1-Carbothiohydrazinoyl-5-hydroxy-3-phenyl-5-(2-thienyl)-2-pyrazoline (3b). This compound was
obtained similarly to compound 3a from 2-phenyl-1-(2-thenoyl)acetylene 1b (1.06 g, 5 mmol) and compound 2a
(0.53 g, 5 mmol). Yield 1.39 g (88%), and the product formed yellow crystals; mp 143-144°C (ethanol).
1
IR spectrum (potassium bromide), ν, cm-1: 3210-3360 (NH, NH2, OH), 1400-1500 (C=N, C=C). H NMR
spectrum, δ, ppm (J, Hz): 3.58, 3.84 (2H, q, JAB = 18.2, CH2); 4.22 (2H, s, NH2); 6.74 (1H, s, NH); 6.93-7.68
(8H, m, C4H3S, C6H5); 8.56 (1H, s, OH). 13C NMR spectrum, δ, ppm (J, Hz): 51.12 (CH2); 94.08 (C(5)); 123.32,
125.26, 126.73, 127.07, 128.84, 130.23, 131.04, 148.45 (C4H3S, C6H5); 152.58 (C=N); 177.19 (C=S). Found, %:
C 53.26; H 4.58; N 17.48; S 20.38. C14H14N4OS2. Calculated, %: C 52.81; H 4.43; N 17.60; S 20.14.
1-[N'-(Phenylmethylene)carbothiohydrazinoyl]-5-hydroxy-3,5-diphenyl-2-pyrazoline
(3c).
A
suspension of benzaldehyde thiocarbazone 2b (0.97 g, 5 mmol) in a mixture of ethanol (10 ml) and water (5 ml)
was heated at 60°C, and a solution of compound 1a (1.03 g, 5 mmol) in ethanol (5 ml) was added dropwise with
stirring. The reaction mixture was stirred at 60°C for 2.5 h, cooled to room temperature, and stirred for 1 h. The
precipitate was filtered off, washed with water, and dried over calcium chloride in a vacuum. Yield 1.28 g
(64%), and the product was a light-yellow powder; mp 123-124°C. IR spectrum (potassium bromide), ν, cm-1:
3150-3340 (NH, OH), 1415-1515 (C=N, C=C). 1H NMR spectrum, δ, ppm (J, Hz): 3.53, 3.78 (2H, q, JAB = 18.5,
CH2); 6.93 (1H, s, OH); 7.32-7.95 (15H, m, 3C6H5); 8.59 (1H, c, N=CHPh); 11.84 (1H, s, NH). 13C NMR
spectrum, δ, ppm: 50.79 (CH2); 95.08 (C(5)); 124.13, 125.08, 127.08, 127.34, 128.32, 128.69, 128.81, 130.04,
130.39, 130.88, 134.29, 144.34 (3C6H5); 148.62 (N=CHPh); 152.37 (C=N); 171.86 (C=S). Found, %: C 68.86;
H 5.38; N 14.18; S 8.31. C23H20N4OS. Calculated, %: C 69.00; H 5.00; N 14.00; S 8.00.
1-[N'-(Phenylmethylene)carbothiohydrazinoyl]-5-hydroxy-3-phenyl-5-(2-thienyl)-2-pyrazoline (3d).
This compound was obtained similarly to compound 3c from compound 1b (1.06 g, 5 mmol) and compound 2b
(0.97 g, 5 mmol). Yield 1.22 g (60%), and the product formed a light-yellow powder; mp 143-145°C. IR
1
spectrum (potassium bromide), ν, cm-1: 3160-3290 (NH, OH), 1410-1510 (C=N, C=C). H NMR spectrum,
δ, ppm (J, Hz): 3.66, 3.92 (2H, q, JAB = 18.3, CH2); 6.94 (1H, s, OH); 7.01-7.77 (13H, m, C4H3S, 2C6H5); 8.17
13
(1H, s, N=CHPh); 10.48 (1H, s, NH). C NMR spectrum, δ, ppm: 51.35 (CH2); 94.64 (C(5)); 123.53, 125.37,
127.05, 127.20, 127.94, 127.79, 129.06, 130.64, 131.43, 133.57, 148.21 (C4H3S, 2C6H5); 148.10 (N=CHPh);
152.94 (C=N); 172.18 (C=S). Found, %: C 62.26; H 4.68; N 13.98; S 15.51. C21H18N4OS2. Calculated, %:
C 62.07; H 4.43; N 13.79; S 15.76.
1-[N'-(1-Methylethylene)carbothiohydrazinoyl]-5-hydroxy-3,5-diphenyl-2-pyrazoline
(3e).
A
solution of compound 3a (0.72 g, 2.3 mmol) in dry acetone (20 ml) was boiled for 2 h and was then kept at
5-8°C for two days. The precipitate was filtered off and dried under vacuum. Yield 0.74 g (91%), and the
product formed colorless needles; mp 136-137°C. IR spectrum (potassium bromide), ν, cm-1: 3190-3330 (NH,
1
OH), 1410-1510 (C=N, C=C). H NMR spectrum, δ, ppm (J, Hz): 1.97 (6H, br. s, 2CH3); 3.52, 3.77 (2H, q,
J
AB = 17.9, CH2); 6.96 (1H, s, NH); 7.25-7.85 (10H, m, 2C6H5); 10.50 (1H, s, OH). 13C NMR spectrum, δ, ppm:
17.94 (CH3); 25.30 (CH3); 51.39 (CH2); 96.02 (C(5)); 124.57, 127.45, 127.81, 128.72, 128.89, 129.20, 130.78,
131.21, 144.81 (2C6H5); 152.26 (C=N); 159.33 (CMe2); 172.01 (C=S). Found, %: C 65.06; H 5.58; N 15.78;
S 9.23. C19H20N4OS. Calculated, %: C 64.75; H 5.72; N 15.90; S 9.10.
REFERENCES
1.
T. E. Glotova, N. I. Protsuk, A. I. Albanov, V. A. Lopyrev, and G. V. Dolgushin, Cent. Europ. J. Chem.,
3, 222 (2003).
2.
3.
4.
T. E. Glotova, N. I. Protsuk, M. Yu. Dvorko, and A. I. Albanov, Zh. Org. Khim., 40, 1269 (2004).
T. E. Glotova, M. Yu. Dvorko, and A. I. Albanov, Zh. Org. Khim., 41, 638 (2005).
T. E. Glotova, G. V. Dolgushin, A. I. Albanov, M. Yu. Dvorko, and N. I. Protsuk, J. Sulfur Chem., 26,
359 (2005).
5.
M. D. Mashkovskii, Drugs [in Russian], Vol. 2, Novaya Volna, Moscow (2003), p. 306.
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