PTC with Fluorinated Anions in a Heterogeneous System
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in Tables 2 and 3). The mixture was stirred until the reaction was
2i: Oil; nD = 1.5170. H NMR: δ = 1.45 (s, 3 H, CH3), 1.75 (s, 3
complete (TLC and GLC monitoring). The organic phase was de- H, CH3), 2.05–2.25 (m, 1 H, CH), 2.30–2.45 (m, 4 H, 2ϫCH2),
canted, and the residue extracted with Et2O (3ϫ5 mL). The com-
bined organic solutions were washed with water (3ϫ20 mL) and
dried with anhydrous MgSO4. The solvents were evaporated under
reduced pressure (15 Torr). The residue was purified by column
chromatography [silica gel, 0.060–0.200 µm; eluents n-hexane and
n-hexane/PhH (95:5, 90:10, 80:20, 50:50)] yielding compounds 2, 3,
and 7–9 (the yields are given in Tables 2 and 3).
2.65 (m, 1 H, CH), 4.58 (s, 1 H, CH=), 4.85 (s, 1 H, CH=) ppm.
C11H14Cl2O (233.13): calcd. C 56.67, H 6.05, Cl 30.41; found C
56.89, H 6.22, Cl 30.24.
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2j: Oil; nD = 1.5210. H NMR: δ = 1.25 (s, 2 H, CH2C=), 1.27
(s, 3 H, CH3), 1.75 (s, 3 H, CH3C=), 2.10–2.65 (m, 5 H, 2ϫCH2,
CH), 6.73 (br. s, 1 H, CH=) ppm. C11H14Cl2O (233.13): calcd. C
56.67, H 6.05, Cl 30.41; found C 56.81, H 5.98, Cl 30.30.
2a: Oil; nD20 = 1.5215 (ref.[17] 1.5220, data for corresponding diethyl
1
7a: Colorless crystals; m.p. 39–40 °C (ref.[22] 41 °C). H NMR: δ =
1
acetal). H NMR: δ = 2.32 (dd, J = 6.0, 8.5 Hz, 1 H, CHcPr), 2.88
2.82, 3.07 (2 t, J = 7.8 Hz, 2 H, CH2) ppm.
(d, J = 8.5 Hz, 1 H, CHcPr), 3.42 and 3.51 (2 s, 3 H, OMe), 4.52
[d, J = 6.0 Hz, 1 H, CH(OMe)2], 7.25–7.45 (m, 5 H, Ph) ppm.
7b: Oil; nD = 1.4660 (ref.[35] nD = 1.4648 for Me ester). 1H
NMR: δ = 1.28 (t, J = 7.8 Hz, 3 H, CH3), 2.80, 3.05 (2 t, J =
8.0 Hz, 2 H, CH2), 4.18 (q, J = 7.8 Hz, 2 H, OCH2) ppm.
C6H9Cl3O2 (219.49): calcd. C 32.83, H 4.13, Cl 48.46; found C
33.01, H 3.98, Cl 48.29.
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2b: Oil; nD = 1.4675 (ref.[18] 1.4660). 1H NMR: δ = 1.24, 1.38,
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2.09 (3 s, 3 H, CH3), 1.55 (t, J = 7.0 Hz, 1 H, CHcPr), 4.18 (d, J =
7.0 Hz, 2 H, CH2) ppm.
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2c: Oil; nD = 1.4860. 1H NMR: δ = 1.12, 1.27, 1.31 (3 s, 3 H,
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7c: Oil; nD = 1.4540 (ref.[28] 1.4574). H NMR: δ = 1.62 (d, J =
6.6 Hz, 3 H, CH3), 2.30 [s, 3 H, C(O)CH3], 5.50 (q, J = 6.6 Hz, 1
H, CH) ppm.
CH3), 1.40–1.76 (m, 6 H, 2ϫCH2, CHcPr and OH), 5.05 (d, J =
10.3 Hz, 1 H, CH=), 5.20 (d, J = 17.4 Hz, 1 H, CH=), 5.90 (dd, J
= 10.3, 17.4 Hz, 1 H, CH=) ppm. C11H18Cl2O (237.17): calcd. C
55.71, H 7.65, Cl 29.90; found C 55.90, H 7.52, Cl 29.64.
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8a: Oil; nD = 1.5670 (ref.[25b] 1.5650). H NMR: δ = 3.70 (br. s, 1
H, OH), 5.23 (s, 1 H, CH), 7.42 (m, 3 H, Ph), 7.66 (d, J = 8.5 Hz,
2 H, Ph) ppm.
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2d: Oil; nD = 1.4770 (ref.[20] nD = 1.4833). H NMR: δ = 1.13,
1.32, 1.70, 2.05 (4 s, 3 H, CH3), 1.45–1.78 (m, 3 H, CH2, CHcPr),
2.10–2.20 (m, 2 H, CH2C=), 4.57 (d, J = 7.0 Hz, 2 H, CH2O), 5.36
(t, J = 7.0 Hz, 1 H, CH=) ppm.
1
8b: Colorless crystals; m.p. 62–63 °C (ref.[36] 65–66 °C). H NMR:
δ = 2.98 (d, J = 5.9 Hz, 1 H, OH), 4.80 (t, J = 5.9 Hz, 1 H, CHOH),
6.4 (dd, J = 5.9, 17.4 Hz, CH=), 6.92 (d, J = 17.4 Hz, 1 H,
PhCH=), 7.25–7.50 (m, 5 H, Ph) ppm.
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3d: Oil; nD = 1.4950. H NMR: δ = 1.15, 1.23, 1.32, 2.08 (4 s, 3
H, CH3), 1.55–1.82 (m, 6 H, 2ϫCH2, 2ϫCHcPr), 4.12 (ddd, J =
1.8, 7.3, 11.8 Hz, 1 H, CHHO), 4.26 (dd, J = 7.3, J = 11.8 Hz, 1
H, CHHO) ppm. 13C NMR: δ = 17.1, 20.8, 22.5, 23.9, 24.8, 28.4,
32.5, 35.7, 37.0, 37.9, 38.1, 38.2, 61.0 (CH2OAc), 69.6 (CCl2), 71.5
(CCl2), 170.6 (C=O) ppm. C14H20Cl4O2 (362.12): calcd. C 46.43,
H 5.57, Cl 39.16; found C 46.71, H 5.69, Cl 38.92.
8c: Oil; nD20 = 1.5100 (ref.[27] 1.5095). 1H NMR: δ = 1.60 1.68, 1.80
(3 s, 3 H, CH3), 2.15 (br. s, 4 H, 2ϫCH2), 2.78 (br. s, 1 H, OH),
4.80 (br. s, 1 H, CHOH), 5.09 (br. s, 1 H, CH=), 5.38 (d, J =
8.4 Hz, 1 H,=CH) ppm.
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2e: Oil; nD = 1.4575. 1H NMR: δ = 0.90 (d, J = 6.0 Hz, 3 H,
1
9a: Colorless crystals; m.p. 88–89 °C (ref.[37] 87.5 °C). H NMR: δ
CH3), 1.06 (t, J = 6.0 Hz, 1 H); 1.12, 1.30 (2 s, 1 H); 1.16 (t, J =
7.0 Hz, 6 H, 2ϫCH3), 1.35–1.50 (m, 5 H, 2ϫCH2, CH); 1.60–1.70
(m, 2 H, CH2); 3.43–3.55, 3.57–3.70 (2 m, 2 H, OCH2), 4.59 [t, J
= 5.8 Hz, 1 H, CH(OEt)2] ppm. C15H28Cl2O2 (311.29): calcd. C
57.88, H 9.07, Cl 22.78; found C 58.09, H 8.98, Cl 22.57.
= 2.25 (s, 3 H, CH3), 6.40 (s, 1 H, CH), 7.40 (m, 3 H, Ph), 7.63
(br. s, 2 H, Ph).
9b: Oil; nD = 1.4690 (ref.[28] 1.4705). H NMR: δ = 1.78 (d, J =
7.5 Hz, 3 H, CH3), 2.15 [s, 3 H, C(O)CH3], 5.60 (dd, J = 7.5,
15.8 Hz, 1 H, CH=), 5.77 (d, J = 7.5 Hz, 1 H, CHOAc), 6.03 (dq,
J = 7.5, 15.8 Hz, 1 H, CH=) ppm.
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2f: Oil; nD = 1.5040 (ref.[21] 1.5060). H NMR: δ = 1.03–1.20 (m,
1 H, CHcPr), 1.12, 1.30 (2 s, 3 H, CH3), 1.6–1.75 (m, 2 H, CH2),
1.98 [s, 1.2 H, CH3C=, (Z) isomer], 2.17 [s, 1.8 H, CH3C=, (E)
isomer], 2.25–2.40 [m, 0.8 H, CH2C=, (Z) isomer], 2.70 [t, J =
7.5 Hz, 1.2 H, CH2C=, (E) isomer], 5.87 [d, J = 8.2 Hz, 0.6 H,
CH=C, (E) isomer], 5.91 [d, J = 8.2 Hz, 0.4 H, CH=C, (Z) isomer],
9.95 [d, J = 8.2 Hz, 0.4 H, CH=O, (Z) isomer], 9.97 [d, J = 8.2 Hz,
0.6 H, CH=O, (E) isomer] ppm.
Regeneration of nBu4NPF6: Water (5 mL) was added to the solid
left after extractions of compounds 2, 3, and 7–9 with Et2O, the
precipitate was filtered, washed successively with water (3ϫ2 mL)
and Et2O (2ϫ2 mL), and then dried in air to afford nBu4NPF6
(33 mg, 85%); m.p. 242–246 °C (ref.[10a] 243–246 °C). 1H NMR
([D6]DMSO): δ = 1.00 (t, J = 7.5 Hz, 12 H, 4ϫCH3), 1.35, 1.60 (2
m, 8 H, 4ϫCH2), 3.15 (t, J = 7.5 Hz, 8 H, 4ϫCH2) ppm. 13C
NMR ([D6]DMSO): δ = 13.4 (CH3), 19.2, 23.0, 57.5 (3ϫCH2)
ppm. 19F NMR ([D6]DMSO): δ = –70.7 (d, JP,F = 708 Hz) ppm.
C16H36F6NP (387.43): calcd. C 49.60, H 9.37, F 29.42, N 3.62;
found C 49.35, H 9.54, F 29.18, N 3.71.
3f: Oil; nD = 1.4850 (ref.[21] 1.4885). H NMR: δ = 1.12–1.40 (m,
15 H, 5ϫCH3), 1.5–1.85 (m, 6 H, 2ϫCH2, CHcPr), 3.45–3.70 (m,
4 H, 2ϫCH2O), 4.37 [d, J = 7.8 Hz, 0.6 H, CH(OEt)2], 4.47, 4.50
[2 d, J = 7.8 Hz, 0.2 H, CH(OEt)2] ppm.
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2g: Oil; nD25 = 1.4490 (ref.[24] nD20 = 1.4519 for iPr ester). 1H NMR:
δ = 1.26 (t, J = 7.0 Hz, 3 H, CH3), 1.40 (dd, J = 7.5, 1.5 Hz, 1 H,
CHH), 1.57 (s, 3 H, CH3), 2.25 (dd, J = 7.5, 1.5 Hz, 1 H, CHH),
4.20 (q, J = 7.0 Hz, 2 H, CH2O) ppm.
nBu4NOH-Promoted Reaction between Cinnamaldehyde (5b) and
CHCl3: A solution of aldehyde 5b (0.66 g, 5.0 mmol) in CHCl3
(0.8 mL) was added to a solution of freshly prepared nBu4NOH
(1.30 g, 5.0 mmol) in PhH (8 mL). The reaction mixture was stirred
1
2h: Colorless crystals; m.p. 63–64 °C (ref.[15c] 64–65 °C). H NMR: at 20 °C for 6 h, diluted with Et2O (20 mL) and poured into water
δ = 1.0, 1.32, 1.38 (3 s, 3 H, CH3), 1.51 (d, J = 9.6 Hz, 1 H), 1.67– (20 mL). The organic phase was separated, washed with water
1.72 (m, 1 H), 1.98 (d, J = 11.7 Hz, 1 H), 2.00 (dtd, J = 13.1, 5.7,
2.3 Hz, 1 H), 2.12 (t, J = 5.7 Hz, 1 H), 2.23 (dddd, J = 13.1, 9.6,
3.5, 2.3 Hz, 1 H), 2.38 (d, J = 11.7 Hz, 1 H) ppm.
(3ϫ10 mL) and dried with anhydrous MgSO4. The solvents were
evaporated (40 °C, 40 Torr) to afford a mixture of compounds 5b
and 8b in a 53:47 ratio (1H NMR).
Eur. J. Org. Chem. 2008, 1777–1782
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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