576
V. G. Nenajdenko et al.
PAPER
Anal. Calcd for C10H10ClNO2: C, 56.75; H, 4.76. Found: C, 56.69;
H, 4.96.
1H NMR (400 MHz, CDCl3): (major isomer) = 8.20 (d, J = 8.8
Hz, 2 H), 7.32 (d, J = 8.8 Hz, 2 H), 4.00 (q, J = 7.3 Hz, 2 H, CH2),
2.30 (s, 3 H, CH3), 0.99 (t, J = 7.3 Hz, 3 H, CH3CH2); (minor
isomer) = 8.25 (d, J = 8.8 Hz, 2 H), 7.41 (d, J = 8.8 Hz, 2 H), 4.34
(q, J = 7.3 Hz, 2 H, CH2), 2.40 (s, 3 H, CH3), 1.38 (t, J = 7.3 Hz, 3
H, CH3CH2).
Hydrazones 5a–c; General Procedure
The hydrazones 5a–c were prepared by refluxing for several hours
the ketone (1 equiv) and 100% hydrazine hydrate (3 equiv) dis-
solved in a minimum amount of EtOH to achieve homogeneity at
boiling point. In the case of 5b,c, the reaction mixture was poured
into H2O (300 mL) and filtered. The crude hydrazones were washed
with H2O (3 × 100 mL) and dried in vacuo. In the case of 5a, EtOH,
H2O and excess of hydrazine were removed in vacuo, the crude hy-
drazone was dissolved in Et2O and washed with brine. The solvent
was removed under reduced pressure and the hydrazone was crys-
tallized by cooling.
13C NMR (100 MHz, CDCl3): (major isomer) = 162.8 (C=O),
148.0 (CCH3), 145.1, 144.3, 127.8, 123.6, 121.8 (ClC=), 62.1
(OCH2), 22.9 (CH3), 13.6 (CH3CH2);
(signals of minor
isomer) = 163.3 (C=O), 148.0 (CCH3), 145.1, 144.3, 128.2, 123.8,
122.1 (ClC=), 62.3 (OCH2), 23.8 (CH3), 14.1 (CH3CH2).
MS: m/z (%) for major isomer = 271 (3), 269 (10), 252 (22), 224
(100), 194 (50), 178 (15), 149 (20), 131 (11), 115 (70), 103 (11), 89
(12), 78 (27), 44 (78); for minor isomer = 271 (1), 269 (3), 252 (5),
224 (39), 194 (11), 178 (3), 149 (6), 115 (19), 78 (43), 44 (100).
1-Phenylethanone Hydrazone (5a)
Yield: 70%; colorless crystals; mp 23–24 °C (Lit.20 mp 22–26 °C).
Anal. Calcd for C12H12ClNO4: C, 53.44; H, 4.49. Found: C, 53.77;
H, 4.30.
1-(4-Methoxyphenyl)ethanone Hydrazone (5b)
Yield: 93%; colorless crystals; mp 119–120 °C (Lit.21 mp 122–123
°C) .
Acknowledgment
Financial support from Russian Fundamental Investigation Found-
ation (Grant 03-03-32052a) is gratefully acknowledged.
1-(4-Nitrophenyl)ethanone Hydrazone (5c)
Yield: 92%; orange crystals; mp 148–149 °C (Lit.22 mp 149–151
°C).
References
-Chlorocinnamates 6 from Hydrazones; General Procedure
To a solution of hydrazone 5 (5 mmol) in DMSO (5 mL) were added
CuCl2·2H2O (9 mg, 0.05 mmol) and Et3N (2.1 mL, 0.015 mmol).
After 5 min, ethyl trichloroacetate (2.1 mL, 0.015 mmol) was added
dropwise keeping the reaction temperature at 20 °C. The reaction
mixture was stirred for 24 h, then quenched with aq 5% HCl (300
mL) and extracted with CH2Cl2 (3 × 50 mL). The combined extracts
were dried (Na2SO4), the CH2Cl2 was evaporated in vacuo and the
residue was purified by column chromatography (hexane–CH2Cl2)
(Table 1).
(1) Suzuki, T.; Oriyama, T. Synlett 2000, 859.
(2) Tago, K.; Kogen, H. Tetrahedron 2000, 56, 8825.
(3) (a) Shastin, A. V.; Korotchenko, V. N.; Nenajdenko, V. G.;
Balenkova, E. S. Tetrahedron 2000, 56, 6557. (b) Shastin,
A. V.; Korotchenko, V. N.; Nenajdenko, V. G.; Balenkova,
E. S. Russ. Chem. Bull. 2001, 50, 1401. (c) Korotchenko,
V. N.; Shastin, A. V.; Nenajdenko, V. G.; Balenkova, E. S.
Tetrahedron 2001, 57, 7519. (d) Shastin, A. V.;
Korotchenko, V. N.; Nenajdenko, V. G.; Balenkova, E. S.
Synthesis 2001, 2081. (e) Korotchenko, V. N.; Shastin, A.
V.; Nenajdenko, V. G.; Balenkova, E. S. J. Chem. Soc.,
Perkin Trans.1 2002, 883. (f) Nenajdenko, V. G.; Shastin,
A. V.; Korotchenko, V. N.; Varseev, G. N.; Balenkova, E. S.
Eur. J. Org. Chem. 2003, 302.
Ethyl 2-Chloro-3-(4-methoxyphenyl)but-2-enoate (6b)
Pale yellow oil mixture of isomers (1.1:1); Rf 0.61 (hexane–CH2Cl2,
1:2).
IR (CHCl3): 1730 (C=O), 1620 cm–1.
(4) (a) Chari, R. U. J.; Wemple, J. Tetrahedron Lett. 1979, 20,
111. (b) Nakamura, I.; Harada, K. Heterocycles 1978, 9,
473. (c) McDonald, I. A.; Lacoste, J.; Bey, P.; Wagner, M.;
Zreida, M.; Palfreyman, M. G. J. Am. Chem. Soc. 1984, 106,
3354. (d) Rulev, A. Yu. Russ. Chem. Rev. 1998, 67, 317.
(e) Arai, S.; Nakayama, K.; Suzuki, Y.; Hatano, K.; Shioiri,
T. Tetrahedron Lett. 1998, 39, 9739.
(5) Burton, D. J.; Greenwald, J. R. Tetrahedron Lett. 1967, 16,
1535.
(6) Makosza, M.; Podraza, R.; Bialecki, M. Gazz. Chim. Ital.
1995, 125, 601.
(7) Terent’ev, A. B.; Vasil’eva, T. T.; Kuz’mina, N. A.; Mysov,
E. I.; Ikonnikov, N. S.; Kuznetsov, N. Yu.; Belokon, Y. N.
Russ. Chem. Bull. 1999, 48, 1121.
(8) Miura, M.; Hattori, A.; Nomura, M. J. Chem. Soc., Perkin
Trans. 2 1988, 1643.
1H NMR (400 MHz, CDCl3): (first isomer) = 7.11 (d, J = 9.0 Hz,
2 H), 6.86 (d, J = 9.0 Hz, 2 H), 4.01 (q, J = 7.2 Hz, 2 H, CH2O), 3.81
(s, 3 H, CH3O), 2.27 (s, 3 H, CH3), 0.99 (t, J = 7.2 Hz, 3 H,
CH3CH2); (second isomer) = 7.23 (d, J = 9.0 Hz, 2 H), 6.92 (d,
J = 9.0 Hz, 2 H), 4.33 (q, J = 7.2 Hz, 2 H, CH2O), 3.83 (s, 3 H,
CH3O), 2.39 (s, 3 H, CH3), 1.38 (t, J = 7.2 Hz, 3 H, CH3CH2).
13C NMR (100 MHz, CDCl3):
159.2, 144.8 (CCH3), 133.1, 128.2, 113.6, 118.4 (ClC=), 61.5
(OCH2), 55.2 (CH3O), 23.4 (CH3), 13.6 (CH3CH2); (second
(first isomer) = 164.3 (C=O),
isomer) = 164.4 (C=O), 159.4, 147.1 (CCH3), 133.7, 128.7, 113.6,
119.8 (ClC=), 61.9 (OCH2), 55.2 (CH3O), 23.4 (CH3), 14.1
(CH3CH2).
MS: m/z (%) for the first isomer = 256 (15), 254 (46), 208 (100), 145
(50), 131 (21), 115 (19), 108 (96), 102 (13), 77 (23); for the second
isomer = 256 (13), 254 (39), 208 (92), 145 (51), 131 (19), 115 (18),
108 (100), 103 (28), 77 (23).
(9) Son, J. S.; Jung, K. S.; Kim, H. R.; Kim, J. N. Synth.
Commun. 1998, 28, 1847.
Anal. Calcd for C13H15ClO3: C, 61.30; H, 5.94. Found: C, 61.12; H,
6.09.
(10) Kruper, W. J. Jr.; Emmons, A. H. J. Org. Chem. 1991, 56,
3323.
(11) Goumain, S.; Jubault, P.; Feasson, C.; Collignon, N.
Synthesis 1999, 981.
(12) Ishino, Y.; Mihara, M.; Nishihama, S.; Nishiguchi, I. Bull.
Chem. Soc. Jpn. 1998, 71, 2669.
Ethyl 2-Chloro-3-(4-nitrophenyl)but-2-enoate (6c)
Pale yellow oil mixture of isomers (0.4:1); Rf 0.61 (hexane–CH2Cl2,
1:2).
IR (CHCl3): 1720 (C=O), 1600 cm–1.
Synthesis 2004, No. 4, 573–577 © Thieme Stuttgart · New York