Job/Unit: O21757
/KAP1
Date: 02-04-13 16:25:19
Pages: 9
B. S. Lee, D. O. Jang
NЈ-[1-(4-Fluorophenyl)but-3-enyl]benzohydrazide (2a):[6b] Colorless 1 H, =CH2), 5.20 (dd, J = 17.2 Hz, J = 1.4 Hz, 1 H, =CH2), 5.26
FULL PAPER
oil (397 mg, 95% yield); Rf = 0.7 (EtOAc/hexane, 3:7). IR (neat):
(d, J = 6.4 Hz, 1 H, NH), 5.80–5.91 (m, 1 H, –CH=), 6.73 (d, J =
8.8 Hz, 2 H, Ar), 7.31 (m, 2 H, Ar), 7.32 (d, J = 6.4 Hz, 1 H, NH),
7.38 (dd, J = 7.8 Hz, J = 7.4 Hz, 2 H, Ar), 7.47 (dd, J = 7.5 Hz, J
= 7.3 Hz, 1 H, Ar), 7.60 (d, J = 8.8 Hz, 2 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 167.0, 150.2, 135.0, 133.1, 131.7, 129.2,
128.6, 128.5, 117.7, 112.6, 63.4, 40.6, 40.3 ppm.
1
ν = 3275, 1643, 1604, 1224 cm–1. H NMR (400 MHz, CDCl ): δ
˜
3
= 2.37–2.52 (m, 2 H, –CH2–), 4.13 (t, J = 6.8 Hz, 1 H, –CH), 5.08
(dd, J = 18.6 Hz, J = 11.2 Hz, 2 H, =CH2), 5.20 (d, J = 5.3 Hz, 1
H, NH), 5.69–5.80 (m, 1 H, –CH=), 6.99 (t, J = 8.6 Hz, 2 H, Ar),
7.30 (m, 4 H, Ar), 7.45 (dd, J = 7.6 Hz, J = 7.2 Hz, 1 H, Ar), 7.61
(d, J = 7.6 Hz, 2 H, Ar), 7.98 (d, J = 6.3 Hz, 1 H, NH) ppm. 13C
NMR (100 MHz, CDCl3): δ = 167.5, 162.2 (JC,F = 240 Hz), 137.3,
NЈ-[1-(2-Bromophenyl)but-3-enyl]benzohydrazide (2g):[6b] White so-
lid (477 mg, 94% yield); m.p. 76–77 °C. Rf = 0.7 (EtOAc/hexane,
134.3, 132.8, 131.9, 129.4, 129.3, 128.6, 127.0, 118.1, 115.3 (JC,F
=
3:7). IR (neat): ν = 3070, 1633, 1602, 1315 cm–1. 1H NMR
˜
21 Hz), 63.2, 40.3 ppm.
(400 MHz, CDCl3): δ = 2.35–2.55 (m, 2 H, –CH2–), 4.71 (t, J =
5.9 Hz, 1 H, –CH), 5.09 (d, J = 10.2 Hz, 1 H, =CH2), 5.14 (dd, J
= 17.1 Hz, J = 1.2 Hz, 1 H, =CH2), 5.28 (dd, J = 6.4 Hz, J =
2.1 Hz, 1 H, NH), 5.81–5.92 (m, 1 H, –CH=), 7.05 (td, J = 7.8 Hz,
J = 1.6 Hz, 1 H, Ar), 7.27 (t, J = 7.7 Hz, 3 H, Ar), 7.39 (t, J =
13.8 Hz, 1 H, Ar), 7.48 (dd, J = 8.0 Hz, J = 1.1 Hz, 1 H, Ar), 7.60
(d, J = 7.1 Hz, 2 H, Ar), 7.64 (dd, J = 7.8 Hz, J = 1.6 Hz, 1 H,
Ar), 8.16 (d, J = 6.4 Hz, 1 H, NH) ppm. 13C NMR (100 MHz,
CDCl3): δ = 167.4, 140.7, 134.1, 133.0, 132.8, 131.7, 128.8, 128.5,
127.7, 127.0, 124.6, 118.4, 62.1, 39.3 ppm.
NЈ-(1-Phenylbut-3-enyl)benzohydrazide (2b):[6b] White solid
(371 mg, 95% yield); m.p. 98–99 °C. Rf = 0.7 (EtOAc/hexane, 3:7).
1
IR (neat): ν = 3300, 1635, 1578, 1314 cm–1. H NMR (400 MHz,
˜
CDCl3): δ = 2.39–2.51 (m, 2 H, –CH2–), 4.13 (td, J = 3.0 Hz, J =
2.1 Hz, 1 H, –CH), 5.05 (d, J = 10.1 Hz, 1 H, =CH2), 5.10 (dd, J
= 17.1 Hz, J = 1.3 Hz, 1 H, =CH2), 5.23 (dd, J = 6.7 Hz, J =
2.3 Hz, 1 H, NH), 5.71–5.81 (m, 1 H, –CH=), 7.23–7.34 (m, 7 H,
Ar), 7.41 (td, J = 2.7 Hz, J = 1.1 Hz, 1 H, Ar), 7.58 (d, J = 7.0 Hz,
2 H, Ar), 8.07 (d, J = 6.6 Hz, 1 H, NH) ppm. 13C NMR (100 MHz,
CDCl3): δ = 167.1, 141.4, 134.3, 132.7, 131.5, 128.4, 128.3, 127.6,
127.5, 126.8, 117.7, 63.7, 40.0 ppm.
NЈ-[1-(2-Fluorophenyl)but-3-enyl]benzohydrazide (2h): Colorless oil
(401 mg, 96% yield); R = 0.7 (EtOAc/hexane, 3:7). IR (neat): ν =
˜
f
NЈ-[1-(4-Ethylphenyl)but-3-enyl]benzohydrazide (2c):[6b] White solid
3282, 1634, 1603, 1229 cm–1. 1H NMR (400 MHz, CDCl3): δ =
2.53 (t, J = 7.3 Hz, 2 H, –CH2–), 4.55 (td, J = 12.4 Hz, J = 6.8 Hz,
1 H, –CH), 5.09 (d, J = 10.2 Hz, 1 H, =CH2), 5.14 (dd, J = 17.1 Hz,
J = 1.3 Hz, 1 H, =CH2), 5.26 (dd, J = 6.7 Hz, J = 2.8 Hz, 1 H,
NH), 5.78–5.88 (m, 1 H, –CH=), 7.01 (dd, J = 9.6 Hz, J = 9.0 Hz,
1 H, Ar), 7.13 (dd, J = 7.6 Hz, J = 7.2 Hz, 1 H, Ar), 7.20–7.26 (m,
1 H, Ar), 7.34 (dd, J = 7.8 Hz, J = 7.4 Hz, 2 H, Ar), 7.45 (dd, J =
7.6 Hz, J = 7.2 Hz, 1 H, Ar), 7.52 (td, J = 7.4 Hz, J = 1.5 Hz, 1
H, Ar), 7.61 (d, J = 7.5 Hz, 2 H, Ar), 7.80 (d, J = 6.6 Hz, 1 H,
(419 mg, 97% yield); m.p. 63–64 °C. Rf = 0.7 (EtOAc/hexane, 3:7).
1
IR (neat): ν = 3272, 1641 cm–1. H NMR (400 MHz, CDCl ): δ =
˜
3
1.21 (t, J = 3.0 Hz, J = 2.1 Hz, 3 H, –CH3), 2.41–2.54 (m, 2 H,
–CH2–), 2.61 (d, J = 7.6 Hz, 2 H, –CH2–), 4.11 (t, J = 7.0 Hz, 1
H, –CH), 5.06 (d, J = 10.0 Hz, 1 H, =CH2), 5.13 (dd, J = 17.1 Hz,
J = 1.2 Hz, 1 H, =CH2), 5.24 (s, 1 H, NH), 5.75–5.80 (m, 1 H,
–CH=), 7.14 (d, J = 8.0 Hz, 2 H, Ar), 7.25 (d, J = 8.0 Hz, 2 H,
Ar), 7.31 (dd, J = 7.8 Hz, J = 7.4 Hz, 2 H, Ar), 7.42 (dd, J =
7.5 Hz, J = 7.3 Hz, 1 H, Ar), 7.59 (d, J = 7.2 Hz, 2 H, Ar), 7.81
(s, 1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.3, 143.5,
138.8, 134.8, 133.0, 131.7, 128.5, 128.0, 127.8, 127.1, 117.7, 63.7,
40.2, 28.5, 15.5 ppm.
NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.3, 161.2 (JC,F
240 Hz), 160.0, 134.2, 132.8, 131.8, 129.0, 128.9, 128.6, 128.5,
126.9, 124.3, 118.2, 115.6 (JC,F 22 Hz), 57.1, 39.0 ppm.
=
=
C17H17FN2O (284.33): calcd. C 71.81, H 6.03, N 9.85; found C
71.90, H 6.08, N 9.70.
NЈ-[1-(4-Methoxyphenyl)but-3-enyl]benzohydrazide (2d):[6b] White
solid (244 mg, 56% yield); m.p. 167–168 °C. Rf = 0.7 (EtOAc/hex-
NЈ-[1-(3-Fluorophenyl)but-3-enyl]benzohydrazide (2i): White solid
(397 mg, 95% yield); m.p. 55–56 °C. Rf = 0.7 (EtOAc/hexane, 3:7).
ane, 3:7). IR (neat): ν = 3271, 1640, 1613, 1248 cm–1. 1H NMR
˜
IR (neat): ν = 3294, 1632 cm–1. H NMR (400 MHz, CDCl ): δ =
(400 MHz, CDCl3): δ = 2.41–2.55 (m, 2 H, –CH2–), 3.78 (s, 3 H,
–CH3), 4.10 (td, J = 7.2 Hz, J = 1.8 Hz, 1 H, –CH), 5.08 (d, J =
10.2 Hz, 1 H, =CH2), 5.14 (d, J = 17.1 Hz, 1 H, =CH2), 5.22 (dd,
J = 6.8 Hz, J = 2.0 Hz, 1 H, NH), 5.77–5.83 (m, 1 H, –CH=), 6.86
(d, J = 8.8 Hz, 2 H, Ar), 7.27 (d, J = 8.8 Hz, 2 H, Ar), 7.35 (t, J
= 7.7 Hz, 2 H, Ar), 7.46 (t, J = 7.4 Hz, 1 H, Ar), 7.59 (d, J =
7.3 Hz, 2 H, Ar), 7.68 (d, J = 6.8 Hz, 1 H, NH) ppm. 13C NMR
(100 MHz, CDCl3): δ = 167.3, 159.0, 134.7, 133.5, 133.0, 132.7,
128.9, 128.5, 127.0, 117.7, 113.8, 63.3, 55.2, 40.1 ppm.
1
˜
3
2.38–2.51 (m, 2 H, –CH2–), 4.16 (t, J = 6.5 Hz, 1 H, –CH), 5.08
(d, J = 10.5 Hz, 1 H, =CH2), 5.12 (d, J = 18.9 Hz, 1 H, =CH2),
5.21 (dd, J = 6.5 Hz, J = 1.8 Hz, 1 H, NH), 5.72–5.82 (m, 1 H,
–CH=), 6.93 (td, J = 8.4 Hz, J = 2.5 Hz, 1 H, Ar), 7.12 (dd, J =
8.1 Hz, J = 7.1 Hz, 1 H, Ar), 7.25 (dd, J = 7.8 Hz, J = 5.7 Hz, 1
H, Ar), 7.33 (dd, J = 7.7 Hz, J = 7.6 Hz, 2 H, Ar), 7.44 (dd, J =
7.6 Hz, J = 7.2 Hz, 1 H, Ar), 7.61 (d, J = 7.8 Hz, 2 H, Ar), 8.03
(d, J = 6.5 Hz, 1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ =
167.6, 163.0 (JC,F = 240 Hz), 144.6, 144.5, 134.1, 132.7, 131.8,
130.0, 130.0, 129.9, 128.6, 127.0, 123.6, 118.2, 114.5 (JC,F = 21 Hz),
114.4 (JC,F = 21 Hz), 114.3, 63.5, 40.3 ppm. C17H17FN2O (284.33):
calcd. C 71.81, H 6.03, N 9.85; found C 71.78, H 6.11, N 9.80.
NЈ-[1-(4-Hydroxyphenyl)but-3-enyl]benzohydrazide (2e):[6b] Off-
white solid (110 mg, 53% yield); m.p. 88–90 °C. Rf = 0.7 (EtOAc/
hexane, 3:7). IR (neat): ν = 3236, 1627, 1596, 1252 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 2.41–2.54 (m, 2 H, –CH2–), 4.07 (dd, J =
7.2 Hz, J = 6.8 Hz, 1 H, –CH), 5.06 (d, J = 10.2 Hz, 1 H, =CH2),
5.12 (d, J = 17.1 Hz, 1 H, =CH2), 5.26 (br. s, 1 H, NH), 5.72–5.82
(m, 1 H, –CH=), 6.82 (d, J = 8.0 Hz, 2 H, Ar), 7.19 (d, J = 8.4 Hz,
2 H, Ar), 7.35 (dd, J = 8.0 Hz, J = 7.6 Hz, 2 H, Ar), 7.46 (t, J =
7.2 Hz, 1 H, Ar), 7.59 (d, J = 7.6 Hz, 2 H, Ar), 7.72 (br. s, 1 H,
NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.1, 155.2, 134.6,
133.7, 132.9 131.8, 129.0, 128.7, 126.8, 118.0, 115.4, 63.5, 40.4 ppm.
NЈ-[1-(2–Chlorophenyl)but-3-enyl]benzohydrazide (2j): White solid
(414 mg, 94% yield); m.p. 80–81 °C. Rf = 0.7 (EtOAc/hexane, 3:7).
1
IR (neat): ν = 3260, 1627 cm–1. H NMR (400 MHz, CDCl ): δ =
˜
3
2.37–2.55 (m, 2 H, –CH2–), 4.75 (t, J = 7.6 Hz, 1 H, –CH), 5.08
(d, J = 10.2 Hz, 1 H, =CH2), 5.13 (d, J = 17.2 Hz, 1 H, =CH2),
5.28 (dd, J = 6.5 Hz, J = 2.3 Hz, 1 H, NH), 5.79–5.90 (m, 1 H,
–CH=), 7.13 (td, J = 7.6 Hz, J = 1.2 Hz, 1 H, Ar), 7.20–7.30 (m,
4 H, Ar), 7.39 (dd, J = 7.6 Hz, J = 7.2 Hz, 1 H, Ar), 7.64 (d, J =
7.7 Hz, 1 H, Ar), 7.60 (d, J = 7.4 Hz, 2 H, Ar), 8.20 (d, J = 6.5 Hz,
1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.3, 139.2,
134.2, 134.1, 132.8, 131.7, 129.7, 128.6, 128.4, 128.2, 127.1, 126.9,
NЈ-{1-[4-(Dimethylamino)phenyl]but-3-enyl}benzohydrazide (2f):[5a]
1
Colorless oil (32 mg, 7% yield); Rf = 0.7 (EtOAc/hexane, 3:7). H
NMR (400 MHz, CDCl3): δ = 2.46–2.57 (m, 2 H, –CH2–), 2.96 (s,
6 H, –CH3), 4.07 (t, J = 7.0 Hz, 1 H, –CH), 5.12 (d, J = 10.1 Hz,
4
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