3.2.1. General Synthesis and Characterization Data for Chalcones C1–C18
To a stirring solution of the proper chalcone (1 eq.) in ethanol (10 mL) was added a dispersion of barium hydroxide (1 eq.) in ethanol (40 mL). The appropriate (un)substituted benzaldehyde (1 eq.), dissolved in ethanol (20 mL), was added dropwise and the reaction stirred at reflux for 24–72 h. The synthesis was quenched with 150 mL of ice/water and the resulting suspension filtered. The crude solid was washed with petroleum ether (2 × 20 mL) and
n-hexane (2 × 20 mL) giving the title compounds without further purification requirements. For compound
C18 the suspension obtained after quenching with 150 mL of ice/water, was extracted with chloroform (3 × 20 mL). The organics reunited were dried over sodium sulphate and evaporated in vacuo. Purification by column chromatography on silica gel (ethyl acetate:
n-hexane 1:4) gave the title compounds. Characterization data obtained for compounds
C1–
C5,
C7–
C8 were in accordance with [
26,
30], while for compound
C15 were in accordance with [
23].
(E)-1-(4-((-3,7-dimethylocta-2,6-dien-1-yl)oxy)phenyl)-3-phenylprop-2-en-1-one (C6), white solid (82% yield); mp 66–68 °C. 1H-NMR (400 MHz, DMSO-d6): δ 1.56 (s, 3H, CH3), 1.62 (s, 3H, CH3), 1.73 (s, 3H, CH3), 2.06 (br, 4H, 2 × CH2), 4.68 (d, J = 6 Hz, 2H, CH2), 5.06 (br, 1H, =CH), 5.44 (br, 1H, =CH), 7.08 (d, J = 8 Hz, 2H, Ar), 7.45 (br, 3H, Ar), 7.71 (d, Jxy = 16 Hz, 1H, Hx), 7.88 (d, J = 3.6 Hz, 2H, Ar), 7.95 (d, Jxy = 15.6 Hz, 1H, Hy), 8.16 (d, J = 8.4 Hz, 2H, Ar).
(E)-1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-3-(o-tolyl)prop-2-en-1-one (C9), yellow solid (92% yield); mp 72–75 °C. 1H-NMR (400 MHz, CDCl3): δ 1.79 (s, 3H, CH3), 1.83 (s, 3H, CH3), 2.50 (s, 3H, CH3), 4.62 (d, J = 6.4 Hz, 2H, CH2), 5.52 (br, 1H, =CH), 7.01 (d, 2H, J = 8.8 Hz, Ar), 7.24-7.33 (m, 3H, Ar), 7.49 (d, Jxy = 15.6 Hz, 1H, Hx), 7.71 (d, J = 7.6 Hz, 1H, Ar), 8.06 (d, J = 8.4 Hz, 2H, Ar), 8.12 (d, Jxy = 15.6 Hz, 1H, Hy).
(E)-1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-3-(m-tolyl)prop-2-en-1-one (C10), yellow solid (77% yield); mp 99–101 °C. 1H-NMR (400 MHz, DMSO-d6): δ 1.74 (s, 3H, CH3), 1.76 (s, 3H, CH3), 2.36 (s, 3H, CH3), 4.65–4.66 (m, 2H, CH2), 5.45 (br, 1H, =CH), 7.08 (d, J = 7.6 Hz, 2H, Ar), 7.26–7.27 (m, 1H, Ar), 7.33–7.35 (m, 1H, Ar), 7.65–7.72 (m, 3H, 2 × Ar + Hx), 7.92 (d, Jxy = 16 Hz, 1H, Hb), 8.16 (d, J = 7.6 Hz, 2H, Ar).
1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-3-(p-tolyl)prop-2-en-1-one (C11): yellow solid (87% yield); 95–98 °C. 1H-NMR (400 MHz, DMSO-d6): δ 1.74 (m, 6H, 2 × CH3), 2.35 (s, 3H, CH3), 4.64 (s, 2H, CH2), 5.44 (s, 1H, =CH), 7.08–8.15 (m, 10H, 8 × Ar + 2 × =CH).
(E)-3-(2,4-dimethylphenyl)-1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)prop-2-en-1-one (C12), yellow solid (75% yield); mp 102–105 °C. 1H-NMR (400 MHz, CDCl3): δ 1.58–1.59 (m, 6H, 2 × CH3), 2.37 (s, 3H, CH3), 2.47 (s, 3H, CH3), 4.62 (d, J = 6.8 Hz, 2H, CH2) 5.51 (m, 1H, =CH), 7.00–7.09 (m, 4H, Ar), 7.47 (d, Jxy = 15.6 Hz, 1H, Hx), 7.63 (d, J = 8.4 Hz, 1H, Ar), 8.06 (d, J = 9.2 Hz, 2H, Ar), 8.11 (d, Jxy = 15.6 Hz, 1H, Hy).
(E)-3-(2-chlorophenyl)-1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)prop-2-en-1-one (C13), white solid (94% yield); mp 98–100 °C. 1H-NMR (400 MHz, CDCl3): δ 1.79 (s, 3H, CH3), 1.84 (s, 3H, CH3), 4.62 (d, J = 6.7 Hz, 2H, CH2), 5.52 (br, 1H, =CH), 6.99–7.03 (m, 2H, Ar), 7.33–7.36 (m, 2H, Ar), 7.45–7.48 (m, 1H, Ar), 7.53 (d, Jxy = 15.7 Hz, 1H, Hx), 7.76–7.78 (m, 1H, Ar), 8.01 (d, J = 8.8 Hz, 1H, Ar), 8.05 (d, J = 8.8 Hz, 1H, Ar), 8.19 (d, Jxy = 15.6 Hz, 1H, Hy).
3-(3-chlorophenyl)-1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)prop-2-en-1-one (C14), white solid (94% yield); mp 92–94 °C. δ 1.78 (s, 3H, CH3), 1.83 (s, 3H, CH3), 4.61 (m, 2H, CH2), 5.49 (br, 1H, =CH), 7.05–7.08 (m, 2H, Ar), 7.30–7.34 (m, 2H, Ar), 7.49–7.51 (m, 1H, Ar), 7.55 (d, Jxy = 15.7 Hz, 1H, Hx), 7.74–7.72 (m, 1H, Ar), 8.00–8.02 (m, 1H, Ar), 8.03–8.05 (m, 1H, Ar), 8.21 (d, Jxy = 15.6 Hz, 1H, Hy).
(E)-3-(2,4-dichlorophenyl)-1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)prop-2-en-1-one (C16), yellow solid (96% yield); mp 127–130 °C. 1H-NMR (400 MHz, DMSO-d6): δ 1.74 (s, 3H, CH3), 1.76 (s, 3H, CH3), 4.66 (d, J = 6.8 Hz, 2H, CH2), 5.44–5.47 (m, 1H, =CH), 7.09 (d, J = 9.2 Hz, 2H, Ar), 7.54–7.57 (m, 1H, Ar), 7.76 (s, 1H, Ar), 7.94 (d, Jxy = 15.2 Hz, 1H, Hx), 8.04 (d, Jxy = 15.2 Hz, 1H, Hy), 8.18 (d, J = 8.8 Hz, 2H, Ar), 8.27 (d, J = 8.8 Hz, 1H, Ar).
3-([1,1′-biphenyl]-4-yl)-1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)prop-2-en-1-one (C17), yellow solid (75% yield); mp 122–124 °C. 1H-NMR (400 MHz, DMSO-d6): δ 1.74 (s, 3H, CH3), 1.76 (s, 3H, CH3), 4.66 (d, J = 6.4 Hz, 2H, CH2), 5.46 (t, J = 6.8 Hz, 1H, =CH), 7.09 (d, J = 8.8 Hz, 2H, Ar), 7.39–7.52 (m, 3H, Ar), 7.75–7.79 (m, 5H, 4 × Ar + =CH), 7.98–8.03 (m, 3H, 2 × Ar + =CH), 8.19 (d, J = 8.8 Hz, 2H, Ar).
(E)-1-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-3-(naphthalen-1-yl)prop-2-en-1-one (C18), yellow solid (67% yield); mp 82–84 °C. 1H-NMR (400 MHz, CDCl3): δ 1.80 (s, 3H, CH3), 1.84 (s, 3H, CH3), 4.60–4.64 (m, 2H, CH2), 5.51–5.55 (m, 1H, =CH), 7.03 (d, J = 8.8 Hz, 2H, Ar), 7.54–7.61 (m, 3H, Ar), 7.66 (d, Jxy = 15.6 Hz, 1H, Hx), 7.92–7.94 (m, 3H, Ar), 8.11 (d, J = 8.8 Hz, 2H, Ar), 8.28–8.30 (m, 1H, Ar), 8.68 (d, Jxy = 15.2 Hz, 1H, Hy).
3.2.3. Synthesis and Characterization Data for 3,5-disubstituted-N-acetylated Pyrazolines P7–P18
To a stirring solution of the proper chalcone (1 eq.) in acetic acid (15 mL) was added dropwise hydrazine hydrate (4 eq.). The reaction was stirred at reflux for 24–48 h and quenched with 200 mL of ice/water. The resulting suspension was extracted with chloroform (3 × 20 mL). The organics reunited were dried over sodium sulfate and evaporated in vacuo. Purification by column chromatography on silica gel with appropriate mixtures of ethyl acetate and
n-hexane as mobile phase, gave the title compounds. Characterization data for compound
P8 were in accordance with [
26].
1-(3-(4-(allyloxy)phenyl)-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P7), orange solid (71% yield) mp 95–98 °C. 1H-NMR (400 MHz, DMSO-d6): δ 2.44 (s, 3H, CH3), 3.13 (d, Jab = 17.4, Hz, Jac = 4.6 Hz, 1 1H, Ha), 3.71 (dd, Jab = 17.6 Hz, Jbc = 12.0 Hz, 1H, Hb), 4.36 (d, J = 5.2 Hz, 2H, CH2), 5.33 (d, Jcis = 11.2 Hz, 1H, =CH-H), 5.45 (d, Jtrans = 17.2 Hz, 1H, =CH-H), 5.58 (dd, Jbc = 11.6 Hz, Jac = 4.4 Hz, 1H, Hc), 6.02–6.12 (m, 1H, =CH), 6.97 (d, J = 8.8 Hz, 2H, Ar), 7.24–7.26 (m, 3H, Ar), 7.32 (d, J = 7.2 Hz, Ar), 7.70 (d, J = 8.8 Hz, Ar). 13C-NMR (101 MHz, CDCl3): δ 22.0 (CH3), 42.5 (C(4)H2, pyr), 59.8 (C(5)H2, pyr), 68.9 (CH2-O), 114.9 (2 × Ar), 118.0 (=CH), 124.2 (Ar), 125.6 (2 × Ar), 127.6 (Ar), 128.2 (2 × Ar), 128.9 (2 × Ar), 132.78 (Ar), 142.0 (=CH2), 153.7 (C=N, pyr), 160.4 (Ar), 168.6 (C=O). Calcd. for C20H20N2O2: C, 74.98; H, 6.29; N, 8.74. Found: C, 74.77; H, 6.19; N, 8.65.
1-(3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-5-(o-tolyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P9), yellow solid (61% yield); mp 110–112 °C. 1H-NMR (400 MHz, CDCl3): δ 1.78 (s, 3H, CH3), 1.83 (s, 3H, CH3), 2.47 (s, 3H, CH3), 2.48 (s, 3H, CH3), 3.00 (dd, Jab = 17.4 Hz, Jac = 4.6 Hz, 1H, Ha), 3.74 (dd, Jab = 17.4 Hz, Jbc = 11.8 Hz, 1H, Hb), 4.57 (d, J = 6.8 Hz, 2H, CH2), 5.52 (t, J = 6.8 Hz, 1H, =CH), 5.74 (dd, Jbc = 11.8 Hz, Jac = 4.6 Hz, 1H, Hc), 6.96 (d, J = 9.2 Hz, 2H, Ar), 7.01–7.03 (m, 1H, Ar), 7.13–7.20 (m, 3H, Ar), 7.69 (d, J = 8.8 Hz, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 19.5 (CH3), 21.9 (CH3), 25.9 (CH3), 41.7 (C(4)H2, pyr), 57.0 (C(5)H2, pyr), 65.0 (CH2-O), 114.9 (2 × Ar), 119.2 (=CH), 123.9 (Ar), 124.0 (Ar), 126.6 (Ar), 127.4 (Ar), 128.2 (2 × Ar), 130.7 (Ar), 134.1 (Ar), 138.6 (C=), 139.9 (Ar), 153.8 (C=N, pyr), 160.7 (Ar), 168.5 (C=O). Calcd. for C23H26N2O2: C, 76.21; H, 7.23; N, 7.73. Found: C, 76.33; H, 7.37; N, 7.66.
1-(3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-5-(m-tolyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P10), orange solid (67% yield); mp 120–122 °C. 1H-NMR (400 MHz, CDCl3): δ 1.79 (s, 3H, CH3), 1.84 (s, 3H, CH3), 2.34 (s, 3H, CH3), 2.45 (s, 3H, CH3), 3.13 (dd, Jab = 17.6 Hz, Jac = 4.4 Hz, 1H, Ha), 3.71 (dd, Jab = 17.4 Hz, Jbc = 11.8 Hz, 1H, Hb), 4.58 (d, J = 6.8 Hz, 2H, CH2), 5.51-5.54 (m, 1H, =CH), 5.55 (dd, Jbc = 11.6 Hz, Jac = 4.4 Hz, 1H, Hc), 6.97 (d, J = 8.4 Hz, 2H, Ar), 7.04–7.08 (m, 3H, Ar), 7.14–7.24 (m, 1H, Ar), 7.70 (d, J = 8.8 Hz, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 21.5 (CH3), 22.0 (CH3), 25.9 (CH3), 42.5 (C(4)H2, pyr), 59.80 (C(5)H2, pyr), 65.0 (CH2-O), 114.9 (2 × Ar), 119.3 (=CH), 122.6 (Ar), 124.0 (Ar), 126.2 (Ar), 128.2 (2 × Ar), 128.4 (Ar), 128.8 (Ar), 138.5 (Ar), 138.6 (C=), 142.0 (Ar), 153.8 (C=N, pyr), 160.7 (Ar), 168.6 (C=O). Calcd. for C23H26N2O2: C, 76.21; H, 7.23; N, 7.73. Found: C, 76.33; H, 7.17; N, 7.85.
1-(3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-5-(p-tolyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P11), yellow oil (75% yield). 1H-NMR (400 MHz, CDCl3): δ 1.78 (s, 3H, CH3), 1.83 (s, 3H, CH3), 2.32 (s, 3H, CH3), 2.43 (s, 3H, CH3), 3.11–3.15 (m, 1H, Ha), 3.67–3.74 (m, 1H, Hb), 4.57 (d, J = 5.6 Hz, 2H, CH2), 5.52–5.58 (m, 1H, =CH + 1H, Hc), 6.96 (d, J = 8.0 Hz, 2H, Ar), 7.10–7.14 (m, 4H, Ar), 7.68–7.70 (m, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 21.1 (CH3), 22.0 (CH3), 25.9 (CH3), 42.5 (C(4)H2, pyr), 59.6 (C(5)H2, pyr), 64.9 (CH2-O), 114.9 (2 × Ar), 119.2 (=CH), 123.9 (Ar), 125.6 (2 × Ar), 128.2 (2 × Ar), 129.5 (2 × Ar), 137.2 (Ar), 138.7 (C=), 139.1 (Ar), 153.8 (C=N, pyr), 160.6 (Ar), 168.6 (C=O). Calcd. for C23H26N2O2: C, 76.21; H, 7.23; N, 7.73. Found: C, 76.01; H, 7.25; N, 7.88.
1-(5-(2,4-dimethylphenyl)-3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P12), orange solid (97% yield); mp 117–119 °C. 1H-NMR (400 MHz, CDCl3): δ 1.78 (s, 3H, CH3), 1.83 (s, 3H, CH3), 2.28 (s, 3H, CH3), 2.43 (s, 3H, CH3), 2.47 (s, 3H, CH3), 3.00 (dd, Jab = 17.4 Hz, Jac = 4.6 Hz, 1H, Ha), 3.74 (dd, Jab = 17.4 Hz, Jbc = 11.8 Hz, 1H, Hb), 4.57 (d, J = 6.4 Hz, 2H, CH2), 5.51 (t, J = 6.8 Hz, 1H, =CH), 5.71 (dd, Jbc = 11.6 Hz, Jac = 4.4 Hz, 1H, Hc), 6.89–7.01 (m, 5H, Ar), 7.68 (d, J = 8.8 Hz, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 19.4 (CH3), 20.9 (CH3), 21.9 (CH3), 25.8 (CH3), 41.9 (C(4)H2, pyr), 56.8 (C(5)H2, pyr), 64.9 (CH2-O), 114.8 (2 × Ar), 119.2 (=CH), 124.0 (Ar), 124.1 (Ar), 127.3 (Ar), 128.2 (2 × Ar), 131.5 (Ar), 133.9 (Ar), 136.9 (Ar), 137.1 (Ar), 138.7 (C=), 153.8 (C=N, pyr), 160.6 (Ar), 168.6 (C=O). Calcd. for C24H28N2O2: C, 76.56; H, 7.50; N, 7.44. Found: C, 76.41; H, 7.41; N, 7.53.
1-(5-(2-chlorophenyl)-3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P13), orange solid, (73% yield); mp 131–134 °C. 1H-NMR (400 MHz, CDCl3): δ 1.78 (s, 3H, CH3), 1.82 (s, 3H, CH3), 2.50 (s, 3H, CH3), 3.05 (dd, Jab = 17.6 Hz, Jac = 4.7 Hz, 1H, Ha), 3.84 (dd, Jab = 17.6 Hz, Jbc = 11.8 Hz, 1H, Hb), 4.57 (d, J = 6.7 Hz, 2H, CH2), 5.50 (t, J = 6.7 Hz, 1H, =CH), 5.92 (dd, Jbc = 11.7 Hz, Jac = 4.7 Hz, 1H, Hc), 6.95 (d, J = 8.8 Hz, 2H, Ar), 7.07–7.09 (m, 1H, Ar), 7.21–7.23 (m, 2H, Ar), 7.40–7.42 (m, 1H, Ar), 7.68 (d, J = 8.8 Hz, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 21.9 (CH3), 25.8 (CH3), 41.5 (C(4)H2, pyr), 57.6 (C(5)H2, pyr), 65.0 (CH2-O), 114.9 (2 × Ar), 119.3 (=CH), 123.7 (Ar), 125.9 (Ar), 127.3 (Ar), 128.2 (2 × Ar), 130.0 (Ar), 131.7 (Ar), 138.6 (Ar), 138.7 (C=), 154.1 (C=N, pyr), 160.8 (Ar), 168.7 (C=O). Calcd. for C22H23ClN2O2: C, 69.01; H, 6.06; N, 7.32. Found: C, 69.19; H, 6.13; N, 7.17.
1-(5-(3-chlorophenyl)-3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P14), white solid, (61% yield); mp 85–88 °C. 1H-NMR (400 MHz, CDCl3): δ 1.78 (s, 3H, CH3), 1.83 (s, 3H, CH3), 2.45 (s, 3H, CH3), 3.12 (dd, Jab = 17.6 Hz, Jac = 4.4 Hz, 1H, Ha), 3.74 (dd, Jab = 17.6 Hz, Jbc = 12.0 Hz, 1H, Hb), 4.58 (d, J = 6.4 Hz, 2H, CH2), 5.50 (d, J = 6.4 Hz, 1H, =CH), 5.55 (dd, Jbc = 12.0 Hz, Jac = 4.4 Hz, 1H, Hc), 6.97 (d, J = 8.8 Hz, 2H, Ar), 7.14 (d, J = 6.8 Hz, 1H, Ar), 7.22–7.29 (m, 3H, Ar), 7.69 (d, J = 8.8 Hz, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 21.9 (CH3), 25.8 (CH3), 42.4 (C(4)H2, pyr), 59.4 (C(5)H2, pyr), 65.0 (CH2-O), 114.9 (2 × Ar), 119.2 (=CH), 123.6 (Ar), 123.9 (Ar), 125.8 (Ar), 127.9 (Ar), 128.2 (2 × Ar), 130.2 (Ar), 134.8 (Ar), 138.8 (C=), 143.9 (Ar), 153.8 (C=N, pyr), 160.8 (Ar), 168.8 (C=O). Calcd. for C22H23ClN2O2: C, 69.01; H, 6.06; N, 7.32. Found: C, 68.84; H, 5.99; N, 7.35.
1-(5-(4-chlorophenyl)-3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P15), yellow solid (72% yield); 57–60 °C. 1H-NMR (400 MHz, CDCl3): δ 1.78 (s, 3H, CH3) 1.82 (s, 3H, CH3), 2.42 (s, 3H, CH3), 3.10 (dd, Jab = 17.6 Hz, Jac = 4.4 Hz, 1H, Ha), 3.72 (dd, Jab = 17.6 Hz, Jbc = 11.6 Hz, 1H, Hb), 4.57 (d, J = 6.4 Hz, 2H, CH2), 5.49-5.51 (m, 1H, =CH), 5.54 (dd, Jac = 4.4 Hz, Jbc = 11.6 Hz, 1H, Hc), 6.96 (d, J = 8.8 Hz, 2H, Ar), 7.18 (d, J = 8.4 Hz, 2H, Ar), 7.29 (d, J = 8.8 Hz, 2H, Ar), 7.68 (d, J = 8.8 Hz, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 21.9 (CH3), 25.8 (CH3), 42.3 (C(4)H2, pyr), 59.2 (C(5)H2, pyr), 65.0 (CH2-O), 114.9 (2 × Ar), 119.2 (=CH), 123.7 (Ar), 127.1 (2 × Ar), 128.2 (2 × Ar), 129.0 (2 × Ar), 133.3 (Ar), 138.7 (=C=), 140.5 (Ar), 153.7 (C=N, pyr), 160.8 (Ar), 168.7 (C=O). Calcd. for C22H23ClN2O2: C, 69.01; H, 6.06; N, 7.32. Found: C, 68.91; H, 6.05; N, 7.41.
1-(5-(2,4-dichlorophenyl)-3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P16), white solid (80% yield); mp 128–130 °C. 1H-NMR (400 MHz, CDCl3) 1.77 (s, 3H, CH3) 1.82 (s, 3H, CH3), 2.49 (s, 3H, CH3), 2.99–3.04 (m, 1H, Ha), 3.79–3.86 (m, 1H, Hb), 4.56 (d, J = 6 Hz, 2H, CH2), 5.50 (br, 1H, =CH), 5.84–5.86 (m, 1H, Hc), 6.94 (d, J = 8.4 Hz, 2H, Ar), 7.01 (d, J = 7.6 Hz, 1H, Ar), 7.20 (d, J = 7.2 Hz, 1H, Ar), 7.43 (s, 1H, Ar), 7.67 (d, J = 8.4 Hz, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 21.9 (CH3), 25.9 (CH3), 41.4 (C(4)H2, pyr), 57.3 (C(5)H2, pyr), 64.9 (CH2-O), 114.9 (2 × Ar), 119.1 (=CH), 123.5 (Ar), 127.0 (Ar), 127.6 (Ar), 128.2 (2 × Ar), 129.8 (Ar), 132.4 (Ar), 133.8 (Ar), 137.3 (Ar), 138.8 (C=), 154.1 (C=N, pyr), 160.8 (Ar), 168.8 (C=O). Calcd. for C22H22Cl2N2O2: C, 63.32; H, 5.31; N, 6.71. Found: C, 63.17; H, 5.35; N, 6.76.
1-(5-([1,1′-biphenyl]-4-yl)-5-methyl-3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P17), white solid (63% yield); mp 132–135 °C. 1H-NMR (400 MHz, CDCl3): δ 1.79 (s, 3H, CH3) 1.84 (s, 3H, CH3), 2.47 (s, 3H, CH3), 3.20 (dd, Jab = 17.6 Hz, Jac = 4.8 Hz, 1H, Ha), 3.77 (dd, Jab = 17.6 Hz, Jbc = 11.6 Hz, 1H, Hb), 4.59 (d, J = 6.8 Hz, 2H, CH2), 5.51–5.54 (m, 1H, =CH), 5.65 (dd, Jac = 4.6 Hz, Jbc = 11.8 Hz, 1H, Hc), 6.98 (d, J = 8.8 Hz, 2H, Ar), 7.32–7.35 (m, 3H, Ar), 7.42–7.44 (m, 2H, Ar), 7.55–7.57 (m, 4H, Ar), 7.72 (d, J = 8.8 Hz, 2H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 22.0 (CH3), 25.9 (CH3), 42.4 (C(4)H2, pyr), 59.6 (C(5)H2, pyr), 65.0 (CH2-O), 114.9 (2 × Ar), 119.2 (=CH), 123.9 (Ar), 126.1 (2 × Ar), 127.1 (2 × Ar), 127.3 (Ar), 127.7 (2 × Ar), 128.2 (2 × Ar), 128.8 (2 × Ar), 138.7 (C=), 140.6 (Ar), 140.8 (Ar), 141.0 (Ar), 153.8 (C=N, pyr), 160.7 (Ar), 168.7 (C=O). Calcd. for C28H28N2O2: C, 79.22; H, 6.65; N, 6.60. Found: C, 79.41; H, 6.69; N, 6.45.
1-(3-(4-((3-methylbut-2-en-1-yl)oxy)phenyl)-5-(naphthalen-1-yl)-4,5-dihydro-1H-pyrazol-1-yl)ethan-1-one (P18), orange solid (77% yield); mp 78–80 °C. 1H-NMR (400 MHz, CDCl3): δ 1.75 (s, 3H, CH3), 1.84 (s, 3H, CH3), 2.45 (s, 3H, CH3), 3.19 (dd, Jab = 17.7 Hz, Jac = 4.2 Hz, 1H, Ha), 3.77 (dd, Jab = 17.4 Hz, Jbc = 11.7 Hz, 1H, Hb), 4.55 (d, J = 6.9 Hz, 2H, CH2), 5.47–5.52 (m, 1H, =CH), 5.63–5.67 (dd, Jbc = 11.7 Hz, Jac = 4.8 Hz, 1H, Hc), 6.95 (d, J = 9.0 Hz, 1H, Ar), 7.31–7.34 (m, 1H, Ar), 7.40–7.45 (m, 2H, Ar), 7.68–7.74 (m, 3H, Ar), 7.77–7.81 (m, 4H, Ar). 13C-NMR (101 MHz, CDCl3): δ 18.3 (CH3), 22.0 (CH3), 25.9 (CH3), 42.5 (C(4)H2, pyr), 60.0 (C(5)H2, pyr), 65.0 (CH2-O), 114.9 (2 × Ar), 119.1 (=CH), 123.5 (Ar), 123.9 (Ar), 124.5 (Ar), 125.9 (Ar), 126.2 (Ar), 127.6 (Ar), 128.0 (Ar), 128.2 (2 × Ar), 129.0 (Ar), 132.9 (Ar), 133.3 (Ar), 138.8 (C=), 139.2 (Ar), 153.9 (C=N, pyr), 160.7 (Ar), 168.8 (C=O). Calcd. for C26H26N2O2: C, 78.36; H, 6.58; N, 7.03. Found: C, 78.21; H, 6.71; N, 6.99.