´
C. Najera, L. Botella / Tetrahedron 61 (2005) 9688–9695
9694
4.3. General procedure for the synthesis of ethyl
3-arylpropanoates (3)
MS: m/z (rel int.) 223 (MC, 29), 195 (MCK28, 9), 178
(MCK45, 23), 153 (15), 152 (31), 150 (37), 149 (100), 136
(18), 133 (10), 119 (16), 103 (30), 91 (23), 78 (35), 77 (35),
63 (17); HRMS: calcd for C11H13NO4: 223.0845; found:
223.0842.
A solution of aryl halide (1 mmol), acrolein diethyl acetal
(229 mL, 1.5 mmol), dicyclohexylmethylamine (321 mL, 1.
5 mmol), tetra-n-butylammonium bromide (322 mg,
1 mmol, only for aryl bromides), 1 (0.1–1 mol% Pd) in
N,N-dimethylacetamide (4 mL) and water (1 mL) was
stirred at 90 8C or at 120 8C (bath temperature) for aryl
iodides or aryl bromides respectively, in air, and the reaction
progress was analyzed by GLC. After the reaction was
completed, the resulting solution was cooled, poured into
ethyl acetate (20 mL) and washed successively with 2 M
HCl (2!20 mL) and H2O (20 mL). The organic layer was
dried over Na2SO4, evaporated (15 mmHg) and the residue
was purified by flash chromatography to afford products 3.
Acknowledgements
We thank DGES of the Spanish Ministerio de Ciencia
y Tecnologia (MCyT) (BQU2001-0724-C02-01), the
Generalitat Valenciana (CITIDIB/2002/320) and the
University of Alicante for financial support. L.B. thanks
the Generalitat Valenciana for a predoctoral fellowship.
The compounds ethyl 3-(p-chlorophenyl)propanoate,28
ethyl 3-phenylpropanoate,29 ethyl 3-(o-tolyl)propanoate,30
ethyl 3-(p-methoxyphenyl)propanoate,29 ethyl 3-(p-acetyl-
phenyl)propanoate,29 ethyl 3-(1-naphtyl)propanoate,31 ethyl
3-(6-methoxy-2-naphtyl)propanoate,28 ethyl 3-(p-cyano-
phenyl)propanoate,32 ethyl 3-[4-(2-ethoxycarbonylethyl)-
phenyl]propanoate,16 and ethyl 3-[2-(2-ethoxycarbo-
nylethyl)phenyl]-propanoate16 have been previously
reported and were characterized by comparison with their
reported data. Data of not described compounds are given
below.
References and notes
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4.3.1. Ethyl 3-(2-formylphenyl)propanoate. Rf 0.27
(hexane–EtOAc: 9/1); oil; IR (film): nZ2740, 1731,
1694 cmK1; 1H NMR: dZ1.22 (t, 3H, JZ7.2 Hz, CH3), 2.
64 (t, 2H, JZ7.6 Hz, ArCH2CH2), 3.36 (t, 2H, JZ7.6 Hz,
ArCH2CH2), 4.11 (c, 2H, JZ7.1 Hz, CH2CH3), 7.33 (d, 1H,
JZ7.5 Hz, ArH), 7.34–7.54 (m, 2H, ArH), 7.82 (dd, 1H, JZ
7.5, 1.4 Hz, ArH), 10.22 (s, 1H, CHO); 13C NMR: dZ4.2,
28.0, 35.5, 60.4, 127.0, 131.2, 133.4, 133.8, 142.9, 172.6,
192.7; MS: m/z (rel int.) 206 (MC, 5), 188 (19), 162 (22),
161 (27), 160 (38), 134 (10), 133 (58), 132 (91), 131 (43),
118 (21), 115 (28), 105 (72), 104 (100), 103 (36), 91 (60), 79
(40), 78 (33), 77 (68), 66 (18), 65 (33), 63 (17), 51 (50);
HRMS: calcd for C12H14O3: 206.0943; found: 206.0944.
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1389–1392.
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183–184. (b) Kwon, B. M.; Lee, S. H.; Cho, Y. K.; Bok, S. H.;
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4.3.2. Ethyl 3-(4-formylphenyl)propanoate. Rf 0.20
(hexane–EtOAc: 9/1); oil; IR (KBr): nZ2736, 1732,
1702 cmK1; 1H NMR: dZ1.23 (t, 3H, JZ7.1 Hz, CH3), 2.
66 (t, 2H, JZ7.6 Hz, ArCH2CH2), 3.04 (t, 2H, JZ7.6 Hz,
ArCH2CH2), 4.13 (c, 2H, JZ7.1 Hz, CH2CH3), 7.38 (d, 2H,
JZ8.0 Hz, ArH), 7.81 (d, 2H, JZ8.0 Hz, ArH); 13C NMR:
dZ14.2, 31.0, 35.2, 60.6, 129.0, 130.0, 134.8, 147.9, 172.4,
191.9; MS: m/z (rel int.) 206 (MC, 33), 177 (15), 161 (13),
135 (36), 133 (31), 132 (63), 131 (28), 119 (19), 107 (13),
105 (28), 104 (20), 103 (21), 91 (31), 79 (24), 78 (18), 77
(34), 76 (12), 66 (12), 65 (15), 63 (12), 60 (29), 51 (32);
HRMS: calcd for C12H14O3: 206.0943; found: 206.0942.
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Howard, J. A. K.; Perepichka, I. F.; Perepichka, D. F.;
Meshulam, G.; Berkovic, G.; Kotler, Z.; Mazor, R.;
4.3.3. Ethyl 3-(4-nitrophenyl)propanoate. Rf 0.17
(hexane–EtOAc: 9/1); oil; IR (film): nZ1732, 1519,
1346 cmK1; 1H NMR: dZ1.24 (t, 3H, JZ7.1 Hz, CH3), 2.
70 (t, 2H, JZ7.5 Hz, ArCH2CH2), 3.08 (t, 2H, JZ7.5 Hz,
ArCH2CH2), 4.14 (c, 2H, JZ7.1 Hz, CH2CH3), 7.40 (d, 2H,
JZ8.5 Hz, ArH) 8.15 (d, 2H, JZ8.5 Hz, ArH); 13C NMR:
dZ14.1, 30.5, 34.9, 60.5, 123.6, 129.2, 146.5, 148.3, 172.0;