650
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 3, March, 2004
Kryshtal et al.
Table 3. Refractive indices (nD20), 1H NMR data, and elemental analysis data for compounds 7, 11, and 13
20
Comꢀ
pound
Molecular
formula
nD
1H NMR (CDCl3), δ, J/Hz
Found
Calculated
(%)
H
C
7
C20H32O5
C21H34O5
C20H32O4
1.4815
1.4940
1.4985
1.23 (t, 6 H, Me, J = 7.0); 1.55—1.70 (m, 9 H, MeC=); 1.90—2.05
(m, 4 H, CH2); 2.10—2.20, 2.40—2.45, 2.55—2.62 (all m, 2 H each,
CH2); 4.15 (q, 4 H, CH2O, J = 7.0); 4.90—5.10 (m, 2 H, CH=);
9.70 (s, 1 H, CHO)
0.97 (d, 3 H, Me, J = 7.0); 1.25 (t, 6 H, Me, J = 7.0); 1.60—1.70
(m, 9 H, MeC=); 1.90—2.10 (m, 4 H, CH2); 2.15—2.25 (m, 1 H, CH);
2.60—2.70 (m, 2 H, CH2); 2.80—2.90 (m, 2 H, CH2); 4.15 (q, 4 H,
CH2O, J = 7.0); 5.05—5.15 (m, 2 H, CH=); 9.72 (s, 1 H, CHO)
0.96 (d, 3 H, Me, J = 7.0); 1.22 (t, 3 H, Me, J = 7.0); 1.50—1.60
(m, 9 H, MeC=); 1.90—2.00 (m, 4 H, CH2); 2.00—2.15 (m, 1 H, CH);
2.10 (s, 3 H, MeCO); 2.25—2.35 (m, 2 H, CH2); 2.50—2.60 (m, 2 H,
CH2); 4.12 (q, 2 H, CH2O, J = 7.0); 5.05—5.15 (m, 2 H, CH=);
9.65 (s, 1 H, CHO)
68.43
68.15
8.94
9.15
11
13*
68.65
68.82
9.18
9.35
71.02
71.39
9.71
9.59
* Compound 13 was formed as a mixture of diаstereomers.
(10 mmol), metal carbonate (10 mmol), an aldehyde (10 mmol),
and [bmim][PF6]16a (14.2 g, 50 mmol) was vigorously stirred
and sonicated if indicated under conditions given in Tables 1
and 2 and the products were extracted with Et2O (3×3 mL). The
combined ethereal extracts were washed with water (2 mL) and
dried with anhydrous MgSO4. The solvent was removed under
reduced pressure, compounds 6, 8, 10, and 12 were distilled
in vacuo (1 Torr), and compounds 7, 9, 11, and 13—16 were
chromatographed on a column with SiO2 (elution with a light
petroleum—benzene mixture, 80 : 20). The physicochemical
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 03ꢀ03ꢀ32659)
and by the Russian Academy of Sciences (the Fundaꢀ
mental Research Program of the Presidium of the RAS).
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20
1
characteristics (nD and H NMR parameters) of compounds
6, 8—10, 12, and 14—16 correspond to published data.6,14b The
characteristics of newly synthesized compounds 7, 11, and 13
are listed in Table 3.
Reactions of CHꢀacids with α,βꢀunsaturated aldehydes in the
K2CO3/PhH/[bmim][Br] system (general procedure). Reactions
of CHꢀacids (10 mmol) with aldehydes (10 mmol) in benꢀ
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and [bmim][Br]16b (0.22 g, 1 mmol) were carried out as deꢀ
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[bmim][PF6].
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products with Et2O (see Table 1), the ionic liquid [bmim][PF6]
was filtered to remove inorganic salts, washed with water (5 mL),
and kept for 2 h at 60 °C in vacuo (2 Torr) to give 97—99% of a
paleꢀyellow liquid identical, according to 1H, 31P, and 19F NMR
in acetoneꢀd6, to the freshly prepared salt [bmim][PF6].
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7.5 Hz); 1.89 (quint, 2 H, J = 7.5 Hz); 4.00 (s, 3 H); 4.3 (t, 2 H,
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J = 7.5 Hz); 7.62, 7.68 (both d, 1 H each, J = 1.8 Hz); 8.82 (s,
1
1 H). 31P NMR (relative to H3PO4), δ: –142.4 (sept, JP,F
=
=
1
708 Hz). 19F NMR (relative to CFCl3), δ: –71.0 (d, JP,F
708 Hz).