Self-Assembling Dendrons
FULL PAPER
71.41 (ArOCH2Ar, 3’,4’ positions), 113.07 (ArCH, G1: 2’ positions),
114.04 (ArCH, G1: 5’ positions), 114.43 (ArCH, 2’ position), 115.18
(ArCH, 5’ position), 119.56(Ar CH, G1: 6’ positions), 120.55 (ArCH, 6’
position), 126.54 (ArCH, 2,6 positions), 126.91 (ArCH, G1: 2,6positions),
127.68, 127.89 (ArCH, G1: 3,5 positions), 128.39 (ArCCO2CH3), 130.05
(ArCH, 3,5 positions), 133.40 (ArC, G1: 1’ position), 133.73 (ArC, 1’ po-
sition), 135.48, 135.51 (ArC, G1: 1 positions), 140.72, 140.76(Ar C, G1: 4
positions), 145.15 (ArC, 1 position), 148.94, 149.16, 149.33, 149.35 (ArC,
3’,4’, G1: 3’,4’ positions), 166.96 ppm (CO2CH3); MS (ESI-TOF): m/z:
1336.7 [M+Na]+; elemental analysis calcd (%) for C88H128O8 (1313.95): C
80.44, H 9.82; found: C 80.59, H 10.12.
(ArC, 3’,4’, G1: 3’,4’ positions); MS (ESI-TOF): m/z: 1308.7 [M+Na]+;
elemental analysis calcd (%) for C87H128O7 (1285.94): C 81.26, H 10.03;
found: C 81.52, H 9.83.
4-Chloromethyl-3’,4’-bis(3’,4’-bisdodecyloxybiphenyl-4-ylmethoxy)biphen-
yl [(3,4Bp)212G2-CH2Cl] (32): Compound 31 (1.00G, 0.78 mmol), SOCl2
(0.09 mL, 1.20 mmol), and DTBMP (0.32G, 1.57 mmol) in CH2Cl2
(150 mL) were stirred for 3 h at 228C. After workup as described for 27,
the product 32 was obtained as a white solid. Two recrystallizations from
acetone gave fine white crystals (0.88G, 87%). A similar subsequent re-
action yielded 92% from a single recrystallization from EtOH. Rf =0.36
(hexanes/CH2Cl2 5:1); m.p. 128.0–1298C; 1H NMR (500 MHz, CDCl3,
Ethyl
3’,4’-bis(3’,4’-bisdodecyloxybiphenyl-4-ylmethoxy)biphenyl-4-car-
mixture of 4b (0.75G,
208C): d=0.89 (t, J=6.9 Hz, 12H; CH2CH3), 1.27 (m, CH3CAHTRE(UNG CH2)8), 64H;
boxylate [(3,4Bp)212G2-CO2C2H5] (30):
A
1.48 (m, 8H; ArOCH2CH2CH2), 1.84 (m, 8H; ArOCH2CH2), 4.04 (2t
overlapped, J=6.9 Hz, 8H; ArOCH2), 4.62 (s, 2H; CH2Cl), 5.25, 5.27
(2s, 4H; 3’,4’ ArOCH2Ar), 6.94 (d, J=8.1 Hz, 2H; G1: 5’ ArH), 7.04 (d,
J=8.3 Hz, 1H; 5’ ArH), 7.12 (m, 5H; 6’ and G1: 2’,6’ ArH), 7.21 (d, J=
1.8 Hz, 1H; 2’ ArH), 7.42 (d, J=8.3 Hz, 2H; 2,6Ar H), 7.53 ppm (m,
10H); 13C NMR (125 MHz, CDCl3, 208C): d=14.10 (CH3), 22.68
(CH2CH3), 26.06 (CH2CH2CH2OAr), 29.34–29.70 (ArOCH2CH2,
2.9 mmol), K2CO3 (1.2G, 8.7 mmol), and 20 (3.3G, 5.8 mmol) in DMF
(150 mL) was stirred at 708C for 15 h then poured into water and fil-
tered. The solid was dissolved in CHCl3, dried and purified by column
chromatography (silica gel, CHCl3). After the solvent was evaporated,
the product was recrystallized from EtOAc to yield 2.53G (65.7%) of
white crystals. Rf =0.47 (CHCl3); m.p. 78.6; purity (HPLC) 99 + %;
1H NMR (500 MHz, CDCl3, 208C): d=0.88 (m, 12H; CH2CH3), 1.27 (m,
CH3CH2CH2ACTHRE(UGN CH2)6), 31.92 (CH3CH2CH2), 46.06 (CH2Cl), 69.35, 69.45
67H; CH3ACHTREUNG(CH2)8), 1.48 (m, 8H; ArOCH2CH2CH2), 1.81 (m, 8H; Ar-
(ArOCH2CH2, G1: 3’,4’ positions), 71.14, 71.38 (ArOCH2Ar, 3’,4’ posi-
tions), 113.08 (ArCH, G1: 2’ positions), 114.06(Ar CH, G1: 5’ positions),
114.42 (ArCH, 2’ position), 115.28 (ArCH, 5’ position), 119.57 (ArCH,
G1: 6’ positions), 120.28 (ArCH, 6’ position), 126.92 (ArCH, G1: 2,6posi-
tions), 126.10 (ArCH, 2,6positions), 127.70, 127.85 (Ar CH, G1: 3,5 posi-
tions), 129.02 (ArCH, 3,5 positions), 133.78, 133.80 (ArC, G1: 1’ posi-
tions), 134.08 (ArC, 1’ position), 135.63 (ArC, G1: 1 positions), 136.02
(ArC, 4 position), 140.70 (ArC, G1: 4 positions), 140.99 (ArC, 1 position),
148.67, 148.92, 149.11, 149.33 ppm (ArC, 3’,4’, G1: 3’,4’ positions); MS
(ESI-TOF): m/z: 1327.8 [M+Na]+ elemental analysis calcd (%) for
C87H127ClO6 (1304.39): C 80.11, H 9.81; found: C 79.88, H 10.03.
OCH2CH2), 4.04 (2t overlapped, J=6.8 Hz, 8H ArOCH2), 3.93 (q, J=
7.0 Hz, 2H; CO2CH2CH3), 5.26, 5.28 (2s, 4H; 3’,4’ ArOCH2Ar), 6.94 (m,
2H; G1: 5’ ArH), 7.11 (m, 5H; 5’ and G1: 2’,6’ ArH), 7.18 (dd, J=2.2,
8.3 Hz, 1H; 6’ ArH), 7.26(overlapped with solvent peak, m, 1H; 2 ’
ArH), 7.53 (m, 10H), 8.07 ppm (d, J=8.6Hz, 2H; 3,5 Ar H); 13C NMR
(125 MHz, CDCl3, 208C): d=14.08 (CH3), 14.34 (CO2CH2CH3) 22.67
(CH2CH3), 26.07 (CH2CH2CH2OAr), 29.36–29.70 (ArOCH2CH2,
CH3CH2CH2ACHTREUNG(CH2)6), 31.92 (CH3CH2CH2), 60.89 (CO2CH2CH3), 69.42,
69.54 (ArOCH2CH2, G1: 3’,4’ positions), 71.16, 71.51 (ArOCH2Ar, 3’,4’
positions), 113.25 (ArCH, G1: 2’ positions), 114.23 (ArCH, G1: 5’ posi-
tions), 114.62 (ArCH, 2’ position), 115.35 (ArCH, 5’ position), 119.63
(ArCH, G1: 6’ positions), 120.60 (ArCH, 6’ position), 126.53 (ArCH, 2,6
positions), 126.93 (ArCH, G1: 2,6positions), 127.72, 127.89 (Ar CH, G1:
3,5 positions), 128.82 (ArCCO2CH3), 130.03 (ArCH, 3,5 positions),
133.57 (ArC, G1: 1’ position), 133.82 (ArC, 1’ position), 135.54, 135.58
(ArC, G1: 1 positions), 140.76, 140.80 (ArC, G1: 4 positions), 145.08
(ArC, 1 position), 149.03, 149.25, 149.35, 149.43 (ArC, 3’,4’, G1: 3’,4’ posi-
tions), 166.96 ppm (CO2CH3); MS (ESI-TOF): m/z: 1350.6[ M+Na]+; el-
emental analysis calcd (%) for C89H130O8 (1327.98): C 80.49, H 9.87;
found: C 80.61, H 10.04.
Methyl 3’,4’-bis[3’,4’-bis(3’,4’-dodecyloxybiphenyl-4-ylmethoxy)biphenyl-
4-ylmethoxy]biphenyl-4-carboxylate [(3,4Bp)312G3-CO2CH3] (33):
A
mixture of 32 (65 mg, 0.49 mmol), K2CO3 (276mg, 2.0 mmol), and 4a
(59 mg, 0.25 mmol) in DMF (200 mL) was maintained at 808C for 15 h,
then poured into H2O. The precipitate was filtered and washed with H2O
and acetone. The solid was subsequently recrystallized from CH2Cl2 to
give 540 mg (80.0%) of a fine white powder. Rf =0.40 (hexanes/CH2Cl2
1:2); m.p. 68.78C; purity (HPLC): 99+ %; 1H NMR (500 MHz, CDCl3,
208C): d=0.88 (m, 24H; CH2CH3), 1.27 (m, 128H; CH3CAHTRE(UNG CH2)8), 1.48 (m,
16H; ArOCH2CH2CH2), 1.82 (m, 16H; ArOCH2CH2), 3.93 (s, 3H;
CO2CH3), 4.02 (2t overlapped, J=6.8 Hz, 16H; ArOCH2), 5.22, 5.23 (2s,
8H; G1: 3’,4’ ArOCH2Ar), 5.25, 5.26(2s, 4H; 3 ’,4’ ArOCH2Ar), 6.92 (m,
4H; G2: 5’ ArH), 7.03 (m, 3H; 5’ and G1: 5’ ArH), 7.11 (m, 10H; G1: 6’
and G2: 2’,6’ ArH), 7.18 (dd, J=2.2, 8.3 Hz, 1H; 6’ ArH), 7.24 (m, 3H;
2’ and G1: 2’ ArH), 7.52 (m, 26H), 8.60 ppm (d, J=8.6Hz, 2H; 3,5
ArH); 13C NMR (125 MHz, CDCl3, 208C): d=14.10 (CH3), 22.68
(CH2CH3), 26.07 (CH2CH2CH2OAr), 29.38–29.69 (ArOCH2CH2,
[3’,4’-Bis(3’,4’-bisdodecyloxybiphenyl-4-ylmethoxy)biphenyl-4-yl]metha-
nol [(3,4Bp)212G2-CH2OH] (31): Compound 29 (1.80G, 1.38 mmol) was
added portionwise under Ar to
a suspension of LiAlH4 (150 mg,
4.2 mmol) in THF (100 mL) at 08C, then stirred as it was warmed to
228C over 15 h. The reaction mixture was filtered through Celite, washed
with THF, and the filtrate was evaporated. The residue was dissolved in
hot CHCl3 (300 mL), then filtered to remove residual inorganic solids.
Evaporation and recrystallization from acetone yielded 1.47G (83%) of
a fine white solid. Rf =0.72 (hexanes/CH2Cl2 1:2); m.p. 83.08C; purity
(HPLC) 99+ %; 1H NMR (500 MHz, CDCl3, 208C): d=0.89 (t, J=
CH3CH2CH2ACHTERU(GN CH2)6), 31.92 (CH3CH2CH2), 52.07 (CO2CH3), 69.35, 69.45
(ArOCH2CH2, G1: 3’,4’ positions), 71.11. 71.19, 71.37, 71.47 (ArOCH2Ar,
3’,4’ and G1: 3’,4’ positions), 113.12 (ArCH, G2: 2’ positions), 114.10
(ArCH, G2: 5’ positions), 114.37 (ArCH, G1: 2’ positions), 114.58
(ArCH, 2’ position), 115.31, 115.40 (ArCH, 5’ and G1: 5’ positions),
119.58 (ArCH, G2: 6’ positions), 120.26(Ar CH, G1: 6’ positions), 120.62
(ArCH, 6’ position), 126.54 (ArCH, 2,6 positions), 126.88 (ArCH, G2:
2,6positions), 12.692 (Ar CH, G1: 2,6positions), 127.72 (overlapped),
127.89, 127.93 (ArCH, G1: 3,5 and G2: 3,5 positions), 128.44 (ArC-
CO2CH3), 130.07 (ArCH, 3,5 positions), 133.49 (ArC, G1: 1’ positions),
133.80 (ArC, G2: 1’ positions), 134.41 (ArC, 1’ position), 135.68, 135.72
overlapped (ArC, G1: 1 and G2: 1 positions), 140.31, 140.76(Ar C, G1: 4
positions), 140.65, 140.69 (ArC, G2: 4 positions), 145.14 (ArC, 1 posi-
tion), 148.81, 148.94, 149.20, 149.36, 149.39 overlapped (ArC, 3’,4’, G1:
3’,4’, G2: 3’,4’ positions), 166.95 ppm (CO2CH3); MS (MALDI-TOF):
m/z: 2800.6[ M+Na]+; elemental analysis calcd (%) for C188H264O16
(2780.10): C 81.22, H 9.57; found: C 81.40, H 9.68.
6.9 Hz, 12H; CH2CH3), 1.28 (m, 64H; CH3ACHTRE(UNG CH2)8), 1.46(m, 8H; Ar-
OCH2CH2CH2), 1.67 (t, J=5.7 Hz, 1H; CH2OH), 1.84 (m, 8H; Ar-
OCH2CH2), 4.04 (2t overlapped, J=6.9 Hz, 8H; ArOCH2), 4.72 (d, J=
5.4 Hz, 2H; CH2OH), 5.25, 5.27 (2s, 4H; 3’,4’ArOCH2Ar), 6.94 (d, J=
8.5 Hz, 2H; G1, 5’ ArH), 7.04 (d, J=8.3 Hz, 1H; 5’ ArH), 7.13 (m, 5H;
6’ and G1: 2’,6’ ArH), 7.23 (d, J=1.8 Hz, 1H; 2’ ArH), 7.40 (d, J=
8.0 Hz, 2H; 2,6Ar H), 7.54 ppm (m, 10H); 13C NMR (125 MHz, CDCl3,
208C): d=14.10 (CH3), 22.68 (CH2CH3), 26.06 (CH2CH2CH2OAr),
29.34–29.70 (ArOCH2CH2, CH3CH2CH2ACHTER(UNG CH2)6), 31.91 (CH3CH2CH2),
65.08 (CH2OH), 69.35, 69.45 (ArOCH2CH2, G1: 3’,4’ positions), 71.17,
71.37 (ArOCH2Ar, 3’,4’ positions), 113.08 (ArCH, G1: 2’ positions),
114.06(Ar CH, G1: 5’ positions), 114.39 (ArCH, 2’ position), 115.33
(ArCH, 5’ position), 119.56(Ar CH, G1: 6’ positions), 120.21 (ArCH, 6’
position), 126.90 (ArCH, G1: 2,6positions), 126.93 (Ar CH, 2,6positions),
127.42 (ArCH, 3,5 positions), 127.70, 127.86(Ar CH, G1: 3,5 positions),
133.78, 133.80 (ArC, G1: 1’ positions), 134.45 (ArC, 1’ position), 135.62
(ArC, G1: 1 positions), 139.46(Ar C, 4 position), 140.21 (ArC, 1 position),
140.66, 140.69 (ArC, G1: 4 positions), 148.64, 148.90, 149.12, 149.32 ppm
Methyl 3’,5’-bis[3’,4’-bis(4’-dodecyloxybiphenyl-4-ylmethoxy)biphenyl-4-yl-
methoxy]biphenyl-4-carboxylate [(4Bp-3,4Bp-3,5Bp)12G2-CO2CH3] (34):
A mixture of 10 (65 mg, 0.27 mmol), K2CO3 (150 mg, 1.08 mmol), and 27
Chem. Eur. J. 2006, 12, 6216 – 6241
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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