4-carboxamide (3e). Yield 2.98 g (81%), white powder, mp 152–153°С. IR spectrum, ν, cm–1: 1634 (С=О), 3275, 3382 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.29 (6H, s, 2OCH3); 3.58 (2H, t, J = 5.3, CH2CH(OMe)2); 3.73 (3H, s, OCH3); 5.17 (1H, t, J = 5.1, CH2CH(OMe)2); 5.35 (2H, s, CH2Ph); 6.27 (2H, s, NH2); 6.90 (2H, d, J = 7.2, H Ar); 7.21 (2H, d, J = 7.2, H Ar); 7.70 (1H, t, J = 5.2, NH). 13C NMR spectrum, δ, ppm: 40.3; 54.3 (2С); 102.8; 122.6; 123.9 (2С); 129.6; 130.1 (2С); 134.7; 143.7; 162.7. Mass spectrum, m/z (Irel, %): 290 [М–Н]– (100). Found, %: C 53.81; H 5.76; N 23.85. С13H17N5O3. Calculated, %: C 53.60; H 5.88; N 24.04.
5-Amino-1-(4-chlorophenyl)- N -(2,2-dimethoxyethyl)1 Н -1,2,3-triazole-4-carboxamide (3f). Yield 3.33 g (93%), yellow powder, mp 159–160°С. IR spectrum, ν, cm–1: 1637 (С=О), 3281, 3396 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.43 (6H, s, 2OCH3); 3.58 (2H, t, J = 5.4, CH2CH(OMe)2); 4.48 (1H, t, J = 5.2, CH2CH(OMe)2); 5.31 (2H, s, NH2); 7.03 (1H, t, J = 5.2, NH); 7.48–7.57 (4H, m, H Ar). 13C NMR spectrum, δ, ppm: 40.3; 54.3 (2С); 102.8; 122.8; 125.1 (2С); 130.3 (2С); 133.2; 135.6; 143.7; 162.5. Mass spectrum, m/z (Irel, %): 324 [М–Н]– (100). Found, %: C 47.78; H 4.84; N 21.76. С13H16ClN5O3. Calculated, %: C 47.93; H 4.95; N 21.50.
5-Amino- N -(2,2-dimethoxyethyl)-1-(4-methylphenyl)1 Н -1,2,3-triazole-4-carboxamide (3g). Yield 295 g (88%), beige powder, mp 108–109°С. IR spectrum, ν, cm–1: 1629 (С=О), 3294, 3405 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 2.44 (3H, s, ArCH3); 3.43 (6H, s, 2OCH3); 3.60 (2H, t, J = 5.4, CH2CH(OMe)2); 4.49 (1H, t, J = 5.2, CH2CH(OMe)2); 5.25 (2H, s, NH2); 7.30 (1H, t, J = 5.2, NH); 7.31–7.42 (4H, m, H Ar). 13C NMR spectrum, δ, ppm: 21.3; 40.3; 54.3 (2С); 102.8; 122.5; 123.9 (2С); 130.6 (2С); 132.0; 139.9; 143.8; 162.7. Mass spectrum, m/z (Irel, %): 304 [М–Н]– (100). Found, %: C 55.26; H 6.14; N 23.16. С14H19N5O3. Calculated, %: C 55.07; H 6.27; N 22.94.
5-Amino- N -(2,2-dimethoxyethyl)-1-(4-methoxyphenyl)1 Н -1,2,3-triazole-4-carboxamide (3h). Yield 3.04 g (86%), beige powder, mp 123–124°С. IR spectrum, ν, cm–1: 1632 (С=О), 3282, 3398 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.42 (6H, s, 2OCH3); 3.57 (2H, t, J = 5.4, CH2CH(OMe)2); 3.86 (3H, s, ArOCH3); 4.46 (1H, t, J = 5.2, CH2CH(OMe)2); 5.22 (2H, s, NH2); 7.02–7.07 (3H, m, NH, H Ar); 7.42 (2H, d, J = 8.8, H Ar). 13C NMR spectrum, δ, ppm: 40.3; 54.4 (2С); 55.7; 102.9; 115.2 (2С); 122.5; 125.8 (2С); 127.2; 143.9; 160.5; 162.7. Mass spectrum, m/z (Irel, %): 320 [М–Н]– (100). Found, %: C 52.56; H 5.74; N 21.58. С14H19N5O4. Calculated, %: C 52.33; H 5.96; N 21.79.
5-Amino- N -(2,2-dimethoxyethyl)-1-(4-nitrophenyl)1 Н -1,2,3-triazole-4-carboxamide (3i). Yield 3.47 g (91%), yellow powder, mp 174–175°С. IR spectrum, ν, cm–1: 1637 (С=О), 3275, 3395 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.29 (6H, s, 2OCH3); 3.36 (2H, t, J = 5.4, CH2CH(OMe)2); 4.56 (1H, t, J = 5.2, CH2CH(OMe)2); 6.71 (2H, s, NH2); 7.93 (2H, d, J = 8.4, H Ar); 8.23 (1H, t, J = 5.2, NH); 8.44 (2H, d, J = 8.4, H Ar). 13C NMR spectrum, δ, ppm: 41.3; 53.3 (2С); 102.2; 121.2; 124.9 (2С); 125.6 (2С); 140.4; 145.3; 147.3; 162.4. Mass spectrum, m/z (Irel, %): 335 [М–Н]– (97). Found, %: C 46.22; H 4.69; N 25.21. С13H16N6O5. Calculated, %: C 46.43; H 4.80; N 24.99.
5-Amino-1-(2,4-difluorophenyl)- N -(2,2-dimethoxyethyl)1 Н -1,2,3-triazole-4-carboxamide (3j). Yield 3.27 g (91%), beige powder, mp 182–183°С. IR spectrum, ν, cm–1: 1634 (С=О), 3275, 3395 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.30 (6H, s, 2OCH3); 3.38 (2H, t, J = 5.4, CH2CH(OMe)2); 4.56 (1H, t, J = 5.2, CH2CH(OMe)2); 6.51 (2H, s, NH2); 7.31–7.36 (1H, m, H Ar); 7.57–7.74 (2H, m, H Ar); 8.04 (1H, t, J = 5.2, NH). 13C NMR spectrum, δ, ppm (J, Hz): 40.4; 53.3 (2С); 102.2; 106.0 (d, 2JCF = 22.6, C-3'); 106.1 (d, 2JCF = 22.6, C-3'); 106.2 (d, 2JCF = 22.6, C-3'); 113.2 (dd, 2J = 22.6, 4J = 3.7, C-5'); 119.3 (dd, 2J = 22.6, 4J = 3.7, C-1'); 120.8; 131.3 (d, 3J = 10.0, C-6'); 146.5; 157.6 (dd, 1J = 253.6, 3J = 13.8, C-4'); 162.6; 163.5 (dd, 1J = 251.4, 3J = 12.5, C-2'). Mass spectrum, m/z (Irel, %): 326 [М–Н]– (100). Found, %: C 47.97; H 4.49; N 21.17. С13H15F2N5O3. Calculated, %: C 47.71; H 4.62; N 21.40.
5-Amino- N -(2,2-dimethoxyethyl)-1-(2,4-dimethylphenyl)-1 Н -1,2,3-triazole-4-carboxamide (3k). Yield 2.84 g (81%), beige powder, mp 133–134°С. IR spectrum, ν, cm–1: 1638 (С=О), 3294, 3410 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 2.09 (3H, s, ArCH3); 2.40 (3H, s, ArCH3); 3.42 (6H, s, 2OCH3); 3.58 (2H, t, J = 5.4, CH2CH(OMe)2); 4.48 (1H, t, J = 5.2, CH2CH(OMe)2); 5.03 (2H, s, NH2); 7.15 (1H, t, J = 5.2, NH); 7.20 (2H, m, H Ar); 7.26 (1H, s, H Ar). 13C NMR spectrum, δ, ppm: 17.4; 21.3; 40.3; 54.3 (2С); 102.9; 122.0; 127.0; 128.0; 130.2; 132.4; 135.8; 141.1; 144.5; 162.8. Mass spectrum, m/z (Irel, %): 318 [М–Н]– (100). Found, %: C 56.27; H 6.46; N 22.19. С15H21N5O3. Calculated, %: C 56.41; H 6.63; N 21.93.
5-Amino- N -(2,2-dimethoxyethyl)-1-(1-methylpyrazol3-yl)-1 Н -1,2,3-triazole-4-carboxamide (3l). Yield 2.98 g (92%), white powder, mp 150–151°С. IR spectrum, ν, cm–1: 1632 (С=О), 3291, 3407 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.27 (6H, d, 2OCH3); 3.35 (2H, t, J = 5.4, CH2CH(OMe)2); 3.92 (3H, s, NCH3); 4.54 (1H, t, J = 5.2, CH2CH(OMe)2); 6.59 (1H, s, H Ar); 6.63 (1H, s, NH2); 7.91 (1H, s, H Ar); 8.11 (1H, t, J = 5.2, NH). 13C NMR spectrum, δ, ppm: 38.5; 39.1; 53.3 (2С); 97.5; 102.2; 121.6; 133.5; 143.9; 145.4; 162.2. Mass spectrum, m/z (Irel, %): 294 [М–Н]– (100). Found, %: C 44.91; H 5.66; N 33.04. С11H17N7O3. Calculated, %: C 44.74; H 5.80; N 33.20.
Synthesis of compounds 4a–l (General method). A solution of amide 3a–l (7 mmol) in НСО2Н (10 ml) was stirred at room temperature for 10–12 h, diluted with water (10 ml), the obtained precipitate was filtered off, washed with water (50 ml), and air-dried.
5-Hydroxy-3-isobutyl-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4а). Yield 1.28 g (81%), white powder, mp 241–244°С. IR spectrum, ν, cm–1: 1632 (С=О), 3252, 3297 (N–H), 3347 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 0.82–0.88 (6H, m, CH2CH(CH3)2); 2.04–2.11 (1H, m, CH2CHMe2); 3.00–3.18 (1H, m) and 3.22–3.31 (1H, m, 6-CH2); 3.92 (2H, d, J = 7.2, CH2CH(CH3)2); 4.97–5.02 (1H, m, 5-CH); 5.82 (1H, d, J = 4.4, OH); 7.35–7.39 (1H, m, NH); 7.73 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 19.5 (2С); 27.7; 44.9; 52.3; 74.0; 122.9; 144.7; 163.8. Mass spectrum, m/z (Irel, %): 226 [М+Н]+ (100). Found, %: C 47.64; H 6.59; N 31.27. С9H15N5O2. Calculated, %: C 47.99; H 6.71; N 31.09.
3-Benzyl-5-hydroxy-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4b). Yield 1.62 g (89%), white powder, mp 185–187°С. IR spectrum, ν, cm–1: 1636 (С=О), 3256, 3299 (N–H), 3356 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 3.02–3.09 (1H, m) and 3.18–3.31 (1H, m, 6-CH2); 4.97–5.03 (1H, m, 5-CH); 5.41 (2H, s, CH2Ph); 5.92 (1H, br. s, OH); 7.18–7.41 (6H, m, NH, H Ph); 7.92 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 44.9; 48.5; 74.0; 127.1 (2C); 127.3; 127.7; 128.7 (2C); 135.8; 141.1; 163.6. Mass spectrum, m/z (Irel, %): 260 [М+Н]+ (100). Found, %: C 55.33; H 4.96; N 27.27. С12H13N5O2. Calculated, %: C 55.59; H 5.05; N 27.01.
5-Hydroxy-3-(4-methoxybenzyl)-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4c). Yield 1.78 g (87%), white powder, mp 180–182°С. IR spectrum, ν, cm–1: 1631 (С=О), 3251, 3305 (N–H), 3360 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 2.98–3.06 (1H, m) and 3.18–3.31 (1H, m, 6-CH2); 3.72 (3H, s, OCH3); 4.97–5.03 (1H, m, 5-CH); 5.31 (2H, s, CH2Ar); 5.88 (1H, br. s, OH); 6.89 (2H, d, J = 8.4, H Ar); 7.18 (2H, d, J = 8.4, H Ar); 7.39–7.46 (1H, m, NH); 7.90 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 45.3; 48.5; 55.5; 114.4 (2С); 123.6; 128.2 (2С); 141.3; 159.3; 163.9. Mass spectrum, m/z (Irel, %): 290 [М+Н]+ (100). Found, %: C 54.19; H 5.29; N 24.47. С13H15N5O3. Calculated, %: C 53.97; H 5.23; N 24.21.
3-(3-Chlorobenzyl)-5-hydroxy-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4d). Yield 1.81 g (88%), yellow powder, mp 176–178°С. IR spectrum, ν, cm–1: 1634 (С=О), 3249, 3301 (N–H), 3361 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 3.04–3.13 (1H, m) and 3.22–3.32 (1H, m, 6-CH2); 4.98–5.05 (1H, m, 5-CH); 5.43 (2H, s, CH2Ar); 5.81 (1H, br. s, OH); 7.13–7.44 (5H, m, NH, H Ar); 7.82 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 45.3; 48.3; 74.6; 123.7; 126.4; 127.6; 128.2; 131.0; 133.6; 138.7; 141.6; 163.9. Mass spectrum, m/z (Irel, %): 294 [М+Н]+ (100). Found, %: C 50.23; H 4.24; N 23.67. С12H12ClN5O2. Calculated, %: C 49.07; H 4.12; N 23.84.
5-Hydroxy-3-phenyl-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4e). Yield 1.58 g (92%), white powder, mp 237–239°С. IR spectrum, ν, cm–1: 1629 (С=О), 3253, 3307 (N–H), 3378 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 3.11–3.19 (1H, m) and 3.32–3.38 (1H, m, 6-CH2); 4.96–5.04 (1H, m, 5-CH); 5.72 (1H, d, J = 4.4, OH); 7.40–7.48 (1H, m, NH); 7.52–7.66 (6H, m, NH, H Ph). 13C NMR spectrum, δ, ppm: 45.1; 74.4; 123.8; 125.5 (2С); 129.9; 130.5 (2С); 135.1; 141.5; 163.8. Mass spectrum, m/z (Irel, %): 246 [М+Н]+ (100). Found, %: C 53.63; H 4.41; N 28.88. С11H11N5O2. Calculated, %: C 53.87; H 4.52; N 28.56.
3-(4-Chlorophenyl)-5-hydroxy-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4f). Yield 1.96 g (95%), white powder, mp 258–260°С. IR spectrum, ν, cm–1: 1630 (С=О), 3249, 3303 (N–H), 3371 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 3.14–3.21 (1H, m) and 3.23–3.31 (1H, m, 6-CH2); 4.92–5.00 (1H, m, 5-CH); 5.82 (1H, d, J = 4.4, OH); 7.49–7.55 (1H, m, NH); 7.57 (2H, d, J = 8.8, H Ar); 7.69 (2H, d, J = 8.8, H Ar); 7.75 (1H, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 45.1; 74.5; 123.8; 127.5 (2С); 130.3 (2С); 133.9; 134.4; 141.7; 163.7. Mass spectrum, m/z (Irel, %): 280 [М+Н]+ (100). Found, %: C 47.47; H 3.53; N 24.84. С11H10ClN5O2. Calculated, %: C 47.24; H 3.60; N 25.04.
5-Hydroxy-3-(4-methylphenyl)-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4g). Yield 1.65 g (91%), white powder, mp 197–199°С. IR spectrum, ν, cm–1: 1628 (С=О), 3247, 3311 (N–H), 3366 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 2.37 (3H, s, CH3); 3.09– 3.16 (1H, m) and 3.26–3.32 (1H, m, 6-CH2); 4.93–5.02 (1H, m, 5-CH); 5.79 (1H, d, J = 4.4, OH); 7.38–7.48 (4H, m, H Ar); 7.49–7.51 (1H, m, NH); 7.59 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 21.2; 45.2; 74.4; 123.6; 125.4 (2С); 130.6 (2С); 132.6; 139.6; 141.5; 163.8. Mass spectrum, m/z (Irel, %): 260 [М+Н]+ (99). Found, %: C 55.77; H 4.94; N 26.86. С12H13N5O2. Calculated, %: C 55.59; H 5.05; N 27.01.
5-Hydroxy-3-(4-methoxyphenyl)-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4h). Yield 1.79 g (93%), white powder, mp 251–253°С. IR spectrum, ν, cm–1: 1631 (С=О), 3251, 3308 (N–H), 3369 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 3.07–3.15 (1H, m) and 3.24–3.33 (1H, m, 6-CH2); 3.84 (3H, s, OCH3); 4.91–4.97 (1H, m, 5-CH); 5.76 (1H, br. s, OH); 7.14 (2H, d, J = 8.8, H Ar); 7.40–7.48 (3H, m, NH, H Ar); 7.51 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 45.3; 56.5; 74.3; 115.2 (2С); 122.9; 130.1 (2С); 135.3; 141.0; 163.4; 164.6. Mass spectrum, m/z (Irel, %): 276 [М+Н]+ (100). Found, %: C 52.07; H 4.55; N 25.69. С12H13N5O3. Calculated, %: C 52.36; H 4.76; N 25.44 .
5-Hydroxy-3-(4-nitrophenyl)-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4i). Yield 1.95 g (96%), yellow powder, mp 242–244°С. IR spectrum, ν, cm–1: 1628 (С=О), 3254, 3306 (N–H), 3361 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 3.08–3.15 (1H, m) and 3.27–3.33 (1H, m, 6-CH2); 4.97–5.02 (1H, m, 5-CH); 5.91 (1H, br. s, OH); 7.54–7.62 (1H, m, NH); 7.88 (2H, d, J = 8.8, H Ar); 8.01 (1H, d, J = 3.6, NH); 8.45 (2H, d, J = 8.8, H Ar). 13C NMR spectrum, δ, ppm: 45.1; 74.7; 124.3; 125.7 (2С); 126.2 (2С); 140.3; 141.7; 147.6; 163.5. Mass spectrum, m/z (Irel, %): 291 [М+Н]+ (100). Found, %: C 45.39; H 3.35; N 29.18. С11H10N6O4. Calculated, %: C 45.52; H 3.47; N 28.96.
3-(2,4-Difluorophenyl)-5-hydroxy-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4j). Yield 1.77 g (90%), white powder, mp 223–225°С. IR spectrum, ν, cm–1: 1634 (С=О), 3253, 3307 (N–H), 3368 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 3.07–3.14 (1H, m) and 3.26–3.32 (1H, m, 6-CH2); 4.90–4.98 (1H, m, 5-CH); 5.88 (1H, br. s, OH); 7.29–7.35 (1H, m, H Ar); 7.44–7.49 (1H, m, NH); 7.60–7.69 (2H, m, H Ar); 7.81–7.89 (1H, m, NH). 13C NMR spectrum, δ, ppm (J, Hz): 45.2; 74.4; 106.0 (d, 2JCF = 22.6, C-3'); 106.2 (d, 2JCF = 22.6, C-3'); 113.1 (dd, 2J = 22.6, 4J = 3.7, C-5'); 119.2 (dd, 2J = 22.6, 4J = 3.7, C-1'); 122.8; 131.6 (d, 3J = 10.0, C-6'); 143.0; 157.6 (dd, 1J = 253.6, 3J = 13.8, C-4'); 163.7; 164.5 (dd, 1J = 251.4, 3J = 12.5, C-2'). Mass spectrum, m/z (Irel, %): 282 [М+Н]+ (98). Found, %: C 47.19; H 3.13; N 24.76. С11H9F2N5O2. Calculated, %: C 46.98; H 3.23; N 24.90.
3-(2,4-Dimethylphenyl)-5-hydroxy-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4k). Yield 1.70 g (89%), beige powder, mp 258–260°С. IR spectrum, ν, cm–1: 1627 (С=О), 3257, 3312 (N–H), 3379 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 1.99 (3H, s, CH3); 2.34 (3H, s, CH3); 3.06–3.12 (1H, m) and 3.26–3.32 (1H, m, 6-CH2); 4.89–4.93 (1H, m, 5-CH); 5.69 (1H, br. s, OH); 7.18–7.22 (2H, m, H Ar); 7.26–7.29 (2H, m, NH, H Ar); 7.38–7.42 (1H, m, NH). 13C NMR spectrum, δ, ppm: 17.4; 21.2; 45.3; 74.2; 122.9; 128.1; 128.2; 131.1; 132.2; 135.9; 140.5; 142.2; 163.9. Mass spectrum, m/z (Irel, %): 274 [М+Н]+ (97). Found, %: C 57.34; H 5.41; N 25.47. С13H15N5O2. Calculated, %: C 57.13; H 5.53; N 25.63.
5-Hydroxy-3-(1-methylpyrazol-3-yl)-4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (4l). Yield 1.74 g (94%), white powder, mp 218–220°С. IR spectrum, ν, cm–1: 1626 (С=О), 3254, 3298 (N–H), 3359 (О–Н). 1H NMR spectrum, δ, ppm (J, Hz): 3.13–3.19 (1H, m) and 3.21–3.33 (1H, m, 6-CH2); 3.92 (3H, s, NCH3); 5.12–5.18 (1H, m, 5-CH); 6.07 (1H, d, J = 4.4, OH); 6.59 (1H, s, H Ar); 7.50–7.57 (1H, m, NH); 7.87 (1H, d, J = 3.6, NH); 7.92 (1H, s, H Ar). 13C NMR spectrum, δ, ppm: 45.0; 74.6; 98.0; 123.4; 133.7; 140.6; 145.2; 163.5; 163.6. Mass spectrum, m/z (Irel, %): 250 [М+Н]+ (96). Found, %: C 43.19; H 4.36; N 39.71. С9H11N7O2. Calculated, %: C 43.37; H 4.45; N 39.34.
Synthesis of compounds 6a–i (General procedure). Method I. Thio derivative 5a–g (4 mmol) was added to a solution of triazolodiazepine 4a,e–i,l (4 mmol) in НСО2Н (10 ml), the reaction mixture was stirred at room temperature for 8 h, diluted with water (10 ml), the obtained precipitate was filtered off, washed with water (10 ml), dried, and recrystallized from МеCN.
Method II. Thio compound 5a,d,e,g (5 mmol) was added to a solution of amide 3a,e,i (5 mmol) in НСО2Н (15 ml), the reaction mixture was stirred at room temperature for 12 h, diluted with water (10 ml), the obtained precipitate was filtered off, washed with water (10 ml), dried, and recrystallized from МеCN.
Methyl [(3-isobutyl-8-oxo-3,4,5,6,7,8-hexahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-5-yl)sulfanyl]acetate (6a). Yield 1.20 g (96%, method I), 1.44 g (92%, method II), white powder, mp 239–240°С. IR spectrum, ν, cm–1: 1670 (С=О), 1734–1756 (CO2Me), 3321, 3415 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 0.79–0.88 (6H, m, СН2СН(CH3)2); 2.03–2.12 (1H, m, СН2СНMe2); 3.35–3.62 (4H, m, 6-CH2, SCH2); 3.64 (3H, s, OCH3); 3.95 (2H, d, J = 7.2, СН2СНMe2); 5.09–5.19 (1H, m, 5-СН); 7.59–7.68 (1H, m, NH); 8.04 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 19.8 (2С); 27.9; 30.9; 44.8; 52.1; 52.4; 60.6; 123.4; 140.2; 163.3; 170.7. Mass spectrum, m/z (Irel, %): 314 [М+Н]+ (100). Found, %: C 46.21; H 5.95; N 22.19. С12H19N5O3S. Calculated, %: C 45.99; H 6.11; N 22.35.
S -(3-Isobutyl-8-oxo-3,4,5,6,7,8-hexahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-5-yl)ethanethioate (6b). Yield 1.11 g (98%, method I), 1.35 g (95%, method II), white powder, mp 256– 257°С. IR spectrum, ν, cm–1: 1670 (С=О), 1715 (С=О), 3317, 3447 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 0.77–0.85 (6H, m, СН2СН(CH3)2); 1.97–2.05 (1H, m, СН2СНMe2); 2.34 (3H, s, COCH3); 3.31–3.53 (2H, m, 6-CH2); 3.95 (2H, d, J = 7.2, СН2СН(CH3)2); 5.61–5.70 (1H, m, 5-СН); 7.72–7.79 (1H, m, NH); 8.07 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 19.7 (2С); 28.5; 31.4; 45.2; 52.8; 60.7; 123.6; 140.9; 163.4; 194.9. Mass spectrum, m/z (Irel, %): 284 [М+Н]+ (100). Found, %: C 46.85; H 6.01; N 24.79. С11H17N5O2S. Calculated, %: C 46.63; H 6.05; N 24.72.
[(8-Oxo-3-phenyl-3,4,5,6,7,8-hexahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-5-yl)sulfanyl]acetic acid (6c). Yield 1.24 g (97%, method I), 1.49 g (93%, method II), white powder, mp 206–208°С. IR spectrum, ν, cm–1: 1675 (С=О), 2530–2851 (CO2Н), 3302, 3391 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.29–3.51 (4H, m, 6-CH2, SCH2); 4.97–5.04 (1H, m, 5-СН); 7.53–7.64 (5H, m, H Ph); 7.74–7.78 (1H, m, NH); 7.93 (1H, d, J = 3.6, NH); 12.59 (1Н, br. s, СО2Н). 13C NMR spectrum, δ, ppm: 31.7; 45.2; 61.5; 125.6 (2С); 130.0; 130.3 (2С); 134.9; 140.9; 163.6; 172.2. Mass spectrum, m/z (Irel, %): 320 [М+Н]+ (96). Found, %: C 48.69; H 3.98; N 22.21. С13H13N5O3S. Calculated, %: C 48.90; H 4.10; N 21.93.
S -[3-(4-Chlorophenyl)-8-oxo-3,4,5,6,7,8-hexahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-5-yl]ethanethioate (6d). Yield 1.31 g (97%, method I), white powder, mp 272–274°С. IR spectrum, ν, cm–1: 1668 (С=О), 1721 (С=О), 3323, 3449 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.33 (3H, s, COCH3); 3.39–3.48 (1H, m) and 3.56–3.65 (1H, m, 6-CH2); 5.57–5.62 (1H, m, 5-СН); 7.54 (2H, d, J = 8.8, H Ar); 7.66 (2H, d, J = 8.8, H Ar); 7.88–7.96 (1H, m, NH); 8.04 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 31.4; 44.8; 60.9; 123.8; 127.7 (2С); 130.3 (2С); 133.7; 134.6; 141.5; 163.1; 194.7. Mass spectrum, m/z (Irel, %): 338 [М+Н]+ (100). Found, %: C 46.01; H 3.46; N 21.01. С13H12ClN5O2S. Calculated, %: C 46.23; H 3.58; N 20.73.
5-[(4-Chlorophenyl)sulfanyl]-3-(4-methylphenyl)-4,5,6,7tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (6e). Yield 1.48 g (96%, method I), white powder, mp 281– 284°С. IR spectrum, ν, cm–1: 1658 (С=О), 3298, 3394 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 2.38 (3H, s, CH3); 3.41– 3.51 (1H, m) and 3.54–3.67 (1H, m, 6-CH2); 5.23–5.31 (1H, m, 5-СН); 7.24–7.50 (9H, m, NH, H Ar); 7.85 (1H, br. s, NH). 13C NMR spectrum, δ, ppm: 21.4; 45.8; 64.1; 122.9; 123.2 (2С); 123.9; 127.8 (2С); 130.1 (2С); 130.9 (2С); 132.1; 133.4; 141.5; 163.1; 164.7. Mass spectrum, m/z (Irel, %): 386 [М+Н]+ (99). Found, %: C 55.89; H 4.06; N 18.34. С18H16ClN5OS. Calculated, %: C 56.03; H 4.18; N 18.15.
5-[(2,4-Dichlorophenyl)sulfanyl]-3-(4-methoxyphenyl)4,5,6,7-tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )one (6f). Yield 1.64 g (94%, method I), white powder, mp 289–292°С. IR spectrum, ν, cm–1: 1657 (С=О), 3309, 3407 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 3.45–3.54 (1H, m) and 3.60–3.71 (1H, m, 6-CH2); 3.82 (3H, s, OCH3); 5.32–5.43 (1H, m, 5-СН); 7.09 (2H, d, J = 8.4, H Ar); 7.31–7.47 (3H, m, H Ar); 7.65–7.77 (2H, m, H Ar); 7.81 (1H, d, J = 3.6, NH); 7.87–7.93 (1H, m, NH). 13C NMR spectrum, δ, ppm: 45.7; 56.1; 64.2; 115.3 (2С); 123.9; 127.4; 127.7 (2С); 128.2; 129.6; 131.9; 133.6; 136.6; 137.6; 140.9; 160.5; 163.5. Mass spectrum, m/z (Irel, %): 437 [М+Н]+ (99). Found, %: C 49.78; H 4.34; N 15.89. С18H15Cl2N5O2S. Calculated, %: C 49.55; H 3.47; N 16.05.
S -[3-(4-Methoxyphenyl)-8-oxo-3,4,5,6,7,8-hexahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-5-yl]ethanethioate (6g). Yield 1.31 g (98%, method I), white powder, mp 265–267°С. IR spectrum, ν, cm–1: 1658 (С=О), 1727 (С=О), 3323, 3452 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 2.33 (3H, s, COCH3); 3.38–3.49 (1H, m) and 3.52–3.63 (1H, m, 6-CH2); 3.84 (3H, s, ОCH3); 5.52–5.59 (1H, m, 5-СН); 7.13 (2H, d, J = 8.4, H Ar); 7.40 (2H, d, J = 8.4, H Ar); 7.79 (1H, d, J = 3.6, NH); 7.83–7.89 (1H, m, NH). 13C NMR spectrum, δ, ppm: 30.6; 45.8; 56.1; 60.5; 60.9; 115.3 (2С); 123.5; 127.5 (2С); 141.4; 160.4; 163.2; 194.8. Mass spectrum, m/z (Irel, %): 334 [М+Н]+ (99). Found, %: C 50.28; H 4.46; N 21.33. С14H15N5O3S. Calculated, %: C 50.44; H 4.54; N 21.01.
5-[(4-Methylphenyl)sulfanyl]-3-(4-nitrophenyl)-4,5,6,7tetrahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-8(3 Н )-one (6h). Yield 1.52 g (96%, method I), 1.82 g (92%, method II), white powder, mp 275–278°С. IR spectrum, ν, cm–1: 1662 (С=О), 3303, 3396 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 2.29 (3H, s, CH3); 3.44–3.55 (1H, m) and 3.60– 3.72 (1H, m, 6-CH2); 5.20–5.29 (1H, m, 5-СН); 7.17 (2H, d, J = 8.0, H Ar); 7.37 (2H, d, J = 8.0, H Ar); 7.72 (2H, d, J = 8.8, H Ar); 7.91–7.99 (1H, m, NH); 8.20 (1H, d, J = 3.6, NH); 8.38 (2H, d, J = 8.8, H Ar). 13C NMR spectrum, δ, ppm: 21.1; 45.5; 65.1; 124.7; 125.5 (2С); 129.8; 130.2 (2С); 134.0; 140.1; 140.9; 147.7; 163.4. Mass spectrum, m/z (Irel, %): 397 [М+Н]+ (100). Found, %: C 54.29; H 3.98; N 21.44. С18H16N6O3S. Calculated, %: C 54.54; H 4.07; N 21.20.
Methyl 3-[3-(1-methyl- 1Н -pyrazol-3-yl)-8-oxo-3,4,5,6,7,8-hexahydro[1,2,3]triazolo[4,5- е ][1,4]diazepin-5-yl)sulfanyl]propanoate (6i). Yield 1.35 g (91%, method I), white powder, mp 269–272°С. IR spectrum, ν, cm–1: 1669 (С=О), 1731–1764 (CO2Me), 3319, 3420 (N–H). 1H NMR spectrum, δ, ppm (J, Hz): 2.61–2.71 (2H, m, CH2); 2.78– 2.87 (2H, m, CH2); 3.39–3.50 (1H, m) and 3.57–3.62 (1H, m, 6-CH2); 3.55 (3H, s, ОCH3); 5.19–5.24 (1H, m, 5-СН); 6.60 (1H, s, H Ar); 7.69–7.75 (1H, m, NH); 7.95 (1H, s, H Ar); 8.16 (1H, d, J = 3.6, NH). 13C NMR spectrum, δ, ppm: 24.6; 34.9; 45.5; 51.7; 51.9; 60.5; 98.7; 123.7; 133.8; 140.2; 144.6; 163.3; 172.5. Mass spectrum, m/z (Irel, %): 352 [М+Н]+ (98). Found, %: C 44.29; H 4.76; N 28.13. С13H17N7O3S. Calculated, %: C 44.44; H 4.88; N 27.90.
References
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2018, 54(8), 789–795
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Kemskiy, S.V., Syrota, N.A., Bol’but, A.V. et al. Synthesis of 5-hydroxy- and 5-sulfanyl-substituted [1,2,3]triazolo[4,5-е][1,4]diazepines. Chem Heterocycl Comp 54, 789–795 (2018). https://doi.org/10.1007/s10593-018-2350-7
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DOI: https://doi.org/10.1007/s10593-018-2350-7