Paper
NJC
6.98 (d, J = 9.0 Hz, 4H, Ar), 7.26 (d, J = 8.5 Hz, 4H, Ar), 7.82 (t, J = 7.0 Hz, 6H, CH3), 1.37–1.48 (m, 8H, CH2), 1.86 (quin,
(t, J = 8.0 Hz, 1H, Py), 7.85 (d, J = 8.5 Hz, 4H, Ar), 7.94 (d, J = 8.5 Hz, J = 7.0 Hz, 4H, CH2), 4.16 (t, J = 6.5 Hz, 4H, CH2), 7.17 (d, J =
4H, Ar), 8.12 (d, J = 8.0 Hz, 2H, Py), 8.34 (s, 2H, CHQN), 8.37 (s, 2H, 9.0 Hz, 4H, Ar), 7.68 (d, J = 9.5 Hz, 4H, Ar), 7.76 (d, J = 8.5 Hz,
NH–CQO) ppm; 13C NMR (125 MHz, CDCl3): d 14.06 (CH3), 22.59 4H, Ar), 8.33 (d, J = 9.0 Hz, 4H, Ar), 8.84 (t, J = 8.0 Hz, 1H, Py),
(CH2), 25.95 (CH2), 29.02 (CH2), 29.14 (CH2), 31.75 (CH2), 68.27 8.97 (d, J = 8.0 Hz, 2H, Py), 9.13 (s, 2H, CHQN) ppm; 13C NMR
(CH2), 109.7 (Py), 114.8 (Ar), 121.2 (Ar), 128.4 (Ar), 128.5 (Ar), 130.7 (125 MHz, CDCl3): d 14.50 (CH3), 24.07 (CH2), 29.79 (CH2),
(Ar), 130.9 (Ar), 141.0 (Py), 149.8 (Ar), 156.1 (Py), 161.1 (CHQN), 162.4 30.38 (CH2), 72.13 (CH2), 119.1 (Ar), 124.6 (Ar), 125.6 (Ar), 127.8
(Ar), 165.0 (CQO) ppm. Elemental analysis, found: C, 74.80; H, 7.01; (Py), 131.1 (Ar), 133.8 (Ar), 136.3 (Ar), 145.9 (Ar), 148.8 (Py),
N, 9.22. Calc. for C47H53N5O4: C, 75.07; H, 7.10; N, 9.31%.
159.6 (Py), 161.2 (Ar), 163.3 (CQO), 164.6 (CHQN) ppm.
Elemental analysis, found: C, 73.73; H, 6.14; N, 5.95. Calc. for
N,N0-Bis[4-(4-dodecyloxyphenyl)methyliminobenzoyl]-2,6-
diaminopyridine (Ic). Yield 47%; FTIR (KBr) n = 3293, 2919, 2851,
1648, 1590, 1509, 1462, 1305, 1249, 1167, 852, 796 cmꢀ1; 1H NMR
(500 MHz, CDCl3): d 0.88 (t, J = 7.5 Hz, 6H, CH3), 1.27–1.50 (m, 36H,
CH2), 1.82 (quin, J = 7.0 Hz, 4H, CH2), 4.04 (t, J = 6.5 Hz, 4H, CH2),
6.99 (d, J = 9.0 Hz, 4H, Ar), 7.27 (d, J = 9.0 Hz, 4H, Ar), 7.83 (t, J =
8.5 Hz, 1H, Py), 7.86 (d, J = 9.0 Hz, 4H, Ar), 7.95 (d, J = 8.5 Hz, 4H,
Ar), 8.13 (d, J = 8.0 Hz, 2H, Py), 8.32 (s, 2H, CHQN), 8.38 (s, 2H,
NH–CQO) ppm; 13C NMR (125 MHz, CDCl3): d 14.11 (CH3), 22.68
(CH2), 25.99 (CH2), 29.15 (CH2), 29.34 (CH2), 29.37 (CH2), 29.55
(CH2), 29.58 (CH2), 29.63 (CH2), 29.65 (CH2), 31.91 (CH2), 68.29
(CH2), 109.7 (Py), 114.8 (Ar), 121.2 (Ar), 128.4 (Ar), 128.5 (Ar), 130.8
(Ar), 130.9 (Ar), 141.0 (Py), 149.8 (Ar), 156.2 (Py), 161.1 (CHQN),
162.4 (Ar), 165.0 (CQO) ppm. Elemental analysis, found: C, 76.43;
H, 8.16; N, 7.78. Calc. for C57H73N5O4: C, 76.73; H, 8.25; N, 7.85%.
Preparation of di[4-(4-n-alkyloxyphenyliminomethyl)phenyl]
pyridine-2,6-dicarboxylates (IIa–IIc)
C
43H43N3O6: C, 74.01; H, 6.21; N, 6.02%.
Di[4-(4-n-heptyloxyphenyliminomethyl)phenyl] pyridine-2,6-
dicarboxylate (IIb). Yield 49%; FTIR (KBr) n = 3068, 2953,
2935, 2858, 1762, 1623, 1604, 1578, 1508, 1254, 1231, 1162,
1
1148, 867, 835, 554 cmꢀ1; H NMR (500 MHz, CDCl3): d 0.85
(t, J = 7.0 Hz, 6H, CH3), 1.28–1.51 (m, 16H, CH2), 1.85 (quin,
J = 7.0 Hz, 4H, CH2), 4.16 (t, J = 6.5 Hz, 4H, CH2), 7.16 (d, J =
9.0 Hz, 4H, Ar), 7.68 (d, J = 9.5 Hz, 4H, Ar), 7.75 (d, J = 9.0 Hz,
4H, Ar), 8.32 (d, J = 8.5 Hz, 4H, Ar), 8.83 (t, J = 8.0 Hz, 1H, Py),
8.96 (d, J = 8.0 Hz, 2H, Py), 9.12 (s, 2H, CHQN) ppm; 13C NMR
(125 MHz, CDCl3): d 14.69 (CH3), 24.35 (CH2), 27.62 (CH2),
30.71 (CH2), 30.86 (CH2), 33.69 (CH2), 72.19 (CH2), 119.1 (Ar),
124.6 (Ar), 125.6 (Ar), 127.8 (Py), 131.2 (Ar), 133.8 (Ar), 136.4
(Ar), 146.0 (Ar), 148.8 (Py), 159.6 (Py), 161.2 (Ar), 163.3 (CQO),
164.6 (CHQN) ppm. Elemental analysis, found: C, 74.61; H,
6.74; N, 5.52. Calc. for C47H51N3O6: C, 74.88; H, 6.82; N, 5.57%.
Di(4-formylphenyl) pyridine-2,6-dicarboxylate (2d). To an ice-
cold solution of 4-hydroxybenzaldehyde (2c, 20.8 g, 0.171 mol)
in dry pyridine (100 cm3) a dipicolinic acid chloride (2b, 17.6 g,
0.095 mol) was added gradually. The reaction mixture was
stirred at room temperature for 2 days, the solvent was removed
under reduced pressure, and the residue was rinsed with plenty
of water. The crude product was purified by recrystallization from
dimethylformamide, and the obtained yield was 62%. m.p. = 220–
222 1C; FTIR (KBr) n = 3063, 1761, 1683, 1597, 1573, 1395, 1308,
Di[4-(4-n-dodecyloxyphenyliminomethyl)phenyl]
pyridine-
2,6-dicarboxylate (IIc). Yield 57%; FTIR (KBr) n = 3070, 2956,
2919, 2850, 1762, 1624, 1605, 1578, 1509, 1253, 1162, 1024, 867,
836, 554 cmꢀ1; 1H NMR (500 MHz, CDCl3): d 0.83 (t, J = 7.0 Hz,
6H, CH3), 1.27–1.52 (m, 36H, CH2), 1.86 (quin, J = 7.0 Hz, 4H,
CH2), 4.16 (t, J = 6.5 Hz, 4H, CH2), 7.16 (d, J = 9.0 Hz, 4H, Ar),
7.68 (d, J = 9.0 Hz, 4H, Ar), 7.75 (d, J = 9.0 Hz, 4H, Ar), 8.32 (d, J =
9.0 Hz, 4H, Ar), 8.83 (t, J = 8.0 Hz, 1H, Py), 8.96 (d, J = 8.0 Hz, 2H,
Py), 9.12 (s, 2H, CHQN) ppm; 13C NMR (125 MHz, CDCl3): d
14.75 (CH3), 24.45 (CH2), 27.61 (CH2), 30.67 (CH2), 31.14 (CH2),
31.28 (CH2), 31.40 (CH2), 31.46 (CH2), 31.54 (CH2), 33.89 (CH2),
72.15 (CH2), 119.1 (Ar), 124.6 (Ar), 125.6 (Ar), 127.7 (Py), 131.1
(Ar), 133.8 (Ar), 136.3 (Ar), 145.9 (Ar), 148.7 (Py), 159.6 (Py), 161.2
(Ar), 163.2 (CQO), 164.6 (CHQN) ppm. Elemental analysis, found:
C, 76.32; H, 7.92; N, 4.64. Calc. for C57H71N3O6: C, 76.56;
H, 8.00; N, 4.70%.
1233, 1208, 1171, 1156, 995, 907, 831, 752, 727, 565, 417 cmꢀ1
;
1H NMR (200 MHz, CDCl3): d 7.62 (d, J = 8.4 Hz, 4H, Ar), 8.07
(d, J = 8.6 Hz, 4H, Ar), 8.39 (t, J = 7.8 Hz, 1H, Py), 8.58 (d, J = 7.8 Hz,
2H, Py), 10.05 (s, 2H, CHO) ppm; 13C NMR (50 MHz, CDCl3): d 123.1
(Ar), 129.9 (Py), 131.5 (Ar), 134.6 (Ar), 140.1 (Py), 147.2 (Py), 155.4 (Ar),
162.6 (COO), 192.4 (CHO) ppm. Elemental analysis, found: C, 66.94;
H, 3.53; N, 3.70. Calc. for C21H13NO6: C, 67.20; H, 3.49; N, 3.73%.
Di[4-(4-n-alkyloxyphenyliminomethyl)phenyl] pyridine-2,6-
dicarboxylates (IIa–IIc). To the solution of di(4-formylphenyl)
pyridine-2,6-dicarboxylate (2d) (3.00 mmol) in dimethyl sulfoxide
(35 cm3) a solution of the respective 4-n-alkoxyaniline (2e–2g)
(6.00 mmol) in DMSO (15 cm3) was added dropwise. The reaction
was carried out at 90 1C for 24 h. After cooling to the room
temperature, the precipitate was filtered off and recrystallized
from toluene.
Preparation of 2,6-bis[2-(4-(4-alkyloxybenzoyloxy)phenyl)-
ethenyl]pyridines (IIIa–IIIc)
2,6-Bis[2-(4-hydroxyphenyl)ethenyl]pyridine (3c) was synthesized
by a modified literature procedure.15. A mixture of 2,6-lutidine
(3a, 2.7 g, 0.025 mol), 4-hydroxybenzaldehyde (2c, 9.2 g, 0.075 mol)
and acetic anhydride (25 cm3) was refluxed for 24 hours at 155 1C.
The reaction mixture was poured into cold water (150 cm3)
and shaken until the excess acetic anhydride was completely
Di[4-(4-n-pentoxyphenyliminomethyl)phenyl] pyridine-2,6- hydrolyzed. The product was filtered, washed with water and
dicarboxylate (IIa). Yield 54%; FTIR (KBr) n = 3067, 2957, recrystallized repeatedly from ethanol. A mixture of obtained
2937, 2864, 1762, 1624, 1604, 1578, 1508, 1253, 1230, 1161, 2,6-bis-[2-(4-ethanoyloxyphenyl)ethenyl]pyridine (3b, 1.5 g) and
1
1022, 867, 836, 553 cmꢀ1; H NMR (500 MHz, CDCl3): d 0.91 0.75 mol dmꢀ3 alcoholic potassium hydroxide (15 cm3) was
1758 | New J. Chem., 2014, 38, 1751--1760
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