Alkylation of Hydroquinone by Geraniol in the Presence ofAl(OPh) andAl(O-i-Pr) (General Method). Phenol
3
3
(0.08 g, 0.85 mmol) in a two-necked flask equipped with a thermometer and condenser was heated to 160°C. Aluminum chips
(0.008 g, 0.3 mmol) were added in small portions. After the Al was completely dissolved in the phenol, the solution was
cooled to 40°C and treated with 1 (1.0 g, 9 mmol) and the calculated amount of 2. If Al(O-i-Pr) was used, the reagents and
3
catalyst were added simultaneously. The reaction was performed at 120 or 160°C. The course of the reaction was monitored
by TLC. Then, the reaction mixture was separated by CC. Table 1 presents the conditions and yields of reaction products.
The spectral characteristics of 3 agreed with those in the literature [9].
–1
2-Methyl-2-(4-methylpent-3-enyl)chroman-6-ol (4), brown oil. IR spectrum (KBr, ꢃ, cm ): 3388 (ꢃꢄÎÍ phenol),
2970 and 2856 (ꢃ ÑÍ , ꢃ ÑÍ ), 1650 è 1616 (ꢃ Ñ=Ñ), 1494 and 1450 (ꢀ ÑÍ , ꢀ ÑÍ ), 1377 (ꢀ ÑÍ ), 1219 (ꢃꢄ=іΖÑ), 812
s
2
s
3
2
as
3
s
3
[10, 11].
1
Í NMR spectrum (300 MHz, CDCl , ꢀ, ppm, J/Hz): 1.31 (3Í, s, CH -7), 1.63 (3Í, s, CH -8), 1.71 (3Í, s, CH -1),
3
3
3
3
1.78–1.91 (4Í, m, Í-4, 5), 2.11–2.13 (2Í, m, Í-9), 2.74 (2Í, t, J = 6.9, Í-10), 4.58 (1Í, s, ÎÍ), 5.13–5.14 (1Í, m, Í-3),
13
6.58–6.71 (2Í, m, Í-13, 15), 6.81 (1Í, d, J = 8.7, Í-14). C NMR spectrum (75 MHz, CDCl , ꢀ, ppm): 17.59 (Ñ-8), 22.32
3
(C-4), 24.16 (C-1), 25.67 (Ñ-7), 30.99 (C-10), 39.29 (C-9), 39.57 (C-5), 75.69 (C-6), 114.48 (C-14), 115.42 (C-13), 117.88
(Ñ-16), 122.02 (Ñ-11), 124.28 (C-3), 131.60 (Ñ-2), 147.92 (Ñ-12), 148.46 (Ñ-15).
1
3,4,5,6-Tetrahydro-2-isopropyl-5-methyl-2,6-methano-2H-1-benzo[b]oxocin-10-ol (5), light-brown oil. Í NMR
spectrum (300 MHz, CDCl , ꢀ, ppm): 1.63 (6Í, s, CH -8, 9), 1.71 (3Í, s, CH -10), 1.78–1.83 (2Í, m, H-5), 2.12–2.13 (6Í,
3
3
3
13
m, 2Í-2, 6, 1Í-7, 4), 3.16–3.19 (1Í, m, Í-3), 4.73 (1Í, s, ÎÍ), 6.50–6.65 (3Í, m, 1Í-13, 15, 16). C NMR spectrum
(75 MHz, CDCl , ꢀ, ppm): 16.14 (Ñ-9, 8), 17.59 (C-10), 23.83 (C-4), 23.93 (Ñ-7), 24.15 (C-3), 25.68 (C-5), 27.54 (C-2),
3
29.56 (Ñ-6), 74.57 (C-1), 115.86 (C-13), 121.59 (C-15), 124.36 (Ñ-16), 138.06 (Ñ-12), 149.38 (C-11), 153.82 (Ñ-14).
1
2,6(5)-bis[(E)-3,7-Dimethylocta-2,6-dienyl]cyclohexa-2,5-diene-1,4-dione (6). a) Brown oil. Í NMR spectrum
(300 MHz, CDCl , ꢀ, ppm): 1.62 (6Í, s, CH -10, 10ꢅ), 1.63 (6Í, s, CH -8, 8ꢅ), 1.79 (6Í, s, CH -9, 9ꢅ), 2.07–2.13 (8Í, m,
3
3
3
3
H-5, 5ꢅ, 4, 4ꢅ), 3.12–3.15 (4Í, m, Í-1, 1ꢅ), 5.10–5.12 (1Í, m, Í-2ꢅ), 5.16–5.20 (1Í, m, Í-2), 6.54 (2Í, s, 1Í-14, 16).
13
C NMR spectrum (75 MHz, CDCl , ꢀ, ppm): 16.08 (Ñ-10, 10ꢅ), 17.70 (C-9, 9ꢅ), 25.68 (C-8, 8ꢅ), 26.39 (Ñ-5, 5ꢅ), 26.90
3
(C-1, 1ꢅ), 39.65 (C-4, 4ꢅ), 118.00 (C-2, 2ꢅ), 123.95 (Ñ-6, 6ꢅ), 131.80 (C-7, 7ꢅ), 132.46 (C-14, 16), 139.78 (C-3, 3ꢅ), 148.28
(Ñ-11, 13), 188.17 (Ñ-12, 15);
1
b) Brown oil. Í NMR spectrum (300 MHz, CDCl , ꢀ, ppm): 1.62 (6Í, s, CH -10, 10ꢅ), 1.63 (6Í, s, CH -8, 8ꢅ), 1.79
3
3
3
(6Í, s, CH -9, 9ꢅ), 2.07–2.13 (8Í, m, H-5, 5ꢅ, 4, 4ꢅ), 3.12–3.17 (4Í, m, Í-1, 1ꢅ), 5.10–5.12 (1Í, m, Í-2ꢅ), 5.16–5.20 (1Í, m,
3
13
Í-2), 6.48 (1Í, s, Í-13), 6.52 (1H, s, Í-16). C NMR spectrum (75 MHz, CDCl , ꢀ, ppm): 16.08 (Ñ-10, 10ꢅ), 17.70 (C-9, 9ꢅ), 25.69
3
(C-8, 8ꢅ), 26.45 (Ñ-5, 5ꢅ), 27.54 (C-1, 1ꢅ), 39.65 (C-4, 4ꢅ), 118.08 (C-2, 2ꢅ), 123.81 (Ñ-6, 6ꢅ), 131.78 (C-7, 7ꢅ), 132.15 (C-13), 132.28
(Ñ-16), 139.80 (C-3, 3ꢅ), 148.28 (Ñ-11), 148.59 (Ñ-14), 188.29 (Ñ-12, 15).
1
(E)-2-(3,7-Dimethylocta-2,6-dienyl)benzene-1,4-diol (7), brown oil. Í NMR spectrum (300 MHz, CDCl , ꢀ,
3
ppm, J/Hz): 1.64 (3Í, s, CH -8), 1.72 (3Í, s, CH -10), 1.79 (3Í, s, CH -9), 2.13–2.15 (4Í, m, H-4, 5), 3.34 (2H, d, J = 7.20,
3
3
3
Í-1), 4.64 (1Í, s, OH), 4.85 (1Í, s, ÎÍ), 5.11–5.13 (1H, m, Í-6), 5.31–5.35 (1H, m, Í-2), 6.60–6.73 (3Í, m, 1Í-13, 14, 16).
13
C NMR spectrum (75 MHz, CDCl , ꢀ, ppm): 16.20 (C-10), 17.73 (C-9), 25.71 (C-8), 26.45 (C-5), 29.76 (Ñ-1), 39.69 (C-4),
3
113.76 (C-16), 116.62 (C-13, 14), 121.31 (C-2), 123.86 (C-6), 128.32 (C-3), 131.82 (C-7), 138.69 (C-11), 148.24 (C-15),
149.32 (C-12).
1
2-(3,7-Dimethylocta-1,6-dien-3-yl)benzene-1,4-diol (8), brown oil. Í NMR spectrum (300 MHz, CDCl , ꢀ, ppm):
3
1.32 (3Í, s, CH -10), 1.62 (3Í, s, CH -8), 1.72 (3Í, s, CH -9), 2.09–2.12 (4Í, m, 2H-4, 5), 5.09–5.18 (3H, m, 1Í-6, 2Í-1),
3
3
3
13
5.22 (1Í, s, OH), 5.28 (1Í, s, ÎÍ), 5.90–6.00 (1H, m, Í-2), 6.51–6.79 (3Í, m, 1Í-13, 14, 16). C NMR spectrum (75 MHz,
CDCl , ꢀ, ppm): 16.62 (C-8), 25.70 (C-9, 10), 26.71 (C-5), 39.54 (Ñ-3), 42.05 (C-4), 111.77 (C-1), 112.57 (C-16), 115.94
3
(C-14), 116.57 (C-13), 123.92 (C-6), 130.54 (C-7), 131.98 (C-11), 144.95 (C-2), 147.32 (C-12), 149.95 (Ñ-15).
–1
4-[(2E,9E)-3,7,7,10,14-Pentamethylpentadeca-2,9,13-trienyloxy]phenol (9), brown oil. IR spectrum (KBr, ꢃ, cm ):
1612, 1585 è 1506 (ꢃ Ñ=Ñ, arom. ring), 1220 (ꢃ =Ñ–Î), 1448 and 1379 (=Ñ(ÑÍ ) ), 1664 (ꢃ Ñ=C, geranyl group), 823.
3 2
1
Í NMR spectrum (300 MHz, CDCl , ꢀ, ppm, J/Hz): 1.65 (6Í, s, CH -18, 19), 1.73 (6Í, s, CH -15, 16), 1.76 (6Í, s, CH -17,
3
3
3
3
20), 2.13–2.16 (12Í, m, H-4, 5, 6, 8, 11, 12), 4.52 (2Í, d, J = 6.6, Í-1), 5.13–5.18 (2H, m, Í-9, 13), 5.38 (1Í, s, OH),
13
5.61–5.65 (1H, m, Í-2), 6.60–6.86 (3Í, m, 1Í-23, 25, 26). C NMR spectrum (75 MHz, CDCl , ꢀ, ppm): 16.64 (C-20),
3
17.71 (C-15, 17), 22.74 (C-5), 25.69 (Ñ-18, 19), 25.98 (C-16), 26.33 (C-12), 32.42 (C-7), 39.48 (C-4), 39.56 (C-11), 40.87
(C-4), 40.92 (C-8), 65.73 (C-1), 116.08 (C-22, 26), 122.68 (C-2), 123.75 (C-13), 131.80 (Ñ-14), 134.01 (Ñ-10), 141.13 (Ñ-3),
149.66 (Ñ-21), 152.91 (Ñ-24).
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