POLY SUBSTITUTED QUINOLINE SYNTHESIS
995
o-ethoxyphenol 2 (13.8 g, 0.1 mol) in ethanol (400 ml) to maintain the temperature
below 5 ꢀC for 4 h and then evaporated to dryness. The residue was dissolved with
ethanol, filtered, and washed with ethanol; the solvent was evaporated under vacuum
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and dried overnight at 80 ꢀC to yield 34 g of 3 (99%) as a yellow solid. H NMR
(300 MHz, d-DMSO, ppm) d 1.35 (t, 3H, J ¼ 7.2 Hz), 4.09 (q, 2H, J ¼ 7.2 Hz), 6.95
(d, 1H, J ¼ 8.1 Hz), 7.42 (s, 1H), 7.46 (d, 1H, J ¼ 8.1 Hz), 7.73 (s, 4H). 13C NMR
(75 MHz, d-DMSO, ppm): d 15.2, 64.3, 104.4, 116.2, 122.0, 127.2, 144.8, 148.6,
149.6, 152.6, 154.3. MS (MALDI): 321 (Mþ).
Sodium 4-((4-Decyloxy-3-ethoxyphenyl)diazenyl)benzenesulfonate 4
Sodium 4-((3-ethoxy-4-hydroxyphenyl)diazenyl)benzenesulfonate 3 (3.44 g,
0.01 mol), KOH (0.56 g 0.01 mol), CaO (2.8 g 0.05 mol), and KI (0.1 g) were dissolved
in 40 ml of DMSO, and 3 ml of N-decylbromide were added. The mixture was stirred
at reflux for 12 h. The residue was dissolved with dimethylformamide (DMF),
filtered, and washed with DMF. After the solvent was evaporated, the product
was dried under vacuum to give 4.72 g of 4 (98%) as yellow solid. 1H NMR
(300 MHz, d-DMSO, ppm) d 0.84 (t, 3H, J ¼ 6.6 Hz), 1.24–1.36 (m, 14H), 1.73
(t, 2H, J ¼ 6.9 Hz), 1.74 (m, 2H), 4.04–4.13 (m, 4H), 7.16 (d, 1H, J ¼ 8.7 Hz), 7.44
(s, 1H), 7.57 (d, 1H, J ¼ 8.7 Hz), 7.42 (s, 1H), 7.77 (s, 4H). 13C NMR (75 MHz,
d-DMSO, ppm): d 14.5, 15.2, 22.6, 26.0, 29.1, 29.2, 29.5, 29.6, 21.2, 64.5, 69.1,
104.4, 113.1, 119.0, 120.9, 121.0, 122.3, 127.2, 146.6, 149.4, 150.5, 152.3, 152.5.
MS (MALDI): 461 (Mþ).
4-Decyloxy-3-ethoxyaniline Hydrochloride 5
Sodium 4-((4-n-decyloxy)-3-ethoxyphenyl) diazenylbenzenesulfonate 4 (1.0 g,
2.07 mmol) was dissolved in 25 ml water. The resulting yellow solution was reduced
by stirring with Na2S2O4 (2.1 g, 10.3 mmol) under argon for 0.5 h at 90 ꢀC. The
reaction mixture was cooled to room temperature. The resulting white precipitate
was filtered, washed with water, and then dissolved in ethyl acetate. The filtrate
was extracted with ethyl acetate (3 ꢁ 20 mL). The dried organic layers (Na2SO4) were
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bubbled with anhydrous HCl to gave 0.511 g of 5 (75%) as a white solid. H NMR
(300 MHz, d-DMSO, ppm) d 0.84 (t, 3H, J ¼ 6.6 Hz), 1.24 (m, 14H), 1.35 (t, 3H,
J ¼ 6.9 Hz), 1.67 (m, 2H), 3.89–4.02 (m, 4H), 6.72 (d, 1H, J ¼ 8.7 Hz), 6.96 (s, 1H),
7.00 (d, 1H, J ¼ 8.7 Hz), 10.0 (br, 2H). 13C NMR (75 MHz, d-DMSO, ppm): d
13.9, 14.5, 22.0, 25.4, 28.6, 28.6, 28.9, 28.9, 31.2, 64.2, 68.7, 108.9, 114.0, 115.2,
124.5, 126.8, 148.0, 148.7. MS (MALDI): 294 (M þ 1).
3-Ethoxy-4-n-decyloxy-anilionmethylene-malonic Acid Diethyl Ester 6
A mixture of 4-(decyloxy)-3-ethoxyaniline hydrochloride (2.0 g, 6.08 mmol),
triethylamine (1.2 g, 12.16 mmol), and EMME (1.20 g, 5.47 mmol) in isopropanol
(50 mL) was heated at reflux for 10 h. The residue was dissolved with n-hexane
(50 mL), filtered, and washed with n-hexane. The solvent was evaporated under
vacuum and dried overnight at 40 ꢀC to yield 2.72 g of 3-ethoxy-4-n-
decyloxy-anilionmethylene-malonic acid diethyl ester 6 (90%) as a brown liquor.