J. Chem. Sci. (2018) 130:87
2.4b (E)-Butyl 3-(5-methoxy-2-(1H-pyrazol-1-yl) 2.4g
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1-{2,6-Bis[(E)-2-(Butoxycarbonyl)ethenyl]p
phenyl) acrylate 1b15: The general procedure was fol- -methoxyphenyl}-1H-pyrazole 1g15: The general proce-
lowed using 4-methoxy phenylpyrazole (87 mg, 0.5 mmol) dure was followed using 4-methoxy phenylpyrazoles (87 mg,
and butyl acrylate (0.049 mL, 0.55 mmol) in ethanol. Purifi- 0.5 mmol) and butyl acrylate (0.147 mL, 1.5 mmol) in ethanol
cation by column chromatography (Hexane/EtOAc: 90/10) under sealed tube conditions for more than 20 h. Purification
yielded 1b.1H NMR(300 MHz, CDCl3): δ 7.79 (d, 1H), 7.56 by column chromatography (petroleum ether/Et2O : 90/10)
(d, 1H); 7.37 (d, 1H), 7.17 (d, 1H), 7.04 (d, J = 16.0 Hz, yielded 1g. 1H NMR (300 MHz, CDCl3): δ 7.8 (d 1H), 7.47
1H), 7.00 (dd, 1H), 6.52 (t, 1H), 6.27 (d, J = 16.0 Hz, 1H), (d, 1H), 7.22 (s, 2H), 7.04 (d, J = 16.02 Hz, 1H), 6.52
4.12 (t, 2H), 3.91 (s,3H), 1.63–1.58 (m, 2H), 1.39–1.35 (m, (t, 1H), 6.27 (d, J = 16.02 Hz, 2H), 4.12 (t, 4H), 3.92 (s,
2H), 0.88 (t, 3H); ESI-MS [M+H]+301.
3H), 1.65–1.59 (m, 4H), 1.40–1.34 (m, 4H), 0.93 (t, 6H).
ESI-MS [M+H]+ 427.
2.4c (E)-butyl 3-(5-fluoro-2-(1H-pyrazol-1-yl)phenyl)
acrylate 1c15: The general procedure was followed using
4-fluoro phenylpyrazole (87 mg, 0.5 mmol) and butyl acry-
late (0.049 mL, 0.55 mmol) in ethanol. Purification by
column chromatography (Hexane/EtOAc: 90/10) yielded
1c.1H NMR (300 MHz, CDCl3): δ 7.76 (d,1H), 7.79 (d,1H),
7.48 (d, J = 16.0 Hz, 1H), 7.45–7.38 (m, 2H), 7.20–7.15
(m, 1H), 6.49 (t, 1H), 6.36 (d, J = 16.0 Hz, 1H), 4.16 (t,
2H), 1.67–1.61 (m, 2H), 1.44–1.35 (m, 2H), 0.94 (t, 3H);
ESI-MS (M+H)+ 289.
2.4h (2E)-Butyl 3-(2-(4,5-dihydrooxazol-2-yl)phenyl)
acrylate 1h15: The general procedure was followed using
phenyloxazoline (66 µL, 0.5 mmol) and butylacrylate
(0.07 mL, 0.55 mmol) in ethanol for 4 h. Purification by
column chromatography (Hexane/EtOAc: 70/30) yielded 1h.
1H NMR (300 MHz, CDCl3): δ 8.53 (d, J = 16.0 Hz,
1H), 7.86 (dd,1H), 7.65 (dd, 1H), 7.51–7.41 (m, 2H), 6.36
(d, J = 16.0 Hz, 1H), 4.45 (t, 2H), 4.21 (t, 2H), 4.07 (t,
2H), 1.73–1.65 (m, 2H), 1.49–1.43 (m, 2H), 0.97 (t, 3H);
ESI-MS: (M+H)+ = 274.
2.4i (2E)-butyl 3-(2-(4,5-dihydro-4,4-dimethyloxazol-
2-yl)phenyl)acrylate 1i15: The general procedure was fol-
lowedusing4,4ꢀ-dimethylphenyloxazoline(66µL, 0.5mmol)
and butylacrylate (0.07 mL, 0.55 mmol) in ethanol for
6 h. Purification by column chromatography (Hexane/EtOAc:
2.4d (E)-Butyl3-(2-fluoro-6-(1H-pyrazol-1-yl)phenyl)
acrylate 1d15: The general procedure was followed using
3-fluoro pheylpyrazoles (87 mg, 0.5 mmol) and butyl acrylate
(0.049 mL, 0.55 mmol) in ethanol. Purification by col-
umn chromatography (Hexane/EtOAc: 90/10) yielded 1d.
1H NMR (300 MHz, CDCl3): δ 7.79 (d, 1H), 7.70 (m, 1H),
7.64 (d, 1H), 7.60 (d, J = 16.021 Hz, 1H), 7.25 (dd, 1H),
7.17–7.13 (m, 1H), 6.51 (t, 1H), 6.34 (d, J = 16.021 Hz,
1H), 4.17 (t, 2H), 1.68–1.61 (m, 2H), 1.43–1.37 (m, 2H),
0.95 (t, 3H); ESI-MS (M+H)+ 289.
1
70/30) yielded 1i. H NMR (300 MHz, CDCl3): δ 8.48 (d,
J = 16.0 Hz, 1H), 7.81 (dd, 1H), 7.65 (dd, 1H), 7.48–7.38
(m, 2H), 6.37 (d, J = 16 Hz, 1H), 4.21 (t, 2H), 4.13 (s, 2H),
1.72–1.65 (m,2H), 1.50–1.45 (m, 2H), 1.25 (s, 6H), 0.97 (t,
3H); ESI-MS: (M+H)+ = 302.
2.4j 1-{2,6-Bis[(E)-2-(Butoxycarbonyl)ethenyl]p-ace-
tylphenyl}-1H-pyrazole 1j15: The general procedure
was followed using 1-(4-(1H-pyrazol-1-yl)phenyl)ethanone
(93 mg, 0.5 mmol) and butyl acrylate (0.147 mL, 1.5 mmol)
in ethanol under sealed tube conditions for more than
20 h. Purification by column chromatography (Hexane/
2.4e 1-{2,6-Bis[E-2-(Butoxycarbonyl)ethenyl]p-fluo-
rophenyl}-1H-pyrazole 1e15: The general procedure was
followed using 4-fluoro phenylpyrazoles (87 mg, 0.5 mmol)
and butyl acrylate (0.147 mL, 1.5 mmol) in ethanol under
sealed tube conditions for more than 20 h. Purification by
column chromatography (Hexane/EtOAc: 90/10) yielded 1e.
1H NMR (300 MHz, CDCl3): δ 7.82 (d, 1H); 7.49 (d, 1H),
7.02 (d, J = 16.017 Hz, 2H), 6.55 (t, 1H), 6.30 (d, J =
16.017 Hz, 2H); 4.13 (t, 4H), 1.64–1.58 (m, 4H), 1.39–1.33
(m, 4H), 0.93 (t, 6H); ESI-MS [M+H]+ 415.
1
EtOAc: 70/30) yielded 1j. H NMR (300 MHz, CDCl3): δ
8.28 (s, 2H), 7.86 (d, 1H), 7.53 (d, 1H), 7.15 (d, J = 16 Hz,
2H), 6.58 (t, 1H), 6.42 (d, J = 16 Hz, 2H), 4.15 (t, 4H), 2.71
(s, 3H), 1.65–1.42 (m, 4H), 1.41–1.37 (m, 4H), 0.94 (t, 6H);
ESI-MS: (M+H)+ = 439.
2.4k 1-{2,6-Bis[(E)-2-(Butoxycarbonyl)ethenyl]benz-
2.4f 1-{2,6-Bis[E-2-(Butoxycarbonyl)ethenyl]m-fluo- amidophenyl}-1H-pyrazole 1k15: The general procedure
rophenyl}-1H-pyrazole 1f15: The general procedure was was followed using 4-(1H-pyrazol-1-yl)benzonitrile (43 mg,
followed using 3-fluoro phenylpyrazoles (87 mg, 0.5 mmol) 0.25 mmol) and butyl acrylate (0.147 mL, 1.5 mmol) in
and butyl acrylate (0.147 mL, 1.5 mmol) in ethanol under ethanol under sealed tube conditions for more than 20 h.
sealed tube conditions for more than 20 h. Purification by Purification by column chromatography (Hexane/EtOAc:
1
column chromatography (Hexane/EtOAc: 90/10) yielded 1f. 70/30) yielded 1k. H NMR (300 MHz, CDCl3): δ 8.16 (s,
1H NMR (300 MHz, CDCl3): δ 7.84 (d, 1H), 7.70 (dd, 1H), 2H), 7.85 (d, 1H), 7.52 (d,1H), 7.11 (d, J = 16 Hz, 2H), 6.58
7.51 (d, 1H), 7.33–7.27 (m, 2H), 6.98 (dd, 2H), 6.56 (t, 1H), (t, 1H), 6.41 (d, J = 16 Hz, 2H), 4.14 (t, 4H), 1.66–1.58 (m,
6.31 (dd, 2H), 4.31 (t, 4H), 1.64–1.57 (m, 4H), 1.40–1.33 (m, 4H), 1.42–1.34 (m, 4H), 0.93 (t, 6H); ESI-MS: (M+H)+
=
4H), 0.93 (t, 6H); ESI-MS [M+H]+ 415.
440.