Synthesis of prenylacetic acids in ionic liquids
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 3, March, 2004
657
Diethyl isopentylmalonate (7a) (see Ref. 24), b.p. 125—127 °C
(s, COMe (10с)); 2.24 (s, =CMe (11с)); 3.30 (t, CH (10с), J =
7.5 Hz); 3.74 (t, OCH2 (11с), J = 7.5 Hz); 4.16 (m, 2 H, CH2);
4.96 (s, =CH (11с)); 5.04 (t, 1 H, =CH, J = 7.0 Hz).
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(10 Torr); nD 1.4215. 1H NMR (CDCl3), δ: 0.82 (d, 6 H,
2 Me, J = 6.0 Hz); 1.10—1.25 (m, 2 H, CH2); 1.20 (t, 6 H,
2 Me, J = 7.0 Hz); 1.50 (m, 1 H, CH); 1.76 (m, 2 H, CH2); 3.35
(t, 1 H, CH, J = 7.5 Hz); 4.16 (q, 4 H, 2 CH2, J = 7.0 Hz).
Diethyl 3ꢀmethylbutꢀ2ꢀenylmalonate (7b) (see Ref. 24), b.p.
120—122 °C (10 Torr); nD20 1.4410. 1H NMR (CDCl3), δ: 1.22
(t, 6 H, 2 Me, J = 7.0 Hz); 1.58, 1.64 (both s, 3 H each, Me);
2.55 (t, 2 H, CH2, J = 7.5 Hz); 3.26 (t, 1 H, CH, J = 7.5 Hz);
4.14 (q, 4 H, 2 CH2, J = 7.0 Hz); 5.02 (t, 1 H, =CH, J = 7.0 Hz).
Diethyl 3,7ꢀdimethyloctꢀ6ꢀenylmalonate (7с) (see Ref. 24),
b.p. 120—122 °C (0.5 Torr); nD20 1.4500. 1H NMR (CDCl3), δ:
0.92 (d, 3 H, Me, J = 6.0 Hz); 1.24 (t, 6 H, 2 Me, J = 7.0 Hz);
1.60, 1.66 (both s, 3 H each, Me); 1.05—1.45 (m, 7 H);
1.80—2.00 (m, 2 H); 3.24 (t, 1 H, CH, J = 7.5 Hz); 4.16 (q, 4 H,
2 CH2, J = 7.0 Hz); 5.06 (t, 1 H, =CH, J = 7.0 Hz).
Ethyl 2ꢀacetylꢀ5,9ꢀdimethyldecaꢀ4,8ꢀdienoate (10d) (see
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1
Ref. 30), b.p. 120—125 °C (0.2 Torr); nD 1.4675. H NMR
(CDCl3), δ: 1.28 (t, 3 H, Me, J = 7.0 Hz); 1.58, 1.62, 1.68 (all s,
3 H each, Me); 2.00 (m, 4 H, 2 CH2); 2.22 (s, 3 H, Me); 2.55 (t,
2 H, CH2, J = 7.5 Hz); 3.42 (t, 1 H, CH, J = 7.5 Hz); 4.18 (q,
4 H, 2 CH2, J = 7.0 Hz); 5.04 (m, 2 H, 2 CH=).
Diethyl [(2E)ꢀ3,7ꢀdimethyloctaꢀ2,6ꢀdienyl](cyclohexyl)maꢀ
lonate (14) (see Refs. 4, 5), b.p. 150—155 °C (0.2 Torr);
nD20 1.4645. 1H NMR (CDCl3), δ: 0.85—1.00 (m, 4 H, 2 CH2);
1.25 (t, 6 H, 2 Me, J = 7.0 Hz); 1.30—1.40 (m, 2 H, CH2);
1.55—1.75 (m, 4 H, 2 CH2); 1.60, 1.62, 1.68 (all s, 3 H, Me);
1.90—2.10 (m, 6 H, 3 CH2); 2.65 (m, 1 H, CH); 4.12 (q, 4 H,
2 CH2, J = 7.0 Hz); 5.10 (m, 2 H, 2 CH=).
Diethyl [(2E)ꢀ3,7ꢀdimethyloctaꢀ2,6ꢀdienyl]malonate (7d) (see
Diethyl [3ꢀ(dimethylamino)propyl][(2E)ꢀ3,7ꢀdimethyloctaꢀ
2,6ꢀdienyl]malonate (15) (see Refs. 10, 11), b.p. 145—148 °C
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Ref. 24), b.p. 130—135 °C (0.8 Torr); nD 1.4610. H NMR
(CDCl3), δ: 1.26 (t, 6 H, 2 Me, J = 7.0 Hz); 1.58, 1.62, 1.68
(all s, 3 H each, Me); 2.00 (m, 4 H, 2 CH2); 2.60 (t, 2 H, CH2,
J = 7.50 Hz); 3.32 (t, 1 H, CH, J = 7.50 Hz); 4.18 (q, 4 H,
2 CH2, J = 7.0 Hz); 5.10 (m, 2 H, 2 CH=).
(0.2 Torr); nD 1.4660. 1H NMR (CDCl3), δ: 1.29 (t, 6 H,
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2 Me, J = 7.0 Hz); 1.25—1.35 (m, 2 H, CH2); 1.54, 1.57, 1.63
(all s, 3 H each, Me); 1.75—1.85, 1.90—2.05 (both m, 8 H,
4 CH2); 2.58 (m, 2 H, CH2); 4.12 (q, 4 H, 2 CH2, J = 7.0 Hz);
5.00 (m, 2 H, 2 CH=).
Ethyl 2ꢀcyanoꢀ5ꢀmethylhexanoate (8a) (see Ref. 24), b.p.
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106—108 °C (6 Torr); nD 1.4310. H NMR (CDCl3), δ: 0.92
(d, 6 H, 2 Me, J = 6.0 Hz); 1.10—1.20 (m, 2 H, CH2); 1.28 (t,
3 H, Me, J = 7.0 Hz); 1.60 (m, 1 H, CH); 1.95 (m, 2 H, CH2);
3.48 (t, 1 H, CH, J = 7.5 Hz); 4.28 (q, 2 H, 2 CH2, J = 7.0 Hz).
Ethyl 2ꢀcyanoꢀ5ꢀmethylhexꢀ4ꢀenoate (8b) (see Ref. 25), b.p.
A mixture of ethyl (4E)ꢀ2ꢀacetylꢀ2ꢀcyclohexylꢀ5,9ꢀdimethylꢀ
decaꢀ4,8ꢀdienoate (16) and ethyl (4E)ꢀ2ꢀ[1ꢀ(cyclohexyloxy)ethylꢀ
idene]ꢀ5,9ꢀdimethyldecaꢀ4,8ꢀdienoate (17), b.p. 147—150 °C
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(0.2 Torr); nD 1.4680. Found (%): C, 75.64; H, 10.33.
C22H36O3. Calculated (%): C, 75.82; H, 10.41. A mixture of
isomers 16 and 17 was separated into components on a column
with SiO2 using a light petroleum—benzene mixture as the eluꢀ
ent (5% PhH for 17, 10% PhH for 16) to give (in the order of
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110—112 °C (6 Torr); nD 1.4470. H NMR (CDCl3), δ: 1.30
(t, 3 H, Me, J = 7.0 Hz); 1.65, 1.70 (both s, 3 H each, Me); 2.60
(t, 2 H, CH2, J = 7.5 Hz); 3.46 (t, 1 H, CH, J = 7.5 Hz); 4.22 (q,
2 H, CH2, J = 7.0 Hz); 5.12 (t, 1 H, CH=, J = 7.0 Hz).
Ethyl 2ꢀcyanoꢀ5,9ꢀdimethyldecaꢀ4,8ꢀdienoate (8d) (see Ref.
25), b.p. 120—124 °C (0.3 Torr); nD20 1.4685. 1H NMR (CDCl3),
δ: 1.32 (t, 3 H, Me, J = 7.0 Hz); 1.60, 1.68, 1.76 (all s, 3 H each,
Me); 2.06 (m, 4 H, 2 CH2); 2.66 (t, 2 H, CH2, J = 7.5 Hz); 3.46
(t, 1 H, CH, J = 7.5 Hz); 4.25 (q, 2 H, CH2, J = 7.0 Hz);
5.10—5.20 (m, 2 H, 2 CH=).
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elution): (1) compound 17, colorless oil, H NMR (CDCl3), δ:
0.85—0.95 (m, 4 H, 2 CH2); 1.28 (t, 3 H, Me, J = 7.0 Hz);
1.30—1.40 (m, 2 H, CH2); 1.55—1.75 (m, 4 H, 2 CH2); 1.62,
1.65, 1.70 (all s, 3 H each, Me); 1.90—2.10 (m, 6 H, 3 CH2);
2.35 (d, 3 H, =CMe, J = 1.5 Hz); 3.65 (m, 1 H, OCH); 4.16 (q,
2 H, CH2, J = 7.0 Hz); 5.10 (m, 2 H, 2 CH=); (2) compound 16,
colorless oil, 1H NMR (CDCl3), δ: 0.85—0.95 (m, 4 H, 2 CH2);
1.28 (t, 3 H, Me, J = 7.0 Hz); 1.30—1.40 (m, 2 H, CH2);
1.55—1.75 (m, 4 H, 2 CH2); 1.62, 1.65, 1.70 (all s, 3 H each,
Me); 1.90—2.10 (m, 7 H, 3 CH2, CH); 2.08 (s, COMe); 4.16 (q,
2 H, CH2, J = 7.0 Hz); 5.10 (m, 2 H, 2 CH=).
Ethyl 5ꢀmethylꢀ2ꢀcyanoꢀ2ꢀ(3ꢀmethylbutꢀ2ꢀenyl)hexꢀ4ꢀenoate
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(9b) (see Ref. 26), b.p. 135—137 °C (6 Torr); nD 1.4625.
1H NMR (CDCl3), δ: 1.28 (t, 3 H, Me, J = 7.0 Hz); 1.62, 1.70
(both s, 6 H each, 2 Me); 2.50 (m, 4 H, 2 CH2); 4.20 (q, 2 H,
CH2, J = 7.0 Hz); 5.18 (t, 2 H, 2 CH=, J = 7.0 Hz).
A mixture of ethyl (4E)ꢀ2ꢀacetylꢀ2ꢀ[3ꢀ(dimethylamino)proꢀ
pyl]ꢀ5,9ꢀdimethyldecaꢀ4,8ꢀdienoate (18) and (4E)ꢀ2ꢀ{1ꢀ[3ꢀ(diꢀ
methylamino)propoxy]ethylidene}ꢀ5,9ꢀdimethyldecaꢀ4,8ꢀdienoate
A mixture of ethyl 2ꢀacetylꢀ5ꢀmethylhexanoate (10a) and ethyl
3ꢀisopentyloxybutꢀ2ꢀenoate (11a) (see Ref. 27), b.p. 122—125 °C
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(10 Torr); nD 1.4350. H NMR (CDCl3), δ: 0.88 (m, 6 H,
2 Me); 1.15—1.25 (m, 2 H, CH2); 1.28 (t, 3 H, Me, J = 7.0 Hz);
1.55 (m, 1 H, CH); 1.85 (m, CH2); 2.20 (s, COMe (10a));
2.28 (s, =CMe (11a)); 3.35 (t, CH (10a), J = 7.5 Hz); 3.76
(t, OCH2 (11a), J = 7.5 Hz); 4.15 (m, 2 H, CH2); 5.00
(s, =CH (10a)).
(19) (see Ref. 39), b.p. 158—162 °C (0.1 Torr); nD 1.4760.
A mixture of isomers 18 and 19 was separated into components
on a column with SiO2 using a CHCl3—MeOH mixture as the
eluent (2% MeOH for 19, 5% MeOH for 18) to give (in the
1
order of elution) (1) compound 19, pale yellow oil, H NMR
(CDCl3) δ: 1.28 (t, 3 H, Me, J = 7.0 Hz); 1.58, 1.62, 1.68 (all s,
3 H each, Me); 1.80—1.90, 1.90—2.10 (both m, 4 H each,
2 CH2); 2.20 (s, 6 H, 2 Me); 2.26 (s, =CMe); 2.60 (m, 2 H,
CH2); 3.95 (t, OCH2, J = 7.5 Hz); 4.18 (q, 2 H, CH2, J =
7.0 Hz); 4.90 (m, 1 H, CH=); 5.10 (m, 1 H, CH=); (2) comꢀ
Ethyl 2ꢀacetylꢀ5ꢀmethylhexꢀ4ꢀenoate (10b) (see Ref. 29), b.p.
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114—116 °C (12 Torr); nD20 1.4462. H NMR (CDCl3), δ: 1.22
(t, 3 H, Me, J = 7.0 Hz); 1.58, 1.64, 2.20 (all s, 3 H each, Me);
2.50 (t, 2 H, CH2, J = 7.5 Hz); 3.38 (t, 1 H, CH, J = 7.5 Hz);
4.14 (q, 4 H, 2 CH2, J = 7.0 Hz); 5.00 (t, 1 H, =CH, J = 7.0 Hz).
A mixture of ethyl 2ꢀacetylꢀ5,9ꢀdimethyldecꢀ8ꢀenoate (10с)
and 3ꢀ[(3,7ꢀdimethyloctꢀ6ꢀenyl)oxy]butꢀ2ꢀenoate (11с) (see
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pound 18, pale yellow oil, H NMR (CDCl3), δ: 1.28 (t, 3 H,
Me, J = 7.0 Hz); 1.58, 1.62, 1.68 (all s, 3 H each, Me);
1.70—1.80, 1.85—2.00 (both m, 4 H each, 2 CH2); 2.12
(s, COMe); 2.20 (s, 6 H, 2 Me); 2.20—2.25, 2.50 (both m,
2 H each, CH2); 4.18 (q, 2 H, CH2, J = 7.0 Hz); 4.90, 5.10
(both m, CH=).
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Ref. 28), b.p. 120—122 °C (0.5 Torr); nD 1.4500. H NMR
(CDCl3), δ: 0.82 (m, 3 H, Me); 1.00—1.90 (m, CH2, CH); 1.22
(t, 3 H, Me, J = 7.0 Hz); 1.55, 1.63 (both s, 3 H each, Me); 2.18