Directed synthesis of semicarbazones, thiosemicarbazones, and guanylhydrazones of 1-vinylpyrrole-2-carbaldehydes

Article abstract of DOI:10.1007/s10593-008-0162-x

Previously unknown 1-vinylpyrrole semicarbazones, thiosemicarbazones, and guanylhydrazones have been obtained in 68.0-90.5% yield by the reaction of 1-vinylpyrrole-2-carbaldehydes with semicarbazide, thiosemicarbazide, and aminoguanidine.

Full text of DOI:10.1007/s10593-008-0162-x

Chemistry of Heterocyclic Compounds, Vol. 44, No. 9, 2008
DIRECTED SYNTHESIS OF SEMICARBA-
ZONES, THIOSEMICARBAZONES, AND
GUANYLHYDRAZONES OF 1-VINYL-
PYRROLE-2-CARBALDEHYDES*
A. I. Mikhaleva1, A. V. Ivanov1, A. M. Vasil'tsov1,
I. A. Ushakov1, Jin Shi Ma2, and Gwokyang Yang2
Previously unknown 1-vinylpyrrole semicarbazones, thiosemicarbazones, and guanylhydrazones have
been obtained in 68.0-90.5% yield by the reaction of 1-vinylpyrrole-2-carbaldehydes with
semicarbazide, thiosemicarbazide, and aminoguanidine.
Keywords: 1-vinylpyrrole-2-carbaldehydes, guanylhydrazones, semicarbazones, thiosemicarbazones.
Semicarbazones, thiosemicarbazones, guanylhydrazones, and metal complexes based on them display
antitubercular, antibacterial, antimalarial, antiviral, antitumor, anticonvulsive, and other forms of biological
activity [1-12]. Thiosemicarbazones of heterocyclic aldehydes and ketones containing the chemically reactive
chromophore =NNH(C=S)- are model compounds for sulfur-containing analogs of purine and pyrimidine bases,
consequently study of their coordination with metal cations raises considerable interest [13]. On interacting
thiosemicarbazones of pyrrole-2-carbaldehyde and 2-acetylpyrrole with halides of Zn(II), Cd(II), and Hg(II),
complexes are formed in which the metal atom is tetracoordinated, but the ligand is neutral and S-monodentate
[6]. However, after deprotonation of the hydrazine fragment N(2)H isomerization of the ligand into a Z-form and
bonding of the metal in the N(3),S chelate form usually occurs [11].
1-Vinylpyrrole-2-carbaldehyde, having become available recently [14], is a convenient constructional
block for fine organic synthesis [15].
In a continuation of the study of their chemical properties, and with the aim of obtaining promising
pharmacological preparations based on 1-vinylpyrroles [16], the corresponding semicarbazones 2a-c,
thiosemicarbazones 3a-c, and guanylhydrazones 4a-c have been synthesized from 1-vinylpyrrole-2-carb-
aldehydes 1a-c in the present work.
_______
* Dedicated to Academician B. A. Trofimov on his 70th jubilee.
__________________________________________________________________________________________
1A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
2
Irkutsk 664033; e-mail: mikh@irioch.irk.ru. CAS Key Laboratory of Photochemistry, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100080, China; e-mail: jsma@iccas.ac.cn. Translated from Khimiya
Geterotsiklicheskikh Soedinenii, No. 9, pp. 1384-1390, September, 2008. Original article submitted April 29,
2008.
0009-3122/08/4409-1117©2008 Springer Science+Business Media, Inc.
1117

Usually the condensation of amidohydrazines with aldehydes (including pyrrole-2-carbaldehyde [13]) is
carried out in aqueous or absolute ethanol, occasionally in the presence of acetic acid, on heating and without it
[16-18], and in the case of guanylhydrazones on boiling (1-12 h) with the addition of conc. HCl [5, 9]. However
stirring an alcohol solution of a mixture of aldehyde 1b and thiosemicarbazide (20-25oC, 24 h) did not lead to
the formation of thiosemicarbazone 3b. On boiling the same mixture in ethanol for 5 h the yield of product 3b
was only 7%. This is a fairly unexpected result. According to the correlation of Hettler [19], the reaction rate
constants for oximation are always less than the reaction rate constants for the formation of the corresponding
semicarbazones, thiosemicarbazones, and guanylhydrazones. In the case of aldehydes 1 oximation proceeds
practically quantitatively (95-99%) even without additional heating (ethanol, 20-25°C, 3 h). Evidently this is a
result of the lower steric hindrance caused by the vinyl group in the case of hydroxylamine in comparison with
the more bulky amidohydrazines. It is known for example that semicarbazones are readily decomposed on
adding mineral acids [18]. In spite of that we found that azomethines 2-4 are formed in high yield (68.0-90.5%)
from carbaldehydes 1 and semicarbazide, thiosemicarbazide, and aminoguanidine, respectively, on stirring the
reactants in ethanol (20-25°C, 3 h) after adding ~0.1% trifluoroacetic acid as catalyst.
1. NaHCO3
2. 0.1% CF3COOH
O
H2N
R
CHO
+
N
.
EtOH,
20-25°C, 4 h
N
NH2
HCl
H
O
1a–c
N
R
NH2
N
H
N
2a–c
S
S
0.1% CF3COOH
H2N
N
1a–c
+
N
H
NH2
R
NH2
N
EtOH,
N
H
20-25°C, 3 h
3a–c
NH
NH2 HCl
NH
NH2
1. KOH
2. 0.1% CF3COOH
H2N
N
1a–c
+
.
N
R
N
N
EtOH
20-25°C, 4 h
H
H
4a–c
1–4 a R = H, b R = Ph, c R = 2-naphthyl
The hydrochlorides of semicarbazide and aminoguanidine were first converted into bases by stirring for
1 h at room temperature with an equimolar quantity of NaHCO3 in the first case or KOH in the second (with
NaHCO3 insoluble aminoguanidine carbonate is formed). The consumption of aldehyde 1 was checked by GLC.
The synthesized compounds 2-4 were fine, colored crystals with high melting points, readily soluble in DMSO
and acetone, and moderately soluble in chloroform and diethyl ether.
Advantages of the developed method in comparison with known include the mild reaction conditions
and the simplicity of carrying it out, which enables avoidance of conversions at the vinyl group sensitive to
acidic reagents in 1-vinylpyrroles [16] (especially in the case of guanylcarbazones).
In the 1H and 13C NMR spectra of compounds 2-4 there was no doubling, which affords the conclusion
1
that they exist in solution as one isomer. Characteristic signals in the H NMR spectra are the singlet for the
azomethine proton, signals of the pyrrole ring protons, and of the N-vinyl substituent. Assignment of the signals was
carried out using COSY, NOESY, HSQC, and HMBC two-dimensional homo- and heteronuclear experiments. On
1118

the basis of characteristic values for the chemical shifts of the azomethine proton (7.85-8.24 ppm) and the direct
1H–13C coupling constant (164-168 Hz) in the azomethine fragment [20, 21], it was established that all
compounds 2-4 are E-isomers.
In the IR spectra of the synthesized compounds characteristic absorption bands were observed for the
vinyl (νC=C 1639±5 cm-1) and azomethine (νC=N 1614±15 cm-1) functional groups [15, 22]. For the amide
functions C(=X)NH2 stretching vibrational bands at 1693±6 (X = O), 1591±11 (X = S), and 1657±13 cm-1
(X = NH) were characteristic.
A general efficient method has therefore been developed for the synthesis of previously unknown
semicarbazones, thiosemicarbazones, and guanylhydrazones of 1-vinylpyrrole-2-carbaldehydes, which are
promising as pyrrole ligands, biologically active compounds, and constructional blocks.
EXPERIMENTAL
The IR spectra were obtained on a Bruker IFS 25 instrument in KBr disks (compounds 2-4) and in a thin
1
13
film (compound 1c). The H and C NMR spectra were recorded on a Bruker DPX 400 (400 and 100 MHz
respectively) in CDCl3 (compound 1c) and DMSO-d6 (compounds 2-4), internal standard was HMDS. The
initial aldehydes 1a-c were synthesized according to the known method of [14]. A check on the progress of
reactions (by the decrease of aldehyde 1) was effected by GLC on an Agilent 6890N instrument (internal
standard was n-hexanol). Compound 1c was synthesized for the first time.
5-(2-Naphthyl)-1-vinylpyrrole-2-carbaldehyde (1c). Yield was 72.0%, viscous liquid of a raspberry
color. IR spectrum, ν, cm-1: 3295, 3120, 3055, 2957, 2923, 2834, 2805, 2780, 2725, 1664, 1601, 1536, 1489,
1451, 1424, 1361, 1320, 1292, 1271, 1249, 1219, 1133, 1094, 1038, 957, 898, 861, 839, 821, 785, 767, 750,
696, 679, 668, 630, 517, 478. 1H NMR spectrum, δ, ppm (J, Hz): 9.69 (1H, s, CHO); 7.97 (1H, s, H arom); 7.88
3
3
(3H, m, H arom); 7.54 (3H, m, H arom); 7.52 (1H, dd, JB,X = 15.7, JAX = 8.6, HX); 7.14 (1H, d, J = 4, H-3);
3
3
13
6.51 (1H, d, J = 4.1, H-4); 5.12 (1H, d, JA,X = 8.6, HA); 4.92 (1H, d, JB,X = 15.7, HB). C NMR spectrum, δ,
ppm: 179.51 (COH); 142.33 (C-5); 133.55 (C-2); 133.22 (C arom); 132.99 (C arom); 131.38 (Cα);
129.07-126.72 (8C, C arom); 124.56 (C-3); 113.15 (C-4); 112.70 (Cβ). Found, %: C 83.05; H 5.83; N 5.12.
C17H13NO. M 247.30. Calculated, %: C 82.57; H 5.30; N 5.66.
Interaction of N-Vinylpyrrolecarbaldehydes 1 with Semicarbazide. Semicarbazide hydrochloride
(1.4 g, 12 mmol) and NaHCO3 (1.0 g, 12 mmol) were added to a solution of aldehyde 1 (10 mmol) in ethanol
(25 ml). The mixture was stirred for 1 h, then CF3COOH (~25 mg, ~0.1%)) was added and the mixture stirred a
further 3 h. The precipitated solid product 2 was filtered off on a Schott funnel, washed with water, with ethanol,
dried in vacuum, and product 2 was obtained as colored crystals.
2-[(1-Vinylpyrrol-2-yl)methylidene]hydrazinecarboxamide (2a). Yield 1.27 g (71.5%), light-yellow
crystals; mp 197-199°C (decomp.). IR spectrum, ν, cm-1: 3471, 3302, 3194, 3141, 3060, 2999, 2926, 2855,
1687, 1643, 1603, 1536, 1510, 1461, 1433, 1320, 1283, 1232, 1180, 1138, 1079, 970, 939, 884, 876, 804, 758,
1
723, 702, 648, 635, 574, 495, 420. H NMR spectrum, δ, ppm (J, Hz); 9.97 (1H, br. s, NH); 7.73 (1H, dd,
3JB,X = 15.6, 3JA,X = 8.8, HX); 7.85 (1H, s, N=CH); 7.40 (1H, m, H-5); 6.48 (1H, m, H-3); 6.26 (2H, br. s, NH2);
3
3
13
6.22 (1H, m, H-4); 5.31 (1H, d, JB,X = 15.6, HB); 4.80 (1H, d, JA,X = 8.8, HA). C NMR spectrum, δ, ppm:
156.71 (C=O); 133.31 (N=CH); 132.43 (Cα); 127.15 (C-2); 121.41 C-5); 114.95 (C-3); 110.74 (C-4); 100.34
(Cβ). Found, %: C 53.99; H 5.90; N 30.91. C8H10N4O. M 178.19. Calculated, %: C 53.92; H 5.66; N 31.44.
2-[(5-Phenyl-1-vinylpyrrol-2-yl)methylidene]hydrazinecarboxamide (2b). Yield 1.73 g (68.0%),
light-yellow crystals; mp 221-223°C (decomp.). IR spectrum, ν, cm-1: 3473, 3341, 3273, 3211, 3149, 3065,
3038, 2989, 2927, 1686, 1636, 1578, 1550, 1488, 1460, 1414, 1368, 1319, 1286, 1234, 1200, 1139, 1098, 1074,
1
1027, 1001, 965, 934, 919, 818, 782, 761, 735, 699, 656, 643, 597, 559, 480, 449. H NMR spectrum, δ,
1119

ppm (J, Hz): 10.07 (1H, br. s, NH); 7.90 (1H, s, N=CH); 7.39 (4H, m, Ho,m); 7.29 (1H, m, Hp); 7.14 (1H, dd,
3
3JB,X = 15.6, JA,X = 8.4, HX); 6.73 (1H, d, J = 3.7, H-3); 6.35 (1H, d, J = 3.7, H-4); 6.30 (2H, br. s, NH2); 5.23
(1H, d, 3JA,X = 8.4, HA); 4.87 (1H, d, 3JB,X = 15.6, HB. 13C NMR spectrum, δ, ppm: 157.19 (C=O); 136.18 (C-5);
133.18 (N=CH); 132.39 (Cα); 132.26 (Ci); 130.07 (C-2); 128.83 (Cm); 128.67 (Co); 127.49 (Cp); 113.36 (Cβ);
112.05 (C-3); 111.54 (C-4). Found, %: C 65.94; H 5.54; N 22.24. C14H14N4O. M 254.29. Calculated, %:
C 66.13; H 5.55; N 22.03.
2-[(5-(2-Naphthyl)-1-vinylpyrrol-2-yl)methylidene]hydrazinecarboxamide (2c). Yield was 2.31 g
76.0%), light-pink crystals; mp 234-236°C (decomp.). IR spectrum, ν, cm-1: 3473, 3352, 3277, 3216, 3153,
3050, 2930, 1699, 1638, 1625, 1593, 1548, 1503, 1440, 1412, 1387, 1341, 1309, 1287, 1249, 1221, 1195, 1139,
1128, 1087, 1014, 973, 922, 895, 860, 819, 780, 765, 748, 600, 553, 491, 475, 454. 1H NMR spectrum, δ, ppm
(J, Hz): 10.07 (1H, br. s, NH); 7.97 (1H, s, H arom); 7.96 (1H, s, N=CH); 7.90 (2H, m, H arom); 7.53 (4H, m, H
3
3
arom); 7.28 (1H, dd, JB,X = 15.7, JA,X = 8.3, HX); 6.80 (1H, d, J = 3.8, H-3); 6.50 (1H, d, J = 3.8, H-4); 6,36
(2H, br. s, NH2); 5.26 (1H, d, 3JA,X = 8.3, HA); 4.92 (1H, d, 3JB,X = 15.7, HB). 13C NMR spectrum, δ, ppm: 156.69
(C=O); 135.70 (C-5); 132.89 (C arom); 132.45 (N=CH); 132.19 (Cα); 131.80, 129.68, 127,87-126.13 (9C,
C arom); 130.19 (C-2); 113.03 (Cβ); 111.82 (C-3); 111.75 (C-4). Found, %: C 71.76; H 5.69; N 18.13.
C18H16N4O. M 304.35. Calculated, %: C 71.04; H 5.30; N 18.41.
Interaction of N-Vinylpyrrolecarbaldehydes 1 with Thiosemicarbazide. Thiosemicarbazide (1.1 g, 12
mmol) and CF3COOH (~25 mg, ~0.1%) were added to a solution of aldehyde 1 (10 mmol) in ethanol (25 ml), and
the mixture was stirred for 3 h. The precipitated solid product 3 was separated and treated as described for product 2.
2-[(1-Vinylpyrrol-2-yl)methylidene]hydrazinecarbothioamide (3a). Yield was 1.38 g (71.0%),
light-yellow crystals; mp 203-205°C (decomp.). IR spectrum, ν, cm-1: 3406, 3247, 3156, 3041, 2984, 2814,
1639, 1617, 1602, 1545, 1520, 1471, 1455, 1430, 1360, 1324, 1280, 1229, 1102, 1079, 1059, 966, 938, 872,
846, 790, 737, 727, 680, 645, 619, 589, 568, 535, 500, 442, 406. 1H NMR spectrum, δ, ppm (J, Hz): 11.14 (1H,
3
3
br. s, NH); 8.08 (1H, br. s, NH2); 8.06 (1H, s, N=CH); 7.75 (1H, dd, JB,X = 15.7, JA,X = 8.8, HX); 7.50 (1H,
br. s, NH2); 7.47 (1H, m, H-5); 6.61 (1H, m, H-3); 6.26 (1H, m, H-4); 5.35 (1H, d, 3JB,X = 15.7, HB); 4.83 (1H, d,
3JA,X = 8.8, HA). 13C NMR spectrum, δ, ppm: 177.13 (C=S); 136.17 (N=CH); 132.47 (Cα); 126.48 (C-2); 122.60
(C-5); 116.89 (C-3); 111.11 (C-4); 100.96 (Cβ). Found, %: C 50.08; H 5.38; N 28.26; S 16.44. C8H10N4S.
M 194.25. Calculated, %: C 49.47; H 5.19; N 28.84; S 16.50.
2-[(5-Phenyl-1-vinylpyrrol-2-yl)methylidene]hydrazinecarbothioamide (3b). Yield was 1.93 g
(71.5%), finely crystalline, yellow powder; mp 206-208°C. IR spectrum, ν, cm-1: 3425, 3386, 3242, 3032, 2991,
1644, 1589, 1550, 1503, 1464, 1448, 1415, 1393, 1341, 1325, 1299, 1238, 1116, 1076, 1056, 966, 919, 851,
1
804, 780, 762, 700, 669, 620, 519, 441. H NMR spectrum, δ, ppm (J, Hz): 11.24 (1H, br. s, NH); 8.12 (1H, s,
N=CH); 8.01 (1H, br. s, NH2); 7.59 (1H, br. s, NH2); 7.40 (4H, m, Ho, Hm); 7.29 (1H, m, Hp); 7.12 (1H, dd,
3JB,X = 15.7, 3JA,X = 8.4, HX); 6.87 (1H, d, J = 3.9, H-3); 6.37 (1H, d, J = 3.9, H-4); 5.26 (1H, d, 3JA,X = 8.4, HA); 4.92
3
13
(1H, d, JB,X = 15.7, HB). C NMR spectrum, δ, ppm: 177.22 (C=S); 137.16 (C-5); 135.92 (N=CH); 132.12 (Cα);
132.07 (Ci); 129.41 (C-2); 128.81 (Cm); 128.66 (Co); 127.64 (Cp); 113.77 (Cβ); 113.44 (C-3); 111.75 (C-4). Found,
%: C 61.66; H 5.53; N 21.01; S 11.80. C14H14N4S. M 270.35. Calculated, %: C 62.20; H 5.22; N 20.72; S 11.86.
2-[(5-(2-Naphthyl)-1-vinylpyrrol-2-yl)methylidene]hydrazinecarbothioamide (3c). Yield was 2.90 g
(90.5%), yellow crystals; mp 238-240°C. IR spectrum, ν, cm-1: 3523, 3454, 3373, 3258, 3161, 3123, 3048,
2986, 2814, 1635, 1607, 1581, 1553, 1506, 1472, 1450, 1412, 1385, 1362, 1344, 1322, 1292, 1250, 1224, 1135,
1
1112, 1091, 1060, 1015, 922, 856, 821, 803, 785, 752, 669, 645, 479, 447. H NMR spectrum, δ, ppm (J, Hz):
11.31 (1H, br. s, NH); 8.20 (1H, s, N=CH); 8.15 (1H, br. s, NH2); 7.98 (1H, s, H arom); 7.91 (2H, m, H arom);
3
3
7.66 (1H, br. s, NH2); 7.52 (4H, m, H arom); 7.28 (1H, dd, JB,X = 15.7, JA,X = 8.3, HX); 6.96 (1H, d, J = 3.9,
H-3); 6.54 (1H, d, J = 3.9, H-4); 5.30 (1H, d, 3JA,X = 8.3, HA); 4.98 (1H, d, 3JB,X = 15.7, HB). 13C NMR spectrum,
δ, ppm: 177.09 (C=S); 136.67 (C-5); 135.32 (N=CH); 132.85 (C arom); 132.03 (Cα); 131.87, 129.43-126.24
(9C, C arom); 129.55 (C-2); 113.53 (Cβ); 113.22 (C-3); 111.99 (C-4). Found, %: C 67.45; H 5.24; N 17.47; S
9.84. C18H16N4S. M 320.41. Calculated, %: C 67.48; H 5.03; N 17.49; S 10.01.
1120

Interaction of N-Vinylpyrrolecarbaldehydes 1 with Aminoguanidine. Aminoguanidine hydrochloride
(1.3 g, 12 mmol) and KOH·0.5H2O (0.78 g, 12 mmol) were added to a solution of aldehyde 1 (10 mmol) in ethanol
(25 ml). The mixture was stirred for 1 h, then CF3COOH (~25 mg, ~0.1%) was added, and stirring was continued
for a further 3 h. The precipitated solid product 4 was isolated and treated as for product 2.
2-[(1-Vinylpyrrol-2-yl)methylidene]hydrazinecarboximidamide (4a). Yield was 1.22 g (69.0%),
orange crystals; mp 186-188°C (decomp.). IR spectrum, ν, cm-1: 3454, 3359, 3099, 2964, 2848, 1644, 1619,
1595, 1539, 1444, 1428, 1362, 1332, 1312, 1278, 1222, 1182, 1155, 1078, 970, 934, 864, 801, 793, 725, 702,
1
3
690, 590, 524, 418. H NMR spectrum, δ, ppm (J, Hz): 8.01 (1H, s, N=CH); 7.92 (1H, dd, JB,X = 15.7,
3JA,X = 8.8, HX); 7.32 (1H, m, H-5); 6.36 (1H, m, H-3); 6.18 (1H, m, H-4); 5.67 (2H. br. s, NH); 5.46 (2H, br. s,
NH2); 5.26 (1H, d, 3JB,X = 15.7, HB); 4.72 (1H, d, 3JA,X = 8.8, HA). 13C NMR spectrum, δ, ppm: 159.59 (C=NH);
137.21 (N=CH); 132.98 (Cα); 129.48 (C-2); 119.86 (C-5); 113.31 (C-3); 110.56 (C-4); 98.81 (Cβ). Found, %:
C 55.30; H 5.86; N 38.84. C8H11N5. M 177.21. Calculated, %: C 54.22; H 6.26; N 39.52.
2-[(5-Phenyl-1-vinylpyrrol-2-yl)methylidene]hydrazinecarboximidamide (4b). Yield was 2.05 g
(80.8%), light-orange crystals; mp 192-194°C. IR spectrum, ν, cm-1: 3484, 3373, 3318, 3161, 3108, 1662, 1638,
1598, 1550, 1529, 1467, 1447, 1416, 1401, 1367, 1328, 1285, 1230, 1200, 1160, 1075, 1029, 1008, 970, 933,
901, 817, 777, 757, 733, 701, 657, 615, 523, 494, 462. 1H NMR spectrum, δ, ppm (J, Hz): 8.02 (1H, s, N=CH);
7.40 (4H, m, Ho, Hm,); 7.30 (1H, dd, 3JB,X = 15.7, 3JA,X = 8.3, HX); 7.27 (1H, m, Hp); 6.59 (1H, d, J = 3.9, H-3);
6.30 (1H, d, J = 3.9, H-4); 5.73 (2H, br. s, NH); 5.39 (2H, br. s, NH2); 5.13 (1H, d, 3JA,X = 8.3, HA); 4.76 (1H, d,
3JB,X = 15.7, HB). 13C NMR spectrum, δ, ppm: 159.60 (C=NH); 136.32 (N=CH); 134.77 (C-5); 132.63 (Ci);
132.56 (Cα); 132.17 (C-2); 128.32 (Cm); 128.25 (Co); 126.68 (Cp); 111.33 (C-4); 111.27 (Cβ); 110.66 (C-3).
Found, %: C 66.09; H 6.23; N 28.00. C14H15N5. M 253.31. Calculated, %: C 66.38; H 5.97; N 27.65.
2-[(5-(2-Naphthyl)-1-vinylpyrrol-2-yl)methylidene]hydrazinecarboximidamide (4c). Yield was 2.61
g (86.0%), light-pink crystals; mp 210-212°C. IR spectrum, ν, cm-1: 3400, 3332, 3236, 3163, 3052, 2991, 2895,
2834, 1670, 1639, 1624, 1548, 1506, 1468, 1447, 1411, 1384, 1341, 1323, 1291, 1252, 1224, 1208, 1194, 1155,
1131, 1079, 1022, 959, 939, 899, 862, 823, 782, 754, 743, 726, 671, 625, 478, 448. 1H NMR spectrum, δ, ppm
(J, Hz): 11.98 (2H, br. s, NH); 8.24 (1H, s, N=CH); 7.99 (1H, s, H arom); 7.92 (2H, m, H arom); 7.68 (2H, br. s,
NH2); 7.54 (4H, m, H arom); 7.32 (1H, dd, 3JB,X = 15.2, 3JA,X = 8.3, HX); 7.02 (1H, d, J = 3.9, H-3); 6.57 (1H, d,
3
3
13
J = 3.9, H-4); 5.33 (1H, d, JA,X = 8.3, HA); 5.01 (1H, d, JB,X = 15.2, HB). C NMR spectrum, δ, ppm: 154.99
(C=NH); 139.25 (N=CH); 137.10 (C-5); 132.84 (C arom); 132.02 (Cα); 131.95, 129.28, 127.95-126.34 (9C, C
arom); 128.81 (C-2); 113.99 (Cβ); 113.99 (C-3); 112.05 (C-4). Found, %: C 71.30; H 5.88; N 22.82. C18H17N5.
M 303.37. Calculated, %: C 71.27; H 5.65; N 23.09.
The work was carried out with the financial support of the Russian Foundation of Fundamental
Investigations (RFFI) (project RFFI-GFEN 06-03-39003) and the Presidium of the Siberian Branch of the
Russian Academy of Sciences (project 8.20).
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