Z.-B. Huang, L.-L. Li, Y.-W. Zhao, H.-Y. Wang, and D.-Q. Shi
Vol 000
7.58 (d, J= 8.7 Hz, 2H, ArH), 7.63 (d, J= 9.0 Hz, 2H, ArH); HRMS
7.43 (d, J= 7.2 Hz, 2H, ArH), 7.76 (d, J= 7.6 Hz, 2H, ArH), 12.63
Calcd for C10H9BrNO [M + H]+: 237.9868; Found: 237.9857.
(s, 1H, NH); HRMS Calcd for C10H10ClN2 [M + H]+: 193.0532;
5-(2,4-Dichlorophenyl)-3-methylisoxazole (3c). mp 79–80ꢀC;
Found: 193.0530.
IR (KBr, cmÀ1): 1609, 1450, 1230, 1078, 789, 672; 1H NMR
(400 MHz, CDCl3): d (ppm) 2.39 (s, 3H, CH3), 6.79 (s, 1H, CH),
7.37 (d, J= 8.8 Hz, 1H, ArH), 7.52 (d, J= 2.0 Hz, 1H, ArH), 7.88
(d, J= 8.4 Hz, 1H, ArH); HRMS Calcd for C10H8Cl2NO [M + H]+:
5-(4-Bromophenyl)-3-methyl-1H-pyrazole (5b). mp 152–153ꢀC;
IR (KBr, cmÀ1): 3443, 1584, 1433, 1288, 1074, 827; 1H NMR
(300 MHz, DMSO-d6): d (ppm) 2.24 (s, 3H, CH3), 6.45 (s, 1H, CH),
7.57–7.70 (m, 4H, ArH), 12.68 (s, 1H, NH); HRMS Calcd for
C10H10BrN2 [M + H]+: 237.0027; Found: 237.0025.
227.9983; Found: 227.9986.
5-(4-Methoxyphenyl)-3-methylisoxazole (3d). mp 98–99ꢀC;
5-(2,4-Dichlorophenyl)-3-methyl-1H-pyrazole (5c).
mp
100–102ꢀC; IR (KBr, cmÀ1): 3427, 1629, 1397, 1098, 1069,
804; 1H NMR (400 MHz, DMSO-d6): d (ppm) 2.27 (s, 3H,
CH3), 6.50 (s, 1H, CH), 7.45 (d, J = 8.0 Hz, 1H, ArH), 7.64
(s, 1H, ArH), 7.79 (s, 1H, ArH), 12.83 (s, 1H, NH); 13C NMR
(101 MHz, CDCl3): d (ppm) 11.6, 106.0, 127.3, 130.3, 130.5,
131.4, 133.1, 134.2, 142.4, 146.5; HRMS Calcd for
C10H9Cl2N2 [M + H]+: 227.0143; Found: 227.0125.
1
IR (KBr, cmÀ1): 1612, 1520, 1443, 1240, 1178, 1100, 835; H
NMR (300MHz, DMSO-d6): d (ppm) 2.33 (s, 3H, CH3), 3.87
(s, 3H, CH3O), 6.25 (s, 1H, CH), 6.97 (d, J = 8.7 Hz, 2H, ArH),
7.70 (d, J = 8.7 Hz, 2H, ArH); HRMS Calcd for C11H12NO2
[M+ H]+: 190.0868; Found: 190.0872.
Methyl 4-(3-methylisoxazol-5-yl)benzoate (3e). mp 82–83ꢀC;
IR (KBr, cmÀ1): 1722, 1594, 1282, 1184, 1044, 874, 773; 1H NMR
(400 MHz, CDCl3): d (ppm) 2.36 (s, 3H, CH3), 3.93 (s, 3H, CH3O),
6.46 (s, 1H, CH), 7.81 (d, J = 8.0Hz, 2H, ArH), 8.10 (d, J = 8.4Hz,
2H, ArH); 13C NMR (101MHz, CDCl3): d (ppm) 11.7, 52.6, 101.9,
125.8, 130.4, 131.4, 160.7, 166.5, 168.6; HRMS Calcd for
C12H12NO3 [M + H]+: 218.0817; Found: 218.0827.
5-(4-Methoxyphenyl)-3-methyl-1H-pyrazole (5d).
130–131ꢀC; IR (KBr, cmÀ1): 3123, 2910, 1612, 1440, 1258,
1022, 835; 1H NMR (400 MHz, CDCl3):
(ppm) 2.23
mp
d
(s, 3H, CH3), 3.80 (s, 3H, CH3O), 6.23 (s, 1H, CH), 6.84
(d, J = 8.4 Hz, 2H, ArH), 7.60 (d, J = 8.0 Hz, 2H, ArH), 9.74
(s, 1H, NH); HRMS Calcd for C11H13N2O [M + H]+:
189.1028; Found: 189.1025.
tert-Butyl 4-(3-methylisoxazol-5-yl)phenylcarbamate (3f). mp
120–121ꢀC; IR (KBr, cmÀ1): 1701, 1520, 1413, 1237, 1160, 835,
772, 625; 1H NMR (400 MHz, CDCl3): d (ppm) 1.48 (s, 9H,
(CH3)3C), 2.25 (s, 3H, CH3), 6.71 (s, 1H, CH), 7.59 (d, J=8.8Hz,
2H, ArH), 7.71 (d, J= 8.4 Hz, 2H, ArH), 9.65 (s, 1H, NH); HRMS
Calcd for C15H19N2O3 [M + H]+: 275.1396; Found: 275.1392.
Methyl 4-(5-methyl-2H-pyrazol-3-yl)benzoate (5e).
mp
194–195ꢀC; IR (KBr, cmÀ1): 3139, 2856, 1634, 1276, 1038,
827; 1H NMR (400 MHz, DMSO-d6): d (ppm) 2.28 (s, 3H,
CH3), 3.85 (s, 3H, CH3O), 6.55 (s, 1H, CH), 7.90 (d, J = 8.0 Hz,
2H, ArH), 7.96 (d, J = 8.0 Hz, 2H, ArH), 12.77 (s, 1H, NH);
HRMS Calcd for C12H13N2O2 [M + H]+: 217.0977; Found:
5-(4-Chlorophenyl)isoxazole (3g).
mp 85–87ꢀC (Lit. [18]
84–85ꢀC); IR (KBr, cmÀ1): 1648, 1447, 1256, 1128, 1109, 826;
1H NMR (400 MHz, CDCl3): d (ppm) 6.52 (d, J = 2.0 Hz, 1H,
CH), 7.45 (d, J = 8.4 Hz, 2H, ArH), 7.73 (d, J = 8.4 Hz, 2H,
ArH), 8.30 (d, J = 2.0 Hz, 1H, CH); HRMS Calcd for
217.0972.
tert-Butyl 4-(5-methyl-2H-pyrazol-3-yl)-phenylcarbamate
(5f).
mp 160–161ꢀC; IR (KBr, cmÀ1): 3116, 2902, 1643,
1028, 937, 827; 1H NMR (400 MHz, CDCl3): d (ppm) 1.52
(s, 9H, (CH3)3C), 2.28 (s, 3H, CH3), 6.27 (s, 1H, CH), 6.75
(s, 1H, NH), 7.34 (d, J = 7.2 Hz, 2H, ArH), 7.59 (d,
J = 8.4 Hz, 2H, ArH); 13C NMR (101 MHz, CDCl3): d (ppm)
12.0, 28.6, 80.8, 101.9, 119.1, 126.5, 138.2, 153.1; HRMS
Calcd for C15H20N3O2 [M + H]+: 274.1556; Found: 274.1559.
C9H7ClNO [M + H]+: 180.0216; Found: 180.0215.
5-(4-Methoxyphenyl)isoxazole (3h). mp 60–61ꢀC (Lit. [18]
64–65ꢀC); IR (KBr, cmÀ1): 1669, 1454, 1289, 1200, 1096, 812;
1H NMR (300 MHz, CDCl3): d (ppm) 3.85 (s, 3H, CH3O), 6.39
(s, 1H, CH), 6.95 (d, J = 8.7 Hz, 2H, ArH), 7.73 (d, J = 8.7 Hz,
2H, ArH), 8.25 (s, 1H, CH); HRMS Calcd for C10H10NO2
[M + H]+: 176.0712; Found: 176.0715.
5-(4-Chlorophenyl)-1H-pyrazole (5g).
mp 99–100ꢀC; IR
(KBr, cmÀ1): 3057, 2923, 1491, 1185, 1089, 957, 817; 1H
NMR (300 MHz, CDCl3): d (ppm) 6.62 (s, 1H, CH), 7.38 (d,
J = 8.4 Hz, 2H, ArH), 7.62 (s, 1H, CH), 7.71 (d, J = 8.1 Hz, 2H,
ArH), 11.65 (s, 1H, NH); HRMS Calcd for C9H8ClN2
[M + H]+: 179.0376; Found: 179.0364.
5-(Naphthalen-1-yl)isoxazole (3i).
mp 91–92ꢀC; IR (KBr,
cmÀ1): 1679, 1426, 1257, 1235, 1091, 843; H NMR (300 MHz,
CDCl3): d (ppm) 6.63 (s, 1H, CH), 7.53-7.56 (m, 2H, ArH),
7.84–7.93 (m, 4H, ArH), 8.32 (d, J = 1.5 Hz, 2H, CH and ArH);
HRMS Calcd for C13H10NO [M+ H]+: 196.0762; found: 196.0768.
1
mp 90–91ꢀC;
5-(4-Methoxyphenyl)-1H-pyrazole (5h).
mp 120–123ꢀC;
3-Methyl-5-(4-methylphenyl)isoxazole (3j).
IR (KBr, cmÀ1): 3088, 2932, 1486, 1089, 987, 839, 753, 676;
1H NMR (400 MHz, DMSO-d6): d (ppm) 3.77 (s, 3H, CH3O),
6.60 (s, 1H, CH), 6.93–7.00 (m, 2H, ArH), 7.49–7.72 (m, 3H,
CH and ArH), 12.76 (s, 1H, NH); HRMS Calcd for C10H11N2O
[M + H]+: 175.0871; Found: 175.0866.
IR (KBr, cmÀ1): 1607, 1414, 1114, 1045, 956, 793; 1H NMR
(400 MHz, CDCl3): d (ppm) 2.13 (s, 3H, CH3), 2.18 (s, 3H,
CH3), 6.09 (s, 1H, CH), 7.04 (d, J = 8.8 Hz, 2H, ArH), 7.43
(d, J = 8.0 Hz, 2H, ArH); HRMS Calcd for C11H12NO [M + H]+:
174.0919; Found: 174.0914.
5-(4-Bromophenyl)-1H-pyrazole (5i). mp 128–129ꢀC (Lit.
[31] 132–134ꢀC); IR (KBr, cmÀ1): 3162, 2910, 1426, 1189,
3-Methyl-5-phenylisoxazole (3k).
mp 68–70ꢀC; IR (KBr,
cmÀ1): 1601, 1424, 1087, 1037, 767, 686; H NMR (400 MHz,
CDCl3): d (ppm) 2.36 (s, 3H, CH3), 6.37 (s, 1H, CH), 7.41–7.47
(m, 3H, ArH), 7.76 (dd, J1 =1.6Hz, J2 = 8.0 Hz, 2H, ArH); HRMS
1
1
1024, 998, 862; H NMR (400 MHz, CDCl3): d (ppm) 6.59 (d,
J = 2.0 Hz, 1H, CH), 7.50 (d, J = 8.4 Hz, 2H, ArH), 7.56–7.62
(m, 3H, CH and ArH), 10.70 (s, 1H, NH); HRMS Calcd for
C10H11N2 [M + H]+: 159.0922; Found: 159.0931.
Calcd for C10H10NO [M + H]+: 160.0762; Found: 160.0770.
5-(4-Bromophenyl)isoxazole (3l). mp 110–112ꢀC (Lit. [18]
114–116ꢀC); IR (KBr, cmÀ1): 1629, 1427, 1077, 1021, 846, 775;
1H NMR (400 MHz, CDCl3): d (ppm) 6.53 (d, J = 1.6 Hz, 1H,
CH), 7.59–7.67 (m, 4H, ArH), 8.30 (s, 1H, CH). HRMS Calcd
for C9H7BrNO [M + H]+: 223.9711; Found: 223.9716.
3-Methyl-5-phenyl-1H-pyrazole (5j).
mp 104–105ꢀC (Lit.
[32] 98–100ꢀC); IR (KBr, cmÀ1): 3125, 2920, 1612, 1528,
1434, 1126, 1001, 842; 1H NMR (400 MHz, DMSO-d6): d
(ppm) 2.24 (s, 3H, CH3), 6.43 (s, 1H, CH), 7.25–7.28 (m, 1H,
ArH), 7.36–7.40 (m, 2H, ArH), 7.73 (d, J = 7.6 Hz, 2H, ArH),
12.56 (s, 1H, NH); HRMS Calcd for C9H8BrN2 [M + H]+:
222.9871; Found: 222.9867.
5-(4-Chlorophenyl)-3-methyl-1H-pyrazole (5a). mp 142–144ꢀC;
IR (KBr, cmÀ1): 3458, 1579, 1433, 1198, 1093, 1017, 834; 1H NMR
(400 MHz, DMSO-d6): d (ppm) 2.25 (s, 3H, CH3), 6.46 (s, 1H, CH),
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet