Covalent Fixation of Helical Chirality in an Enantiomeric Nanoscale Architecture
FULL PAPER
silica gel (WAKO C-300) with chloroform/hexane (1/1) as eluant to give
2 f in 60% yield (812 mg, 1.42 mmol) as colorless oil; 1H NMR
(270 MHz, CDCl3): d=0.88 (t, J=6.6 Hz, 3H; CH3), 1.21–1.36 (m, 24H;
CH2), 1.37–1.54 (m, 6H; ArOCH2CH2CH2), 1.69–1.87 (m, 6H; Ar-
OCH2CH2), 2.06 (q, J=6.5Hz, 4H; CH 2=CHCH2), 3.89 (s, 3H;
COOCH3), 4.01 (t, J=6.3 Hz, 6H; ArOCH2), 4.94 (d, J=11.3 Hz, 2H;
olefinic H), 5.00 (d, J=18.6 Hz, 2H; olefinic H), 5.74–5.89 (m, 2H; ole-
finic H), 7.25ppm (s, 2H; ArH); IR (NaCl): n˜ =3076, 2925, 2854, 1722
(C=O), 1640, 1587, 1500, 1465, 1432, 1387, 1336, 1219, 1118, 1014, 909,
1641, 1585, 1496, 1467, 1428, 1385, 1328, 1235, 1144, 1119, 994, 909, 851,
770 cmÀ1
2,4,6-Tris(4-aminophenyl)-1,3,5-triazine (7):
.
A
solution of P(tBu)3 in
hexane (0.05m, 700 mL, 0.35mmol) was added to a solution of [Pd(dba) 2]
(201 mg, 0.35mmol; dba =trans,trans-dibenzylideneacetone) in dry tolu-
ene (17.5mL) at room temperature under an argon atmosphere and al-
lowed to stand for 10 min. 2,4,6-Tri(4-bromophenyl)-1,3,5-triazine (6,
1.91 g, 3.5mmol) and a solution of lithium bis(trimethylsilyl)amide in
hexane (1.06m 10.9 mL, 11.55 mmol) were added to the mixture, which
was heated at 808C for 39 h (dark violet solution to dark greenish brown
suspension). After the reaction mixture (brown suspension) was cooled
to room temperature, it was quenched by addition of aqueous 1.2n hy-
drochloric acid solution (7 mL) and diluted with water (10 mL) and di-
ethyl ether (10 mL). The suspension was filtered and washed with aque-
ous 1.2n hydrochloric acid solution (40 mL), water (110 mL), and diethyl
ether (100 mL). The combined filtrate was transferred to a separating
funnel. The separated water phase was washed with diethyl ether
(50 mL2) and treated with cold aqueous 1n sodium hydroxide solution
(15mL). The obtained white precipitate was collected by filtration and
washed with water (150 mL), methanol (30 mL), and dichloromethane
(20 mL) to give 7 in 34% yield (417 mg, 1.18 mmol) as a pale yellow
solid: m.p. 415–4208C (decomp); 1H NMR (395MHz, (CD 3)2SO): d=
5.90 (s, D2O exchange, 6H; NH2), 6.68, 8.34 ppm (d, J=8.6 Hz, each 6H;
ArH); IR (KBr): n˜ =3461 (NH), 3378 (NH), 3323 (NH), 3211 (NH),
863, 766, 724 cmÀ1 FAB-MS (NBA): m/z: 572 [M+]; HR-FAB-MS
;
(NBA): m/z: calcd for C36H60O5 [M+]: 572.4441; found: 572.4446.
3,4,5-Tris(oct-7-enyloxy)benzoic acid (4e): Compound 2e (340 mg,
0.66 mmol) was added to a solution of potassium hydroxide (110 mg,
1.98 mmol) in ethanol (1 mL) and water (1 mL). After the mixture was
heated to reflux for 1 h, it was poured into water (5mL), acidified to
pH 4 by addition of 1n hydrochloric acid, and extracted with dichlorome-
thane (2 mL2). The organic layer was washed with water (4 mL), dried
over anhydrous magnesium sulfate, and evaporated in vacuo to give 4e
in 97% yield (320 mg, 0.64 mmol) as a colorless oil. Without further puri-
fication, 4e was used for the next reaction. 1H NMR (270 MHz, CDCl3):
d=1.29–1.59 (m, 18H; CH2), 1.63–1.90 (m, 6H; ArOCH2CH2CH2), 1.93–
2.16 (m, 6H; ArOCH2CH2), 4.02 (t, J=6.5Hz, 6H; ArOCH 2), 4.94 (d,
J=11.3 Hz, 3H; olefinic H), 4.99 (d, J=18.6 Hz; 3H, olefinic H), 5.74–
5.89 (m, 3H; olefinic H), 7.32 ppm (s, 2H; ArH); IR (NaCl): n˜ =3076,
2928, 2856, 2638, 1686 (C=O), 1640, 1586, 1502, 1433, 1386, 1330, 1270,
3030, 1633, 1606, 1578, 1497, 1433, 1366, 1294, 1179, 1147, 1129, 813 cmÀ1
;
1228, 1119, 994, 909, 865, 768, 728 cmÀ1
.
EI-MS (70 eV): m/z: 35 4 M[ +]; elemental analysis calcd (%) for
C21H18N6·0.5H2O (354.4): C 69.40; H 5.30; N 23.23; found: C 69.12; H
5.06; N 22.62.
3,5-Bis(oct-7-enyloxy)-4-dodecyloxybenzoic acid (4 f): Compound 2 f
(712 mg, 1.24 mmol) was added to a solution of potassium hydroxide
(350 mg, 6.2 mmol) in ethanol (10 mL) and water (10 mL). After the re-
action mixture was heated to reflux for 30 min, it was poured into water
(50 mL), acidified to pH 4 by addition of 1n hydrochloric acid, and ex-
tracted with dichloromethane (20 mL2). The organic layer was washed
with water (20 mL2), dried over anhydrous magnesium sulfate, and
evaporated to give 4 f in 97% yield (637.1 mg, 1.20 mmol) as colorless
oil. Without further purification, 4 f was used for the next reaction.
1H NMR (270 MHz, CDCl3): d=0.88 (t, J=6.6 Hz; 3H; CH3), 1.21–1.36
(m, 24H; CH2), 1.37–1.54 (m, 6H; ArOCH2CH2CH2), 1.69–1.87 (m, 6H;
ArOCH2CH2), 2.06 (q, J=6.5Hz, 4H; CH 2=CHCH2), 4.03 (t, J=6.3 Hz,
6H; ArOCH2), 4.94 (d, J=11.3 Hz, 2H; olefinic H), 5.00 (d, J=18.6 Hz,
2H; olefinic H), 5.74–5.89 (m, 2H; olefinic H), 7.32 ppm (s, 2H; ArH);
IR (NaCl): n˜ =3077, 2924, 2852, 1685 (C=O), 1642, 1587, 1504, 1467,
2,4,6-Tris{4-[3,4,5-tris(propyloxyphenyl)carbonylamino]phenyl}-1,3,5-tri-
azine (8a): Compound 5a (315mg, 1.0 mmol) in dry THF (2 mL) was
added dropwise to a solution of 7 (106 mg, 0.3 mmol) and triethylamine
(0.17 mL, 1.2 mmol) in dry THF (8 mL) at 08C under an argon atmos-
phere. The mixture was stirred at room temperature for 3 h. The reaction
mixture was filtered to remove triethylamine hydrochloride and the fil-
trate was evaporated in vacuo to dryness. The residue was suspended in
diethyl ether (10 mL), collected by filtration, and washed with diethyl
ether (20 mL). The solid was purified by column chromatography on
silica gel (KANTO 60N) with chloroform/methanol (200/1) as eluant to
give 8a in 53% yield (190 mg, 0.16 mmol) as a white powder: m.p. 306–
3078C; 1H NMR (395MHz, CDCl 3): d=0.97 (t, J=7.3 Hz, 9H; CH3),
1.07 (t, J=7.3 Hz, 18H; CH3), 1.69–1.84 (m, 18H; OCH2CH2), 3.90 (t,
J=5.9 Hz, 12H; OCH2), 4.00 (t, J=6.4 Hz, 6H; OCH2), 7.23 (s, 6H;
ArH), 7.38 (brs, 6H; ArH), 8.01 (brs, 6H; ArH), 8.83 ppm (brs, 3H;
NH); IR (KBr): n˜ =3317 (NH), 2964, 2876, 1653 (C=O), 1591, 1489,
1427, 1405, 1370, 1332, 1237, 1205, 1178, 1119 cmÀ1; FAB-MS (NBA): m/
z: 1190 [(M+1)+]; elemental analysis calcd (%) for C69H84N6O12·H2O
(1189.4): C 68.64; H 7.18; N 6.96; found: C 68.81; H 7.09; N 6.99.
1432, 1384, 1333, 1227, 1125, 990, 907, 863, 768, 723 cmÀ1
.
3,4,5-Tris(oct-7-enyloxy)benzoyl chloride (5e): Thionyl chloride (300 mg,
0.17 mL, 2.48 mmol) was added to a solution of 4e (310 mg, 0.62 mmol)
in dichloromethane (2 mL) at room temperature under an argon atmos-
phere. After the reaction mixture was stirred for 30 min at room temper-
ature, the solvent and excess thionyl chloride were removed by distilla-
tion to give 5e in 99% yield (320 mg, 0.62 mmol) as a colorless oil. With-
out further purification, 5e was treated with 7. 1H NMR (270 MHz,
CDCl3): d=1.29–1.59 (m, 18H; CH2), 1.63–1.90 (m, 6H; Ar-
OCH2CH2CH2), 1.93–2.16 (m, 6H; ArOCH2CH2), 4.02 (t, J=6.5Hz; 6H,
ArOCH2), 4.94 (d, J=11.3 Hz, 3H; olefinic H), 4.99 (d, J=18.6 Hz, 3H;
olefinic H), 5.74–5.89 (m, 3H; olefinic H), 7.31 ppm (s, 2H; ArH); IR
(NaCl): n˜ =3076, 2929, 2856, 1751 (C=O), 1640, 1585, 1496, 1466, 1428,
2,4,6-Tris{4-[3,4,5-tris(octyloxyphenyl)carbonylamino]phenyl}-1,3,5-tri-
azine (8b): Compound 5b (525 mg, 1.0 mmol) in dry THF (2 mL) was
added dropwise to a solution of 7 (106 mg, 0.3 mmol) and triethylamine
(0.14 mL, 1.0 mmol) in dry THF (8 mL) at 08C under an argon atmos-
phere. The mixture was stirred at room temperature for 1 h. The reaction
mixture was filtered to remove triethylamine hydrochloride and the fil-
trate was evaporated in vacuo to dryness. The residue was purified by
column chromatography on silica gel (KANTO 60N) with chloroform/
methanol (300/1 v/v) as eluant to give 8b in 59% yield (321 mg,
1388, 1329, 1235, 1144, 1119, 994, 909, 851, 771, 692 cmÀ1
.
3,5-Bis(oct-7-enyloxy)-4-dodecyloxybenzoyl chloride (5 f): Thionyl chlo-
ride (500 mg, 0.28 mL, 4.16 mmol) was added to a solution of 4 f (600 mg,
1.07 mmol) in dichloromethane (4 mL) at room temperature under an
argon atmosphere. After the reaction mixture was stirred for 30 min at
room temperature under an argon atmosphere, the solvent and excess
thionyl chloride were removed by distillation to give 5 f in 100% yield
(617 mg, 1.07 mmol) as colorless oil. Without further purification, 5 f was
treated with 7. 1H NMR (270 MHz, CDCl3): d=0.88 (t, J=6.6 Hz, 3H;
CH3), 1.21–1.36 (m, 24H; CH2), 1.37–1.54 (m, 6H; ArOCH2CH2CH2),
1.69–1.87 (m, 6H; ArOCH2CH2), 2.06 (q, J=6.5Hz, 4H; CH 2=CHCH2),
4.03 (t, J=6.3 Hz, 6H; ArOCH2), 4.94 (d, J=11.3 Hz, 2H; olefinic H),
5.00 (d, J=18.6 Hz, 2H; olefinic H), 5.74–5.89 (m, 2H; olefinic H),
7.33 ppm (s, 2H; ArH); IR (NaCl): n˜ =3075, 2925, 2854, 1752 (C=O),
1.76 mmol) as
a
white solid: m.p. 269–2738C; 1H NMR (395MHz,
CDCl3): d=0.88 (t, J=6.3 Hz, 27H; CH3), 1.23–1.38 (m, 72H;
OCH2CH2CH2(CH2)4), 1.43–1.53 (m, 18H; OCH2CH2CH2), 1.72–1.86 (m,
18H; OCH2CH2), 3.99 (t, J=6.6 Hz 12H; CH2), 4.02 (t, J=6.6 Hz, 6H;
OCH2), 7.21 (s, 6H; ArH), 7.77 (d, J=8.6 Hz, 6H; ArH), 8.18 (s, 3H;
NH), 8.63 ppm (d, J=8.6 Hz, 6H; ArH); IR (KBr) n˜ =3317 (NH), 2925,
2855, 1649 (C=O), 1584, 1490, 1427, 1406, 1372, 1335, 1239, 1177, 1114,
805, 760 cmÀ1; FAB-MS (NBA): m/z: 1821 [(M+1)+]; elemental analysis
calcd (%) for C114H174N6O12 (1820.6): C 75.21; H 9.63; N 4.62; found: C
75.58 ; H 9.59; N 4.66.
2,4,6-Tris{4-[3,4,5-(trisdodecyloxyphenyl)carbonylamino]phenyl}-1,3,5-tri-
azine (8c): Compound 5c (694 mg, 1.0 mmol) in dry THF (2 mL) was
Chem. Eur. J. 2006, 12, 763 – 776
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
773