8
JOURNAL OF CHEMICAL RESEARCH 2008
to the prepared solution, and the suspension was stirred at 60°C
for 72 h. Physically absorbed palladium species were removed by
extraction with refluxing dichloromethane and acetonitrile for 8 h.
The conditioned catalyst was dried at 90°C under vacuum for 8 h.
(E)-n-Butyl3-(3-thiophenyl)-acrylate:Oil;26purity:97.0%;1HNMR
(CDCl3/TMS): δH 7.66 (d, J = 15.8 Hz, 1H), 7.48 (s, 1H), 7.32 (m,
2H), 6.26 (d, J = 15.8 Hz, 1H), 4.17 (t, J = 6.8 Hz, 2H), 1.68 (tt,
J = 6.8, 6.8 Hz, 2H), 1.42 (qt, J = 7.3, 6.8 Hz, 2H), 0.95 (q, J = 7.3 Hz,
3H); 13C NMR (75 MHz, CDCl3): δ 167.3, 138.0, 137.5, 128.0,
127.1, 125.1, 117.9, 64.6, 30.6, 19.1, 13.7; IR: 2956, 2359, 1701,
1635, 1305, 1165 cm-1.
General procedure
Aryl or heteroaryl halide (1 mmol), n-butyl acrylate (1.5 mmol), base
(1.5 mmol), solvent (0.5 ml), NBu4Br (0.1 mmol) (sometimes omitted)
and PM–Pd(׀׀
) (0.0005 mmol) were placed in a 25 ml two-neck flask.
The mixture was heated at 140°C in air atmosphere for the required
time with magnetic stirring. After cooling to room temperature, the
product was diluted with H2O, extracted with EtOAc, washed with
H2O and brine, and dried over Na2SO4. The solvent was filtered, and
evaporated. The product was purified by chromatography on silica
(eluent: EtOAc/petroleum ether = 1:5). The purity of the isolated
product was determined by GC analysis or 1H NMR.
(E)-n-Butyl 3-(2-thiophenyl)-acrylate: Oil;27 purity: 98.3%; 1H NMR
(CDCl3/TMS): δH 7.76 (d, J = 15.7 Hz, 1H), 7.35 (d, J = 4.9 Hz, 1H),
7.23 (d, J = 3.4 Hz, 1H), 7.04 (dd, J = 3.7 Hz; 3.7 Hz, 1H), 6.23 (d,
J = 15.7 Hz, 1H), 4.18 (t, J = 6.6 Hz, 2H), 1.72–1.62 (m, 2H), 1.48–
1.36 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H). 13C NMR (75 MHz, CDCl3):
δ 167.3, 140.0, 137.3, 131.3, 128.7, 128.5, 117.5, 64.8, 31.2, 19.6,
14.1; IR: 2957, 1708, 1624, 1306 cm-1.
(E)-n-Butyl 4-nitrocinnamate: M.p. 60–63°C (lit21. m.p. 59.6–
64.4°C); purity: 97.4%; 1H NMR (CDCl3/TMS): δH 8.24 (d, J = 8.7 Hz,
2H), 7.73–7.66 (m, 3 H), 6.56 (d, J = 16.1 Hz, 1H), 4.24 (t, J = 6.7 Hz,
2H), 1.75–1.66 (m, 2H), 1.51–1.38 (m, 2H), 0.97 (t, J = 7.4 Hz, 3H).
13C NMR (75 MHz, CDCl3): δ 166.1, 148.5, 141.5, 140.5, 128.6,
124.1, 123.2, 122.6, 64.9, 30.5, 19.1, 13.6; IR: 2959, 1709, 1641,
1599, 1518, 1343 cm-1.
Product data
(E)-n-Butyl cinnamate: Oil;21 purity: 98.0%; 1H NMR (CDCl3/TMS):
δH 7.68 (d, J = 16.0 Hz, 1H), 7.54–7.51 (m, 2H), 7.42–7.37 (m, 3H),
6.45 (d, J = 16.0 Hz, 1H), 4.21 (t, J = 6.7 Hz, 2H), 1.72–1.67 (m,
2H), 1.50–1.40 (m, 2H), 0.96 (t, J = 7.4 Hz, 3H); 13C NMR (75 MHz,
CDCl3): δ 167.5, 144.9, 134.9, 130.6, 129.3, 128.4, 118.7, 64.8, 31.2,
19.6, 14.2; IR: 2953, 1710, 1628, 1498, 1320, 770 cm-1.
(E)-Stilbene: M.p. 123–124°C (lit.22 m.p. 122–123°C); purity:
This work was supported by the Open Foundation of the Key
Discipline of Industrial Catalysis of Zhejiang.
1
99.0%; H NMR (CDCl3/TMS): δH 7.51 (d, 4H, J = 7.7 Hz), 7.36
(t, 4H, J = 7.5 Hz), 7.27–7.23 (m, 2H), 7.11 (s, 2H); 13C NMR
(75 MHz, CDCl3): δ 137.5, 128.9, 128.8, 127.8, 126.7; IR: 3019,
1631, 1493, 1451, 1071, 962, 764 cm-1.
Received 18 December 2007; accepted 18 January 2008
Paper 07/5023
doi: 10.3184/030823408X283720
(E)-Methyl cinnamate: Oil;23 purity: 97.2%; 1H NMR (CDCl3/
TMS): δH 7.69 (d, J = 16.1 Hz, 1H), 7.53–7.50 (m, 2H), 7.39–7.37
(m, 3H), 6.44 (d, J = 16.1 Hz, 1H), 3.80 (s, 3H). 13C NMR (75 MHz,
CDCl3): δ 167.1, 134.2, 130.2, 128.8, 128.0, 117.7, 114.7, 51.5.
IR: 2951, 1719, 1638, 1450, 1434, 1276, 1203, 1172, 980, 768 cm-1.
(E)-Cinnamonitrile and (Z)-cinnamonitrile were isolated as an
E:Z mixture.22
References
1
2
3
R.F. Heck, Acc. Chem. Res., 1979, 12, 146.
I.P. Beletskaya and A.V. Cheprakov, Chem. Rev., 2000, 100, 3009.
N.J. Whitcombe, K.K.M. Hii and S.E. Gibson, Tetrahedron., 2001, 57,
7449.
4
5
A. Hallberg and L. Westfelt, J. Chem. Soc. Perkin Trans. 1., 1984, 933.
F.Y. Zhao, B.M. Bhanage, M. Shirai and M. Arai, Chem. Eur. J., 2000, 6,
843
1
(E)-Cinnamonitrile: H NMR (CDCl3/TMS): δH 7.50–7.38 (m,
5H), 7.39 (d, 1H, J = 16.6 Hz), 5.87 (d, 1H, J = 16.6 Hz). IR: 2952,
2206, 1643, 1614, 1600, 1181, 1110, 978, 801 cm-1.
6
7
8
L. Djakovitch and K. Koehler, J. Mol. Catal. A., 1999, 142, 275
L. Djakovitch and K. Koehler, J. Am. Chem. Soc., 2001, 123, 5990
C.P. Mehnert, D.W. Weaver and J.Y. Ying, J. Am. Chem. Soc., 1998, 120,
12289
(E)-n-Butyl 2-nitrocinnamate: Oil;24 purity: 97.0%; 1H NMR
(CDCl3/TMS): δH 8.15 (d, 1H), 8.10–8.05 (m, 1H), 7.67 (m, 2H),
7.60–7.56 (m, 1H), 6.41 (d, 1H, J = 15.7 Hz), 4.25 (t, 2H, J = 6.8 Hz),
1.72–1.69 (m, 2H), 1.50–1.42 (m, 2H), 0.99 (t, 3H, J = 7.4 Hz).
13C NMR (75 MHz, CDCl3): δ 165.8, 148.2, 139.8, 133.5, 130.5,
130.2, 129.0, 124.8, 123.2, 64.5, 30.6, 19.0, 13.6. IR: 2961, 1716,
1526, 1346, 1180, 975, 757 cm-1.
9
R.L. Augustine and S.T.O’Leary, J. Mol. Catal. A., 1995, 95, 277.
10 C.M. Andersson, K. Karabelas, A. Hallberg and C. Andersson, J. Org.
Chem., 1985, 50, 3891.
11 A. Dahan and M. Portnoy, Org. Lett., 2003, 5, 1197.
12 Y. Uozumi and T. Kimura, Synlett., 2002, 12, 2045.
13 M. Nowotny, U. Hanefeld, H. van Koningsveld and T. Maschmeyer,
Chem. Commun., 2000, 1877.
14 M.R. Buchmeiser and K. Wurst, J. Am. Chem. Soc., 1999, 121, 11101.
15 V. Chandrasekhar and A. Athimoolam, Org. Lett., 2002, 4, 2113.
16 J. Schwarz, V.P.W. Böhm, M.G. Gardiner, M. Grosche, W.A. Herrmann,
W. Hieringer and G. Raudaschl-Sieber, Chem. Eur. J., 2000, 6, 1773.
17 S. Bräse and M. Schroen, Angew. Chem. Int. Ed., 1999, 38, 1071.
18 T. Jeffery. Tetrahedron., 1996, 52, 10113.
19 T. Jeffery and M. David, Tetrahedron Lett., 1998, 39, 5751.
20 Ö. Aksýn, H. Türkmen and L. Artok, J. Organomet. Chem., 2006, 691,
3027.
21 X. Cui, Z. Li and C.Z. Tao, Org. Lett., 2006, 8, 2467.
22 A. Cwik, Z. Hell and F. Figueras, Adv. Synth. Catal., 2006, 348, 523.
23 Z.H. Zhang, Z.G. Zha and C.S. Gan, J. Org. Chem., 2006, 71, 4339.
24 A.G. Myers, D. Tanaka and M.R. Mannion, J. Am. Chem. Soc., 2002, 124,
11250.
25 M.J. Dai, B. Liang, C.H. Wang, J.H. Chen and Z. Yang, Org. Lett., 2004,
6, 221.
26 M. Feuerstein, H. Doucet and M. Santelli, J. Org. Chem., 2001, 66, 5923.
27 F. Berthiol, M. Feuerstein, H. Doucet and M. Santelli, Tetrahedron Lett.,
2002, 43, 5625.
(E)-2-Nitrostilbene: Oil;25 purity: 97.5%. 1H NMR (CDCl3/TMS):
δH 7.95–7.92 (m, 1H), 7.73–7.70 (m, 1H), 7.59–7.49 (m, 4H), 7.38–
7.28 (m, 4H), 7.04 (d, J = 16.2 Hz, 1H); 13C NMR (75 MHz, CDCl3):
δ 147.8, 136.3, 133.7, 132.9, 132.8, 128.6, 128.5, 128.0, 127.8, 126.9,
124.6, 123.3; IR: 3022, 1604, 1508, 1339, 955, 855, 752 cm-1.
(E)-n-Butyl 3-(3-quinolyl)-acrylate: M.p. 80–82°C, purity: 98.0%;
1HNMR12 (CDCl3/TMS):δH 9.09(d,J=2.2Hz,1H),8.24(d,J=2.0Hz,
1H), 8.11 (d, J = 8.3 Hz, 1H), 7.84 (d, J = 6.3 Hz, 1H), 7.78 (d,
J = 16.1 Hz, 1H), 7.73 (d, J = 6.9 Hz, 1H), 7.61–7.58 (m, 1H), 6.67
(d, J = 16.1 Hz, 1H), 4.25 (t, J = 6.7 Hz, 2H), 1.77–1.67 (m, 2 H),
1.47–1.42(m, 2 H), 0.98 (t, J = 7.4 Hz, 3 H). 13C NMR (75 MHz,
CDCl3): δ 166.5, 149.2, 148.6, 141.1, 135.4, 130.6, 129.5, 128.3,
127.5, 120.3, 64.7, 30.7, 19.2, 13.7; IR: 2957, 1710, 1636, 1342,
1318, 1296, 1184 cm-1.
1
(E)-n-Butyl 3-(3-pyridyl)-acrylate: Oil;26 purity: 99.0%; H NMR
(CDCl3/TMS): δH 8.75 (d, J = 1.9 Hz, 1H), 8.60 (dd, J = 1.5 Hz; 1.5 Hz,
1H), 7.86–7.83 (m, 1H), 7.67 (d, J = 16.1 Hz, 1H), 7.35–7.31 (m,
1H), 6.53 (d, J = 16.1 Hz, 1H), 4.23 (t, J = 6.6 Hz, 2H), 1.74–1.65 (m,
2H), 1.50–1.38 (m, 2H), 0.97 (t, J = 7.4 Hz, 3H). 13C NMR (75 MHz,
CDCl3): δ 166.3, 150.7, 149.6, 140.7, 134.1, 130.1, 123.7, 120.4,
64.5, 30.5, 19.1, 13.6. IR: 2957, 1711, 1639, 1415, 1310 cm-1.
PAPER: 08/5023