Synthesis of Novel Tris-Crown Ether Structures

Abstract

Six unique tris-crown ether structures were successfully synthesized from trimethylolpropane triacrylate (TMPTA) with amino- and aza-crown ethers through Michael addition. The crown ethers contained a primary amine group such as 2-amino­methyl crown ethers and 4-aminobenzo crown ethers, others contained a secondary amine group, like 1-aza crown ethers.

Key words

amino-crown ether - aza-crown ether - tris-crown ether - TMPTA - Michael addition

References

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41

TMPTA: Trimethylolpropane (13.42 g, 0.1 mol) was dissolved in benzene (50 mL). Pyridine (3 mL) was added and the mixture stirred for 30 min. In an ice bath acryloyl chloride (29.90 g, 0.33 mol) was added dropwise to the flask over 3 h, then the reaction was stirred below 50 °C. After 30 h the solution was washed with aqueous K₂CO₃ (2 N, 20 mL), water (3 × 20 mL), active carbon was added, and the mixture was dried over magnesium sulfate for 12 h. After filtration, the solvent was evaporated and filtered again through a pad of silica to give a colorless oil (24.1 g, isolated yield 81%). ¹H NMR (300 MHz, CDCl₃): d = 0.94 (t, J = 7.5 Hz, 3 H), 1.53-1.61 (q, 2 H), 4.18 (s, 6 H), 5.83-5.88 (d, J = 10.5 Hz, 3 H), 6.07-6.17 (dd, J = 10.8 Hz, 6.6 Hz, 3 H), 6.38-6.44 (d, J = 17.1 Hz, 3H); ¹³C NMR (75 MHz, CDCl₃): d = 165.87, 131.33, 128.27, 64.10, 40.88, 23.19, 7.41; MS(GC): m/z = 296 [M]⁺. Anal. calcd for C₁₅H₂₀O₆: C, 60.80; H, 6.80. Found: C, 60.68; H, 6.81.

42

Tris-crown ether 1: TMPTA (30 mg, 0.1 mmol) and 1-aza-15-crown-5 (88 mg, 0.4 mmol) were dissolved in MeOH (5 mL), the reaction was stirred at 50 °C; after 24 h the solvent was evaporated in vacuo and purified via column chromatography on silica gel (EtOAc), affording tris-crown ether 1 as a yellow oil (79 mg, isolated yield 82.8%). IR (NaCl): 2921.6, 2878.3, 1957.4, 1730.8, 1581.4, 1458.9, 1393.3, 1355.7, 1297.9, 1252.5, 1196.6, 1119.5, 1062.6, 989.3, 940.1, 852.4, 829.2, 778.1 cm^-1; ¹H NMR (300 MHz, CDCl₃): d = 0.84 (t, J = 7.5 Hz, 3 H), 1.22-1.27 (q, 2 H), 2.49 (t, J = 7.2 Hz, 6 H), 2.75 (t, J = 6.0 Hz, 12 H), 2.88 (t, J = 7.5 Hz, 6 H), 3.48-3.75 (m, 54 H); ¹³C NMR (75 MHz, CDCl₃): d = 173.16, 70.96, 70.38, 70.16, 69.92, 66.58, 54.47, 51.98, 42.75, 32.49, 23.09, 7.50; MS (EI): m/z = 954.5 [M]⁺; MS (FAB): m/z = 955.4 [M + H]⁺; Anal. calcd for C₄₅H₈₃N₃O₁₈: C, 56.65; H, 8.77; N, 4.40. Found: C, 56.38; H, 8.81; N 4.32.
Tris-crown ether 2: TMPTA (30 mg 0.1 mmol) and 1-aza-18-crown-6 (105 mg 0.4 mmol) were dissolved in MeOH (5 mL), the reaction was carried out as above, to afford a yellow oil (88 mg, isolated yield 81.0%). IR (NaCl): 2877.3, 2500.3, 1968.9, 1730.8, 1644.0, 1577.5, 1459.9, 1352.8, 1289.2, 1249.7, 1110.8, 988.3, 951.7, 835.0, 777.2 cm^-1; ¹H NMR (300 MHz, CDCl₃): δ = 0.84 (t, J = 7.5 Hz, 3 H), 1.22-1.27 (q, 2 H), 2.48 (t, J = 7.2 Hz, 6 H), 2.77 (t, J = 6.0 Hz, 12 H), 2.88 (t, J = 7.2 Hz, 6 H), 3.46-3.70 (m, 66 H); ¹³C NMR (75 MHz, CDCl₃): δ = 173.19, 70.83, 70.72, 70.70, 70.49, 70.45, 70.36, 70.25, 70.17, 70.03, 69.80, 65.55, 53.85, 51.56, 42.80, 32.43, 22.89, 7.53; MS(FAB): m/z = 1087.4 [M + H]⁺. Anal. calcd for C₅₁H₉₅N₃O₂₁: C, 56.39; H, 8.81; N, 3.87. Found: C, 56.12; H, 8.90; N, 3.78.

43

Tris-crown ether 3: TMPTA (30 mg, 0.1 mmol) and 2-aminomethyl-15-crown-5 (125 mg, 0.5 mmol) were dissolved in MeOH (5 mL), the reaction was carried out as above, to afford tris-crown ether 3 as a slight yellow oil (77 mg, isolated yield 73.8%). IR (NaCl): 2926.5, 2880.2, 1731.8, 1644.0, 1596.8, 1460.8, 1382.1, 1354.8, 1250.6, 1194.7, 1117.6, 1061.6, 989.3, 947.8, 871.7, 844.7, 778.1 cm^-1; ¹H NMR (300 MHz, CDCl₃): d = 0.84 (t, J = 7.8 Hz, 3 H), 1.22-1.27 (q, 2 H), 2.51 (t, J = 6.6 Hz, 6 H), 2.70 (d, J = 6.0 Hz, 6 H), 2.88 (t, J = 6.6 Hz, 6 H), 3.58-3.78 (m, 66 H); ¹³C NMR (75 MHz, CDCl₃): d = 173.05, 70.90, 70.64, 70.53, 70.45, 66.49, 51.57, 50.21, 42.75, 32.56, 23.04, 7.48; MS (FAB): m/z = 1044.5 [M + H]⁺. Anal. calcd for C₄₈H₈₉N₃O₂₁: C, 55.21; H, 8.59; N, 4.02. Found: C, 54.94; H, 8.62; N, 3.95.
Tris-crown ether 4: TMPTA (30 mg, 0.1 mmol) and 2-aminomethyl-18-crown-6 (147 mg, 0.5 mmol) were dissolved in MeOH (5 mL), operated the same as above, afforded tris-crown ether 4 as a slight yellow oil (86 mg, isolated yield 73.1%). IR (NaCl): 2922.6, 2881.1, 1730.8, 1665.2, 1592.0, 1461.8, 1384.6, 1352.8, 1285.3, 1249.7, 1187.9, 1107.9, 1060.7, 989.3, 882.3, 835.0, 777.2 cm^-1; ¹H NMR (300 MHz, CDCl₃): d = 0.83 (t, J = 7.8 Hz, 3 H), 1.22-1.27 (q, 2 H), 2.52 (t, J = 6.9 Hz, 6 H), 2.70 (d, J = 6.0 Hz, 6 H), 2.89 (t, J = 6.6 Hz, 6 H), 3.53-3.82 (m, 78 H); ¹³C NMR (75 MHz, CDCl₃): d = 173.09, 70.95, 70.71, 70.52, 70.45, 70.31, 70.01, 69.55, 69.52, 65.76, 51.68, 50.15, 42.84, 32.57, 22.78, 7.44; MS (FAB): m/z = 1177.6 [M + H]⁺. Anal. calcd for C₅₄H₁₀₁N₃O₂₄: C, 55.13; H, 8.65; N, 3.57. Found: C, 54.89; H, 8.57; N, 3.53.

44

Tris-crown ether 5: TMPTA (30 mg, 0.1 mmol) and 4-aminobenzo-15-crown-5 (142 mg, 0.5 mmol) were dissolved in MeOH (6 mL), triethylamine(catalyst) was added and the reaction was continued for six days at 50 °C. The reaction afforded tris-crown ether 5 as a red brown oil (84 mg, isolated yield 73.3%). IR (NaCl): 3364.2, 3037.4, 2924.5, 2871.5, 1965.1, 1726.0, 1615.1, 1513.9, 1455.0, 1408.8, 1357.6, 1226.5, 1184.1, 1123.3, 1057.8, 984.5, 939.2 cm^-1; ¹H NMR (300 MHz, CDCl₃): d = 0.84 (t, J = 7.5 Hz, 3 H), 1.22-1.27 (q, 2 H), 2.61 (t, J = 6.3 Hz, 6 H), 3.39 (t, J = 6.6 Hz, 6 H), 3.67-3.75 (m, 30 H), 3.86-3.91 (m, 12 H), 4.05-4.11 (m, 12 H), 6.13-6.27 (dd, ArH, 6 H), 6.77-6.79 (d, ArH, 3 H); ¹³C NMR (75 MHz, CDCl₃): d = 172.91, 150.43, 143.19, 141.61, 117.48, 104.80, 101.03, 70.89, 70.80, 70.73, 70.43, 70.39, 69.92, 69.58, 69.55, 67.92, 51.76, 40.17, 33.68, 23.78, 7.44; MS (FAB): m/z = 1146.4 [M + H]⁺. Anal. calcd for C₅₇H₈₃N₃O₂₁: C, 59.72; H, 7.30; N, 3.67. Found: C, 59.84; H, 7.41; N, 3.62.
Tris-crown ether 6: TMPTA (30 mg, 0.1 mmol) and 4-aminobenzo-18-crown-6 (163 mg, 0.5 mmol) were dissolved in MeOH (6 mL), affording tris-crown ether 6 as a deep brown oil (91 mg, isolated yield 71.2%). IR (NaCl): 3367.1, 3037.4, 2917.8, 2880.2, 1967.0, 1729.8, 1617.0, 1516.7, 1455.0, 1408.8, 1354.8, 1280.5, 1230.4, 1186.0, 1117.6, 989.3 cm^-1; ¹H NMR (300 MHz, CDCl₃): d = 0.85 (t, J = 7.5 Hz, 3 H), 1.22-1.27 (q, 2 H), 2.60 (t, J = 6.3 Hz, 6 H), 3.37 (t, J = 6.3 Hz, 6 H), 3.62-3.76 (m, 42 H), 3.84-3.93 (m, 12 H), 4.02-4.12 (m, 12 H), 6.13-6.27 (dd, ArH, 6 H), 6.76-6.79 (d, ArH, 3 H); ¹³C NMR (75 MHz, CDCl₃): δ = 172.88, 150.43, 143.22, 141.30, 117.51, 104.85, 101.20, 70.82, 70.78, 70.75, 70.71, 70.65, 70.56, 70.48, 69.93, 69.67, 69.63, 68.81, 67.91, 51.73, 40.11, 33.65, 22.57, 7.53; MS (FAB): m/z = 1278.6 [M + H]⁺. Anal. calcd for C₆₃H₉₅N₃O₂₄: C, 59.19; H, 7.49; N, 3.29. Found: C, 59.37; H, 7.43; N, 3.22.