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6.8, 15.6Hz, 2″-H, 5″-H), 6.70 (d, 2H, J=8.0Hz, 6-H, 6′-H), 5′-H, 5″-H), 6.45 (m, 6H, 1-H, 6-H, 3-H, 4-H, 3′-H, 3″-H),
6.44 (d, 2H, J=15.6Hz, 1″-H, 6″-H), 6.41 (dd, 2 H, J=2.4, 3.86 (s, 6H, 2×OCH3), 3.84 (s, 6H, 2×OCH3); 13C-nMR
6.8Hz, 3″-H, 4″-H), 4.01 (q, 4H, J=6.8Hz, 2×OCH2), 1.30 (t, (100MHz, CDCl3) δ: 160.5 (C4′, C4″), 158.0 (C2′, C2″), 133.5
6H, J=6.8Hz, 2×OCH2CH3); 13C-nMR (100MHz, DMSO-d6) (C6′, C6″), 128.3, 127.3, 126.5, 120.0 (C1′, C1″), 105.2 (C5′,
δ: 147.6 (C2, C2′), 147.5 (C1, C1′), 133.2 (C1″, C6″), 132.7 (C3″, C5″), 98.7 (C3′, C3″), 55.7 (2′-OCH3, 2″-OCH3), 55.6 (4′-OCH3,
C4″), 129.6 (C4, C4′), 127.3 (C2″, C5″), 120.6 (C5, C5′), 116.3 4″-OCH3); Anal. Calcd for C22H24O4: C, 74.98; H, 6.86. Found:
(C6, C6′), 111.6 (C3, C3′), 64.5 (2×OCH2), 15.4 (2×CH2CH3); C, 75.03; H, 6.70.
Anal. Calcd for C22H24O4: C, 74.98; H, 6.86. Found: C, 75.11;
H, 6.93.
(1E,3E,5E)-1,6-Bis(3,4,5-trimethoxyphenyl)hexa-1,3,5-triene
(13): Light yellow solid; reaction time, 9.5h; yield, 27%;
5,5′-((1E,3E,5E)-Hexa-1,3,5-triene-1,6-diyl)bis(2-methoxy- melting point, 203.5–207.8°C; 1H-nMR (500MHz, CDCl3)
phenol) (8): Dark yellow solid; reaction time, 5h/overnight; δ: 6.81 (ddd, 2H, J=2.5, 7.0, 15.5Hz, 2-H, 5-H), 6.65 (s,
yield, 8% (two-step yield); melting point, 248.5–251.6°C; 4H, 2′-H, 6′-H, 2″-H, 6″-H), 6.53 (d, 2H, J =15.5Hz, 1-H,
1H-nMR (500MHz, DMSO-d6) δ: 8.98 (s, 2H, 2×OH), 6.90 6-H), 6.52 (dd, 2H, J=2.5, 7.0Hz, 3-H, 4-H), 3.91 (s, 12H,
(s, 2H, 6-H, 6′-H), 6.86 (d, 2H, J=8.5Hz, 4-H, 4′-H), 6.84 (d, 3′-OCH3, 5′-OCH3, 3″-OCH3, 5″-OCH3), 3.87 (s, 6H, 4′-OCH3,
2H, J=8.5Hz, 3-H, 3′-H), 6.74 (ddd, 2H, J=3.0, 7.0, 15.5Hz, 4″-OCH3); 13C-nMR (100MHz, CDCl3) δ: 153.6 (C3′, C5′,
2″-H, 5″-H), 6.46 (d, 2H, J=15.5Hz, 1″-H, 6″-H), 6.45 (dd, C3″, C5″), 138.2 (C4′, C4″), 133.5 (C1, C6), 133.3 (C1′, C1″),
2H, J=3.0, 7.0Hz, 3″-H, 4″-H), 3.75 (s, 6H, 2×CH3); 13C-nMR 132.7 (C3, C4), 128.9 (C2, C5), 103.7 (C2′, C6′, C2″, C6″),
(100MHz, DMSO-d6) δ: 148.3 (C2, C2′), 147.3 (C1, C1′), 61.2 (4′-OCH3, 4″-OCH3), 56.3 (3′-OCH3, 5′-OCH3, 3″-OCH3,
133.4 (C1″, C6″), 132.5 (C3″, C4″), 131.0 (C5, C5′), 127.8 5″-OCH3); Anal. Calcd for C24H28O6: C, 69.88; H, 6.84. Found:
(C2″, C5″), 118.9 (C4, C4′), 113.3 (C6, C6′), 112.9 (C3, C3′), C, 69.94; H, 7.01.
56.3 (2×OCH3); Anal. Calcd for C20H20O4: C, 74.06; H, 6.21.
Found: C, 74.20; H, 6.38.
4,4′-((1E,3E,5E)-Hexa-1,3,5-triene-1,6-diyl)bis(2,6-di-
methoxyphenol) (14): Dark brown solid; reaction time,
(1E,3E,5E)-1,6-Bis(4-methoxyphenyl)hexa-1,3,5-triene (9): 5h/overnight; yield, 7% (two-step yield); melting point,
Light yellow solid; reaction time, 12h; yield, 11%; melt- 217.5–220.6°C; 1H-nMR (500MHz, CDCl3) δ: 6.75 (ddd,
ing point, 247.5–248.9°C; 1H-nMR (500MHz, CDCl3) δ: 2H, J=2.5, 7.0, 15.0Hz, 2″-, 5″-H), 6.66 (s, 4H, 3-H, 5-H,
7.37 (d, 4H, J=8.5Hz, 2′-H, 6′-H, 2″-H, 6″-H), 6.88 (d, 4H, 3′-H, 5′-H), 6.49 (d, 2H, J=15.0Hz, 1″-H, 6″-H) 6.48 (dd, 2H,
J=8.5Hz, 3′-H, 5′-H, 3″-H, 5″-H), 6.77 (ddd, 2H, J=2.5, 7.0, J=2.5, 7.0Hz, 3″-H, 4″-H), 5.58 (s, 2H, 2×OH), 3.92 (s, 12H,
15.5Hz, 2-H, 5-H), 6.54 (d, 2H, J=15.5Hz, 1-H, 6-H), 6.47 2-OCH3, 6-OCH3, 2′-OCH3, 6′-OCH3); 13C-nMR (100MHz,
(dd, 2H, J=2.5, 7.0Hz, 3-H, 4-H), 3.84 (s, 6H, 4′-OCH3, CDCl3) δ: 147.4 (C2, C6, C2′, C6′), 135.0 (C1, C1′), 133.0 (C1″,
4″-OCH3); 13C-nMR (100MHz, CDCl3) δ: 159.4 (C4′, C4″), C6″), 132.6 (C3″, C4″), 129.3 (C4, C4′), 127.7 (C2″, C4″),
133.0 (C1, C6), 131.9 (C3, C4), 130.6 (C1′, C1″), 127.7 (C2′, 103.3 (C3, C5, C3′, C5′), 56.5 (2-OCH3, 6-OCH3, 2′-OCH3,
C6′, C2″, C6″), 127.5 (C2, C5), 114.3 (C3′, C5′, C3″, C5″), 6′-OCH3); Anal. Calcd for C22H24O6: C, 68.74; H, 6.29. Found:
55.5 (2×OCH3); Anal. Calcd for C20H20O2: C, 82.16; H, 6.89. C, 68.71; H, 6.17.
Found: C, 82.31; H, 6.83.
Synthesis of Compound 15 A solution of α,α′-dichloro-
(1E,3E,5E)-1,6-Bis(3,4-dimethoxyphenyl)hexa-1,3,5-triene p-xylene (4.0g, 22.85mmol) in triethylphosphite (29mL) was
(10): Light yellow solid; reaction time, 7h; yield, 12%; melting refluxed for 24h. After cooling, volatiles were evaporated.
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point, 238.4–240.9°C; H-nMR (400MHz, CDCl3) δ: 6.95 (s, The residue was purified by silica gel column chromatogra-
2H, 2′-H, 2″-H), 6.94 (d, 2H, J=8.0Hz, 6′-H, 6″-H), 6.80 (d, phy using hexane and etOAc (1:4) to give diphosphonate 15
2H, J=8.0Hz, 5′-H, 5″-H), 6.74 (ddd, 2H, J=3.2, 7.2, 15.6Hz, (8.56g, 99%).
2-H, 5-H), 6.50 (d, 2H, J=15.6Hz, 1-H, 6-H), 6.46 (dd, 2H,
Synthesis of Compounds 17–21, 23, and 26 A solu-
J=3.2, 7.2Hz, 3-H, 4-H), 3.90 (s, 6H, 2×OCH3), 3.87 (s, 6H, tion of 15 (0.6eq) in THF and a solution of TBS-protected
2×OCH3); 13C-nMR (100MHz, CDCl3) δ: 149.3 (C3′, C3″), benzaldehydes (1.0eq, 3a–g) in THF were added to a stirred
149.1 (C4′, C4″), 133.1 (C1, C6), 132.2 (C3, C4), 130.9 (C1′, suspension of naH (1.5eq) in THF and the reaction mixture
C1″), 127.7 (C2, C5), 120.0 (C6′, C6″), 111.5 (C5′, C5″), 108.8 was stirred at room temperature for 4–8.5h. The reaction mix-
(C2′, C2″), 56.2 (2×OCH3), 56.1 (2×OCH3); Anal. Calcd for ture was partitioned between methylene chloride and aqueous
C22H24O4: C, 74.98; H, 6.86. Found: C, 74.75; H, 6.66.
nH4Cl solution and the organic layers were dried, filtered and
5,5′-((1E,3E,5E)-Hexa-1,3,5-triene-1,6-diyl)dibenzene-1,3- evaporated to give crude 1,4-bis-trans-styrylbenzenes. To a
diol (11): Yellow solid; reaction time, 3.5h/overnight; yield, solution of crude 1,4-bis-trans-styrylbenzenes in THF and
1% (two-step yield); 1H-nMR (500MHz, CD3OD) δ: 6.81 methanol (4:1) was added 12n HCl and the reaction mixture
(ddd, 2H, J=3.0, 7.5, 15.5Hz, 2″-H, 5″-H), 6.49 (dd, 2H, J=3.0, was stirred at room temperature overnight. After evapora-
7.5Hz, 3″-H, 4″-H), 6.44 (d, 2H, J=15.5Hz, 1″-H, 6″-H), 6.39 tion of volatiles, the precipitates generated were filtered and
(d, 4H, J=2.0Hz, 4-H, 6-H, 4′-H, 6′-H), 6.17 (t, 2H, J=2.0Hz, washed with water and/or methylene chloride and/or hexane to
2-H, 2′-H); 13C-nMR (100MHz, CD3OD) δ: 158.4 (C1, C3, give compounds 17–21, 23, and 26.
C1′, C3′), 139.7 (C5, C5′), 133.5 (C1″, C6″), 132.8 (C3″, C4″),
Synthesis of Compounds 22, 24, and 25 A solution of 15
129.0 (C2″, C5″), 104.8 (C4, C6, C4′, C6′), 102.0 (C2, C2′); (0.6eq) in THF and a solution of methoxy-substituted benz-
Anal. Calcd for C18H16O4: C, 72.96; H, 5.44. Found: C, 72.95; aldehydes (1.0eq) in THF were added to a stirred suspension
H, 5.35.
of naH (1.5eq) in THF and the reaction mixture was stirred
(1E,3E,5E)-1,6-Bis(2,4-dimethoxyphenyl)hexa-1,3,5-triene at room temperature. After evaporation of volatiles, the pre-
(12): Chrome yellow solid; reaction time, 2d; yield, 15%; cipitates generated were filtered using water and washed with
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melting point, 192.1–194.3°C; H-nMR (500MHz, CDCl3) δ: water and/or methylene chloride and/or hexane to give com-
7.42 (d, 2H, J=8.5Hz, 6′-H, 6″-H), 6.83 (m, 4 H, 2-H, 5-H, pounds 22, 24, and 25.