Table 2. 1H NMR Spectra of Compounds 5a,c,d,f and 6a-c,e-g
Com-
pound
Chemical shifts, , ppm (J, Hz)
1.03 (3H, t, 3J = 7.2, CH2CH3); 2.32 (3H, s, CН3); 2.37 (2H, q, 3J = 7.2, CH2CH3);
5a
2.49 (4H, br. s, CH2NCH2); 3.53 (4H, br. s, CH2OCH2); 3.76 (2H, s, 5'-CH2N);
6.43 (1H, s, H-2); 6.84 (1H, s, H-5); 7.05 (1H, s, H-5''); 9.45 (1H, br. s, 3-OH);
9.69 (1H, br. s, 1-OH); 12.77 (1H, br. s, NH)
5c*
1.06 (3H, t, 3J = 7.2, CH2CH3); 1.21-1.25 (2H, m, CHeqCHCHeq);
1.38-1.43 (1H, m, CHCH2Ph); 1.55 (2Н, d, 2J = 12.8, CHaxCHCHax);
1.95 (2H, t, 2J = 12.8, CHeqNCHeq); 2.40-2.48 (7H, m, CН3, CH2CH3, CH2Ph);
2.89 (2H, d, 2J = 10.4, CHaxNCHax); 3.62 (2H, s, 5'-CH2N); 6.37 (1H, s, H-2);
6.85 (1H, s, H-5); 6.93 (1H, s, H-5''); 7.07 (2H, d, 3J = 7.6, H-2''',6''');
7.12 (1H, t, 3J = 7.6, H-4'''); 7.20 (2H, t, 3J = 7.6, H-3''',5'''); 9.13 (1H, br. s, 3-OH);
10.18 (1H, br. s, 1-OH); 12.70 (1Н, br. s, NH)
1.03 (3H, t, 3J = 7.2, CH2CH3); 2.12 (3H, s, NCH3); 2.32 (3H, s, 4''-CH3);
2.39-2.50 (10H, m, CH2CH3, 4CH2 piperazine); 3.73 (2H, s, 5'-CH2N); 6.42 (1H, s, H-2);
6.84 (1H, s, H-5); 7.06 (1H, s, H-5''); 9.47 (1H, br. s, 3-OH); 9.76 (1H, br. s, 1-OH);
12.78 (1H, br. s, NH)
1.04 (3H, t, 3J = 7.2, CH2CH3); 2.35 (3H, s, CH3); 2.41 (2H, q, 3J = 7.2, CH2CH3);
2.63 (4H, br. s, CH2NCH2); 3.05 (4H, br. s, CH2N(Ar)CH2); 3.86 (2H, s, 5'-CH2N);
6.45 (1H, s, H-2); 6.87 (1H, s, H-5); 6.93-7.07 (5H, m, H-5'', C6H4F);
9.48 (1H, br. s, 3-OH); 9.74 (1H, br. s, 1-OH); 12.81 (1H, br. s, NH)
5d
5f
0.84 (3H, t, 3J = 7.2, (CH2)2CH3); 1.46-1.49 (2H, m, CH2CH2CH3);
2.33-2.44 (9H, m, CH3, CH2CH2CH3, CH2NCH2); 3.54 (4H, br. s, CH2OCH2);
3.77 (2H, s, 5'-CH2N); 6.43 (1H, s, H-2); 6.82 (1H, s, H-5); 7.06 (1H, s, H-5'');
9.38 (0.3H, br. s, 3-OH (B)); 9.44 (0.7H, br. s, 3-OH (A)); 9.67 (1H, br. s, 1-OH);
12.77 (0.7H, br. s, NH (A)); 13.13 (0.3H, br. s, NH (B))
6a
0.87 (3H, t, 3J = 7.2, (CH2)2CH3); 1.41-1.52 (8H, m, CH2CH2CH3, 3,4,5-CH2 piperidine);
2.39-2.42 (9H, m, CH2CH2CH3, CH3, CH2NCH2); 3.60 (2H, s, 5'-CH2N); 6.37 (1H, s, H-2);
6.78 (1H, s, H-5); 6.95 (1H, s, H-5''); 9.11 (1H, br. s, 3-OH); 10.12 (1H, br. s, 1-OH);
12.58 (1H, br. s, NH)
6b
6c
0.84 (3H, t, 3J = 7.2, (CH2)2CH3); 1.17 (2H, m, CHeqCHCHeq);
1.44-1.48 (5H, m, CH2CH2CH3, CHCH2Ph, CHaxCHCHax); 1.95 (2H, t,2J = 13.4, CHeqNCHeq);
2.30-2.32 (5H, m, CН3, CH2Ph); 2.46 (2Н, t,3J = 7.2, CH2CH2CH3);
2.87 (2H, br. s, CHaxNCHax); 3.69 (2H, s, 5'-CH2N); 6.42 (1H, s, H-2); 6.82 (1H, s, H-5);
7.07 (1H, s, H-5''); 7.13-7.17 (3H, m, H-2''',6''',4'''); 7.26 (2H, t, 3J = 7.6, H-3''',5''');
9.39 (1H, br. s, 3-OH); 9.76 (1H, br. s, 1-OH); 12.73 (1H, br. s, NH)
0.83 (3H, t, 3J = 7.2, (CH2)2CH3); 1.42-1.46 (2H, m, CH2CH2CH3);
2.31-2.45 (11H, m CH3, CH2CH2CH3, CH2NCH2, NCH2Ar);
6e
6f
3.32 (4H, br. s, CH2N(CH2Ar)CH2); 3.74 (2H, s, 5'-CH2N); 5.97 (2H, s, OCH2);
6.43 (1H, s, H-2); 6.71 (1H, d,3J = 6.4, H-7'''); 6.81-6.82 (3H, m, H-5,4''',6''');
7.05 (1H, s, H-5''); 9.43 (1H, br. s, 3-OH); 9.74 (1H, br. s, 1-OH); 12.74 (1H, br. s, NH)
0.83 (3H, t, 3J = 6.8, (CH2)2CH3); 1.42-1.45 (2H, m, CH2CH2CH3);
2.32-2.34 (5H, m, CH3, CH2CH2CH3); 2.61 (4H, br. s, CH2NCH2);
3.03 (4H, br. s, CH2N(Ar)CH2); 3.84 (2H, s, 5'-CH2N); 6.45 (1H, s, H-2);
6.82 (1H, s, H-5); 6.90-7.04 (5H, m, H-5'', C6H4F); 9.48 (1H, br. s, 3-OH);
9.69 (1H, br. s, 1-OH); 12. 81 (1H, br. s, NH)
0.89 (3H, t, 3J = 7.2, (CH2)2CH3); 1.46-1.49 (2H, m, CH2CH2CH3);
2.36 (2H, t, 3J = 7.2, CH2CH2CH3); 2.40 (3H, s, CH3); 2.65 (4H, br. s, CH2NCH2);
3.16 (4H, br. s, CH2N(Ar)CH2); 3.78 (2H, s, 5'-CH2N); 6.39 (1H, s, H-2);
6.68 (1H, d, 3J = 8.0, H-6'''); 6.77 (1H, d, 3J = 8.0, H-4'''); 6.80 (1H, s, H-5);
6.84 (1Н, s, Н-5''); 6.90 (1Н, s, Н-2'''); 7.12 (1H, t,3J = 8.0, H-5''');
9.11 (1H, br. s, 3-OH); 9.93 (1H, br. s, 1-OH); 12. 61 (1H, br. s, NH)
6g
_______
*Spin-spin coupling constants with values less than 4.0 Hz were not
successfully measured because of the width of the signals.
7.14 (1H, t, J = 7.6, H-5"); 7.19 (1H, s, H-5'); 7.81 (1H, s, H-5); 10.33 (1H, br. s, 7-OH). Found, %: C 63.76;
H 5.28; N 8.54; S 6.26. C27H28ClN3O3S. Calculated, %: C 63.58; H 5.53; N 8.24; S 6.29.
6-Alkyl-4-[5-dialkylaminomethyl-4-(4-methyl-1,3-thiazol-2-yl)-1H-pyrazol-3-yl]-1,3-benzenediols
5a,c,d,f and 6a-c,e-g (General Method). Hydrazine hydrate (0.1 g, 3.2 mmol) was added to a solution of
6-alkyl-2-dialkylaminomethyl-7-hydroxy-3-(4-methyl-1,3-thiazol-2-yl)-4H-chromen-4-one 1a,c,d,f or 2 a-c,e-g
329