112
stirred at room temperature for 48 h. After addition of 2.282 g
13C NMR (CDCl3, 63 MHz): δ = 155.08 (Cq, Ar–O), 154.94
(16.420 mmol) of K2CO3 and 5 mL of H2O, the reaction mix- (Cq, Ar–O), 137.50 (Cq, Ar), 128.70 (CH, Ar), 127.82 (CH,
ture was stirred at 40 °C for 12 h and extracted with Et2O (3 ´ Ar), 126.40 (Cq, Ar), 113.20 (CH, Ar), 112.21 (Cq, Ar), 67.30
20 mL). The resulting solution was washed with water and (CH2–O), 65.40 (CH2–O), 41.00 (Cq–CH2), 32.60 (CH2), 29.20
dried over sodium sulfate. After removal of the solvent under (CH2), 22.60 (CH2), 19.40 (CH3), 5.40 (ICH2).
vacuum, the product was purified by chromatography on a Elemental analysis calcd (%) for C41H51IO4 (734.7.3): C
silica-gel column with a 6:4 pentane/ether mixture providing 67.02, H 7.00; found: C 67.75, H 7.48.
1.524 g (84%) of 12 as a white solid.
1H NMR (CDCl3, 250 MHz): δ = 7.22 (d, 2H, Ar), 7.05 (d,
(l) Benzylalcohol tri-methylphenyl dendron (15)
6H, Ar), 6.75 (m, 8H, Ar), 3.84 (t, 3JH,H = 6.4 Hz, 6H, CH2–O),
2.27 (s, 9H, CH3), 1.83 (m, 6H, CH2–CH2); 1.59 (m, 6H,
CH2–CH2).
A mixture of 0.232 g (1.860 mmol) of HOCH2-p-C6H4OH,
0.513 g (3.720 mmol) of K2CO3 in 10 mL of DMF was stirred
for 30 min at room temperature. 1.503 g (2.046 mmol) of den-
dron 14 was then added in the reaction mixture and the result-
ing solution stirred at 40 °C for 16 h. The mixture was extract-
ed with CH2Cl2 (3 ´ 20 mL), and the resulting solution washed
with water and dried over sodium sulfate. After removal of the
solvent under vacuum, the product was purified by chromatog-
raphy on a silica-gel column with a 7:3 pentane/ether mixture
providing 1.045 g (70%) of 15 as a yellow oil.
13C NMR (CDCl3, 63 MHz): δ = 156.07 (Cq, Ar–O), 153.34
(Cq, Ar–O), 143. 18 (Cq, Ar), 138.71 (Cq, Ar), 127.73 (CH, Ar),
126.20 (CH, Ar ), 114.99 (CH, Ar), 113.92 (CH, Ar), 68.34 (CH2–
O), 42.20 (Cq–CH2), 33.79 (CH2), 23.81 (CH2), 20.68 (CH3).
Elemental analysis calcd (%) for C37H44O4 (552.75): C
80.40, H 8.02; found: C 79.87, H 8.72.
(j) Chloroalkyl tri-methylphenyl dendron (13)
1H NMR (CDCl3, 250 MHz): δ = 7.27 (m, 4H, Ar), 7.05
A mixture of 2.700 g (4.884 mmol) of phenol 12, 2.022 g
(14.654 mmol) of K2CO3, and 1.2 mL (9.768 mmol) of 1-chlo-
ro-4-iodobutane in 20 mL of DMF was stirred at room temper-
ature for 48 h. The reaction mixture was then extracted with
Et2O (3 ´ 30 mL), and the resulting solution was washed with
water and dried over sodium sulfate. The solvent was removed
under vacuum, and the product was purified by chromatogra-
phy on a silica-gel column with a 99:1 pentane/diethyl ether
mixture to provide 2.513 g (80%) of 13 as a colorless oil.
3
3
(d, JH,H = 8.2 Hz, 6H, Ar), 6.87 (m, 4H, Ar), 6.75 (d, JH,H
8.2 Hz, 6H, Ar), 4.62 (s, 2H, CH2–OH), 4.03 (m, 4H, CH2–O),
=
3
3.85 (t, JH,H = 6.4 Hz, 6H, CH2–O), 2.27 (s, 9H, CH3), 1.99
(m, 4H, CH2–CH2), 1.84 (m, 6H, CH2–CH2), 1.60 (m, 6H,
CH2–CH2).
13C NMR (CDCl3, 63 MHz): δ = 158.39 (Cq, Ar–O), 156.70
(Cq, Ar–O), 138.29 (Cq, Ar), 132.98 (Cq, Ar), 130.65 (CH, Ar),
129.70 (CH, Ar), 128.74 (CH, Ar), 128.42 (CH, Ar), 127.32
(Cq, Ar), 115.18 (CH, Ar), 114.34 (CH, Ar), 114.18 (Cq, Ar),
68.19 (CH2–O), 67.36 (CH2–O), 67.14 (CH2–O), 64.65 (CH2–
OH), 41.86 (Cq–CH2), 33.53 (CH2), 25.90 (CH2), 23.54 (CH2),
20.33 (CH3).
3
1H NMR (CDCl3, 250 MHz): δ = 7.28 (d, JH,H = 8.8 Hz,
3
3
2H, Ar), 7.08 (d, JH,H = 8.2 Hz, 6H, Ar), 6.84 (d, JH,H = 8.8
Hz, 2H, Ar), 6.75 (d, 3JH,H = 8.2 Hz, 6H, Ar), 3.99 (t, 3JH,H = 5.8
Hz, 2H, CH2–O), 3.86 (t, 3JH,H = 6.4 Hz, 6H, CH2-O), 3.62 (t,
3JH,H = 6.1 Hz, 2H, CH2-Cl), 2.28 (s, 9H, CH3), 1.98 (m, 4H;
CH2–CH2), 1.86 (m, 6H, CH2–CH2), 1.60 (m, 6H, CH2–CH2).
13C NMR (CDCl3, 63 MHz): δ = 155.06 (Cq, Ar–O), 154.94
(Cq, Ar–O), 136.74 (Cq, Ar), 128.01 (CH, Ar), 127.82 (CH,
Ar), 125.68 (Cq, Ar), 112.51 (CH, Ar), 112.21 (Cq, Ar), 66.55
(CH2–O), 66.00 (CH2–O), 42.96 (Cl–CH2), 40.24 (Cq–CH2),
41.83 (CH2), 31.88 (CH2), 27.57 (CH2), 24.98 (CH2), 21.89
(CH2), 18.63 (CH3).
Elemental analysis calcd (%) for C54H58O6 (803.04): C
80.77, H 7.28; found: C 81.28, H 7.50.
(m) Benzyl bromide tri-methylphenyl dendron (16)
0.06 mL (0.600 mmol) of PBr3 was added to a cooled mix-
ture (0 °C) of 1.268 g (1.579 mmol) of dendron 15 in 15 mL
of toluene. The resulting solution was stirred at room tempera-
ture for 4 h. After removal of the solvent, the residue was ex-
tracted with Et2O, washed with water, and dried over sodium
sulfate. The solvent was removed under vacuum providing
1.093 g (99%) of 15 as a yellow oil.
Elemental analysis calcd (%) for C41H51ClO4 (643.3): C
76.55, H 7.99; found: C 76.18, H 8.09.
(k) Iodoalkyl tri-methylphenyl dendron (14)
A mixture of 2.500 g (3.886 mmol) of 13 and 2.900 g (d, JH,H = 8.2 Hz, 6H, Ar), 6.90 (m, 4H, Ar), 6.76 (d, JH,H
1H NMR (CDCl3, 250 MHz): δ = 7.30 (m, 4H, Ar), 7.05
3
3
=
(19.400 mmol) of NaI in 30 mL of 2-butanone was stirred for 8.2 Hz, 6H, Ar), 4.45 (s, 2H, CH2–Br), 3.94 (m, 4H, CH2–O),
3
24 h at 80 °C. After removal of the solvent under vacuum, the 3.80 (t, JH,H = 6.4 Hz, 6H, CH2–O), 2.22 (s, 9H, CH3), 1.91
residue was extracted with Et2O (3 ´ 30 mL). The resulting (m, 4H; CH2–CH2), 1.79 (m, 6H; CH2–CH2), 1.63 (m, 6H;
solution was washed with an aqueous solution saturated with CH2–CH2).
Na2S2O3, dried over sodium sulfate, and then filtered. The sol-
vent was removed under vacuum to provide 2.740 g (96%) of (Cq, Ar–O), 138.90 (Cq, Ar), 138.74 (Cq, Ar), 130.89 (Cq, Ar),
14 as a colorless oil. 130.28 (CH, Ar), 130.18 (CH, Ar), 130.07 (CH, Ar), 127.93
13C NMR (CDCl3, 63 MHz): δ = 157.30 (Cq, Ar–O), 157.26
1H NMR (CDCl3, 250 MHz): δ = 7.23 (d, 3JH,H = 8.8 Hz, 2H, (CH, Ar), 115.18 (Cq, Ar), 114.76 (CH, Ar), 114.48 (Cq,
Ar), 7.03 (d, 3JH,H = 8.2 Hz, 6H, Ar), 6.77 (d, 3JH,H = 8.8 Hz, 2H, Ar), 68.80 (CH2–O), 68.00 (CH2–O), 67.69 (CH2–O), 42.49
Ar), 6.74 (d, 3JH,H = 8.2 Hz, 6H, Ar), 3.95 (t, 3JH,H = 5.8 Hz, 2H, (Cq–CH2), 34.52 (Br-CH2), 34.14 (CH2), 26.48 (CH2), 24.14
CH2–O), 3.83 (t, 3JH,H = 6.4 Hz, 6H, CH2–O), 3.26 (t, 3JH,H = 6.1 (CH2), 20.93 (CH3).
Hz, 2H, CH2–I), 2.26 (s, 9H, CH3), 1.98 (m, 4H, CH2–CH2),
1.82 (m, 6H, CH2–CH2), 1.65 (m, 6H, CH2–CH2).
Elemental analysis calcd (%) for C54H57BrO5 (865.94): C
74.90, H 6.63; found: C 74.60, H 6.39.
Israel Journal of Chemistry
49
2009