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the reaction had finished, the reaction mixture was extracted with diethyl ether and brine.
The organic layer was dried with MgSO4 and filtered. The solvent was then evaporated.
The mixture was purified by silica column chromatography with ethyl acetate and hexane.
The product was obtained as a reddish solid (Yield: 55%). 1H-NMR (300 MHz, CDCl3); δ
ppm 1.05 (m, 6H), 1.25 (s, 9H), 1.30 (s, 9H), 1.34 (s, 9H), 2.02 (m, 4H), 6.84 (d, J = 9.0
Hz, 2H), 7.06 (d, J = 9.0 Hz, 2H), 7.33 (m, 5H), 7.50 (d, J = 9.0 Hz, 2H), 7.61 (m, 2H),
9.72 (s, 1H); 13C-NMR (125 MHz): δ ppm 190.4, 157.3, 142.4, 140.1, 138.7, 136,3, 135.7,
134.2, 131.6, 129.8, 129.3, 127.2, 126.5, 125.3, 122.3, 121.4, 121.1, 120.2, 119.2, 118.3,
116.2, 56.9, 38.7, 38.5, 35.7, 35.3, 32.3, 31.8, 31.2, 30.9, 8.7, 8.4; Mass (FAB) m/z = 585
(M+).
4-((3,5-di-tert-butylphenyl)(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-
yl)amino)benzaldehyde. (2b) Compound 2b was prepared by method of compound
2a using 2-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene and 3,5-di-tert-
butylaniline. The obtained compound was yellow solid (Yield : 48%). 1H-NMR (300 MHz,
CDCl3): δ ppm 1.24 (s, 18H), 1.36 (s, 12H) 1.57 (m, 4H), 6.95 (m, 4H), 7.24 (m, 3H), 7.70
(m, 3H), 9.80 (s, 1H); 13C-NMR (125 MHz): δ ppm 191.1, 159.3, 147.8, 145.4, 143.2,
134.7, 132.1, 130.5, 128.7, 126.8, 125.2, 124.3, 123.3, 122.1, 120.9, 36.2, 35.7, 34.9, 34.5,
34.3, 32.2, 31.9, 30.7; Mass (FAB) m/z = 495 (M+).
4-(Bis(3,5-di-tert-butylphenyl)amino)benzaldehyde. (2c) Compound 2c was prepared
by method of compound 2a using 1-bromo-3,5-di-tert-butylbenzene and 3,5-di-tert-
1
butylaniline. The obtained compound was yellow solid (Yield : 39%). H-NMR (300
MHz, CDCl3): δ ppm 1.15 (s, 18H), 1.24 (s, 18H), 7.01 (m, 4H), 7.03 (m, 2H), 7.67 (m,
2H), 9.80(s, 1H). 13C-NMR (125 MHz): δ ppm 190.7, 159.3, 147.3, 145.2, 139.3, 137.7,
129.3, 127.6, 122.5, 34.7, 30.1; Mass (FAB) m/z = 497 (M+).
4-((4-tert-butylphenyl)(3,7-di-tert-butylnaphlen-2-yl)amino)benzaldehyde. (2d) Com-
pound 2d was prepared by method of compound 2a using 1-bromo-3,7-di-tert-
buthylnaphthalene and 4-tert-butylaniline. The obtained compound was yellowish solid
(Yield : 60%). 1H-NMR (300 MHz, CDCl3); δ ppm 1.22 (s, 9H), 1.27 (s, 9H) 1.33 (s, 9H),
6.91 (d, J = 9.0 Hz, 2H), 7.18 (d, J = 9.0 Hz, 2H), 7.30 (d, J = 9.0 Hz, 2H), 7.49(s, 1H),
7.63 (d, J = 9.0 Hz, 2H), 7.71 (s, 2H), 7.79 (d, J = 8.5 Hz, 1H), 7.89 (d, J = 8.5 Hz, 1H),
9.77 (s, 1H); 13C-NMR (125 MHz): δ ppm 189.7, 155.1, 147.5, 133.2, 132.6, 131.5, 130.3,
129.3, 126.3, 125.1, 124.1, 122.7, 121.5, 120.3, 119.2, 118.0, 116.4, 115.2, 110.2, 35.9,
35.1, 34.6, 31.9, 31.6, 31.0; Mass (FAB) m/z = 491 (M+).
2-(6,8-di-tert-butyl-2-(4-((4-tert-butylphenyl)(2,7-di-tert-butyl-9,9-diethyl-9H-
fluoren-4-yl)amino)styryl)-4H-chromen-4-ylidene)malononitrile. (3a) To a solution of
compound 1 (0.26 mmol) and 2a (0.26 mmol) in anhydrous ethyl alcohol (10 ml) was
added piperidine (1.17 mmol) and then heated to 140◦C for 5 h with dean-stark trap.
After cooling in refrigerator, the mixture was filtered with hexane and extracted with
ethyl acetate and brine. After evaporation of solvent, the mixture was purified by silica
column chromatography with ethyl acetate and hexane and re-crystallized with hexane.
The obtained compound was a reddish solid (Yield: 43%). 1H-NMR (300 MHz, CDCl3):
δ ppm 8.81 (d, J = 1.5 Hz, 1H), 7.75 (s, 1H), 7.63 (m, 1H), 7.50 (m, 8H), 7.22 (m, 2H),
7.12 (m, 2H), 6.93 (m, 3H), 6.63 (d, J = 15.8 Hz, 1H), 2.05 (d, J = 7.0 Hz, 5H), 1.39 (s,
12H), 1.32 (t, J = 4.2 Hz, 31H), 0.39 (s, 7H); 13C-NMR (125 MHz, CDCl3): δ ppm 158.2,
154.6, 152.8, 152.4, 150.3, 150.1, 149.5, 148.3, 147.1, 143.1, 139.2, 138.5, 138.3, 137.1,
137.0, 131.8, 130.1, 130.0, 129.8, 128.4, 126.7, 126.5, 125.6, 124.8, 124.2, 123.8, 122.1,
120.5, 119.5, 117.7, 116.0, 115.1, 65.6, 56.3, 35.8, 35.7, 35.2, 35.0, 34.6, 31.8, 31.6 8.9;
FT-IR (KBr): ν = 2969, 2342, 1508, 1496, 1457, 1177, 832 cm−1; Mass (EI) m/z = 887
(M+); HRMS (EI) calcd for C63H73N3O, 887.5754; found, 887.5761; mp: 176◦C.