S. Shinkai et al.
FULL PAPER
sample tube, was freeze-dried by a vacuum pump at À108C. The dried
sample obtained was shielded by Pt. The accelerating voltage of SEM
was 25 kV.
H2, H3, H4, H5), 3.48 3.75 (m, 8H; H6, H6’), 4.61 4.63 (m, 4H; OH6), 4.88
(d, J=7.3 Hz, 4H; H1), 5.04 5.37 (m, 12H; OH2, OH3, OH4), 7.11 (d, J=
8.9 Hz, 8H; Ar-H), 7.83 (d, J=8.9 Hz, 8H; Ar-H), 8.40 8.41 (m, 16H;
Ar-H), 8.92 (s, 8H; b-pyrrole), 10.6 ppm (s, 4H; amide-NH); 13C NMR
(150 MHz, [D6]DMSO): d=60.527 (CH2), 69.986 (CH), 73.505 (CH),
76.889 (CH), 77.273 (CH), 101.097 (CH), 116.682 (CH), 119.695 (Cq),
122.126 (CH), 122.558 (Cq), 126.607 (CH), 133.669 (Cq), 134.871 (CH),
144.342 (Cq), 154.028 (Cq), 165.392 ppm (C=O); ATR-IR: n˜ =3279,
1646, 1607, 1506, 1217, 1038, 1014 cmÀ1; UV/Vis (DMF): lmax (e)=420.0
(316000), 515.0 (17100), 549.5 (10200), 590.0 (6590), 646.0 nm
(5330 molÀ1dm3 cmÀ1); MALDI-TOF MS(matrix: dithranol): calcd m/z
TEM measurements: A piece of the dried gel sample which was prepared
for SEM observation was placed on
a carbon-coated copper grid
(200 mesh). After the sample was stained by one drop of an aqueous so-
lution of phosphotungstic acid (2.0%wt), the specimen was dried in
vacuo, and the sample was examined with a Hitachi H-600 TEM (acceler-
ation voltage: 75 kV) to obtain TEM images.
Sol gel polycondensation method A: Gelator (4.0 mg) was added to a
mixed solvent of DMF (160 mL) and benzylalcohol (480 mL), and the
mixture was heated until the precipitate completely dissolved. Tetraethyl-
orthosilicate (TEOS35 mL), benzylamine (10 mL), and water (10 mL)
was then added to this mixture. The reaction mixture was then heated
until it became homogeneous, and then placed at room temperature in
the dark for two weeks. The product was washed with methanol and
dried in vacuo to give the organic-inorganic composite as a purple solid.
This sample was calcinated to remove gelators at 1508C for 2 h and
5008C for 5 h, under a nitrogen stream, and at 5008C for 5 h under an
aerobic stream. The silica obtained was colorless.
for [M+H]+
: 1805.78; found 1805.23: elemental analysis calcd for
C96H90N8O28¥1.8CH2Cl2: C 60.03, H 4.92, N 5.73; found: C 59.73, H 5.20,
N 5.52.
Preparation of 1d: Compound 5d (0.58 g, 0.42 mmol) was deprotected
with sodium methoxide to give 1d (0.58 g, 0.32 mmol, 70%). M.p. 240
2428C; 1H NMR (600 MHz, [D6]DMSO): d=À2.89 (s, 2H), 3.47 3.53
(m, 12H; H4, H5, H6), 3.63 (d, J=11 Hz, 4H; H3, H6’), 3.70 3.71 (m, 4H;
H3), 3.85 3.86 (m, 4H; H2), 4.51 5.04 (m, 16H; OH2, OH3, OH4, OH6),
5.38 (s, 4H; H1), 7.16 (d, J=9 Hz, 8H; Ar-H), 7.83 (d, J=9 Hz, 8H; Ar-
H), 8.40 8.41 (m, 16H; Ar-H), 8.92 (s, 8H; b-pyrrole), 10.6 ppm (s, 4H;
amide-NH); 13C NMR (150 MHz, [D6]DMSO): d=61.318 (CH2), 69.996
(CH), 70.295 (CH), 70.928 (CH), 75.125 (CH), 99.542 (CH), 117.316
(CH), 119.677 (Cq), 122.102 (CH), 126.500 (CH), 133.836 (Cq), 134.374
(CH), 134.850 (Cq), 144.47 (Cq), 152.934 (Cq), 165.367 ppm (C=O);
ATR-IR: n˜ =3314, 1652, 1606, 1508, 1217, 1005 cmÀ1; UV/Vis (DMF):
lmax (e)=420.5 (130000), 515.0 (9040), 549.0 (6170), 591.0 (4730),
645.5 nm (4130 molÀ1dm3 cmÀ1); MALDI-TOF MS(matrix: dithranol):
calcd m/z for [M+H]+ : 1805.78 (1805.23): elemental analysis calcd (%)
for C96H90N8O28¥0.90CH3OH: C 63.51, H 5.15, N 6.11; found C 63.29, H
4.93, N 6.21.
Sol gel polycondensation method B: Gelator (1.0 mg) was added to a
mixture of DMF (40 mL), benzylalcohol (120 mL), and TEOS(10 mL),
and the resultant mixture was heated until the precipitate completely dis-
solved . After this mixture was cooled to room temperature, benzylamine
(3.0 mL) and water (3.0 mL) were added. Without the heating process,
this reaction mixture was placed at room temperature in the dark for two
weeks. The product was washed with methanol, and dried in vacuo to
give the organic-inorganic composite as a purple solid.
Preparation of 1a: A mixed solution of 5a (0.94 g, 0.38 mmol), sodium
methoxide (0.1m in methanol, 3.0 mL) was added to dry methanol
(20 mL) and dry tetrahydrofuran (6.0 mL), and the mixture was stirred
for 1.5 h under nitrogen. After the removal of the solvent under reduced
pressure, the purple solid was washed by chloroform and purified by re-
precipitation to give 1a (0.55 g, 0.30 mmol, 76%). M.p. 236 2378C; 1H
NMR (600 MHz, [D6]DMSO): d=À2.87 (s, 2H), 3.45 3.58 (m, 16H; H3,
H4, H5, H6, H6’), 3.73 3.74 (m, 4H; H2), 4.54 5.22 (m, 16H; OH2, OH3,
OH4, OH6), 4.85 (d, J=7,5 Hz, 4H; H1), 7.12 (d, J=8.8 Hz, 8H; Ar-H),
7.84 (d, J=8.8 Hz, 8H; Ar-H), 8.41 8.42 (m, 16H; Ar-H), 8.93 (s, 8H; b-
pyrrole), 10.6 ppm (m, 4H; amide-NH); 13C NMR (150 MHz,
[D6]DMSO): d=60.629 (CH2), 68.378 (CH), 70.551 (CH), 73.557 (CH),
75.720 (CH), 101.600 (CH), 116.679 (CH), 119.696 (Cq), 122.113 (CH),
126.508 (CH), 133.585 (Cq), 134.423 (CH), 134.869 (Cq), 144.339 (Cq),
154.109 (Cq), 165.371 ppm (C=O); ATR-IR: n˜ =3314, 1645, 1606, 1507,
1216, 1048, 1019 cmÀ1; UV/Vis (DMF): lmax (e)=420.0 (381000), 515.0
(17900), 549.5 (10000), 590.0 (6050), 646.5 (5200 molÀ1dm3 cmÀ1) nm;
MALDI-TOF MS(matrix: dithranol): calcd m/z for [M+H]+ : 1805.78;
found 1804.28. elemental analysis calcd (%) for C96H90N8O28¥4CH3OH: C
62.17, H 5.53, N 5.80; found C 62.18, H 5.31, N 5.93. The same procedure
was applied for the preparation of 1b e. We thus only recorded their an-
alytical data.
Preparation of 1e: Compound 5e (0.58 g, 0.23 mmol) was deprotected
with sodium methoxide to give 1e (0.32 g, 0.18 mmol, 74%). M.p. 2188C;
1H NMR (600 MHz, [D6]DMSO): d=À2.87 (s, 2H), 3.51 3.57 (m, 12H;
H4, H5, H6), 3.67 3.75 (m, 8H; H3, H6’), 3.89 3.90 (m, 4H; H2), 4.53 5.07
(m, 16H; OH2, OH3, OH4, OH6), 5.68 5.69 (m, 4H; H1), 7.19 7.21 (m,
8H; Ar-H), 7.34 7.36 (m, 4H; Ar-H), 8.33 8.34 (m, 4H; Ar-H), 8.42 8.45
(m, 16H; Ar-H), 8.96 (s, 8H; b-pyrrole), 9.94 ppm (s, 4H; amide-NH);
13C NMR (150 MHz, [D6]DMSO): d=60.654 (CH2), 68.337 (CH), 70.767
(CH), 73.115 (CH), 76.082 (CH), 104.113 (CH), 118.358 (CH), 119.622
(Cq), 122.171 (CH), 123.365 (CH), 125.022 (CH), 126.426 (CH), 129.608
(CH), 134.241 (Cq), 134.751 (CH), 144.681 (Cq), 148.231 (Cq), 154.158
(Cq), 165.131 ppm (C=O); ATR-IR: n˜ =3314, 1647, 1602, 1248,
1048 cmÀ1; UV/Vis (DMF): lmax (e)=420.5 (428000), 515.5 (22000), 550.0
(13500), 590.5 (8800), 646.5 nm (7960 molÀ1dm3 cmÀ1); FAB MS(HR):
calcd m/z for C96H90N8O28: 1802.5865; found 1802.5852.
Acknowledgement
Preparation of 1b: Compound 5b (1.1 g, 0.44 mmol) was deprotected
with sodium methoxide to give 1b (0.63 g, 0.35 mmol, 74%). M.p. 239
2438C decomp; 1H NMR (600 MHz, [D6]DMSO): d=À2.88 (s, 2H),
3.41 3.59 (m, 8H; H6, H6’), 3.77 3.82 (m, 16H; H2, H3, H4, H5), 4.54 4.90
(m, 16H; OH2, OH3, OH4, OH6), 5.40 5.41 (m, 4H; H1), 7.15 (d, J=
8.9 Hz, 8H; Ar-H), 7.82 (d, J=8.9 Hz, 8H; Ar-H), 8.40 8.42 (m, 16H;
Ar-H), 8.92 (s, 8H; b-pyrrole), 10.6 ppm (s, 4H, amide-NH); 13C NMR
(150 MHz, [D6]DMSO): d=60.527 (CH2), 68.273 (CH), 68.735 (CH),
69.673 (CH), 72.415 (CH), 98.829 (CH), 117.478 (CH), 119.681 (Cq),
122.094 (CH), 122.271 (Cq), 126.507 (CH), 133.660 (Cq), 134.384 (CH),
134.849 (Cq), 144.320 (Cq), 153.855 (Cq), 165.336 ppm (C=O); ATR-IR:
n=3316, 1651, 1606, 1509, 1216, 1076, 1026 cmÀ1; UV/Vis (DMF): lmax
(e)=420.0 (494000), 515.0 (21700), 549.5 (11700), 590.0 (6770), 646.5 nm
(6170 molÀ1dm3 cmÀ1); MALDI-TOF MS(matrix: dithranol): calcd m/z
We thank Ms. Hongyue Li for the measurements of NMR spectra. The
present work was supported by a Grant-in-Aid for the 21st Century COE
Program, ™Functional Innovation of Molecular Informatics∫ from the
Ministry of Education, Culture, Science, Sports and Technology of Japan.
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for [M+H]+
: 1805.78; found 1805.20. elemental analysis calcd for
C96H90N8O28¥0.65CH3OH: C 63.62, H 5.12, N 6.14; found C 63.49, H 4.97,
N 6.19.
Preparation of 1c: Compound 5c (1.3 g, 0.52 mmol) was deprotected
with sodium methoxide to give 1c (0.62 g, 0.34 mmol, 62%). M.p. 2368C;
1H NMR (600 MHz, [D6]DMSO): d=À2.88 (s, 2H), 3.17 3.75 (m, 16H;
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Chem. Eur. J. 2004, 10, 343 351