G. V. Kryshtal, G. M. Zhdankina, S. G. Zlotin
FULL PAPER
and PTC (4a–d, 5a–c, or 6b/6d) (Table 1 and Table 2) in benzene
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temperature until the condensation was complete (TLC and GLC
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KOH solid phase, and the residue was extracted with benzene
Kaftzic, Current Opinion Biotech. 2002, 13, 565–571.
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(
(
10 mL). The combined benzene extracts were washed with water
2×5 mL) and dried over anhydrous MgSO . The solvent was evap-
4
orated under reduced pressure, and the residue was distilled in
vacuo or crystallized from hexane. The yields, melting (boiling)
points, and refractive indexes of the enals 3a–q, as well as the
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1
H NMR spectroscopic data for compounds 3a–c, 3e–k, and 3n–q,
were in accordance with those reported in the literature (Table 2).
trans-2-Chloro-β-methylcinnamaldehyde
(3d):
B.p. 80–82 °C
),
0
1
(
0.5 Torr); n2
D
= 1.5970. H NMR (CDCl
3
): δ = 1.95 (s, 3 H, CH
3
Ar
7.20–7.45 (m, 5 H, CH=C and 4×H ), 9.63 (s, 1 H, CHO) ppm.
10 9
C H ClO: calcd. C 66.49, H 5.02, Cl 19.63; found C 66.67, H 5.11,
Cl 19.39.
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trans-3-Nitro-β-propylcinnamaldehyde (3l): M.p. 52–53 °C. 1H
NMR (CDCl
CH ), 2.50 (t, J = 7.0 Hz, 2 H, CH
.60–7.80 (m, 2 H, 2×HAr), 8.20–8.30 (m, 2 H, 2×HAr), 9.58 (s, 1
H, CHO) ppm. C12 13NO : calcd. C 65.74, H 5.98, N 6.39; found
C 65.90, H 6.06, N 6.21.
3
): δ = 1.00 (t, J = 7.0 Hz, 3 H, CH
3
), 1.52 (m, 2 H, [10] a) A. T. Nielsen, W. J. Houlihan, Org. Reactions 1968, 16, 1; b)
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2
2
–C=), 7.25 (s, 1 H, CH=C),
7
H
3
[
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trans-β-Isopropyl-3-nitrocinnamaldehyde (3m): M.p. 49–50 °C. 1
NMR (CDCl ): δ = 1.25 (d, 6 H, 2×CH , J = 7.2 Hz), 3.00 (m, 1
H, CH(CH ), 7.22 (s, 1 H, CH=C), 7.50–7.65 (m, 2 H, 2×H ),
.20–8.30 (m, 2 H, 2×H ), 9.58 (s, 1 H, CHO) ppm. C12
calcd. C 65.88, H 6.01, N 6.39; found C 65.90, H 6.06, N 6.47.
H
3
3
Ar
3 2
)
Ar
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8
3
H13NO :
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In the cases of salts 4b, 5a, 5b, and 6b as PTCs and KOH as a
base the reactions were performed repeatedly with a PTC/solid base
mixture (“wet solid phase”) that remained after the first condensa-
tion cycle, with addition of fresh aldehyde/alkanal (ketone)/benzene
solutions (Table 2 and Table 3).
[
4
nBu NOH-Promoted Condensation of Methyl 4-Formylbenzoate
(1a) with Propanal (2): A solution of aldehyde 1a (1.64 g, 10 mmol)
2
004, 53, 573–579; c) C. Su, Z.-C. Chen, Q.-G. Zheng, Synthe-
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available nBu
4
NOH toluene solution (0.1 n) (Table 1, entries 17,
8). The reaction mixture was stirred at the same temperature for
.5–2.0 hours (TLC and GLC monitoring), washed with water
. The solvent was
1
0
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(2×5 mL), and dried over anhydrous MgSO
4
evaporated under reduced pressure to afford enal 3a.
1804.
[
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Acknowledgments
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We gratefully acknowledge the financial support of the Russian
Foundation of Basic Research (grant 03-03-32659) and the Basic
Research Program of the Russian Academy of Sciences.
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Eur. J. Org. Chem. 2005, 2822–2827