T. Kida et al. / Tetrahedron 61 (2005) 5763–5768
5767
(
7
1
400 MHz, CDCl ) d 7.69 (t, JZ7.7 Hz, 1H), 7.41 (d, JZ
.7 Hz, 1H), 7.19 (d, JZ7.7 Hz, 1H), 5.48 (d, JZ3.7 Hz,
H), 5.45 (d, JZ3.7 Hz, 1H), 5.17 (d, JZ3.7 Hz, 1H), 5.10
d, JZ3.7 Hz, 1H), 5.07 (d, JZ3.7 Hz, 1H), 5.06 (d, JZ
4.7 Hz, 1H), 4.82 (d, JZ14.7 Hz, 1H), 4.79 (d, JZ
3.7 Hz, 1H), 5.21 (d, JZ3.7 Hz, 1H), 5.13 (d, JZ3.3 Hz,
1H), 5.10 (d, JZ3.3 Hz, 1H), 5.06 (d, JZ3.3 Hz, 1H), 4.92
(d, JZ11.7 Hz, 1H), 4.84 (d, JZ11.7 Hz, 1H), 4.57 (d, JZ
3
1
3
(
11.7 Hz, 2H), 3.10–3.89 (m, 90H); C NMR (100 MHz,
CDCl ) d 138.46, 137.19, 128.34, 127.10, 99.29, 99.05,
1
1
1
1
9
8
8
7
7
5
5
1
3
1.4 Hz, 1H), 4.65 (d, JZ11.4 Hz, 1H), 4.24 (d, JZ7.7 Hz,
98.41, 98.18, 97.71, 83.27, 83.10, 82.45, 82.35, 82.29,
82.16, 82.05, 81.83, 81.50, 80.96, 79.57, 79.04, 77.71,
1
H), 3.06–3.91 (m, 90H); C NMR (100 MHz, CDCl ) d
3
3
58.39, 157.30, 137.11, 121.65, 120.74, 101.27, 99.20,
9.18, 98.18, 97.57, 96.95, 86.49, 84.20, 82.69, 82.33,
2.30, 82.22, 82.19, 82.02, 81.85, 81.79, 81.73, 80.84,
0.81, 79.68, 79.54, 76.50, 74.86, 74.16, 73.51, 71.52,
1.43, 71.23, 71.08, 71.06, 71.03, 70.95, 70.85, 70.79,
0.44, 61.73, 61.64, 61.50, 60.69, 60.40, 60.24, 60.02,
9.50, 59.35, 59.29, 59.19, 59.09, 59.04, 59.00, 58.99,
8.50, 58.24, 58.13; IR (KBr) 2933, 2839, 1630, 1101,
7
7
6
5
1
1
5.76, 74.16, 72.45, 71.91, 71.47, 71.21, 71.06, 71.04,
0.98, 70.84, 70.79, 70.68, 70.48, 69.78, 61.46, 61.45,
1.12, 60.94, 60.75, 59.31, 59.24, 58.99, 58.93, 58.91,
8.87, 58.85, 58.30, 57.87; IR (KBr) 2927, 2831, 1647,
K1
C
095, 1039 cm ; MALDI-TOF MS m/z 1368 [MCNa] ,
384 [MCK] . Anal. Calcd (%) for C H O : C, 55.35;
C
6
2 104 31
H, 7.79. Found: C, 55.51; H, 7.43. 5b (yield 10%): mp 91–
1
9
2
3 8C; H NMR (400 MHz, CDCl ) d 7.35 (d, JZ8.1 Hz,
K1
C
3
036 cm ; MALDI-TOF MS m/z 1347 [MCH] , 1369
H), 7.29 (d, JZ8.1 Hz, 2H), 5.37 (d, JZ3.7 Hz, 1H), 5.31
C
C
[
MCNa] , 1385 [MCK] . Anal. Calcd (%) for
C H NO : C, 54.41; H, 7.71; N, 1.04. Found: C,
(d, JZ3.7 Hz, 1H), 5.30 (d, JZ3.7 Hz, 1H), 5.17 (d, JZ
6
1
103
31
3
1
4
3
1
.7 Hz, 1H), 5.08 (d, JZ3.3 Hz, 1H), 4.92 (d, JZ12.8 Hz,
H), 4.78 (d, JZ10.6 Hz, 1H), 4.62 (d, JZ12.8 Hz, 1H),
5
4.23; H, 7.43; N, 0.98.
.58 (d, JZ10.6 Hz, 1H), 4.19 (d, JZ7.3 Hz, 1H), 3.06–
4
.1.6. m-Xylylene-inserted a-cyclodextrin derivatives
4a and 4b). Compounds 4a and 4b were synthesized in
13
.91 (m, 90H); C NMR (100 MHz, CDCl ) d 138.16,
37.38, 128.63, 127.90, 101.31, 98.67, 98.52, 97.84, 97.33,
3
(
a similar manner to 3a and 3b. 4a (yield 4%): mp 82–86 8C;
1
86.06, 84.09, 83.36, 82.77, 82.26, 82.05, 81.95, 81.91,
H NMR (400 MHz, CDCl ) d 7.30–7.40 (m, 3H), 7.19–
3
.20 (m, 1H), 5.51 (d, JZ3.7 Hz, 1H), 5.32 (d, JZ3.3 Hz,
H), 5.19 (d, JZ3.7 Hz, 1H), 5.09 (d, JZ3.9 Hz, 1H), 5.08
8
7
7
6
1.83, 81.68, 80.35, 79.46, 77.81, 77.52, 77.20, 75.26,
4.95, 74.15, 71.64, 71.27, 71.10, 71.05, 71.01, 70.96,
0.86, 70.77, 70.65, 70.62, 70.53, 70.40, 61.49, 61.43,
1.07, 60.89, 60.57, 60.43, 60.13, 59.33, 59.28, 59.04,
7
1
(
d, JZ3.7 Hz, 1H), 5.04 (d, JZ3.3 Hz, 1H), 4.92 (d, JZ
1.7 Hz, 1H), 4.62 (d, JZ11.7 Hz, 1H), 4.62 (s, 2H), 3.07–
1
3
1
9
8
7
7
6
5
2
1
1
.91 (m, 90H); C NMR (100 MHz, CDCl ) d 139.08,
3
58.95, 58.88, 58.82, 58.40, 57.98; IR (KBr) 2925, 2821,
K1
635, 1093, 1039 cm ; MALDI-TOF MS m/z 1368 [MC
3
1
Na] , 1384 [MCK] . Anal. Calcd (%) for C H O : C,
37.43, 128.46, 127.44, 126.92, 126.34, 98.94, 98.73, 98.67,
8.55, 96.68, 96.03, 83.41, 83.36, 82.31, 82.29, 82.16,
2.09, 82.06, 81.89, 81.81, 81.66, 80.56, 80.49, 79.27,
7.68, 77.20, 71.68, 71.28, 71.24, 71.12, 71.03, 70.89,
0.85, 70.80, 70.68, 70.66, 70.64, 70.57, 70.54, 69.47,
1.66, 61.46, 61.15, 60.60, 60.54, 59.30, 59.15, 58.98,
8.94, 58.92, 58.88, 58.58, 58.36, 58.23, 58.01; IR (KBr)
C
C
62 104 31
55.35; H, 7.79. Found: C, 55.70; H, 7.59.
4.2. NMR titration and Job plots
1
The H NMR titrations were performed at 25 8C in CD OD–
K1
3
933, 2821, 1635, 1107, 1039 cm ; MALDI-TOF MS m/z
368 [MCNa] , 1384 [MCK] . Anal. Calcd (%) for
D O (1:4) with DSS (sodium 2,2-dimethyl-2-silapentane-5-
2
C
C
sulfonate) as an external standard. A solution of the host
molecule (0.5 mL, 4.0 mM) was titrated in a NMR tube with
increasing amounts of guest stock solution (0.5 mL, 80 mM)
as follows (in mL): 0, 12.5, 25.0, 37.5, 50.0, 75.0, 100, 150,
C H O : C, 55.35; H, 7.79. Found: C, 55.68; H, 7.47. 4b
6
(
7
2 104 31
1
yield 10%): mp 85–86 8C; H NMR (400 MHz, CDCl ) d
3
.39 (s, 1H), 7.27–7.34 (m, 2H), 7.11–7.15 (m, 1H), 5.50 (d,
JZ3.7 Hz, 1H), 5.47 (d, JZ3.7 Hz, 1H), 5.21 (d, JZ
200, 250. The titration curves (changes in the chemical
3
1
1
.7 Hz, 1H), 5.08 (d, JZ3.7 Hz, 1H), 5.06 (d, JZ3.7 Hz,
H), 4.82 (d, JZ11.4 Hz, 1H), 4.77 (s, 2H), 4.63 (d, JZ
1.4 Hz, 1H), 4.29 (d, JZ7.3 Hz, 1H), 3.07–3.95 (m, 90H);
shift of the host protons (Dd) against the guest/host ratio)
were analyzed by a non-linear least-squares curve fitting
method to generate stability constants of the host–guest
complexes.
1
3
C NMR (100 MHz, CDCl ) d 139.00, 137.68, 128.52,
3
1
9
8
7
7
7
5
27.37, 127.17, 126.66, 100.86, 98.96, 98.86, 98.78, 97.66,
6.35, 86.13, 84.08, 83.48, 82.43, 82.27, 82.24, 82.09,
1.94, 81.92, 81.77, 81.65, 81.61, 80.82, 80.70, 79.07,
7.95, 77.20, 74.67, 74.55, 74.09, 73.17, 71.65, 71.24,
1.21, 71.11, 71.05, 71.00, 70.99, 70.98, 70.86, 70.79,
0.63, 70.35, 69.80, 61.71, 61.46, 61.09, 60.11, 60.04,
Job plots were carried out by monitoring the changes in the
chemical shift of the host protons (Dd) in a series of
solutions with varying host/guest ratios but the total
concentrations of the host and guest being kept constant
(4.0 mM). The relative concentration of the host–guest
9.43, 59.32, 59.17, 59.02, 58.89, 58.48, 58.11, 57.93; IR
K1
(KBr) 2933, 2829, 1637, 1103, 1039 cm ; MALDI-TOF
MS m/z 1368 [MCNa] , 1384 [MCK] . Anal. Calcd (%)
complex estimated from the Dd$ [host] value was plotted
against ([guest]/{[host]C[guest]}).
C
C
for C H O : C, 55.35; H, 7.79. Found: C, 55.59; H,
6
2 104 31
7
.50.
4.1.7. p-Xylylene-inserted a-cyclodextrin derivatives (5a
and 5b). Compounds 5a and 5b were synthesized in a
Acknowledgements
similar manner to 3a and 3b. 5a (yield 5%): mp 86–89 8C;
H NMR (400 MHz, CDCl ) d 7.35 (d, JZ8.1 Hz, 2H), 7.31
This work was supported by a Grant-in-Aid for Scientific
Research (No. 16750120) from the Ministry of Education,
Culture, Sports, Science, and Technology of Japan.
1
3
(
d, JZ8.1 Hz, 2H), 5.41 (d, JZ3.7 Hz, 1H), 5.30 (d, JZ