β-Alanine-DBU: A Highly Efficient Catalytic System for Knoevenagel-Doebner Reaction
1
in 97% yield; white solid; m.p. 217—218 ℃; H NMR
(DMSO-d6, 500 MHz) δ: 6.57 (d, J=15.3 Hz, 1H), 7.37
(m, 1H), 7.43 (t, J=7.5 Hz, 1H), 7.71 (d, J=7.9 Hz,
1H), 7.84 (d, J=15.3 Hz, 1H), 7.90 (d, J=7.5 Hz, 1H),
12.37 (s, 1H); MS (ESI) m/z: 227 (M++1). Anal. calcd
for C9H7BrO2: C 47.61, H 3.11; found C 47.64, H 3.10.
(E)-3-(3-Nitrophenyl)acrylic acid (2j) Obtained
Science Foundation of China (Nos. 30930107,
30973640), the Key Project of Science and Technology
of Shanghai (No. 09431901700), the Major Special
Project for the Creation of New Drugs (No.
2009ZX09301-011) and Shanghai Leading Academic
Discipline Project (No. B906).
1
in 98% yield; yellow solid; m.p. 199—201 ℃; H
References
NMR (DMSO-d6, 500 MHz) δ: 6.75 (d, J=16.2 Hz,
1H), 7.70 (t, J=8.1 Hz, 1H), 7.73 (d, J=16.5 Hz, 1H),
8.18 (d, J=8.1 Hz, 1H), 8.23 (dd, J=2.2, 8.2 Hz, 1H),
8.52 (s, 1H), 12.60 (s, 1H); 13C NMR (DMSO-d6, 500
MHz) δ: 122.7, 123.2, 124.8, 130.7, 134.4, 136.6, 141.9,
148.7, 167.5; MS (ESI) m/z: 192 (M+-1). Anal. calcd
for C9H7NO4: C 55.96, H 3.65; found C 55.93, H 3.66.
(E)-3-(2-Furyl)acrylic acid (2k) Obtained in 90%
yield; white solid; m.p. 141 — 143 ℃ ; 1H NMR
(DMSO-d6, 500 MHz) δ: 6.16 (d, J=15.9 Hz, 1H), 6.62
(m, 1H), 6.92 (d, J=3.3 Hz, 1H), 7.35 (d, J=15.9 Hz,
1H), 7.82 (d, J=1.1 Hz, 1H), 12.37 (s, 1H); MS (ESI)
m/z: 139 (M++1). Anal. calcd for C7H6O3: C 60.87, H
4.38; found C 60.84, H 4.37.
[1] Concellon, J. M.; Concellon, C. J. Org. Chem. 2006, 71, 1728.
[2] Tellers, D. M.; McWilliams, J. C.; Humphrey, G.; Journet, M.; Di-
Michele, L.; Hinksmon, J.; McKeown, A. E.; Rosner, T.; Sun, Y.;
Tillyer, R. D. J. Am. Chem. Soc. 2006, 128, 17063.
[3] Qiu, L.; Li, Y.-M.; Kwong, F.-Y.; Yu, W.-Y.; Fan, Q.-H.; Chan, A. S.
C. Adv. Synth. Catal. 2007, 349, 517.
[4] Palomo, C.; Pazos, R.; Oiarbide, M.; Garcia, J. M. Adv. Synth. Catal.
2006, 348, 1161.
[5] Marquardt, U.; Schmid, D.; Jung, G. Synlett 2000, 1131.
[6] Song, J.; Hesse, M. Tetrahedron 1993, 49, 6797.
[7] Vanderwal, C. D.; Jacobsen, E. N. Science of Synthesis, Thieme,
Stuttgart, 2006, pp. 551—565.
[8] Bellassoued, M.; Gaudemar, M. Tetrahedron Lett. 1988, 29, 4551.
[9] Knoevenagel, E. Chem. Ber. 1894, 27, 2345.
[10] Doebner, O. Chem. Ber. 1900, 33, 2140.
(E)-3-(2-Thioenyl)acrylic acid (2l) Obtained in
1
[11] Wiley, R. H.; Smith, N. R. Org. Synth. 1953, 33, 62.
[12] Jessup, P. J.; Petty, C. B.; Roos, J.; Overman, L. E. Org. Synth. 1979,
59, 1.
91% yield; brown solid; m.p. 146—148 ℃; H NMR
(DMSO-d6, 500 MHz) δ: 6.17 (d, J=15.7 Hz, 1H), 7.14
(dd, J=3.6, 5.1 Hz, 1H), 7.50 (d, J=3.4 Hz, 1H), 7.70
(d, J=5.0 Hz, 1H), 7.73 (d, J=15.7 Hz, 1H), 12.36 (s,
1H); 13C NMR (DMSO-d6, 500 MHz) δ: 117.9, 128.9,
129.9, 132.1, 137.1, 139.3, 167.6; MS (ESI) m/z: 153
(M+-1). Anal. calcd for C7H6O2S: C 54.53, H 3.92;
found C 54.50, H 3.93.
(E)-4-Methyl-2-pentenoic acid (2m) Obtained in
60% yield; brown oil; 1H NMR (DMSO-d6, 500 MHz) δ:
1.00 (d, J=6.5 Hz, 6H), 2.45 (m, 1H), 5.70 (m, 1H),
6.80 (m, 1H), 12.11 (s, 1H); MS (ESI) m/z: 113 (M+-
1). Anal. calcd for C6H10O2: C 63.14, H 8.83; found C
63.18, H 8.81.
[13] Gastaminza, A. E.; Ferracutti, N. N.; Rodriguez, N. M. J. Org. Chem.
1984, 49, 3859.
[14] Maria, V. F.; Fidel, J. L. H.; Teresa, L. C.; Gonzalo, P. E. Carbohyd.
Res. 1983, 118, 286.
[15] Klein, J.; Bergmann, E. D. J. Am. Chem. Soc. 1957, 79, 3452.
[16] Sharp, D. B.; Hudson, G. V. J. Am. Chem. Soc. 1951, 73, 3085.
[17] Hoffmann, R. W. Synthesis 2006, 3531.
[18] Kemme, S. T.; Smejkal, T.; Breit, B. Adv. Synth. Catal. 2008, 350,
989.
[19] This part of the work has not been reported.
[20] Augustine, J. K.; Naik, Y. A.; Mandal, A. B.; Chowdappa, N.;
Praveen, V. B. J. Org. Chem. 2007, 72, 9854.
[21] Bijukumar, G.; Maloyesh, B.; Bhaskar, B. S.; Rajendra, A. Synth.
Commun. 2008, 38, 1512.
Acknowledgement
[22] Stabile, R. G.; Dicks, A. P. J. Chem. Educ. 2004, 81, 1488.
[23] Guyot, J.; Kergomard, A. Tetrehedron 1983, 39, 1167.
This work was supported by the National Natural
(E1102111 Zhao, X.; Lu, Z.)
Chin. J. Chem. 2012, 30, 139—143
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
143