range 70-230°C, 6°C/min, a flame-ionization detector, and He carrier gas. The course of the reactions was monitored by TLC
on Sorbfil plates. Plates were developed by KMnO solution and vanillin solution with subsequent heating to 100-150°C.
4
Column chromatography used silica gel 70/230 μm.
Alkylation of Phenol by Menthol in the Presence of Organoaluminium Catalysts. Phenol (0.60 g, 0.006 mol) and
menthol (1 g, 0.006 mol) were placed in a 100-mL two-necked flask equipped with a thermometer and reflux condenser and
heated in the presence of (PhO) Al or (i-PrO) Al (0.006 mol) until the conversion was complete (GC and TLC monitoring).
3
3
When the reaction was finished, the reaction mixture was cooled, diluted with diethylether, treated with dilute HCl solution to
decompose the aluminium alkoxide, and washed with NaOH solution (5%) and water until the rinsings were neutral. The
organic layer was dried over anhydrous Na SO . The solvent was evaporated.
2
4
The reaction products were separated by column chromatographyover silica gel 70/230 μm with elution by petroleum
ether:diethylether with increasing amounts of the latter to isolate the phenol alkylation products.
4-(2-(4-Methylcyclohexyl)propane-2-yl)phenol (1). IRspectrum (KBr, ν, cm−1): 3329(phenolνOH), 1612and1595
(benzene ν C=C), 1367 and 1382 (δ gem-dimethyl), 1450 (δ CH ), 1242 (δ OH), 1180 (benzene δ CH), 826 (p-substituted
s
as
3
benzene δ CH [13, 14].
PMR spectrum (300 MHz, CDCl , δ, ppm, J/Hz): 0.83-0.85 (d, J = 6, CH -7), 0.87-0.90 (m, 1H -3, 1H -5), 0.92-0.95
3
e
e
3
(m, 1H -2, 1H -6), 0.96-0.97 (m, 1H-4), 1.24 (s, CH -10, CH -9), 1.31-1.40 (tt, J - 3, 11, 1H-1), 4.9 (s, 1H, OH), 6.7-6.79 (d,
e
e
3
3
J = 9, 2H-13,15), 7.17-7.20 (d, J = 9, 2H-12,16).
13
C NMR spectrum (75 MHz, CDCl ): 21.6 (C-7), 25.5 (C-10,9), 27.7 (C-3,5), 32.8 (C-1), 35.8 (C-2,6), 49.6 (C-4),
3
51.7 (C-8), 114.5 (C-13,15), 127.3 (C-12,16), 142.7 (C-11), 152.9 (C-14).
2-(2-(4-Methylcyclohexyl)propane-2-yl)phenol (2). PMR spectrum (300 MHz, CDCl , δ, ppm, J/Hz): 0.79-0.81 (d,
3
J = 6, CH -7), 0.88-1.0 (m, 1H -3, 1H -5), 1.15-1.24 (m, 1H-1), 1.18-1.3 (m, 1H -2, 1H -6), 1.34 (s, CH -10, CH -9), 1.43-1.48
3
e
e
e
e
3
3
(m, 1H -2, 1H -6), 1.63-1.68 (m, 1H -3, 1H -5), 2.05-2.15 (tt, J = 11.7, 2.7, 1H-4), 4.74 (s, 1H, OH), 6.64-6.67 (dd, J = 7.83,
a
a
a
a
1.28, 1H-13), 6.85-6.90 (dt, J = 7.55, 1.26, 1H-15), 7.05-7.10 (dt, J = 7.76, 1.62, 1H-14), 7.19-7.22 (dd, J = 7.78, 1.56, 1H-12).
13
C NMRspectrum (75 MHz, CDCl ): 22.3 (C-7), 24.3 (C-9), 24.4 (C-10), 28.0 (C-3,5), 33.0 (C-1), 35.9 (C-2,6), 40.7
3
(C-7), 43.6 (C-4), 116.6 (C-15), 120.3 (C-13), 126.7 (C-12), 128.5 (C-14), 135.9 (C-11), 159.9 (C-16).
2-(2-(3-Methylcyclohexyl)propane-2-yl)phenol (3). PMR spectrum (300 MHz, CDCl , δ, ppm, J/Hz): 0.87-0.88 (d,
3
J = 5, CH -10), 1.02-1.09 (m, 1H -3, 1H -2), 1.22-1.24 (m, 1H -5), 1.27-1.28 (m, 1H-1), 1.34-1.35 (m, 1H -6), 1.39 (s, CH -
3
e
e
e
e
3
8,9), 1.46-1.49 (m, 1H -6), 1.59-1.69 (m, 1H -5), 1.94-1.96 (d, J = 6, 1H -2), 4.73 (s, 1H, OH), 6.63-6.65 (dd, J = 7.83, 1.28,
a
a
a
1H-13), 6.87-6.90 (d, J = 7.55, 1.26, 1H-15), 7.05-7.08 (dt, J = 7.76, 1.62, 1H-14), 7.24-7.7 (dd, J = 7.78, 1.56, 1H-12).
13
C NMR spectrum (75 MHz, CDCl ): 21.10 (C-10), 29.00 (C-9,8), 32.90 (C-6), 34.10 (C-2), 35.9 (C-4), 37.90 (C-3),
3
38.2 (C-5), 44.20 (C-7), 47.2 (C-1), 116.3 (C-13), 120.5 (C-15), 126.9 (C-12), 128.1 (C-14), 135.0 (C-11), 154.2 (C-16).
(2-Isopropyl-5-methylcyclohexyl)phenol (4). PMR spectrum (300 MHz, CDCl , δ, ppm, J/Hz): 0.69-0.71 (d, J = 6,
3
CH -10), 0.81-0.83 (d, J = 6, CH -9), 0.89-0.91 (d, J = 6, CH -7), 1.01-1.05 (m, 1H-1), 1.06-1.11 (m, 1H -2), 1.17-1.22 (m,
3
3
3
a
1H -6, 1H -6), 1.38-1.40 (m, 1H -2), 1.51-1.53 (m, 1H -4, 1H-8), 1.80-1.85 (m, 1H -5, 1H -5), 2.88-2.96 (t, J = 12, 1H -3),
a
e
e
a
a
e
a
4.68 (s, 1H, OH), 6.74-6.76 (m, 1H-15), 6.89-6.94 (m, 1H-14), 7.02-7.07 (m, 1H-13), 7.14-7.17 (m, 1H-12).
13
C NMR spectrum (75 MHz, CDCl ): 15.8 (C-7), 19.9 (C-9), 21.6 (C-10), 24.7 (C-5), 27.5 (C-1), 33.3 (C-3), 35.3
3
(C-6), 44.6 (C-2), 46.8 (C-4), 115.3 (C-15), 121.0 (C-13), 126.2 (C-14), 126.7 (C-12), 127.4 (C-11), 155.6 (C-16).
(2-Isopropyl-5-methylcyclohexyloxy)benzene (5). PMR spectrum (300 MHz, CDCl , δ, ppm, J/Hz): 0.75-0.77 (d,
3
J = 6, CH -7), 0.89-0.91 (s, CH -10), 0.94-0.96 (d, CH -9), 0.98-0.99 (m, 1H -6), 1.02-1.03 (m, 1H -2) 1.10-1.12 (m, 1H -5),
3
3
3
e
e
a
1.25-1.27 (m, 1H -1), 1.46-1.54 (tt, J = 3, 6.6, 1H-2), 1.68-1.70 (m, 1H -6), 1.73-1.74 (1H -5), 2.18-2.22 (m, 1H -2), 2.23-2.27
e
e
e
a
(m, 1H -8), 4.00-4.07 (dt, J = 6, 10, 1H-3), 6.90-6.95 (m, 1H-12,14,16), 7.25-7.30 (m, 1H-13,15).
a
13
C NMR spectrum (75 MHz, CDCl ): 16.5 (C-7), 21.3 (C-9), 22.5 (C-10), 23.7 (C-5), 26.0 (C-8), 34.5 (C-6), 31.4
3
(C-1), 40.3 (C-2), 48.1 (C-4), 74.4 (C-3), 115.8 (C-12,16), 120.4 (C-14), 129.4 (C-13,15).
Mixture of Δ2- and Δ3-p-methenes (6). IRspectrum (KBr, ν, cm−1): 2951 and 2924 (ν CH , CH ), 1597 (ν CH=CH),
3
2
1367 and 1382 (gem-dimethyl δ ), 1450 (δ CH ), 1375 (gem-dimethyl δ CH).
s
as
3
PMR spectrum (300 MHz, CDCl , δ, ppm, J/Hz): 0.89-0.91 (d, J = 6, CH -10, CH -9), 0.93-0.95 (d, J = 6, CH -10′,
3
3
3
3
CH -9′), 0.98-1.00 (d, J = 6, CH -7, CH -7′), 1.23-1.27 (m, 2H-5, 2H-6, 2H-5′, 2H-6′), 1.53-1.67 (m, 1H-8,8′), 1.97-2.18 (m,
3
3
3
1H-1,1′), 5.36-5.37 (m, 1H-3′), 5.53 (s, 1H-2, 1H-3).
453