C.-F. Chen et al. / Tetrahedron 61 (2005) 3853–3858
3857
8H), 1.57–1.31 (m, 4H), 1.10 (t, JZ7.3 Hz, 12H), 0.75 (t,
JZ7.5 Hz, 6H). 13C NMR (CDCl3): d 156.7, 155.3, 155.0,
137.8, 136.9, 133.5, 133.0, 132.5, 131.8, 130.1, 129.2,
128.6, 128.1, 121.9, 121.2, 115.1, 75.7, 75.2, 71.1, 70.2,
39.6, 35.5, 30.2, 23.6, 21.6, 10.7, 9.5. MALDI-TOF MS m/z:
1273.8 (MCNaC), 1289.8 (MCKC). Anal. Calcd for
C84H98O9$0.5H2O: C, 80.03; H, 7.92. Found: C, 80.01; H,
7.90.
NMR (CDCl3): d 156.0, 154.7, 142.2, 137.2, 133.5, 133.2,
132.1, 130.6, 130.4, 129.8, 129.4, 128.8, 128.2, 122.1,
121.3, 75.9, 75.4, 71.3, 70.5, 38.8, 35.7, 30.5, 22.9, 21.8,
11.0, 9.8. MALDI-TOF MS m/z: 2467.3 (MCNaC), 2483.3
(MCKC). Anal. Calcd for C164H188O18: C, 80.49; H, 7.74.
Found: C, 80.32; H, 7.87.
3.3.2. Compound 7a0. Yield 32%; mp 124–126 8C; 1H
NMR (CDCl3): d 7.13–7.06 (m, 24H), 6.93 (t, JZ7.4 Hz,
2H), 6.92 (t, JZ7.4 Hz, 2H), 6.48–6.41 (m, 8H), 6.31 (t, JZ
6.1 Hz, 8H), 6.14–6.01 (m, 2H), 5.84 (t, JZ4.8 Hz, 2H),
5.17 (d, JZ17.1 Hz, 1H), 5.16 (d, JZ17.1, 1H), 5.13 (d, JZ
9.1 Hz, 1H), 5.12 (d, JZ9.1 Hz, 1H), 4.11–3.93 (m, 16H),
3.91 (t, JZ4.7 Hz, 8H), 3.80–3.74 (m, 8H), 3.72–3.66 (m,
16H), 3.59–3.47 (m, 16H), 3.41 (d, JZ6.8 Hz, 4H), 3.38–
3.33 (m, 4H), 3.08 (d, JZ13.1 Hz, 4H), 3.07 (d, JZ13.3 Hz,
4H), 1.96–1.84 (m, 16H), 1.52–1.45 (m, 8H), 1.13 (t, JZ
7.4 Hz, 12H), 1.12 (t, JZ7.4 Hz, 12H), 0.79–0.74 (m, 12H).
13C NMR (CDCl3): d 156.9, 155.6, 155.2, 138.0, 137.1,
133.8, 133.3, 132.8, 132.1, 130.4, 129.5, 128.9, 128.3,
122.2, 121.5, 115.4, 76.0, 75.4, 71.4, 70.5, 39.9, 35.8, 30.5,
23.88, 23.84, 21.8, 10.2, 9.8. MALDI-TOF MS m/z:
2495.1 (MCNaC), 2511.1 (MCKC). Anal. Calcd for
C166H192O18: C, 80.55; H, 7.82. Found: C, 80.41; H, 7.86.
1
3.2.2. Compound 6b. Yield 62%; mp 64–66 8C; H NMR
(CDCl3): d 7.11 (d, JZ7.4 Hz, 4H), 7.05 (s, 4H), 7.04 (d,
JZ7.8 Hz, 4H), 6.92 (t, JZ7.4 Hz, 2H), 6.42 (t, JZ7.5 Hz,
4H), 6.28 (d, JZ7.5 Hz, 4H), 6.15–6.01 (m, 2H), 5.17 (d,
JZ16.1 Hz, 2H), 5.13 (d, JZ8.9 Hz, 2H), 4.08 (d, JZ
13.1 Hz, 4H), 3.99 (t, JZ4.6 Hz, 4H), 3.85 (t, JZ4.9 Hz,
4H), 3.84 (s, 4H), 3.79–3.72 (m, 4H), 3.68 (ABq, JZ
13.0 Hz, 8H), 3.53 (t, JZ8.0 Hz, 4H), 3.41 (d, JZ6.9 Hz,
4H), 3.35 (t, JZ8.4 Hz, 4H), 3.06 (d, JZ13.2 Hz, 4H),
1.94–1.82 (m, 8H), 1.50–1.42 (m, 4H), 1.12 (t, JZ7.4 Hz,
12H), 0.75 (t, JZ7.4 Hz, 6H). 13C NMR (CDCl3): d 156.9,
155.5, 155.0, 138.0, 137.1, 133.7, 133.2, 132.7, 132.0,
130.4, 129.5, 128.9, 128.3, 122.2, 121.4, 115.4, 76.6, 76.0,
75.4, 71.5, 70.7, 39.9, 35.7, 30.5, 23.8, 21.8, 11.0, 9.8.
MALDI-TOF MS m/z: 1318.4 (MCNaC), 1334.3 (MC
KC). Anal. Calcd for C86H102O10: C, 79.72; H, 7.93. Found:
C, 79.76; H, 7.97.
3.3.3. Compound 7b. Yield 52%; mp 133–134 8C; 1H NMR
(CDCl3): d 7.12 (d, JZ7.3 Hz, 6H), 6.95 (s, 4H), 6.95–6.92
(m, 4H), 6.43 (t, JZ7.5 Hz, 4 H), 6.28 (d, JZ7.5 Hz, 4H),
5.72 (t, JZ6.1 Hz, 2H), 4.09 (d, JZ13.1 Hz, 4H), 4.06–4.01
(m, 4H), 3.82–3.75 (m, 12H), 3.70 (s, 4H), 3.59–3.49 (m,
8H), 3.41–3.32 (m, 8H), 3.08 (d, JZ13.2 Hz, 4H), 1.96–
1.89 (m, 8H), 1.48–1.45 (m, 4H), 1.16 (t, JZ6.3 Hz, 12H),
0.79 (t, JZ7.5 Hz, 6H). 13C NMR (CDCl3): d 157.1, 155.6,
137.1, 133.9, 133.3, 132.1, 131.4, 130.6, 129.0, 128.8,
128.2, 122.2, 121.4, 75.9, 75.6, 71.5, 70.8, 70.3, 37.6, 35.7,
30.4, 23.9, 21.9, 11.0, 9.7. MALDI-TOF MS m/z: 1290.6
(MCNaC). Anal. Calcd for C84H98O10: C, 79.59; H, 7.79.
Found: C, 79.36; H, 7.91.
1
3.2.3. Compound 6c. Yield 64%; mp 60–62 8C; H NMR
(CDCl3): d 7.15 (d, JZ7.4 Hz, 4H), 7.11 (s, 4H), 7.08 (d,
JZ7.2 Hz, 4H), 6.96 (t, JZ7.4 Hz, 2H), 6.48 (t, JZ7.4 Hz,
4H), 6.33 (d, JZ7.5 Hz, 4H), 6.17–6.08 (m, 2H), 5.22 (d,
JZ16.1 Hz, 2H), 5.18 (d, JZ9.1 Hz, 2H), 4.13 (d, JZ
13.1 Hz, 4H), 4.01 (t, JZ4.5 Hz, 4H), 3.86–3.77 (m, 16H),
3.69 (ABq, JZ13.1 Hz, 8H), 3.57 (m, 4H), 3.47 (d, JZ
6.8 Hz, 4H), 3.40 (t, JZ8.4 Hz, 4H), 3.11 (d, JZ13.2 Hz,
4H), 1.99–1.88 (m, 8H), 1.56–1.45 (m, 4H), 1.17 (t, JZ
7.4 Hz, 12H), 0.82 (t, JZ7.4 Hz, 6H). 13C NMR (CDCl3): d
156.9, 155.5, 155.3, 138.0, 137.1, 133.7, 133.2, 132.7,
132.0, 130.4, 129.5, 128.8, 128.3, 122.2, 121.4, 115.4, 76.0,
75.4, 71.5, 70.8, 70.6, 39.8, 35.7, 30.5, 23.8, 21.8, 11.0, 9.8.
MALDI-TOF MS m/z: 1362.2 (MCNaC), 1378.2 (MC
KC). Anal. Calcd for C88H106O11: C, 78.89; H, 7.97. Found:
C, 78.89; H, 7.94.
3.3.4. Compound 7c. Yield 66%; mp 128–130 8C; 1H NMR
(CDCl3): d 7.11–7.00 (m, 12H), 6.90 (t, JZ7.5 Hz, 2H),
6.41 (t, JZ7.5, 4H), 6.24 (d, JZ7.4 Hz, 4H), 5.79 (t, JZ
6.1 Hz, 2H), 4.05 (d, JZ13.1 Hz, 4H), 4.02–3.98 (m, 4H),
3.84 (d, JZ13.0 Hz, 4H), 3.72–3.64 (m, 12H), 3.59–3.46
(m, 12H), 3.37 (d, JZ6.1 Hz, 4H,), 3.32 (t, JZ8.5 Hz, 4H,),
3.03 (d, JZ13.2 Hz, 4H), 1.82–1.77 (m, 8H), 1.08–1.04 (m,
4H), 1.06 (t, JZ7.3 Hz, 12H), 0.76 (t, JZ7.3 Hz, 6H). 13C
NMR (CDCl3): d 157.1, 155.6, 154.8, 137.2, 133.7, 133.2,
132.3, 131.1, 130.9, 129.5, 128.9, 128.2, 122.2, 121.5, 76.0,
75.6, 71.4, 70.7, 70.4, 69.9, 38.1, 35.7, 30.5, 23.9, 21.9,
11.0, 9.9. MALDI-TOF MS m/z: 1333.6 (MCNaC), 1349.5
(MCKC). Anal. Calcd for C86H102O11: C, 78.75; H, 7.84.
Found: C, 78.89; H, 7.93.
3.3. General procedure for RCM reactions
To the solution of a calix[4]arene derivative 6 (0.05 mmol)
in dry CH2Cl2 (10 mL) under argon was added the Grubbs’
catalyst 1 (2.1 mg, 5 mol%). The mixture was stirred at
room temperature and the reaction process was monitored
by TLC. When the reaction was completed, the reaction
mixture was quenched by exposure to air for 6 h. The
solution was concentrated in vacuo and separated by column
chromatography using ethyl acetate: petroleum ether (1:4,
v/v) as the eluent to provide the product 7.
3.4. X-ray crystallographic study
1
3.3.1. Compound 7a. Yield 20%; mpO300 8C; H NMR
Crystals suitable for X-ray diffraction were grown from a
mixture of dichloromethane and n-hexane for compounds 5,
6a and 7b, or a mixture of dichloromethane and acetonitrile
for compound 6c. Data collection was performed at 293 K
using a Rigaku R-AXIS RAPID IP detector, and SHELXS-
97 and SHELXL-97 programs were used for structure
solution and refinement. Crystallographic data for structures
(CDCl3): d 7.11–7.01 (m, 24H), 6.92 (t, JZ7.4 Hz, 4H),
6.45–6.38 (m, 8H), 6.27 (t, JZ6.7 Hz, 8H), 5.76–5.72 (m,
4H), 4.09 (d, JZ12.4 Hz, 16H), 3.89–3.83 (m, 8H), 3.75–
3.51 (m, 32H), 3.40–3.29 (m, 16H), 3.07 (d, JZ12.9, 4H),
3.05 (d, JZ12.9, 4H), 1.92–1.70 (m, 16H), 1.57–1.43 (m,
8H), 1.04–1.01 (m, 24H), 0.75 (t, JZ7.5 Hz, 12H). 13C