3.3. Characterization Data for Thymol Derivatives 2–39
2-ethoxy-1-isopropyl-4-methylbenzene (2): colourless oil, 75% yield. 1H-NMR (400 MHz, CDCl3): δ 1.26–1.28 (m, 6H, 2 × CH3), 1.46–1.50 (m, 3H, CH3), 2.38 (s, 3H, ArCH3), 3.31–3.41 (m, 1H, CH), 4.06–4.11 (m, 2H, OCH2), 6.72 (s, 1H, Ar), 6.79 (d, J = 8.0 Hz, 1H, Ar), 7.15 (d, J = 8.0 Hz, 1H, Ar). 13C-NMR (101 MHz, CDCl3): δ 15.0 (CH3), 15.9 (ArCH3), 24.1 (2 × CH3), 34.2 (CH), 63.5 (OCH2), 109.6 (Ar), 117.9 (Ar), 124.1 (Ar), 130.4 (Ar), 147.8 (Ar), 157.1 (Ar). Anal. Calcd for C12H18O: C, 80.85; H, 10.18. Found: C, 80.79; H, 10.13.
1-isopropyl-4-methyl-2-propoxybenzene (3): colourless oil, 72% yield. 1H-NMR (300 MHz, CDCl3): δ 1.38–1.43 (m, 3H, CH3), 1.58 (d, J = 7.2 Hz, 6H, 2 × CH3), 2.10–2.19 (m, 2H, CH2), 2.66 (s, 3H, ArCH3), 3.64–3.71 (m, 1H, CH), 4.21–4.25 (m, 2H, OCH2), 6.99 (s, 1H, Ar), 7.06 (d, J = 8.1 Hz, 1H, Ar), 7.43 (d, J = 7.5 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 11.1 (CH3), 21.6 (ArCH3), 23.1 (CH2), 23.2 (2 × CH3), 27.0 (CH), 69.6 (OCH2), 112.3 (Ar), 121.2 (Ar), 126.1 (Ar), 134.3 (Ar), 136.4 (Ar), 156.5 (Ar). Anal. Calcd for C13H20O: C, 81.20; H, 10.48. Found: C, 81.20; H, 10.45.
2-(allyloxy)-1-isopropyl-4-methylbenzene (4): colourless oil, 64% yield. 1H-NMR (300 MHz, CDCl3): δ 1.54 (d, J = 6.6 Hz, 6H, 2 × CH3), 2.61 (s, 3H, ArCH3), 3.62–3.72 (m, 1H, CH), 4.77–4.80 (m, 2H, OCH2), 5.52–5.56 (m, 1H, =CH2), 5.70–5.77 (m, 1H, =CH2), 6.30–6.41 (m, 1H, =CH), 6.94 (s, 1H, Ar), 7.04 (d, J = 7.8 Hz, 1H, Ar), 7.40 (d, J = 8.1 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.6 (ArCH3), 23.0 (2 × CH3), 26.9 (CH), 68.9 (OCH2), 112.8 (Ar), 116.8 (=CH2), 121.6 (Ar), 126.8 (Ar), 134.0 (=CH), 134.5 (Ar), 136.4 (Ar), 156.0 (Ar). Anal. Calcd for C13H18O: C, 82.06; H, 9.54. Found: C, 82.03; H, 9.55.
1-isopropyl-4-methyl-2-(prop-2-yn-1-yloxy)benzene (5): colourless oil, 82% yield. 1H-NMR (300 MHz, CDCl3): δ 1.57–1.60 (m, 6H, 2 × CH3), 2.67 (s, 3H, ArCH3), 2.74 (t, J = 2.4 Hz, 1H, ≡CH), 3.67–3.70 (m, 1H, CH), 4.93–4.95 (m, 2H, OCH2), 7.09 (s, 1H, Ar), 7.13 (d, J = 8.4 Hz, 1H, Ar), 7.44–7.48 (m, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.6 (ArCH3), 23.2 (2 × CH3), 26.8 (CH), 56.2 (OCH2), 75.5 (≡CH), 79.5 (C≡), 113.3 (Ar), 122.6 (Ar), 126.4 (Ar), 134.9 (Ar), 136.4 (Ar), 155.1 (Ar). Anal. Calcd for C13H16O: C, 82.94; H, 8.57. Found: C, 82.97; H, 8.60.
2-(2-isopropyl-5-methylphenoxy)acetonitrile (6): white sticky solid, 72% yield. 1H-NMR (300 MHz, CDCl3): δ 1.23–1.25 (m, 6H, 2 × CH3), 2.38 (s, 3H, ArCH3), 3.28–3.30 (m, 1H, CH), 4.77–4.78 (s, 2H, OCH2), 6.75 (s, 1H, Ar), 6.91 (d, J = 7.8 Hz, 1H, Ar), 7.19 (d, J = 7.5 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.3 (ArCH3), 22.9 (2 × CH3), 26.5 (CH), 53.9 (OCH2), 112.9 (Ar), 115.5 (CN), 123.8 (Ar), 126.7 (Ar), 135.0 (Ar), 136.8 (Ar), 153.8 (Ar). Anal. Calcd for C12H15NO: C, 76.16; H, 7.99; N, 7.40. Found: C, 76.20; H, 8.03; N, 7.37.
1-(2-isopropyl-5-methylphenoxy)propan-2-one (7): amber-yellow oil, 90% yield. 1H-NMR (300 MHz, CDCl3): δ 1.30 (d, J = 7.2 Hz, 6H, 2 × CH3), 2.35–2.36 (m, 6H, CH3 + ArCH3), 3.29–3.43 (m, 1H, CH), 4.54 (s, 2H, OCH2), 6.55 (s, 1H, Ar), 6.84 (d, J = 7.8 Hz, 1H, Ar), 7.18 (d, J = 7.5, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.3 (ArCH3), 22.8 (2 × CH3), 26.7 (CH3), 26.8 (CH), 73.2 (OCH2), 112.0 (Ar), 122.3 (Ar), 126.3 (Ar), 134.1 (Ar), 136.5 (Ar), 154.8(Ar), 206.6 (C=O). Anal. Calcd for C13H18O2: C, 75.69; H, 8.80. Found: C, 75.72; H, 8.77.
2-(2-isopropyl-5-methylphenoxy)acetic acid(8): white solid, 87% yield, mp = 143–145 °C. 1H-NMR (300 MHz, CDCl3): δ 1.23 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.32 (s, 3H, ArCH3), 3.32–3.37 (m, 1H, CH), 4.69 (s, 2H, OCH2), 6.57 (s, 1H, Ar), 6.82 (d, J = 7.5 Hz, 1H, Ar), 7.14 (d, J = 7.5 Hz, 1H, Ar), 8.40 (bs, 1H, COOH). 13C-NMR (75 MHz, CDCl3): δ 21.3 (ArCH3), 22.8 (2 × CH3), 26.6 (CH), 65.2 (OCH2), 112.4 (Ar), 122.7 (Ar), 126.4 (Ar), 134.5 (Ar), 136.5 (Ar), 154.5 (Ar), 174.9 (CO). Anal. Calcd for C12H16O3: C, 69.21; H, 7.74. Found: C, 69.27; H, 7.77.
2-butoxy-1-isopropyl-4-methylbenzene (9): colourless oil, 75% yield. 1H-NMR (300 MHz, CDCl3) δ 1.27–1.32 (m, 3H, CH3), 1.53 (d, J = 6.3 Hz, 6H, 2 × CH3), 1.77–1.90 (m, 2H, CH2), 2.04–2.13 (m, 2H, CH2), 2.62 (s, 3H, ArCH3), 3.59–3.68 (m, 1H, CH), 4.21–4.25 (m, 2H, O CH2), 6.96 (s, 1H, Ar), 7.02 (d, J = 7.5 Hz, 1H, Ar), 7.39 (d, J = 7.5 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 14.1 (CH3), 19.8 (CH2), 21.6 (ArCH3), 23.0 (2 × CH3), 26.9 (CH), 31.9 (CH2), 67.6 (OCH2), 112.3 (Ar), 121.1 (Ar), 126.0 (Ar), 134.2 (Ar), 136.4 (Ar), 156.5 (Ar). Anal. Calcd for C14H22O: C, 81.50; H, 10.75. Found: C, 81.55; H, 10.83.
2-(but-2-en-1-yloxy)-1-isopropyl-4-methylbenzene (10): pale yellow oil, 81% yield. 1H-NMR (300 MHz, CDCl3): δ 1.47 (d, J = 7.2 Hz, 6H, 2 × CH3), 1.98–2.00 (m, 3H, =CH3), 2.56 (s, 3H, ArCH3), 3.57–3.61 (m, 1H, CH), 4.66–4.69 (d, 2H, OCH2), 5.95–6.06 (m, 2H, 2 × =CH), 6.90 (s, 1H, Ar), 6.98 (d, J = 7.5 Hz, 1H, Ar), 7.34 (d, J = 7.8 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 18.1 (CH3), 21.5 (ArCH3), 23.0 (2 × CH3), 26.8 (CH), 68.9 (OCH2), 112.9 (Ar), 121.4 (Ar), 126.1 (=CH), 127.0 (Ar), 129.1 (=CH), 134.5 (Ar), 136.3 (Ar), 156.1 (Ar). Mixture of E/Z isomers with ratio of 5.2/1. For sake of clarity, we have reported only the signals related to the major isomer. Anal. Calcd for C14H20O: C, 82.30; H, 9.87. Found: C, 82.33; H, 9.84.
1-isopropyl-4-methyl-2-((3-methylbut-2-en-1-yl)oxy)benzene (11): pale yellow oil, 78% yield. 1H-NMR (300 MHz, CDCl3): δ 1.38 (d, J = 7.2 Hz, 6H, 2 × CH3), 1.90–1.96 (m, 6H, 2 × CH3), 2.49 (s, 3H, ArCH3), 3.45–3.54 (m, 1H, CH), 4.68 (d, 2H, J = 6.6 Hz, OCH2), 5.66–5.71 (m, 1H, =CH), 6.85 (s, 1H, Ar), 6.91 (d, J = 8.1 Hz, 1H, Ar), 7.26 (d, J = 7.5 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 18.3 (CH3), 21.5 (ArCH3), 23.0 (2 × CH3), 25.9 (CH3), 26.6 (CH), 65.2 (OCH2), 112.8 (Ar), 120.7 (-CH=), 121.2 (Ar), 126.0 (Ar), 134.5 (Ar), 136.2 (Ar), 137.0 (=C), 156.1 (Ar). Anal. Calcd for C15H22O: C, 82.52; H, 10.16. Found: C, 82.56; H, 10.12.
1-isopropyl-4-methyl-2-(pentyloxy)benzene (12): colourless oil, 88% yield. 1H-NMR (300 MHz, CDCl3): δ 1.30 (t, J = 6.9 Hz, 3H, CH3), 1.58 (d, J = 6.9 Hz, 6H, 2 × CH3), 1.71–1.85 (m, 4H, CH2), 2.09–2.19 (m, 2H, CH2), 2.66 (s, 3H, ArCH3), 3.63–3.72 (m, 1H, CH), 4.23–4.28 (m, 2H, OCH2), 6.99 (s, 1H, Ar), 7.06 (d, J = 7.5 Hz, 1H, Ar), 7.43 (d, J = 7.5 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 14.4 (CH3), 21.6 (ArCH3), 22.8 (CH2), 23.1 (2 × CH3), 27.0 (CH), 28.8 (CH2), 29.5 (CH2), 68.0 (OCH2), 112.3 (Ar), 121.2 (Ar), 126.0 (Ar), 134.3 (Ar), 136.4 (Ar), 156.5 (Ar). Anal. Calcd for C15H24O: C, 81.76; H, 10.98. Found: C, 81.80; H, 11.02.
ethyl 2-(2-isopropyl-5-methylphenoxy)acetate (13): pale yellow oil, 69% yield. 1H-NMR (300 MHz, CDCl3): δ 1.36–1.40 (m, 9H, 3 × CH3), 2.41 (s, 3H, ArCH3), 3.52–3.55 (m, 1H, CH), 4.30–4.38 (m, 2H, OCH2CH3), 4.70 (s, 2H, OCH2), 6.66 (s, 1H, Ar), 6.89 (d, J = 7.5 Hz, 1H, Ar), 7.23 (d, J = 7.5 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3) δ 14.2 (CH3), 21.3 (ArCH3), 22.8 (2 × CH3), 26.8 (CH), 61.1 (OCH2CH3), 65.6 (OCH2), 112.3 (Ar), 122.3 (Ar), 126.3 (Ar), 134.5 (Ar), 136.2 (Ar), 155.2 (Ar), 169.1 (C=O). Anal. Calcd for C14H20O3: C, 71.16; H, 8.53. Found: C, 71.20; H, 8.49.
(E)-2-((3,7-dimethylocta-2,6-dien-1-yl)oxy)-1-isopropyl-4-methylbenzene (14): colourless oil, 82% yield. 1H-NMR (300 MHz, CDCl3): δ 1.33 (d, J = 6.3 Hz, 6H, 2 × CH3), 1.74 (s, 3H, CH3), 1.81 (s, 3H, CH3), 1.85 (s, 3H, CH3), 2.19–2.27 (m, 4H, 2 × CH2), 2.44 (s, 3H, ArCH3), 3.42–3.44 (m, 1H, CH), 4.65 (d, J = 7.5 Hz, 2H, OCH2), 5.20–5.23 (m, 1H, =CH), 5.61–5.64 (m, 1H, =CH), 6.8 (s, 1H, Ar), 6.85 (d, J = 7.5 Hz, 1H, Ar), 7.21 (d, J = 7.8 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 16.7 (CH3), 17.8 (CH3), 21.5 (ArCH3), 22.9 (2 × CH3), 25.8 (CH3), 26.5 (CH2), 26.6 (CH), 39.6 (CH2), 65.1 (OCH2), 112.8 (Ar), 120.5 (=CH), 121.1 (Ar), 124.0 (=CH), 125.9 (Ar), 131.7 (=C), 134.4 (Ar), 136.2 (Ar), 140.1 (=C), 156.1 (Ar). Mixture of E/Z isomers with ratio of 9.3/1. For sake of clarity, we have reported only the signals related to the major isomer. Calcd for C20H30O: C, 83.86; H, 10.56. Found: C, 83.80; H, 10.51.
2-(benzyloxy)-1-isopropyl-4-methylbenzene (15): pale yellow oil, 88% yield. 1H-NMR (300 MHz, CDCl3): δ 1.30 (d, J = 7.2 Hz, 6H, 2× CH3), 2.40 (s, 3H, ArCH3), 3.41–3.51 (m, 1H, CH), 5.13 (s, 2H, OCH2), 6.83 (s, 1H, Ar), 6.85 (d, J = 8.1 Hz, 1H, Ar), 7.21 (d, J = 7.8 Hz, 1H, Ar), 7.37–7.55 (m, 5H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.4 (ArCH3), 22.9 (2 × CH3), 26.6 (CH), 70.0 (OCH2), 112.7 (Ar), 121.5 (Ar), 126.0 (Ar), 127.2 (2 × Ar), 127.7 (Ar), 128.6 (2 × Ar), 134.4 (Ar), 136.4 (Ar), 137.7 (Ar), 155.9 (Ar). Anal. Calcd for C17H20O: C, 84.96; H, 8.39. Found: C, 84.90; H, 8.33.
1-isopropyl-4-methyl-2-((2-methylbenzyl)oxy)benzene (16): pale yellow oil, 88% yield. 1H-NMR (300 MHz, CDCl3): δ 1.58 (d, J = 7.2 Hz, 6H, 2 × CH3), 2.70 (s, 6H, 2 × ArCH3), 3.72-3.83 (m, 1H, CH), 5.32 (s, 2H, OCH2), 7.13–7.15 (m, 2H, Ar), 7.48–7.58 (m, 4H, Ar), 7.81–7.83 (m, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 19.2 (ArCH3), 21.8 (ArCH3), 23.3 (2 × CH3), 26.8 (CH), 68.7 (OCH2), 112.7 (Ar), 121.8 (Ar), 126.3 (Ar), 126.4 (Ar), 128.3 (Ar), 128.5 (Ar), 135.0 (Ar), 134.6 (Ar), 135.8 (Ar), 136.6 (Ar), 136.6 (Ar), 156.2 (Ar). Anal. Calcd for C18H22O: C, 84.99; H, 8.72. Found: C, 84.95; H, 8.77.
1-isopropyl-4-methyl-2-((4-methylbenzyl)oxy)benzene (17): pale yellow oil, 77% yield. 1H-NMR (300 MHz, CDCl3): δ 1.68 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.75 (s, 6H, 2 × ArCH3), 3.82–3.87 (m, 1H, CH), 5.38 (s, 2H, OCH2), 7.16 (s, 1H, Ar), 7.19 (d, J = 8.1 Hz, 1H, Ar), 7.54–7.59 (m, 3H, Ar), 7.75 (d, J = 8.4 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.6 (ArCH3), 21.8 (ArCH3), 23.3 (2 × CH3), 27.1 (CH), 70.2 (OCH2), 113.0 (Ar), 121.8 (Ar), 126.3 (Ar), 127.7 (2 × Ar), 129.6 (2 × Ar), 128.6 (Ar), 135.0 (Ar), 136.6 (Ar), 137.7 (Ar), 156.3 (Ar). Anal. Calcd for C18H22O: C, 84.99; H, 8.72. Found: C, 84.93; H, 8.70.
2-((3,5-dimethylbenzyl)oxy)-1-isopropyl-4-methylbenzene (18): colourless oil, 67% yield. 1H-NMR (400 MHz, CDCl3): δ 1.28 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.38 (s, 3H, ArCH3), 2.40 (bs, 6H, 2 × ArCH3), 3.40–3.47 (m, 1H, CH), 5.04 (s, 2H, OCH2), 6.80 (s, 1H, Ar), 6.82 (d, J = 7.9 Hz, 1H, Ar), 7.02 (s, 1H, Ar), 7.12 (s, 2H, Ar), 7.18 (d, J = 7.6 Hz, 1H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.3 (2 × ArCH3), 21.4 (ArCH3), 22.9 (2 × CH3), 26.6 (CH), 70.2 (OCH2), 112.8 (Ar), 121.4 (Ar), 125.0 (2 × Ar), 125.9 (Ar), 129.4 (Ar), 134.4 (Ar), 136.4 (Ar), 137.6 (Ar), 138.1 (2 × Ar), 156.0 (Ar). Anal. Calcd for C19H24O3: C, 85.03; H, 9.01. Found: C, 85.08; H, 9.00.
1-isopropyl-2-((3-methoxybenzyl)oxy)-4-methylbenzene (19): colourless oil, 82% yield. 1H-NMR (400 MHz, CDCl3): δ 1.28 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.37 (s, 3H, ArCH3), 3.38–3.48 (m, 1H, CH), 3.87 (s, 3H, OCH3), 5.09 (s, 2H, OCH2), 6.79 (s, 1H, Ar), 6.82 (d, J = 7.8 Hz, 1H, Ar), 6.90–6.92 (m, 1H, Ar), 7.07–7.08 (m, 2H, Ar), 7.17 (d, J = 7.7 Hz, 1H, Ar), 7.35 (t, J = 8.1 Hz, 1H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.4 (ArCH3), 22.8 (2 × CH3), 26.7 (CH), 55.5 (OCH3), 69.8 (OCH2), 112.5 (Ar), 112.7 (Ar), 113.2 (Ar), 119.3 (Ar), 121.5 (Ar), 126.0 (Ar), 129.6 (Ar), 134.4 (Ar), 136.4 (Ar), 139.3 (Ar), 155.8 (Ar). Anal. Calcd for C18H22O2: C, 79.96; H, 8.20. Found: C, 79.90; H, 8.25.
1-isopropyl-4-methyl-2-((2-(trifluoromethyl)benzyl)oxy)benzene (20): colourless oil, 77% yield. 1H-NMR (300 MHz, CDCl3): δ 1.39–1.42 (m, 6H, 2 × CH3), 2.46 (s, 3H, ArCH3), 3.55–3.57 (m, 1H, CH), 5.42 (s, 2H, OCH2), 6.85 (s, 1H, Ar), 6.94 (d, J = 7.5 Hz, 1H, Ar), 7.30 (d, J = 7.5 Hz, 1H, Ar), 7.51–7.54 (m, 1H, Ar), 7.68–7.71 (m, 1H, Ar), 7.82 (d, J = 7.5 Hz, 1H, Ar), 7.96 (d, J = 7.8 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.4 (ArCH3), 22.9 (2 × CH3), 26.7 (CH), 66.3 (t, 4JC-F = 3.4 Hz, OCH2), 112.7 (Ar), 121.9 (Ar), 124.6 (d, 1JC-F = 272.3 Hz, CF3), 125.9 (q, 2JC-F = 57 Hz, Ar), 126.2 (Ar) 127.2 (d, 3JC-F = 30.9 Hz, Ar), 127.6 (Ar), 128.4 (Ar), 132.3 (Ar), 134.4 (Ar), 136.5 (Ar), 136.6 (Ar), 155.5 (Ar). 19F NMR (564.7 MHz, CDCl3) δ−58.69 (s, 3F, CF3). Anal. Calcd for C18H19F3O: C, 70.12; H, 6.21. Found: C, 70.08; H, 6.23.
1-isopropyl-4-methyl-2-((3-(trifluoromethyl)benzyl)oxy)benzene (21): colourless oil, 69% yield. 1H-NMR (300 MHz, CDCl3): δ 1.59–1.63 (m, 6H, 2 × CH3), 2.65–2.66 (m, 3H, ArCH3), 3.74–3.77 (m, 1H, CH), 5.35 (s, 2H, OCH2), 7.06 (s, 1H, Ar), 7.13 (d, J = 7.5 Hz, 1H, Ar), 7.48–7.51 (m, 1H, Ar), 7.75–7.78 (m, 1H, Ar), 7.87 (d, J = 8.4 Hz, 1H, Ar), 7.93 (d, J = 7.5 Hz, 1H, Ar), 8.08 (s, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.5 (ArCH3), 23.0 (2 × CH3), 27.0 (CH), 69.3 (OCH2), 112.9 (Ar), 121.0 (d, 1JC-F = 274.6 Hz, CF3), 122.2 (Ar), 124.0 (m, Ar), 124.7 (q, 4JC-F = 3.4 Hz, Ar), 126.4 (Ar), 129.3 (Ar), 130.5 (Ar), 131.2 (d, 3JC-F = 32.0 Hz, Ar), 134.6 (Ar), 136.7 (Ar), 139.1 (Ar), 155.8 (Ar). 19F NMR (564.7 MHz, CDCl3) δ−60.98 (s, 3F, CF3). Anal. Calcd for C18H19F3O: C, 70.12; H, 6.21. Found: C, 70.10; H, 6.20.
1-isopropyl-4-methyl-2-((4-(trifluoromethyl)benzyl)oxy)benzene (22): colourless oil, 87% yield. 1H-NMR (300 MHz, CDCl3): δ 1.46 (d, J = 7.2 Hz, 6H, 2 × CH3), 2.51 (s, 3H, ArCH3), 3.52–3.61 (m, 1H, CH), 5.27 (s, 2H, OCH2), 6.900 (s, 1H, Ar), 6.99 (d, J = 8.4 Hz, 1H, Ar), 7.35 (d, J = 7.5 Hz, 1H, Ar), 7.73 (d, J = 7.5 Hz, 2H, Ar), 7.83 (d, J = 8.7 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.4 (ArCH3), 22.9 (2 × CH3), 26.8 (CH), 69.1 (OCH2), 112.7 (Ar), 120.8 (d, 1JC-F = 273.4 Hz, CF3), 122.0 (Ar), 125.6 (q, 4JC-F = 3.4 Hz, Ar), 126.3 (Ar) 127.2 (2 × Ar), 129.8 (m, 2 × Ar), 134.4 (Ar), 136.6 (Ar), 141.9 (Ar), 155.6 (Ar). 19F NMR (564.7 MHz, CDCl3) δ−60.80 (s, 3F, CF3). Anal. Calcd for C18H19F3O: C, 70.12; H, 6.21. Found: C, 70.16; H, 6.22.
2-((3,5-bis(trifluoromethyl)benzyl)oxy)-1-isopropyl-4-methylbenzene (23): colourless oil, 80% yield. 1H-NMR (400 MHz, CDCl3): δ 1.27 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.37 (s, 3H, ArCH3), 3.33–3.43 (m, 1H, CH), 5.20 (s, 2H, OCH2), 6.75 (s, 1H, Ar), 6.86 (d, J = 7.7 Hz, 1H, Ar), 7.19 (d, J = 7.7 Hz, 1H, Ar), 7.89 (s, 1H, Ar), 7.96 (s, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.3 (ArCH3), 22.8 (2 × CH3), 26.7 (CH), 68.6 (OCH2), 112.7 (Ar), 119.2 (Ar), 121.6–121.8 (m, Ar), 122.3 (Ar), 123.3 (d, 1JC-F = 272.5 Hz, 2 × CF3), 126.3 (Ar), 126.9 (Ar), 127.0 (Ar), 127.4 (Ar), 131.9 (q, 2JC-F = 33.4 Hz, Ar), 134.4 (Ar), 136.6 (Ar), 140.3 (Ar), 155.1 (Ar). 19F NMR (564.7 MHz, CDCl3) δ−66.85 (s, 3F, CF3). Anal. Calcd for C19H18F6O: C, 60.64; H, 4.82. Found: C, 60.60; H, 4.77.
4-((2-isopropyl-5-methylphenoxy)methyl)benzonitrile (24): pale yellow solid, 71% yield, mp = 76–78 °C. 1H-NMR (300 MHz, CDCl3): δ 1.34–1.36 (m, 6H, 2 × CH3), 2.41 (s, 3H, ArCH3), 3.46–3.50 (m, 1H, CH), 5.19 (s, 2H, OCH2), 6.79 (s, 1H, Ar), 6.89 (d, J = 7.5 Hz, 1H, Ar), 7.24 (d, J = 7.5 Hz, 1H, Ar), 7.63 (d, J = 7.8 Hz, 2H, Ar), 7.72 (d, J = 8.1 Hz, 2H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.4 (ArCH3), 22.9 (2 × CH3), 26.7 (CH), 68.9 (OCH2), 111.5 (Ar), 112.6 (Ar), 118.9 (CN), 122.1 (Ar), 126.2 (Ar), 127.4 (2 × Ar), 132.4 (2 × Ar), 134.3 (Ar), 136.5 (Ar), 143.2 (Ar), 155.3 (Ar). Anal. Calcd for C18H19NO: C, 81.47; H, 7.22; N, 5.28. Found: C, 81.50; H, 7.20; N, 5.31.
2-((3-fluorobenzyl)oxy)-1-isopropyl-4-methylbenzene (25): colourless oil, 82% yield. 1H-NMR (300 MHz, CDCl3): δ 1.59–1.61 (d, J = 6.3 Hz, 6H, 2 × CH3), 2.65 (s, 3H, ArCH3), 3.71–3.81 (m, 1H, CH), 5.30 (s, 2H, OCH2), 7.03 (s, 1H, Ar), 7.12 (d, J = 8.4 Hz, 1H, Ar), 7.25–7.31 (m, 1H, Ar), 7.47–7.52 (m, 3H, Ar), 7.57–7.64 (m, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.6 (ArCH3), 23.1 (2 × CH3), 27.0 (CH), 69.3 (OCH2), 112.8 (Ar), 114.2 (d, 2JC-F = 21.7 Hz, Ar), 114.8 (d, 2JC-F = 21.7 Hz, Ar), 122.1 (Ar), 122.7 (d, 4JC-F = 2.3 Hz, Ar), 126.4 (Ar), 130.3 (d, 3JC-F = 8.0 Hz, Ar), 134.6 (Ar), 136.6 (Ar), 140.6 (d, 3JC-F = 6.8 Hz, Ar), 155.9 (Ar), 163.3 (d, 1JC-F = 244.9 Hz, Ar-F). 19F NMR (564.7 MHz, CDCl3) δ−111.18 (ddd, 1F, JF–H = 7.91 Hz (ortho), 6.2 Hz (meta), CF). Anal. Calcd for C17H19FO: C, 79.04; H, 7.41. Found: C, 79.10; H, 7.50.
1,3-difluoro-2-((2-isopropyl-5-methylphenoxy)methyl)benzene (26): white solid, 83% yield, mp = 91–92 °C. 1H-NMR (300 MHz, CDCl3): δ 1.22 (d, J = 7.2 Hz, 6H, 2 × CH3), 2.42 (s, 3H, ArCH3), 3.26–3.35 (m, 1H, CH), 5.17 (s, 2H, OCH2), 6.86 (d, J = 7.5 Hz, 1H, Ar), 6.93–7.03 (m, 3H, Ar), 7.18 (d, J = 8.1 Hz, 1H, Ar), 7.31–7.41 (m, 2H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.4 (ArCH3), 22.8 (2 × CH3), 26.5 (CH), 58.2 (OCH2), 111.3 (2 × Ar), 111.6 (Ar), 113.0 (Ar), 121.9 (Ar), 126.1 (Ar), 130.5 (t, 3JC-F = 10.3 Hz, Ar), 134.7 (Ar), 136.4 (Ar), 155.7 (Ar), 162.0 (d, 1JC-F = 248.3 Hz, Ar-F), 162.1 (d, 1JC-F = 249.5 Hz, Ar-F). 19F NMR (564.7 MHz, CDCl3) δ−112.97 (t, 2F, JF–H = 7.5 Hz, CF). Anal. Calcd for C17H18F2O: C, 73.89; H, 6.57. Found: C, 73.93; H, 6.52.
2-((3,5-difluorobenzyl)oxy)-1-isopropyl-4-methylbenzene (27): white solid, 90% yield, mp = 35–36 °C. 1H-NMR (400 MHz, CDCl3): δ 1.27 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.35 (s, 3H, ArCH3), 3.35–3.45 (m, 1H, CH), 5.08 (s, 2H, OCH2), 6.70 (s, 1H, Ar), 6.76–6.84 (m, 2H, Ar), 6.99–7.03 (m, 2H, Ar), 7.18 (d, J = 7.7 Hz, 1H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.3 (ArCH3), 22.8 (2 × CH3), 26.6 (CH), 68.7 (OCH2), 103.0 (t, 2JC-F = 25.3 Hz, Ar), 109.5 (d, 2JC-F = 25.7 Hz, 2 × Ar), 112.6 (Ar), 121.9 (Ar), 126.2 (Ar), 134.4 (Ar), 136.5 (Ar), 141.8 (t, 3JC-F = 9.1 Hz, Ar), 155.2 (Ar), 163.1 (d, 1JC-F = 248.5 Hz, C-F), 163.2 (d, 1JC-F = 248.6 Hz, C-F). 19F NMR (564.7 MHz, CDCl3) δ−113.39 (t, 2F, JF–H = 7.5 Hz, CF). Anal. Calcd for C17H18F2O: C, 73.89; H, 6.57. Found: C, 73.93; H, 6.61.
2-((3-chlorobenzyl)oxy)-1-isopropyl-4-methylbenzene (28): yellow sticky oil, 91% yield. 1H-NMR (400 MHz, CDCl3): δ 1.28 (d, J = 6.8 Hz, 6H, 2 × CH3), 2.37 (s, 3H, ArCH3), 3.40–3.44 (m, 1H, CH), 5.08 (s, 2H, OCH2), 6.76 (s, 1H, Ar), 6.84 (d, J = 7.6 Hz, 1H, Ar), 7.19 (d, J = 7.6 Hz, 1H, Ar), 7.35–7.38 (m, 3H, Ar), 7.49 (s, 1H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.4 (ArCH3), 22.9 (2 × CH3), 26.6 (CH), 69.2 (OCH2), 112.7 (Ar), 121.8 (Ar), 125.1 (Ar), 126.1 (Ar), 127.1 (Ar), 127.9 (Ar), 129.8 (Ar), 134.4 (Ar), 136.4 (Ar), 139.8 (Ar), 155.6 (Ar). Anal. Calcd for C17H19ClO: C, 74.31; H, 6.97. Found: C, 74.27; H, 6.90.
2-((4-chlorobenzyl)oxy)-1-isopropyl-4-methylbenzene (29): colourless oil, 74% yield. 1H-NMR (300 MHz, CDCl3): δ 1.43–1.46 (m, 6H, 2 × CH3), 2.52 (s, 3H, ArCH3), 3.55–3.58 (m, 1H, CH), 5.17 (s, 2H, OCH2), 6.90 (s, 1H, Ar), 6.98 (d, J = 7.5 Hz, 1H, Ar), 7.33 (d, J = 7.8 Hz, 1H, Ar), 7.50–7.53 (m, 4H, Ar). 13C-NMR (75 MHz, CDCl3) δ 21.6 (ArCH3), 23.0 (2 × CH3), 26.9 (CH), 69.3 (OCH2), 112.8 (Ar), 121.9 (Ar), 126.2 (Ar), 128.6 (2 × Ar), 128.9 (2 × Ar), 133.6 (Ar), 134.4 (Ar), 136.3 (Ar), 136.5 (Ar), 155.8 (Ar). Anal. Calcd for C17H19ClO: C, 74.31; H, 6.97. Found: C, 74.37; H, 7.01.
2-chloro-1-((2-isopropyl-5-methylphenoxy)methyl)-4-methoxybenzene (30): white solid, 71% yield, mp = 84–86 °C. 1H-NMR (400 MHz, CDCl3): δ 1.25 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.36 (s, 3H, ArCH3), 3.34–3.44 (m, 1H, CH), 3.85 (s, 3H, OCH3), 5.11 (s, 2H, OCH2), 6.79 (s, 1H, Ar), 6.81 (d, J = 7.9 Hz, 1H, Ar), 6.89 (dd, J = 8.6 Hz, 2.5 Hz, 1H, Ar), 7.00 (d, J = 2.5 Hz, 1H, Ar), 7.16 (d, J = 7.6 Hz, 1H, Ar), 7.51 (d, J = 8.6 Hz, 1H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.4 (ArCH3), 22.8 (2 × CH3), 26.6 (CH), 55.6 (OCH3), 67.1 (OCH2), 112.7 (Ar), 112.9 (Ar), 114.9 (Ar), 121.6 (Ar), 126.0 (Ar), 127.3 (Ar), 129.8 (Ar), 133.5 (Ar), 134.4 (Ar), 136.4 (Ar), 155.5 (Ar), 159.7 (Ar). Anal. Calcd for C18H21ClO2: C, 70.93; H, 6.94. Found: C, 70.88; H, 6.96.
2-((2-bromobenzyl)oxy)-1-isopropyl-4-methylbenzene (31): white sticky solid, 71% yield. 1H-NMR (300 MHz, CDCl3): δ 1.47 (d, J = 7.2 Hz, 6H, 2 × CH3), 2.52 (s, 3H, ArCH3), 3.59–3.66 (m, 1H, CH), 5.29 (s, 2H, OCH2), 6.94 (s, 1H, Ar), 6.98 (d, J = 7.5 Hz, 1H, Ar), 7.30–7.35 (m, 2H, Ar), 7.49–7.54 (m, 1H, Ar), 7.73–7.76 (m, 1H, Ar), 7.80 (d, J = 6.9 Hz, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.4 (ArCH3), 22.9 (2 × CH3), 26.6 (CH), 70.0 (OCH2), 112.7 (Ar), 121.5 (Ar), 126.0 (Ar), 127.2 (Ar), 127.7 (Ar), 128.6 (Ar), 134.4 (Ar), 136.4 (Ar), 137.7 (Ar), 155.9 (Ar). Anal. Calcd for C17H19BrO: C, 63.69; H, 6.00. Found: C, 63.71; H, 5.57.
2-((4-bromobenzyl)oxy)-1-isopropyl-4-methylbenzene (32): colourless oil, 71% yield. 1H-NMR (300 MHz, CDCl3): δ 1.52 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.58 (s, 3H, ArCH3), 3.61–3.70 (m, 1H, CH), 5.20 (s, 2H, OCH2), 6.96 (s, 1H, Ar), 7.05 (d, J = 7.5 Hz, 1H, Ar), 7.40 (d, J = 7.5 Hz, 1H, Ar), 7.52–7.54 (d, 2H, Ar), 7.70–7.74 (m, 2H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.7 (ArCH3), 23.1 (2 × CH3), 27.0 (CH), 69.4 (OCH2), 112.8 (Ar), 121.8 (Ar), 122.0 (Ar), 126.3 (Ar), 129.0 (2 × Ar), 131.9 (2 × Ar), 134.5 (Ar), 136.5 (Ar), 136.9 (Ar), 155.8 (Ar). Anal. Calcd for C17H19BrO: C, 63.69; H, 6.00. Found: C, 63.65; H, 6.07.
2-((4-iodobenzyl)oxy)-1-isopropyl-4-methylbenzene (33): yellowish sticky oil, 83% yield. 1H-NMR (400 MHz, CDCl3): δ 1.26 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.36 (s, 3H, ArCH3), 3.33–3.43 (m, 1H, CH), 5.04 (s, 2H, OCH2), 6.74 (s, 1H, Ar), 6.82 (d, J = 7.7 Hz, 1H, Ar), 7.17 (d, J = 7.7 Hz, 1H, Ar), 7.23 (d, J = 8.2 Hz, 2H, Ar), 7.76 (d, J = 8.3 Hz, 1H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.4 (ArCH3), 22.8 (2 × CH3), 26.6 (CH), 69.3 (OCH2), 93.1 (Ar), 112.6 (Ar), 121.7 (Ar), 126.1 (Ar), 129.0 (2 × Ar), 134.3 (Ar), 136.4 (Ar), 137.4 (Ar), 137.6 (2 × Ar), 155.6 (Ar). Anal. Calcd for C17H19IO: C, 55.75; H, 5.23. Found: C, 55.80; H, 5.30.
1-isopropyl-4-methyl-2-((2-nitrobenzyl)oxy)benzene (34): brown solid, 77% yield, mp = 77–79 °C. 1H-NMR (300 MHz, CDCl3): δ 1.26 (d, J = 7.2 Hz, 6H, 2× CH3), 2.32 (s, 3H, ArCH3), 3.38–3.43 (m, 1H, CH), 5.48 (s, 2H, OCH2), 6.73 (s, 1H, Ar), 6.81 (d, J =7.5 Hz, 1H, Ar), 7.16 (d, J =7.5, 1H, Ar), 7.50–7.53 (m, 1H, Ar), 7.69–7.75 (m, 1H, Ar), 7.96 (d, J = 7.8 Hz, 1H, Ar), 8.20 (dd, J = 8.1 Hz, J = 1.2 Hz, 1H, Ar). Anal. Calcd for C17H19NO3: C, 71.56; H, 6.71; N, 4.91. Found: C, 71.60; H, 6.75; N, 4.88.
1-isopropyl-4-methyl-2-((3-nitrobenzyl)oxy)benzene (35): amber-yellow oil, 81% yield. 1H-NMR (300 MHz, CDCl3): δ 1.48–1.52 (m, 6H, 2 × CH3), 2.53 (s, 3H, ArCH3), 3.62–3.67 (m, 1H, CH), 5.27 (s, 2H, OCH2), 6.95 (s, 1H, Ar), 7.00 (d, J = 7.8 Hz, 1H, Ar), 7.33–7.37 (m, 1H, Ar), 7.65–7.71 (m, 1H, Ar), 7.97 (d, J = 6.9 Hz, 1H, Ar), 8.26–8.29 (m, 1H, Ar), 8.51 (s, 1H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.5 (ArCH3), 23.0 (2 × CH3), 27.0 (CH), 68.6 (OCH2), 112.7 (Ar), 121.8 (Ar), 122.3 (Ar), 122.7 (Ar), 126.3 (Ar), 129.7 (Ar), 133.0 (Ar), 134.3 (Ar), 136.6 (Ar), 140.1 (Ar), 148.5 (Ar), 155.5 (Ar). Anal. Calcd for C17H19NO3: C, 71.56; H, 6.71; N, 4.91. Found: C, 71.55; H, 6.73; N, 4.91.
1-isopropyl-4-methyl-2-((4-nitrobenzyl)oxy)benzene (36): white solid, 81% yield, mp = 81–83 °C. 1H-NMR (300 MHz, CDCl3): δ 1.24–1.26 (m, 6H, 2 × CH3), 2.33 (s, 3H, ArCH3), 3.36–3.40 (m, 1H, CH), 5.18 (s, 2H, OCH2), 6.70 (s, 1H, Ar), 6.82 (d, J = 7.5 Hz, 1H, Ar), 7.16 (d, J = 7.8 Hz, 1H, Ar), 7.63 (d, J = 8.4 Hz, 2H, Ar), 8.26–8.28 (m, 2H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.4 (ArCH3), 22.8 (2 × CH3), 26.7 (CH), 68.7 (OCH2), 112.5 (Ar), 122.0 (Ar), 123.9 (2 × Ar), 126.2 (Ar), 127.3 (2 × Ar), 134.3 (Ar), 136.5 (Ar), 145.1 (Ar), 147.4 (Ar), 155.1 (Ar). Anal. Calcd for C17H19NO3: C, 71.56; H, 6.71; N, 4.91. Found: C, 71.51; H, 6.67; N, 4.96.
1-((2-isopropyl-5-methylphenoxy)methyl)naphthalene (37): pale yellow oil, 76% yield. 1H-NMR (400 MHz, CDCl3): δ 1.21 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.41 (s, 3H, ArCH3), 3.31–3.42 (m, 1H, CH), 5.53 (m, 2H, CH2O), 6.86 (d, J = 7.7 Hz, 1H, Ar), 6.95 (s, 1H, Ar), 7.20 (d, J = 7.7 Hz, 1H, Ar), 7.51–7.58 (m, 3H, Ar), 7.68 (d, J = 6.9 Hz, 1H, Ar), 7.90 (d, J = 8.2 Hz, 1H, Ar), 7.93–7.96 (m, 1H, Ar), 8.09–8.11 (m, 1H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.5 (ArCH3), 23.0 (2 × CH3), 26.4 (CH), 68.6 (OCH2), 112.6 (Ar), 121.6 (Ar), 123.8 (Ar), 125.4 (Ar), 125.9 (Ar), 126.0 (Ar), 126.1 (Ar), 126.3 (Ar), 128.7 (Ar), 128.8 (Ar), 131.5 (Ar), 133.0 (Ar), 133.7 (Ar), 134.5 (Ar), 136.4 (Ar), 155.9 (Ar). Anal. Calcd for C21H22O: C, 86.85; H, 7.64. Found: C, 86.84; H, 7.70.
4-((2-isopropyl-5-methylphenoxy)methyl)-1,1′-biphenyl (38): white solid, 78% yield, mp = 91–92 °C. 1H-NMR (400 MHz, CDCl3): δ 1.29 (d, J = 6.9 Hz, 6H, 2 × CH3), 2.38 (s, 3H, ArCH3), 3.40–3.50 (m, 1H, CH), 5.16 (s, 2H, OCH2), 6.83–6.84 (m, 2H, Ar), 7.19 (d, J = 7.8 Hz, 1H, Ar), 7.38–7.42 (m, 1H, Ar), 7.47–7.52 (m, 2H, Ar), 7.57 (d, J = 8.3 Hz, 1H, Ar), 7.64–7.68 (m, 4H, Ar). 13C-NMR (101 MHz, CDCl3): δ 21.4 (ArCH3), 22.9 (2 × CH3), 26.6 (CH), 69.7 (OCH2), 112.7 (Ar), 121.5 (Ar), 127.1 (2 × Ar), 127.3 (2 × Ar), 127.4 (Ar), 127.6 (2 × Ar), 128.8 (2 × Ar), 134.4 (Ar), 136.4 (Ar), 137.4 (Ar), 136.7 (Ar), 140.7 (Ar), 140.9 (Ar), 155.8 (Ar). Anal. Calcd for C23H24O: C, 87.30; H, 7.64. Found: C, 87.35; H, 7.67.
2-((2-isopropyl-5-methylphenoxy)methyl)isoindoline-1,3-dione (39): white solid, 79% yield, mp = 121–122 °C. 1H-NMR (300 MHz, CDCl3): δ 1.18 (d, J = 7.2 Hz, 6H, 2 × CH3), 2.36 (s, 3H, ArCH3); 3.24–3.33 (m, 1H, CH3), 5.67 (s, 2H, OCH2), 6.84 (d, J = 7.8 Hz, 1H, Ar), 7.02 (s, 1H, Ar), 7.12 (d, J = 7.8 Hz, 1H, Ar), 7.73–7.78 (m, 2H, Ar), 7.88–7.92 (m, 2H, Ar). 13C-NMR (75 MHz, CDCl3): δ 21.3 (ArCH3), 23.0 (2 × CH3), 26.5 (CH), 65.7 (OCH2), 115.0 (Ar), 123.2 (2 × Ar), 123.8 (2 × Ar), 126.3 (Ar), 131.8 (Ar), 134.5 (2 × Ar), 135.4 (Ar), 136.5 (Ar), 153.4 (Ar), 167.2 (2 × C=O). Anal. Calcd for C19H19NO3: C, 73.77; H, 6.19; N, 4.53. Found: C, 73.71; H, 6.24; N, 4.50.