10.1002/ejoc.201900008
European Journal of Organic Chemistry
FULL PAPER
Hz, 1H), 6.08-6.15 (m, 1H), 6.47 (s, 1H), 6.96-7.04 (m, 2H),
7.23 (t, J = 7.6 Hz, 1H), 7.67-7.69 (m, 1H), 9.31 (br s, 1H) ppm.
13C NMR (CDCl3, 100 MHz): δ = 13.17, 69.46, 102.81, 112.80,
118.84, 120.97, 121.40, 127.97, 128.83, 132.50, 142.04,
147.73, 154.84 ppm. IR (Neat Film, NaCl): 2944, 1665, 1444,
1435, 788 cm-1. HRMS (ESI) calc’d for C13H14N2ONa [M+Na]+:
237.1004, Found: 237.1005.
5-(2-chloro-6-fluorophenyl)-3-methyl-1H-pyrazole (3v): Red
oil, purified by silica gel column chromatography (elution with
28% EtOAc in hexane), 99mg, yield: 92% (Rf = 0.2; 20%
EtOAc in hexane). 1H NMR (CDCl3, 400 MHz): δ = 2.19 (s, 3H),
6.27 (s, 1H), 7.01-7.06 (m, 1H), 7.22-7.26 (m, 2H), 11.03 (br s,
1H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 10.97, 106.50,
114.07, 121.40, 125.54, 129.61, 134.74, 140.60, 141.64,
162.01 ppm. 19F NMR (377 MHz, CDCl3): δ = -109.99 ppm. IR
(Neat Film, NaCl): 2977, 1668, 1458, 1436, 777 cm-1. HRMS
(ESI) calc’d for C10H835ClFN2Na [M+Na]+: 233.0258, Found:
233.0250.
3-methyl-5-(2-((2-methylallyl)oxy)phenyl)-1H-pyrazole (3p):
Red oil, purified by silica gel column chromatography (elution
with 8% EtOAc in hexane), 100mg, yield: 93% (Rf = 0.2; 20%
EtOAc in hexane). 1H NMR (CDCl3, 400 MHz): δ = 1.87 (s, 3H),
2.36 (s, 3H), 4.60 (s, 3H), 5.07 (s, 1H), .14 (s, 1H), 6.47 (s, 1H),
6.98-7.05 (m, 2H), 7.24 (m, 1H), 7.66 (dd, J = 8.0, 1.6 Hz, 1H)
ppm. 13C NMR (CDCl3, 100 MHz): δ = 13.26, 19.57, 72.42,
102.62, 112.79, 114.04, 118.35, 121.39, 127.93, 128.79,
139.97, 141.77, 147.82, 154.90 ppm. IR (Neat Film, NaCl):
2915, 1655, 1455, 1445, 778 cm-1. HRMS (ESI) calc’d for
C14H16N2ONa [M+Na]+: 251.1160, Found: 251.1169.
5-(2,6-dichlorophenyl)-3-methyl-1H-pyrazole (3w): Yellow
solid, purified by silica gel column chromatography (elution with
8% EtOAc in hexane), 102mg, yield: 95% (Rf = 0.2; 20%
EtOAc in hexane). MP: 135-139 °C. 1H NMR (CDCl3, 400
MHz): δ = 2.33 (s, 3H), 6.16 (s, 1H), 7.23-7.27 (m, 1H), 7.38 (d,
J = 8.0 Hz, 2H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 11.49,
106.12, 127.98, 129.68, 131.74, 135.88, 142.00, 149.00 ppm.
IR (Neat Film, NaCl): 2933, 1688, 1455, 1448, 773 cm-1.
HRMS (ESI) calc’d for C10H835Cl2N2Na [M+Na]+: 248.9962,
Found: 248.9960.
5-(2-(buta-2,3-dien-1-yloxy)phenyl)-3-methyl-1H-pyrazole
(3q): Yellow solid, purified by silica gel column chromatography
(elution with 8% EtOAc in hexane), 102mg, yield: 95% (Rf =
0.2; 20% EtOAc in hexane). MP: 106-108 °C. 1H NMR (CDCl3,
400 MHz): δ = 2.36 (s, 3H), 4.69-4.71 (m, 2H), 5.07 (p, J = 3.2
Hz, 2H), 5.47-5.50 (m, 1H), 6.46 (s, 1H), 6.98 (d, J = 8.0 Hz,
1H), 7.02 (t, J = 7.6 Hz, 1H), 7.25-7.29 (m, 1H), 7.67 (dd, J =
7.6, 1.6 Hz, 1H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 13.35,
65.65, 78.01, 86.90, 102.39, 112.48, 180.20, 121.54, 127.87,
128.75, 141.31, 148.07, 154.48, 208.94 ppm. IR (Neat Film,
NaCl): 2925, 1715, 1484, 1475, 788 cm-1. HRMS (ESI) calc’d
for C14H14N2ONa [M+Na]+: 249.1004, Found: 249.1006.
5-(2,4-dichlorophenyl)-3-methyl-1H-pyrazole (3x): Yellow oil,
purified by silica gel column chromatography (elution with 8%
EtOAc in hexane), 100mg, yield: 93% (Rf = 0.2; 20% EtOAc in
hexane). 1H NMR (CDCl3, 400 MHz): δ = 2.27 (s, 3H), 6.47 (s,
1H), 7.18-7.21 (m, 1H), 7.45 (d, J = 2.0 Hz, 1H), 7.54 (d, J =
8.4 Hz, 1H), 9.47 (br s, 1H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 11.36, 105.70, 127.01, 129.87, 130.09, 131.05, 132.69,
133.94, 142.06, 146.22 ppm. IR (Neat Film, NaCl): 2928, 1668,
1466, 1455, 766 cm-1. HRMS (ESI) calc’d for C10H835Cl2N2Na
[M+Na]+: 248.9962, Found: 248.9966.
5-(3-(benzyloxy)phenyl)-3-methyl-1H-pyrazole (3s): Yellow
oil, purified by silica gel column chromatography (elution with
8% EtOAc in hexane), 98mg, yield: 93% (Rf = 0.4; 30% EtOAc
in hexane). 1H NMR (CDCl3, 400 MHz): δ = 2.27 (s, 3H), 5.01
(s, 2H), 6.35 (s, 1H), 6.93-6.95 (m, 1H), 7.27-7.31 (m, 1H),
7.34-7.45 (m, 7H), 10.31 (br s, 1H) ppm. 13C NMR (CDCl3, 100
MHz): δ = 11.52, 69.77, 102.13, 111.73, 114.55, 118.47,
127.45, 127.84, 128.46, 129.68, 133.79, 136.90, 143.08,
149.65, 159.02 ppm. IR (Neat Film, NaCl): 2970, 1690, 1455,
1430, 772 cm-1. HRMS (ESI) calc’d for C17H16N2ONa [M+Na]+:
287.1160, Found: 287.1155.
5-(5-chloro-2-methoxyphenyl)-3-methyl-1H-pyrazole (3y):
Yellow solid, purified by silica gel column chromatography
(elution with 10% EtOAc in hexane), 100mg, yield: 94% (Rf =
0.4; 30% EtOAc in hexane). MP: 133-135 °C. 1H NMR (CDCl3,
400 MHz): δ = 2.32 (s, 3H), 3.84 (s, 3H), 6.43 (s, 1H), 6.81 (d,
J = 8.8 Hz, 1H), 7.14 (dd, J = 8.8, 1.6 Hz, 1H), 7.63 (d, J = 1.6
Hz, 1H), 10.08 (br s, 1H) ppm. 13C NMR (CDCl3, 100 MHz): δ =
12.61, 55.73, 103.75, 112.54, 120.59, 125.86, 127.51, 128.17,
141.75, 145.96, 154.48 ppm. IR (Neat Film, NaCl): 2938, 1678,
1467, 1459, 766 cm-1. HRMS (ESI) calc’d for C11H1135ClN2ONa
[M+Na]+: 245.0458, Found: 245.0460.
5-(3-bromophenyl)-3-methyl-1H-pyrazole (3t): Yellow oil,
purified by silica gel column chromatography (elution with 8%
EtOAc in hexane), 100mg, yield: 94% (Rf = 0.2; 20% EtOAc in
hexane). 1H NMR (CDCl3, 400 MHz): δ = 2.25 (s, 3H), 6.32 (s,
1H), 7.18 (t, J = 8.0 Hz, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7.63 (d, J
= 7.6 Hz, 1H), 7.88-7.89 (m, 1H), 10.83 (br s, 1H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 11.24, 102.20, 122.72, 124.20,
128.66, 130.10, 130.49, 134.84, 142.53, 149.07 ppm. IR (Neat
Film, NaCl): 2954, 1665, 1453, 1442, 774 cm-1. HRMS (ESI)
calc’d for C10H9BrN2 [M]+: 235.9949, Found: 235.9940.
5-(2-(benzyloxy)-5-chlorophenyl)-3-methyl-1H-pyrazole
(3z): Red oil, purified by silica gel column chromatography
(elution with 10% EtOAc in hexane), 96mg, yield: 92% (Rf =
0.4; 30% EtOAc in hexane). 1H NMR (CDCl3, 400 MHz): δ =
2.33 (s, 3H), 5.15 (s, 2H), 6.46 (s, 1H), 6.98 (d, J = 8.8 Hz, 1H),
7.20 (dd, J = 8.8, 2.8 Hz, 1H) 7.38-7.44 (m, 5H), 7.67 (d, J =
2.4 Hz, 1H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 13.02, 71.26,
103.24, 114.11, 126.57, 127.58, 127.64, 128.22, 128.61,
128.94, 135.48, 140.92, 147.45, 153.48 ppm. IR (Neat Film,
NaCl): 2948, 1677, 1457, 1449, 776 cm-1. HRMS (ESI) calc’d
for C17H1535ClN2ONa [M+Na]+: 321.0771, Found: 321.0777.
5-(2,3-dimethoxyphenyl)-3-methyl-1H-pyrazole (3u): Red oil,
purified by silica gel column chromatography (elution with 10%
EtOAc in hexane), 100mg, yield: 94% (Rf = 0.4; 30% EtOAc in
hexane). 1H NMR (CDCl3, 400 MHz): δ = 2.28 (s, 3H), 3.84 (s,
3H), 3.88 (s, 2H), 6.27 (s, 1H), 6.83 (d, J = 8.0 Hz, 1H), 7.20
(dd, J = 8.4, 1.6 Hz, 1H), 7.26 (d, J = 1.6 Hz, 1H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 11.55, 55.65, 55.75, 101.49,
108.61, 111.03, 118.11, 121.35, 125.29, 142.87, 148.70,
148.89, 149.57 ppm. IR (Neat Film, NaCl): 2920, 1648, 1442,
1435, 774 cm-1. HRMS (ESI) calc’d for C12H14N2O2Na [M+Na]+:
241.0953, Found: 241.0953.
3-methyl-5-(naphthalen-1-yl)-1H-pyrazole (3a1): Red oil,
purified by silica gel column chromatography (elution with 8%
EtOAc in hexane), 100mg, yield: 95% (Rf = 0.2; 20% EtOAc in
hexane).1H NMR (CDCl3, 400 MHz): δ = 2.06 (s, 3H), 6.31 (s,
1H), 7.39 (t, J = 8.0 Hz, 1H), 7.48-7.53 (m, 2H), 7.59 (dd, J =
6.8, 0.8 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.88-7.90 (m, 1H),
8.36-8.38 (m, 1H), 9.87 (br s, 1H) ppm. 13C NMR (CDCl3, 100
MHz): δ = 11.21, 105.73, 125.17, 125.77, 125.82, 126.21,
126.95, 128.15, 128.30, 130.62, 131.41, 133.67, 142.69,
148.27 ppm. IR (Neat Film, NaCl): 2945, 1665, 1454, 1445,
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