3.5. Synthesis of Compounds 8–14, 17–19 and 22–23
Self-metathesis, olefin-metathesis and ring-closing metathesis of compounds 8–14, 17–19 and 22–23, respectively, were carried out by using similar experimental conditions. As a general procedure, the appropriate allyl and vinyl-benzene derivatives (0.6 mmol) were dissolved in dry CH2Cl2 (5.0 mL) in the presence of a catalytic amount of ASIPr/SBA-15 (2.0 × 10−3 mmol of immobilized Ru, corresponding to 8.8 mg of heterogenous catalyst)) under argon atmosphere at 40 °C for 4 h. Thereafter, the crude was filtered using GH-polypro hydrophilic membranes (47 mm 0.2 μm), concentrated at low pressure and purified by flash chromatography (Hexane/Etylacetate 4:1) to afford the desired products.
3.5.1. (E)-4,4’-(but-2-ene-1,4-diyl)bis(2-methoxyphenol) (8)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.31 (d, J = 4 Hz, 4H, CH2), 3.87–3.91 (overlapping singlets, 6H, CH3), 5.71–5.87 (m, 2H, CH), 6.83–6.89 (m, 6Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ (COCH3), 146.8 (COH), 135.6 (CAr), 132.2 (C=C), 122.9 (CAr), 117.3 (CAr), 112.6 (CAr), 56.2 (CH3), 41.1(CH2). MS (ESI): m/z (M + H) + 301.34. Elemental Analysis for C18H20O4 calculated: C, 71.98, H, 6.71, O, 21.31. Found: 71.95, H, 6.74, O, 21.25.
3.5.2. (E)-4,4’-(but-2-ene-1,4-diyl)bis(2,6-dimethoxyphenol) (9)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.23–3.40 (m, 5.2 Hz, 4H, CH2), 3.50–3.75 (overlapping singlets, 12H, CH3), 5.56–5.70 (m, 2H, CH), 6.69 (s, 4Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ (COCH3), 136.2 (COH), 135.2 (CAr), 132.0 (C=C), 109.7 (CAr), 56.3 (CH3), 40.1(CH2). MS (ESI): m/z (M + H) + 361.16. Elemental Analysis for C20H24O6 calculated: C, 66.65, H, 6.71, O, 26.63, Found: C, 66.62, H, 6.74, O, 25.93.
3.5.3. (E)-5,5’-(but-2-ene-1,4-diyl)bis(3-methoxybenzene-1,2-diol) (10)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.32 (d, J = 4 Hz, 4H, CH2), 3.81–3.95 (overlapping singlets, 6H, CH3), 5.90–6.00 (m, 2H, CH), 6.71 (s, 2Har, CH), 6.79 (s, 2Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ (COCH3), 148.8 (COH), 136.2 (CAr), 132.4 (C=C), 125.4 (COH), 107.7 (CAr), 102.9 (CAr), 56.1 (CH3), 39.8 (CH2). MS (ESI): m/z (M + H) + 333.16. Elemental Analysis for C18H20O6 calculated: C, 65.65, H, 6.07, O, 28.88. Found: C, 65.62, H, 6.04, O, 28.78.
3.5.4. (E)-1,1’-(but-2-ene-1,4-diylbis(4-hydroxy-3,1-phenylene))bis(ethan-1-one) (11)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.40 (d, J = 4 Hz, 4H, CH2), 5.89–6.00 (m, 2H, CH), 7.40 (d, 2Har, CH). 7.75 (d, 2Har, CH), 7.98 (overlapped singlets, 2Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ (COCH3), 159.8 (COH), 135.2 (CAr), 130.1 (C=C), 128.3 (CAr), 113.7 (CAr), 112.6 (CAr), 57.3 (CH3), 40.3 (CH2). MS (ESI): m/z (M + H) + 325.14. Elemental Analysis for C20H20O4 calculated: C, 74.06, H, 6.22, O, 19.73. Found: C, 74.08, H, 6.24, O, 19.71.
3.5.5. (E)-2,2’-(but-2-ene-1,4-diyl)diphenol (12)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.38 (d, J = 4 Hz, 4H, CH2), 5.58-5.69 (m, 2H, CH), 6.71–6.79 (m, 4Har, CH), 6.97–7.10 (m, 4Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ COH), 139.1 (CAr), 132.2 (CAr), 130.7 (C=C), 127.9 (CAr), 120.5 (CAr), 113.2 (CAr), 40.0 (CH2). MS (ESI): m/z (M + H) + 241.12. Elemental Analysis for C16H16O2 calculated: C, 79.97, H, 6.71, O, 13.32. Found: C, 79.95, H, 6.58, O, 13.31.
3.5.6. (E)-4,4’-(ethene-1,2-diyl)bis(2-methoxyphenol) (13)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.89 (s, 6H, CH3), 6.75 (d, J = 8 Hz, 2H, CH), 6.89 (d, J = 4, 2 Har, CH) 6.95 (d, J = 8 Hz, 2 Har, CH), 7.09 (s, 2Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ (COCH3), 146.2 (COH), 130.8 (CAr), 130.0 (C=C), 122.7 (CAr), 117.2 (CAr), 112.4 (CAr) 55.9 (CH3). MS (ESI): m/z (M + H) + 273.10. Elemental Analysis for C16H16O4 calculated: C, 70.58, H, 5.92, O, 23.50. Found: C, 70.58, H, 5.92, O, 23.50.
3.5.7. (E)-5,5’-(ethene-1,2-diyl)bis(3-methoxybenzene-1,2-diol) (14)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.88 (s, 6H, CH3), 6.70 (d, J = 8 Hz 2H, CH) 7.05 (overlapped singlets, 4Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ (COCH3), 145.5 (COH), 135.2 (COH), 133.3 (CAr), 130.8 (C=C), 107.4 (CAr), 105.2 (CAr), 55.8 (CH3). MS (ESI): m/z (M + H) + 305.10. Elemental Analysis for C16H16O6 calculated: C, 63.15, H, 5.30, O, 31.55. Found: C, 63.11, H, 5.28, O, 31.50.
3.5.8. (E)-5-(4-(4-hydroxy-3,5-dimethoxyphenyl)but-2-en-1-yl)-3-methoxybenzene-1,2-diol (17)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.08 (10d, J =4 Hz, 4H, CH2), 3.28 (s, 9H, CH3), 5.78–5.89 (m, 2H, CH) 6.31 (s, 1H, Har, CH), 6.33 (s, 1H, Har, CH), 6.68 (overlapped singlets, 2 Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ (COCH3), (COCH3), 146.2 (COH), 136.7 (CAr), 135.2 (CAr), 133.7 (CAr), 131.1 (C=C), 121.7 (CAr), 108.4 (CAr), 107.2 (CAr), 104.7 (CAr), 55.3 (CH3), 39.5(CH2). MS (ESI): m/z [M + H] + 347.14. Elemental Analysis for C19H22O6 calculated: C, 65.88, H, 6.40, O, 27.71. Found: C, 65.84, H, 6.38, O, 27.68.
3.5.9. (E)-3-(4-(4-hydroxy-3, 5-dimethoxyphenyl)but-2-en-1-yl)benzene-1,2-diol (18)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.30 (d, J = 4 Hz, 4H, CH2), 3.90 (overlapped singlets, 6H, CH3), 5.80–5.91 (m, 2H, CH) 6.52–6.63 (m, 3Har, CH) 6.80 (overlapped singlets, 2 Har, CH). 13C-NMR (100 MHz, CDCl3, ppm): δ (COCH3), (COH), 145.3 (COH), 135.8 (CAr), 134.7 (CAr), 133.3 (CAr), 131.0 (C=C), 119.0 (CAr), 117.8 (CAr), 113.1 (CAr), 106.9 (CAr), 57.1 (CH3), 38.2(CH2), 37.8(CH2). MS (ESI): m/z (M + H) + 317.14 Elemental Analysis for C18H20O5 calculated: C, 68.34, H, 6.37, O, 25.29. Found: C, 68.28, H, 6.31, O, 25.20.
3.5.10. (E)-3-(4-(2-hydroxyphenyl)but-2-en-1-yl)benzene-1,2-diol (19)
1H-NMR (400 MHz, CDCl3, ppm): δ 3.39 (d, J = 4 Hz, 4H, CH2), 5.88-5.99 (m, 2H, CH), 6.80-7.10 (m, 5Har, CH), 7.23-7.38 (m, 2Har, CH).13C-NMR (100 MHz, CDCl3, ppm): δ (COH), (COH), 145.3 (COH), 133.6 (CAr), 131.7 (CAr), 130.5 (C=C), 122.9 (CAr), 120.0 (CAr), 119.5 (CAr), 117.8 (CAr), 114.5 (CAr), 112.1 (CAr), 106.5 (CAr), 38.7(CH2), 37.5 (CH2). MS (ESI): m/z [M + H] + 257.11 Elemental Analysis for C16H16O3 calculated: C, 74.98, H, 6.29, O, 18.73. Found: C, 74.95 H, 6.24, O, 18.71.
3.5.11. (3E,8E)-14-hydroxy-6-aza-1(1,3),5(1,4)-dibenzenacyclodecaphane-3,8-dien-2-one (22)
1H-NMR (400 MHz, CD3OD, ppm): δ 3.40 (d, J = 4 Hz, 2H, CH2), 4.09 (d, J = 6 Hz, 2H, CH2), 5.68-5.80 (m, 1H, CH), 6.12-6.26 (m, 1H, CH), 7.25 (d, J = 8 Hz, 1Har, CH), 7.52 (d, J = 6 Hz, 1H, CH), 7.70 (m, 2Har,1H, 3xCH) 7.88 (m, 3Har, CH), 7.98 (d, J = 8 Hz, 1Har, CH). 13C-NMR (100 MHz, CD3OD, ppm): δ (CO), (COH), 149.8 (CNH), 143.6 (C=C), 133.9 (CAr), 132.3 (CAr), 130.9 (CAr), 129.7 (CAr), 128.5 (CAr), 126.0 (C=C), 124.6 (C=C), 123.2 (C=C), 121.7 (CAr), 115.6 (CAr), 112.3 (CAr), 54.5 (CH2), 32.1 (CH2). MS (ESI): m/z (M + H) + 292.12 Elemental Analysis for C19H17NO2 calculated C, 78.33, H, 5.88, N, 4.81, O, 10.98. Found: C, 78.29, H, 5.82, N, 4.71, O, 10.82.
3.5.12. (3E,8E)-14-hydroxy-6-oxa-1(1,3),5(1,4)-dibenzenacyclodecaphane-3,8-dien-2-one (23)
1H-NMR (400 MHz, CD3OD, ppm): δ 3.42 (dd, 2H, CH2), 4.52 (d, J = 4 Hz, 2H, CH2), 5.60–5.78 (m, 1H, CH), 6.10–6.20 (m, 1H, CH), 6.87 (d, J = 8 Hz, 1Har, CH), 6.91 (d, J = 8 Hz, 2Har, CH), 7.05 (d, J = 6 Hz, 1Har, CH), 7.50 (d, J = 8 Hz, 1Har, CH), 7.62–7.80 (m, 2Har, 1H, CH), 7.91 (s, 1H, CH). 13C-NMR (100 MHz, CD3OD, ppm): δ (CO), (COH), 159.8 (CO), 148.9 (C=C), 132.4 (CAr), 131.8 (CAr), 130.9 (CAr), 128.4 (CAr), 127.2 (CAr), 123.4 (C=C), 122.6 (C=C), 122.0 (C=C), 120.5 (CAr), 116.4 (CAr), 111.9 (CAr), 75.0 (CH2), 35.5 (CH2). MS (ESI): m/z (M + H) + 293.11 Elemental Analysis for C19H16O3 calculated: C, 78.29, H, 5.82, N, 4.71, O, 10.82. Found: C, 77.89, H, 5.49, O, 16.39.
3.6. Synthesis of (E)-1-(3-allyl-4-hydroxyphenyl)-3-(4-(allylamino)phenyl)prop-2-en-1-one (20)
Chalcone 20 was prepared by nucleophilic aromatic displacement of previously prepared (E)-1-(3-allyl-4-hydroxyphenyl)-3-(4-fluorophenyl)prop-2-en-1-one (0.01 mol) with commercially available allylamine (0.05 mol). Reagents were dissolved in DMF(10 mL) and heated at 120 °C under magnetic stirring for 18 h in the presence of KOH (0.02 mol). Thereafter the mixture was cooled in ice bath, acidified with HCl 1N and extracted with ethyl acetate (3 × 50 mL). The aqueous phases were collected, basified with NaOH 1N and again extracted with ethyl acetate (3 × 50 mL). The organic phases were collected, concentrated at low pressure and the resulting brown oil purified by flash chromatography (hexane/ethylacetate 3:1) to afford the desired product 21 in quantitative yield.
1H-NMR (400 MHz, CD3OD, ppm): δ 3.46 (d, J = 6 Hz, 2H, CH2), 4.12 (d, J = 4 Hz, 2H, CH2), 4.98–5.10 (dd, 2H, CH), 5.18–5.36 (m, 2H, CH), 5.85–6.30 (m, 2H, CH), 7.48 (d, J = 8 Hz, 2Har, CH), 7.62 (m, 3H, CH), 7.78 (d, J = 6 Hz, 2Har, CH), 7.85 (d, J = 8, 1Har, CH), 7.91 (s, 1H, CH). 13C-NMR (100 MHz, CD3OD, ppm): δ (CO),(COH), 146.8 (CNH), 145.1 (C=C), 136.5 (C=C), 135.6 (C=C), 131.8 (CAr), 129.6 (CAr), 128.4 (CAr), 125.1 (CAr), 122.8 (CAr), 122.2 (CAr), 121.0 (C=C), 116.8 (C=C), 115.1 (C=C), 112.0 (CAr), 46.0 (CH2), 35.7 (CH2). MS (ESI): m/z [M + H] + 320.18 Elemental Analysis for C21H21NO2 calculated: C, 78.97, H, 6.63, N, 4.39, O, 10.02. Found: C, 78.94, H, 6.57, N, 4.31, O, 9.82.
3.7. Synthesis of (E)-1-(3-allyl-4-hydroxyphenyl)-3-(4-fluorophenyl)prop-2-en-1-one
(E)-1-(3-allyl-4-hydroxyphenyl)-3-(4-fluorophenyl)prop-2-en-1-one was prepared by aldolic condensation between 4-hydroxy-3-allyl acetophenone (0.01 mol) and 4-fluorobenzaldehyde (0.011 mol) in EtOH under basic conditions (KOH, 0.02 mol) at 80 °C for 24 h. Thereafter the crude was neutralized with HCl 1N and extracted with ethylacetate (3 × 50 mL). The organic phases were collected and concentrated under reduced pressure. The dark brown solid obtained was recrystallized in MeOH to afford desired product as yellow solid in quantitative yield.
1H-NMR (400 MHz, CD3OD, ppm): δ 3.49 (d, J = 4 Hz, 2H,CH2), 5.10–5.19 (m, 2H, CH2), 6.02–6.10 (m, 1H, CH), 7.50 (d, J = 8 Hz, 2Har, CH), 7.62 (m, 3H, CH), 7.78 (d, J = 6 Hz, 2Har, CH), 7.85 (d, J = 8 (CO), (CF), (COH), 145.1 (C=C), 136.5 (C=C), 131.6 (CAr), 129.4 (CAr), 128.1 (CAr), 124.7 (CAr), 122.7 (CAr), 122.0 (CAr), 121.2 (C=C), 116.3 (CAr), 115.9 (C=C), 112.0 (CAr), 33.6 (CH2). MS (ESI): m/z (M + H) + 283.11 Elemental Analysis for C18H15FO2 calculated: C, 76.58, H, 5.36, F, 6.73, O, 11.33. Found: C, 76.49, H, 5.26, F, 6.51, O, 10.98.
3.8. Synthesis of Compound 21
Chalcone 21 was prepared by aldolic condensation between 4-hydroxy-3-allyl acetophenone (0.01 mol) and 4-(allyloxy)benzaldehyde (0.011 mol) in EtOH under basic conditions (KOH, 0.02 mol) at 80 °C for 24 h. Thereafter the crude was neutralized with HCl 1N and extracted with etylacetate (3 × 50 mL). The organic phases were collected and concentrated under reduced pressure. The orange solid obtained was recrystallized in MeOH to afford desired product as yellow solid in quantitative yield.
1H-NMR (400 MHz, CD3OD, ppm): δ 3.42 (dd, 2H, CH2), 4.52 (d, J = 4 Hz, 2H, CH2), 5.05–5.10 (m, 2H, CH), 5.30–5.47 (m, 2H, CH), 5.90–6.20 (m, 2H, CH), 6.85 (d, J = 6 Hz, 1Har, CH), 6.90 (d, J = 8 Hz, 2Har, CH), 7.01 (d, J = 6 Hz, 1Har, CH), 7.48 (d, J = 8 Hz, 1Har, CH), 7.62–7.80 (m, 2HAr, 1H, CH), 7.91 (s, 1H, CH). 13C-NMR (100 MHz, CD3OD, ppm): δ (CO), (COH), 156.5 (CO), 145.3 (C=C), 136.9 (C=C), 136.2 (C=C), 133.8 (CAr), 131.5 (CAr), 128.7 (CAr), 128.4 (CAr), 125.1 (CAr), 122.8 (CAr), 122.2 (CAr), 121.0 (C=C), 115.2 (C=C), 114.1 (C=C), 113.0 (CAr), 70.1 (CH2), 33.6 (CH2). MS (ESI): m/z (M + H) + 321.14 Elemental Analysis for C21H20O3 calculated C, 78.73, H, 6.29, O, 14.98. Found: C, 78.56, H, 6.21, O, 14.85.