September 2014
Indazole-3-carboxylic Acids
1319
(CDCl3): d 37.9, 52.1, 128.2, 128.3, 129.2, 131.3, 131.9, 132.1,
134.0, 163.9; ms: m/z 261.2.
NMR (CDCl3): d 51.6, 55.5, 114.5, 115.3, 125.3, 126.6, 129.1,
129.2, 131.6, 134.5, 135.6, 136.6, 155.5, 163.7; ms: m/z 319.3
(M+) and 321.2 (M + 2).
Ethyl 2-(2-chloro-5-nitrophenyl)-2-(2-methylhydrazono)acetate
(14f).
1562.17, 1346.59, 1169.51, 769.91 cmÀ1
mp 146–148ꢀC; IR (KBr): 3308.59, 2992.70, 1688.36,
Methyl 2-(5-chloro-2-iodophenyl)-2-(2-(4-methoxyphenyl)
hydrazono)acetate (14p). mp 155–157ꢀC; IR (KBr): 3268.03,
2947.78, 1709.44, 1514.67, 1229.27, 1031.67, 823.05,
;
1H NMR (CDCl3): d
1.29 (t, J = 3.54 Hz, 3H), 3.25 (d, J = 3.96 Hz, 3H), 4.29 (q, 2H),
5.93 (d, J= 3.36 Hz, 1H), 7.62 (d, J= 4.32 Hz, 1H), 8.10 (d,
J= 2.68 Hz, 1H), 8.23 (dd, nJ =5.96Hz, nJ = 2.68 Hz, 1H); 13C
NMR (CDCl3): d 14.2, 38.0, 61.2, 125.2, 126.4, 126.5, 131.0,
131.6, 141.2, 146.8, 163.2; ms: m/z 286.0 and 288.5 (M + 2).
Methyl 2-(2,3-dichlorophenyl)-2-(2-ethylhydrazono)acetate
(14 g). mp 104–106ꢀC; IR (KBr): 3261.42, 2982.67, 1708.74,
529.21 cmÀ1 1H NMR (CDCl3): d 3.78 (s, 3H), 3.87 (s, 3H),
;
6.84 (d, J = 8.85 Hz, 2H), 7.14 (m, 4H), 7.67 (s, 1H), 7.90 (d,
J = 8.25 Hz, 1H); 13C NMR (CDCl3): d 52.3, 55.5, 95.5, 114.5,
115.7, 130.6, 131.3, 132.9, 135.4, 136.0, 137.6, 140.9, 155.6,
163.5; ms: m/z 445.0 and 447.2 (M + 2).
Methyl 2-(5-bromo-2-chlorophenyl)-2-(2-(4-methoxyphenyl)
1
1528.69, 1312.35, 1148.52, 761.78 cmÀ1; H NMR (CDCl3): d
hydrazono)acetate (14q). mp 140–141ꢀC; IR (KBr): 3260.54,
1.18 (t, J = 7.18 Hz, 3H), 3.53 (m, 2H), 3.81 (s, 3H), 5.93
(s, 1H), 7.11 (d, J = 7.52 Hz, 1H), 7.33 (t, J = 7.79 Hz, 1H), 7.53
(d, J = 7.99 Hz, 1H); 13C NMR (CDCl3): d 15.0, 45.7, 52.1,
128.2, 128.3, 129.2, 131.2, 132.0, 132.0, 134.0, 164.0; ms: m/z
275.1 (M+) and 277.2 (M + 2).
2945.86, 1706.29, 1516.12, 1222.79, 831.40, 501.66 cmÀ1 1H
;
NMR (CDCl3): d 3.77 (s, 3H), 3.85 (s, 3H), 6.83 (d,
J = 8.87 Hz, 2H), 7.11 (d, J = 8.88 Hz, 2H), 7.42 (t, J = 4.11 Hz,
2H), 7.56 (dd, nJ = 8.57 Hz, nJ = 2.16 Hz, 2H), 7.79 (s, 1H); 13C
NMR (CDCl3): d 52.3, 55.4, 114.5, 115.6, 121.1, 128.6, 131.1,
131.6, 133.0, 133.8, 134.0, 135.9, 155.6, 163.9; ms: m/z 397.1
and 399.2 (M + 2).
Methyl 2-(2-chloro-5-nitrophenyl)-2-(2-ethylhydrazono)acetate
(14h). IR (KBr): 3269.49, 2951.49, 1708.90, 1523.02, 1347.91,
1
1156.86, 742.08 cmÀ1; H NMR (CDCl3): d 1.21 (t, J =8.24 Hz,
Methyl 2-(2-chloro-5-iodophenyl)-2-(2-(4-methoxyphenyl)
3H), 3.58 (m, 2H), 3.83 (s, 3H), 5.99 (s, 1H), 7.68 (d, J =8.81 Hz,
1H), 8.11 (d, J = 2.60 Hz, 1H), 8.23 (dd, nJ =8.80 Hz,
nJ = 2.64 Hz, 1H); 13C NMR (CDCl3): d 14.9, 45.9, 52.3, 125.3,
126.0, 126.7, 131.1, 131.5, 141.0, 146.9, 163.8.
hydrazono)acetate (14r). mp 138–141ꢀC; IR (KBr): 3247.40,
1
2948.68, 1707.71, 1516.22, 1222.00, 1033.04, 833.36 cmÀ1; H
NMR (CDCl3): d 3.79 (s, 3H), 3.88 (s, 3H), 6.85 (d,
J = 8.94 Hz, 2H), 7.12 (d, J = 8.95 Hz, 2H), 7.29 (d, J = 8.46 Hz,
1H), 7.60 (d, J = 1.99 Hz, 1H), 7.71 (s, 1H), 7.75 (dd,
nJ = 8.46 Hz, nJ = 2.0 Hz, 1H); 13C NMR (CDCl3): d 52.3, 55.5,
92.0, 114.5, 115.6, 128.6, 131.3, 131.8, 133.9, 135.9, 139.5,
139.9, 155.6, 164.00; ms: m/z 445.2.
Methyl
(14i).
2-(2-chlorophenyl)-2-(2-phenylhydrazono)acetate
IR (KBr): 3298.68, 2981.44, 1702.27, 1562.93,
1313.22, 1107.45, 747.14 cmÀ1 1H NMR (DMSO): d 3.70
;
(s, 3H), (t, J = 5.62 Hz, 1H), 7.30 (m, 4H), (dd, nJ = 7.38 Hz,
nJ = 1.52 Hz, 1H), 7.47 (m, 2H), 7.58 (d, J = 7.71 Hz, 1H), 9.89
(s, 1H).
Methyl 2-(2,3-dichlorophenyl)-2-(2-(4-methoxyphenyl)hydrazono)
acetate (14s).
mp 119–121ꢀC; IR (KBr): 3247.57, 2954.38,
Methyl 2-(2,3-dichlorophenyl)-2-(2-phenylhydrazono)acetate
1674.83, 1514.00, 1155.20, 794.72 cmÀ1; 1H NMR (DMSO): d 3.70
(s, 3H), 3.75 (s, 3H), 6.88 (d, J= 8.96 Hz, 2H), 7.25 (d, J=8.92Hz,
2H), 7.40 (t, J= 7.94 Hz, 1H), 7.46 (dd, nJ =7.58Hz, nJ =1.36Hz,
1H), 7.62 (dd, nJ =7.94Hz, nJ = 1.36 Hz, 1H), 12.21 (s, 1H); 13C
NMR (DMSO): d 52.2, 55.6, 114.9, 116.0,124.9, 128.5, 130.5,
131.0, 131.9, 131.9, 136.7, 138.1, 155.7, 162.7.
(14j). mp 119–121ꢀC; IR (KBr): 3265.38, 2947.76, 1411.37,
1541.66, 1432.69, 1225.41, 1086.87, 749.70 cmÀ1 1H NMR
;
(DMSO): d 3.71 (s, 3H), 6.92 (t, J = 6.26 Hz, 1H), 7.24 (m, 4H),
7.54 (d, J = 8.60 Hz, 1H), 7.62 (d, J = 2.2 Hz, 1H), 7.68 (dd,
nJ = 8.54 Hz, nJ = 2.28 Hz, 1H), 10.05 (s, 1H); 13C NMR
(CDCl3): d 52.2, 114.7, 120.6, 122.2, 128.7, 129.3, 131.8,
132.9, 133.3, 134.0, 134.4, 144.1, 164.2; ms: m/z 367.2 and
369.2 (M + 2).
Methyl
2-(5-chloro-2-iodophenyl)-2-(2-p-tolylhydrazono)
acetate (14t).
mp 180–182ꢀC; IR (KBr): 3270.07, 2947.22,
1712.51, 1539.93, 1223.61, 1159.42, 810.21 cmÀ1 1H NMR
;
Methyl
2-(5-chloro-2-iodophenyl)-2-(2-phenylhydrazono)
(CDCl3): d 2.30 (s, 3H), 3.87 (s, 3H), 7.10 (m, 4H), 7.20 (m,
2H), 7.72 (s, 1H), 7.91 (d, J = 8.32 Hz, 1H); 13C NMR (CDCl3):
d 20.6, 52.4, 95.3, 114.3, 129.7, 130.6, 131.3, 132.4, 133.3,
135.5, 137.5, 139.8, 140.9, 163.5; ms: m/z 369.1 (–COOCH3).
Methyl 2-(2,3-dichlorophenyl)-2-(2-p-tolylhydrazono)acetate
(14u). mp 119–121ꢀC; IR (KBr): 3236.69, 2920.47, 1672.14,
acetate (14k).
mp 145–147ꢀC; IR (KBr): 3264.41, 2945.44,
1708.36, 1540.92, 1229.64, 1154.35, 750.41 cmÀ1 1H NMR
;
(DMSO): d 3.71 (s, 3H), 6.92 (t, J = 6.62 Hz, 1H), 7.26 (m, 5H),
7.38 (s, 1H), 7.94 (d, J = 8.44 Hz, 1H), 9.92 (s, 1H); 13C NMR
(DMSO): d 52.2, 98.0, 114.7, 122.1, 129.3, 131.1, 131.2, 133.3,
134.0, 139.5, 140.7, 144.0, 163.8; ms: m/z 415.2 (M+) and
417.2 (M + 2).
Methyl 2-(5-bromo-2-chlorophenyl)-2-(2-phenylhydrazono)
acetate (14l).
1711.37, 1541.66, 1225.41, 1153.59, 749.70 cmÀ1
(DMSO): d 3.71 (s, 3H), 6.92 (t, J = 6.26 Hz, 1H), 7.30 (m, 4H),
7.54 (d, J = 8.60 Hz, 1H), 7.62 (d, J = 2.2 Hz, 1H), 7.70 (dd,
nJ = 8.56 Hz, nJ = 2.28 Hz, 1H), 10.05 (s, 1H); 13C NMR
(DMSO): d 52.2, 114.7, 120.6, 122.2, 128.7, 129.3, 131.8,
132.9, 133.3, 134.0, 134.4, 144.1, 164.2; ms: m/z 367.2
and 369.2.
Methyl 2-(2-chlorophenyl)-2-(2-(4-methoxyphenyl)hydrazono)
acetate (14o).
1679.65, 1516.95, 1157.16, 1036.42, 786.16 cmÀ1
1532.59, 1232.04, 1053.24, 791.54cmÀ1 1H NMR (CDCl3): d
;
2.30 (s, 3H), 3.86 (s, 3H), 7.08 (m, 4H), 7.21 (d, J = 7.58 Hz, 1H),
7.38 (t, J = 7.82Hz, 1H), 7.40 (d, J = 8.02Hz, 1H), 7.76 (s, 1H);
13C NMR (CDCl3): d 20.6, 52.3, 114.3, 128.3, 129.2, 129.7,
129.9, 131.4, 131.7, 132.2, 132.3, 134.3, 139.9, 164.0; ms:
m/z 336.7.
mp 119–121ꢀC; IR (KBr): 3265.38, 1947.76,
;
1H NMR
Methyl
2-(2,3-dichlorophenyl)-2-(2-(2,4-dichlorophenyl)
hydrazono)acetate (14v). mp 113–117ꢀC; IR (KBr): 3320.74,
2951.37, 1727.55, 1566.01, 1499.06, 1158.78, 829.14 cmÀ1; H
1
NMR (CDCl3): d 3.87 (s, 3H), 7.22 (m, 2H), 7.27 (s, 1H), 7.42
(t, J = 7.84 Hz, 1H), 7.63 (dd, nJ = 8.08 Hz, nJ = 1.31 Hz, 1H),
7.70 (t, J = 4.7 Hz, 1H), 8.18 (s, 1H); 13C NMR (CDCl3): d
52.6, 116.3, 119.0, 127.1, 128.2, 128.3, 128.4, 128.6, 130.7,
131.9, 132.1, 134.0, 134.6, 137.0, 163.4; ms: m/z 391.2 (MÀ).
Methyl 2-(2-(2,4-dichlorophenyl)hydrazono)-2-(2-iodophenyl)
mp 128–129ꢀC; IR (KBr): 3256.23, 2956.10,
;
1H NMR
(CDCl3): d 3.80 (s, 6H), 6.87 (d, J = 8.92Hz, 2H), 7.19 (d,
J = 8.92Hz, 2H), 7.42 (m, 2H), 7.47 (m, 2H), 12.42 (s, 1H); 13C
acetate (14w).
mp 122–124ꢀC; IR (KBr): 3306.39, 1944.80,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet