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S1
Electronic Supplementary Information
Triptycene-derived calix[6]arenes: synthesis, structure and tubular
assemblies in the solid state
Xiao-Hong Tian,a,b Xiang Hao,a Tong-Ling Lianga and Chuan-Feng Chen*a
aBeijing National Laboratory for Molecular Sciences, CAS Key Laboratory of
Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of
Sciences, Beijing 100190, China. bGraduate School, Chinese Academy of Sciences,
Beijing 100049, China
E-mail: cchen@iccas.ac.cn
Content
1. Synthesis and characterization data of macrocycles 1 and 2 -----------------------S2
2. Copies of 1H NMR and 13C NMR spectra of new compounds --------------------S6
3. 1H-1H COSY and 13C-1H COSY 2D NMR spectra of 1 and 2 -------------------S14
4. X-ray crystal structures and packing of 1 and 2 ------------------------------------S18
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009
S2
1. Synthesis and characterization data of macrocycles 1 and 2
H3CO H3COHOH2C
CH2OH
KMnO4
66%
CH3OH, H+
reflux, 93% 95%
H3CO H3COH3CO2C
CO2CH3
H3CO H3COHO2C
CO2H
NaBH4
O
O OHOH
O
O OCH3OCH3
88%
Zn powder
OCH3OCH3
85%
H3CO H3CO
4 5 6
7 8
9 3
(CH3)2SO4
92%10% NaOH
benzenediazonium carboxylate
2, 7-Dimethyl-1, 8-dimethoxy-9, 10-anthracenedione (5). To a vigorously stirred
mixture of 2, 7-dimethyl-1, 8- dihydroxy-9, 10-anthracenedione 4S1 (3.0 g, 11.1 mmol)
and K2CO3 (12.3 g, 89.1 mmol) in acetone (100 mL) was added dimethylsulfate (8.4
mL, 88.8 mmol). The reaction mixture was refluxed for 24 h. The solvent was
evaporated under reduced pressure, and then concentrated ammonia solution was
added. The solution was stirred for 3 h at r.t. and filtered. The residue was purified by
column chromatography on silica gel with petroleum ether/EtOAc (4:1) as eluent to
afford 5 (2.9 g, 88 %) as a yellow solid. Mp: 160-162 °C. 1H NMR (300 MHz,
CDCl3): δ 2.42 (s, 6H), 3.95 (s, 6H), 7.53 (d, J = 7.8 Hz, 2H), 7.94 (d, J = 7.8 Hz, 2H). 13C NMR (75 MHz, CDCl3): δ 16.7, 61.6, 122.5, 127.7, 133.1, 135.6, 140.4, 158.4,
183.0, 183.6. EI-MS: 321 [M+Na]+. Anal. calcd. for C18H16O4: C 72.96, H 5.44;
found: C 72.64, H 5.56.
2, 7-Dimethyl-1, 8-dimethoxyanthracene (6). To a 10% NaOH solution (150 mL) of
compound 5 (2.9 g, 9.7 mmol) was added zinc powder (3.3 g, 49.8 mmol). The
mixture was stirred for 4 h at 120 °C, cooled to room temperature and then filtered.
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S3
The filtered cake was washed with CH2Cl2. The organic solution was concentrated,
and the residue was subjected to chromatography on silica gel with petroleum ether/
CH2Cl2 (4:1) as eluent to give compound 6 (2.4 g, 92 %) as a light-yellow crystals.
Mp: 152-153 °C. 1H NMR (300 MHz, CDCl3): δ 2.49 (s, 6H), 4.01 (s, 6H), 7.26 (d, J
= 8.8 Hz, 2H), 7.67 (d, J = 8.8 Hz, 2H), 8.34 (s, 1H), 8.85 (s, 1H). 13C NMR (75 MHz,
CDCl3): δ 16.0, 61.1, 114.3, 123.9, 124.6, 126.4, 126.9, 129.2, 131.8, 153.3. EI-MS:
267 [M+H]+, 289 [M+Na]+. Anal. calcd. for C18H18O2: C 81.17, H 6.81; found: C
81.12, H 6.87.
2, 7-Dimethyl-1, 8-dimethoxytriptycene (7). To a refluxing solution of compound 6
(2.4 g, 9.0 mmol) in 1,2-dichloroethane (100 mL) and 1, 2-epoxypropane (10 mL)
was added portionwise benzenediazonium carboxylate (5.4 g, 36.0 mmol) over 24 h.
The reaction mixture was concentrated under reduced pressure and then purified by
column chromatography (petroleum ether/CH2Cl2 4:1) to give 7 (2.6 g, 85 %) as a
white solid. Mp: 156-158 °C. 1H NMR (300 MHz, CDCl3): δ 2.18 (s, 6H), 3.87 (s,
6H), 5.33 (s, 1H), 6.15 (s, 1H), 6.78 (d, J = 7.4 Hz, 2H), 6.98 (m, 2H), 7.04 (d, J = 7.4
Hz, 2H), 7.30– 7.73 (m, 2H).13C NMR (75 MHz, CDCl3): δ 15.7, 42.3, 53.8, 61.4,
119.2, 123.5, 123.6, 125.1, 127.4, 127.9, 137.0, 144.8, 145.8, 146.4, 153.7. EI-MS:
365 [M+Na]+. Anal. calcd. for C24H22O2: C 84.18, H 6.48; found: C 83.97, H 6.55.
1, 8-Dimethoxytriptycene-2, 7-dicarboxylic acid (8). To a refluxing solution of
compound 7 (2.6 g, 7.7 mmol) in pyridine (60 mL) and H2O (20 mL) was added
portionwise KMnO4 (21.9 g, 138.6 mmol, 9 equiv per CH3 group) over 24 h. After
cooling to r.t., the reaction mixture was filtered and washed with 1 % NaOH solution.
The filtrate was evaporated, and then acidified to pH 1 with 6 N HCl. The suspension
was filtered, dried and further purified by recrystallization from methanol to afford 8
(2.1 g, 66 %) as a white solid. Mp: 254-256 °C. 1H NMR (300 MHz, CDCl3): δ 3.90
(s, 6H), 5.86 (s, 1H), 6.26 (s, 1H), 7.07 (m, 2H), 7.35 (d, J = 7.6 Hz, 2H), 7.45 (d, J =
7.6 Hz, 2H), 7.50 (m, 1H), 7.61 (m, 1H). 13C NMR (75 MHz, CDCl3): δ 52.7, 62.6,
119.6, 123.1, 123.8, 124.2, 125.5, 125.7, 128.6, 137.9, 143.7, 144.2, 150.8, 154.1,
166.8. EI-MS: 401 [M-H]+. Anal. calcd. for C24H22O2: C 71.64, H 4.51; found: C
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009
S4
71.86, H 4.68.
1, 8-Dimethoxytriptycene-2, 7-dicarboxylic acid dimethyl ester (9). To a refluxing
solution of compound 8 (2.1 g, 5.2 mmol) in methanol (40 mL) was added SOCl2 (5.0
mL) dropwise. The mixture was refluxed for another 8 h. After the mixture was
cooled, the suspension was filtered to afford 9 (2.1 g, 93 %) as a white solid. Mp:
200-202 °C. 1H NMR (300 MHz, CDCl3): δ 3.85 (s, 6H), 3.99 (s, 6H), 5.49 (s, 1H),
6.33 (s, 1H), 7.03 (m, 2H), 7.20 (d, J = 7.7 Hz, 2H), 7.38–7.47 (m, 2H), 7.55 (d, J =
7.7 Hz, 2H). 13C NMR (75 MHz, CDCl3): δ 41.7, 52.0, 54.4, 63.1, 119.5, 122.0, 124.0,
124.1, 125.7, 125.9, 129.4, 138.6, 143.8, 144.2, 151.5, 155.2, 166.2. EI-MS: m/z 431
[M+H]+, 453 [M+Na]+. Anal. calcd. for C26H22O6: C 72.55, H 5.15; found: C 72. 21,
H 5.21.
2, 6-Dihydroxymethyl-1, 8-dimethoxytriptycene (3). To a solution of 9 (2.1 g,
4.9mmol) in THF was added sodium borohydride (1.9 g, 49mmol). The mixture was
stirred for 15 min at refluxing temperature. Methanol (8 mL) was then added
dropwise. The mixture was refluxed for another 3 h. After cooling to r.t., 3 N HCl was
added to quench the reaction and extracted with CH2Cl2. The organic phase was dried
and concentrated to give pure alcohol 3 (1.7 g, 95 %) as a white solid. Mp: 170-171
°C. 1H NMR (300 MHz, CDCl3): δ 1.92 (s, 2H), 3.96 (s, 6H), 4.61 (s, 4H), 5.41 (s,
1H), 6.15 (s, 1H), 6.97 (d, J = 7.4 Hz, 2H), 7.02 (m, 2H), 7.14 (d, J = 7.4 Hz, 2H),
7.30–7.52 (m, 2H). 13C NMR (75 MHz, CDCl3): δ 42.2, 54.0, 61.3, 62.7, 119.7, 123.5,
123.9, 125.5, 126.1, 131.1, 137.0, 144.0, 145.6, 147.7, 153.5. EI-MS: m/z 397
[M+Na]+. Anal. calcd. for C24H22O4: C 76.99, H 5.92; found: C 76.64, H 5.94.
Reference:
S1. C. Marschalk, F. Koenig, N. Ouroussoff, Bull. Soc. Chim. Fr., 1936, 5,
1545–1568.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009
S5
+
OH
p-TsOH OH
OH
+OMe
OMe
OH
OMe
OMe OMe
OMe
OH
OMe
OMe3
1 2
Cl
Cl
1 and 2. To a solution of catalytic amount of TsOH in o-dichlorobenzene (60 mL)
was slowly added at 100 °C a solution of 3 (0.374 g, 1 mmol) and p-tert-butylphenol
(0.15 g, 1 mmol) in o-dichlorobenzene (120 mL) under argon atmosphere. After 24 h
an additional quantity of p-tert-butylphenol (0.15g, 1 mmol) was added and the
mixture heated for an additional 24 h. The dark resolution was evaporated in vacuum,
and then the mixture was separated by column chromatography over silica gel (eluent:
1:10 ethyl acetate/petroleum ether) to afford 1 (0.19 g, 19%) and 2 (0.17 g, 17%). 1
and 2 could be further crystallized from CH2Cl2/petroleum ether. 1. Mp: 300 > °C. 1H
NMR (300 MHz, CDCl3): δ 1.30 (s, 18H), 3.35 (d, J = 15.3 Hz, 4H), 3.91 (s, 12H),
4.25 (d, J = 15.3 Hz, 4H), 5.24 (s, 2H), 5.97 (s, 2H), 6.09 (s, 2H), 6.64 (d, J = 7.6 Hz,
4H), 6.88–6.97 (m, 8H), 7.08 (s, 4H), 7.28–7.40 (m, 4H). 13C NMR (75 MHz, CDCl3):
δ 29.9, 31.7, 33.9, 42.6, 53.7, 62.5, 119.9, 123.4, 123.6, 125.1, 125.2, 125.4, 126.5,
127.2, 130.0, 136.7, 141.9, 144.9, 145.8, 146.6, 150.2, 152.6. MALDI-TOF MS: m/z
999 [M+Na]+, 1015 [M+K]+. Anal. Calcd for C68H64O6·1.5CH2Cl2·0.5H2O: C 74.96,
H 6.15; found: C 74.97, H 6.21. 2. Mp: > 300 °C. 1H NMR (300 MHz, CDCl3): δ 1.22
(s, 18H), 3.20 (s, 12H), 3.68 (d, J = 14.5 Hz, 4H), 3.87 (d, J = 14.5 Hz, 4H), 5.34 (s,
2H), 5.86 (s, 2H), 6.00 (s, 2H), 6.97 (m, 8H), 7.16–7.02 (m, 8H), 7.30–7.40 (m, 4H). 13C NMR (75 MHz, CDCl3): δ 31.6, 32.6, 34.0, 42.5, 53.9, 61.9, 119.4, 123.4, 125.1,
125.3, 126.1, 127.3, 128.0, 130.9, 136.8, 143.0, 144.6, 146.3, 146.5, 150.5, 153.2.
MALDI-TOF MS: m/z 999 [M+Na]+, 1015 [M+K]+. Anal. Calcd for
C68H64O6·0.5H2O: C 74.66, H 6.12; found: C 74.84, H 6.36.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009
S6
2. Copies of 1H NMR and 13C NMR spectra of new compounds
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.56.
12
6.00
1.92
1.94
0.02
50
2.39
18
3.95
22
7.24
347.
5150
7.92
087.
9469
O
O OCH3OCH3
Figure S1. 1H NMR spectrum (CDCl3) of 5.
O
O OCH3OCH3
0102030405060708090110130150170190
16.7
309
61.6
284
76.5
803
77.0
036
77.4
273
122.
5164
127.
6959
133.
1156
140.
4462
158.
4090
183.
0028
183.
5410
Figure S2. 13C NMR spectrum (CDCl3) of 5.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009
S7
0.01.02.03.04.05.06.07.08.09.010.0
5.96
5.99
2.32
1.97
0.99
1.00
-0.0
004
2.48
95
3.98
94
7.24
537.
2746
7.66
037.
6890
8.34
24
8.84
73
OCH3OCH3
Figure S3. 1H NMR spectrum (CDCl3) of 6.
OCH3OCH3
-100102030405060708090100110120130140150160170
15.9
752
61.0
931
76.5
704
76.9
937
77.4
168
114.
2817
123.
8916
124.
6116
126.
4271
126.
8765
129.
2179
131.
7831
153.
2670
Figure S4. 13C NMR spectrum (CDCl3) of 6.
Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2009
S8
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
5.92
5.83
1.00
1.03
1.96
1.93
1.81
1.01
0.91
-0.0
004
2.18
91
3.87
08
5.32
85
6.14
67
6.76
596.
9647
7.02
397.
2500
7.34
607.
4056
7.42
24
H3CO H3COH3C
CH3
Figure S5. 1H NMR spectrum (CDCl3) of 7.
H3CO H3COH3C
CH3
-100102030405060708090100110120130140150160
15.7
905
42.3
718
53.9
013
61.5
259
76.7
036
77.1
270
77.5
506
119.
3151
123.
6095
123.
6635
127.
4840
137.
1192
144.
8596
153.
7676
Figure S6. 13C NMR spectrum (CDCl3) of 7.
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S9
0.52.03.55.06.58.09.511.513.5
5.27
1.00
1.00
1.99
1.92
1.74
0.99
1.06
1.93
-0.0
310
2.50
23
3.32
36
3.88
58
5.85
206.
2100
7.32
207.
3476
7.42
547.
4508
7.49
117.
5011
7.58
687.
5977
12.7
931
H3CO H3COHO2C
CO2H
Figure S7. 1H NMR spectrum (CDCl3) of 8.
H3CO H3COHO2C
CO2H
-100102030405060708090110130150170
38.6
882
38.9
680
39.2
455
39.5
234
39.8
017
40.0
804
40.3
590
40.9
340
52.5
196
62.6
458
119.
5662
123.
0778
123.
7963
124.
2143
125.
5918
128.
5956
137.
8988
143.
6528
150.
8199
154.
1277
166.
7840
Figure S8. 1H NMR spectrum (CDCl3) of 8.
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S10
H3CO H3COH3CO2C
CO2CH3
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5
6.02
6.05
1.01
1.00
1.99
2.04
1.04
1.06
1.86
-0.0
246
3.85
623.
9907
5.48
99
6.33
12
7.02
687.
0420
7.05
547.
1957
7.22
137.
2524
7.38
727.
3999
7.53
41
Figure S9. 13C NMR spectrum (CDCl3) of 9.
H3CO H3COH3CO2C
CO2CH3
-100102030405060708090110130150170
41.6
940
52.0
342
54.4
664
63.1
141
76.5
805
77.0
038
77.4
272
119.
4614
122.
0076
123.
9452
124.
0721
125.
6691
125.
9026
129.
3810
138.
5422
143.
7808
144.
2016
151.
4808
155.
2262
166.
1805
Figure S10. 13C NMR spectrum (CDCl3) of 9.
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S11
H3CO H3COHOH2C
CH2OH
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
2.47
6.18
4.29
1.17
1.11
1.95
1.88
1.93
1.00
1.00
-0.0
005
1.92
17
3.93
97
4.61
02
5.40
79
6.14
58
6.95
757.
0049
7.02
347.
1311
7.24
917.
3808
7.39
997.
4345
Figure S11. 1H NMR spectrum (CDCl3) of 3
H3CO H3COHOH2C
CH2OH
-100102030405060708090100110120130140150160170
42.1
649
53.9
886
61.3
328
62.7
168
76.5
805
77.0
042
77.4
277
119.
7481
123.
5391
123.
8555
125.
4624
126.
1337
131.
1010
137.
0131
143.
9776
153.
4555
Figure S12. 13C NMR spectrum (CDCl3) of 3
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S12
OHOMe
OMe OMe
OMe
OH
-1.00.01.02.03.04.05.06.07.08.09.0
16.7
8
3.21
11.1
43.
51
1.66
1.48
1.71
3.26
6.35
3.22
2.23
1.92
0.00
32
1.30
451.
5349
3.32
543.
3764
3.91
424.
2252
4.27
60
5.23
99
5.97
396.
0927
6.62
826.
6535
6.92
016.
9452
6.96
697.
0779
7.25
337.
2680
7.28
097.
2959
7.38
63
7.40
14
Figure S3. 1H NMR spectrum (CDCl3) of 1
OHOMe
OMe OMe
OMe
OH
Figure S14. 13C NMR spectrum (CDCl3) of 1.
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S13
OH
OHOMe
OMe
OMe
OMe
Figure S15. 1H NMR spectrum (CDCl3) of 2
OH
OHOMe
OMe
OMe
OMe
0102030405060708090100110120130140150160
31.6
144
32.6
001
33.9
988
42.5
132
53.8
536
61.9
179
76.5
863
77.0
094
77.4
335
119.
4160
123.
3961
126.
1145
136.
8410
142.
9874
150.
4617
153.
2900
Figure S16. 13C NMR spectrum (CDCl3) of 2.
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S14
3. 1H-1H COSY and 13C-1H COSY 2D NMR spectra of 1 and 2
ppm
3.54.04.55.05.56.06.57.07.58.0 ppm
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
OH
OMe
OMe OMe
OMe
OH
OMe
Ha
Hb
OHHa Hb
Hc
Hc'
Hc' Hc
Figure S17. 1H-1H COSY spectrum of 1.
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S15
ppm
3.54.04.55.05.56.06.57.07.5 ppm
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
OH
OHOMe
OMe
OMe
OMe
Ha
Hb
Hc
Hc'
HOHbHa HcHc'
OMe
Figure S18. 1H-1H COSY spectrum of 2.
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S16
OH
OMe
OMe OMe
OMe
OH
ppm
3.54.04.55.05.56.06.5 ppm
70
60
50
40
30
20
10
Figure S19. 13C-1H COSY spectrum of 1.
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S17
OH
OHOMe
OMe
OMe
OMe
ppm
3.54.04.55.05.56.06.5 ppm
20
30
40
50
60
70
Figure S20. 13C-1H COSY spectrum of 2.
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S18
4. X-ray crystal structures and packing of 1 and 2
The X-ray measurements were carried on a Saturn724+ CCD diffractometer with graphite-monochromator Mo-Kα radiation (λ = 0.71073 Å) at 173 K. Intensities were collected using CrystalClear (Rigaku Inc., 2008) technique and absorption effects were collected using the multi-scan technique. The structure of 1 was solved by direct methods and refined by a full matrix least squares technique based on F2 using SHELXL 97 program. The structure of 2 was solved using SHELXS-97 (Sheldrick, 1990) program and refined by a full matrix least squares technique based on F2 using SHELXL 97 program. Application of the restraints is for confining the thermal vibration parameters of the disordered solvent molecules, which can make them be isotropic. Because highly disordered solvent molecules were difficult to be determined, they were deleted with SQUEEZE program in the crystal structure of 1. For 2, the high R-factor and weighted R-factor might be mainly due to the solvent molecules which haven’t been treated with SQUEEZE program.
Figure S21. A 3D microporous structure of 1 viewed along the b-axis. Solvent molecules and hydrogen atoms were omitted for clarity.
Figure S22. View of the non-covalent interactions between CH2Cl2 molecules and macrocycle 2 during the formation of the organic tube. Other solvent molecules and hydrogen atoms not involved in the interactions are omitted for clarity.
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S19
Figure S23. Packing of 2. View of a 2D layer structure. Dashed lines denote the non-covalent interactions between the CH2Cl2 molecule and its adjacent macrocycles.
Figure S24. Packing of 2. View of the 3D microporous structure (a) without the solvents, and (b) with the solvents situated in the different channels along the a-axis. Hydrogen atoms are omitted for clarity.
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