Figure 2 Molecular structure of cyclopropane derivative D2 in the … · 2008. 1. 18. · College...
Transcript of Figure 2 Molecular structure of cyclopropane derivative D2 in the … · 2008. 1. 18. · College...
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
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One-step synthesis of polysubstituted benzenes by multi-component cyclization
of α-bromoacetate, malononitrile and aromatic aldehydes
Chao Guo Yan,* Xiao Kai Song, Qi Fang Wang, Jing Sun
College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China
Ulrich Siemeling,* Clemens Bruhn
Institute of Chemistry, University of Kassel, Heinrich-Plett-Strasse 40, D-34132 Kassel, Germany
Supporting Information
Figures
Figure 1 2
Figure 2 2
Figure 3 3
Figure 4 3
Scheme1-2 4
General Experimental Methods and
Characterization of compounds 5-21
X-Ray Crystallographic Data CIF in separate file.
Crystallographic data (1a: CCDC 663309; 1b: CCDC 663310; 1c: CCDC 663311; 1h CCDC 663312. D1:
CCDC 663313; D2: CCDC 663314. F CCDC 663315. ) have been deposited vat the Cambridge
Crystallographic Database Centre and is available on request from the Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-336033; e-mail: [email protected] or
www:http//www.ccdc.cam.ac.uk).
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
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Figure 1 Molecular structure of 1c in the crystal
Figure 2 Molecular structure of cyclopropane derivative D2 in the crystal
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
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Figure 3 Molecular structure of intermediate F in the crystal
Figure 4 Molecular structure of 1h in the crystal
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2ArCHO +CN
CNBrCH2CO2Et+ +
N
CO2EtAr
ArCN
NH2
CN2
Scheme 1 One-pot four-component reaction affording polysubstituted benzene derivatives
N
+ Py
N
+ BrCH2CO2Et
ArCH=C(CN)2
-Py + Py
CO2Et
CN
CN
Ar
ArCH=C(CN)2
CO2Et
Ar
NC
NC
CO2Et
Ar
Ar
CN
CN
CN
C N
CO2Et
CN
N
NC CN
Ar
Ar
CO2Et
CN
NH2
NC CN
Ar
Ar
CO2Et
CN
NH2Ar
Ar
CN
CH2CO2EtNCHCO2Et
NCHCO2Et
CO2Et
CN
CN
ArC(CN)2ArCH
- HPy
- HPy- Br
+ Py
- HCN- HPy
A
B
C
D
E
F 1
+ H
Scheme 2 Proposed mechanism for the formation of polysubstituted benzenes 1
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General procedure for the synthesis of polysubstituted Benzenes
A mixture of pyridine (20.0mmol, 1.58g), ethyl α-bromoacetate (4.0mmol, 0.668g),
aromatic aldehyde (4.0mmol, 0.562g) and malononitrile (4.0mmol, 0.264g) in
acetonitrile (20mL) was refluxed for 12 hours. The solvent was removed by
evaporation and the residue was titrated with ethanol (10mL) to give the crude
product, which is recrystallized in ethanol to give light yellow solid
1a: mp151~152�. 1H NMR (CDCl3, 600 MHz) δ(ppm) 7.273 (m, J = 8.4Hz, 3H,
C6H5), 7.132 (m, J = 7.2 Hz, 3H, C6H5), 7.054 (d, J = 8.4 Hz, 2H, C6H5), 6.921 (d, J =
8.4 Hz, 2H, C6H5), 5.380 (s, 2H, NH2), 4.082 (q, J = 7.2 Hz, 2H, CH2), 0.972 (t, J =
7.2 Hz, 3H, CH3); 13C NMR (CDCl3, 600 MHz) δ(ppm) 147.81, 147.48, 146.97,
131.34, 131.14, 128.82, 127.86, 127.24, 126.55, 124.80, 124.52, 124.23, 109.93,
38.44, 34.54, 34.13, 27.43, 27.05, 19.78; IR(KBr)ν3432, 3355, 3254, 2220, 1727,
1648, 1565, 1568, 1454, 1374, 1267, 1231, 1034, 754, 703; Found: C,75.15; H,4.47;
N,11.39. C23H17N3O2 requires C,75.19; H,4.66; N,11.44. The structure of 1a was
further proved by X-ray crystallographic analysis (Figure 1).
ppm (t1)1.02.03.04.05.06.07.0
0
10000
20000
30000
40000
500007.25
87.
244
7.23
17.
154
7.13
87.
126
7.11
5
7.06
17.
047
6.92
86.
917
6.91
5
5.38
0
4.10
04.
088
4.07
64.
064
0.97
2
2.00
2.00
2.002.003.003.00
3.00
O
O CNNH2
CN
5a
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ppm (t1)050100150
0
50000
10000
15000
20000
25000
30000
35000164.
433
149.
821
140.
599
134.
997
134.
870
129.
094
128.
869
128.
294
127.
819
127.
163
126.
846
126.
647
113.
913
113.
160
98.8
57
93.5
07
61.5
07
12.4
54
CN
NH2CN
O
O
5a
Figure 1 X-ray crystallographic structure of 1a
1b mp190~191�. 1H NMR (CDCl3, 600 MHz) δ 7.049 (d, J = 7.8 Hz, 2H,
p-CH3C6H4), 6.942 (d, J = 7.8 Hz, 4H, p-CH3C6H4), 6.801 (d, J = 7.8 Hz, 2H,
p-CH3C6H4) 5.342 (s, 2H, NH2), 4.103 (q, J = 7.2 Hz, 2H, CH2), 2.292 (s, 3H, CH3),
2.251 (s, 3H, CH3), 0.972 (t, J = 7.2 Hz, 3H, CH3); 13C NMR (CDCl3, 600 MHz)
δ(ppm) 164.23, 150.18, 148.60, 140.93, 134.66, 133.42, 133.29, 133.25, 130.57,
129.80, 128.02, 127.59, 113.79, 113.04, 96.97, 94.24, 61.57, 12.74; IR(KBr)ν3467,
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3356, 3256, 2225, 1741, 1640, 1588, 1560, 1449, 1376, 1266, 1232, 1031, 795, 762;
Found: C,76.12; H,5.11; N,10.60. C25H21N3O2 requires C,75.93; H,5.35; N,10.63.
The structure of 5b was further proved by X-ray crystallographic analysis (Figure 2).
ppm (t1)0.01.02.03.04.05.06.07.0
0
10000
20000
30000
40000
50000
60000
7.26
27.
050
7.03
76.
949
6.93
6
6.80
86.
795
5.34
2
4.10
94.
097
2.29
22.
251
1.02
41.
012
1.00
0
3.00
3.003.00
2.00
2.00
2.004.002.00
O
O CNNH2
CN
CH3
H3C
5b
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CNNH2
CN
CH3
H3C
O
O
ppm (t1)050100150
0
50000
10000
15000
20000
164.
227
150.
178
148.
596
140.
932
134.
662
133.
420
133.
294
133.
253
130.
570
129.
795
128.
017
127.
590
113.
792
113.
046
98.9
59
94.2
43
61.9
85
12.7
44
5b
Figure 2 X-ray crystallographic structure of 1b
1c mp231~232�. 1H NMR (CDCl3, 600 MHz) δ 7.257 (d, J = 7.8 Hz, 2H,
p-ClC6H4), 7.156 (d, J = 8.4 Hz, 2H, p-ClC6H4), 6.990 (d, J = 7.8 Hz, 2H, p-ClC6H4),
6.860 (d, J = 8.4 Hz, 2H, p-ClC6H4), 5.423 (s, 2H, NH2), 4.129 (q, J = 7.2 Hz, 2H,
CH2), 1.051 (t, J = 7.2 Hz, 3H, CH3); 13C NMR (CDCl3, 600 MHz) δ(ppm) 162.84,
148.82, 147.13, 139.53, 132.40, 132.36, 129.63, 129.49, 129.21, 126.67, 125.19,
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121.60, 120.25, 112.42, 111.67, 97.54, 92.93, 60.66, 11.37; IR(KBr)ν3469, 3351,
3244, 2221, 1743, 1642, 1557, 1493, 1447, 1375, 1276, 1218, 1016, 789, 743;Found:
C,63.09; H,3.22; N,9.54. C23H15Cl2N3O2 requires C,63.32; H,3.47; N,9.63. The
structure of 5c was further proved by X-ray crystallographic analysis (Figure 3).
ppm (t1)1.02.03.04.05.06.07.0
0
10000
20000
30000
40000
7.26
47.
260
7.25
17.
163
7.14
96.
996
6.98
36.
867
6.85
3
5.42
3
4.14
64.
134
4.12
34.
111
1.05
1
3.00
2.00
2.00
2.002.002.00
2.00
OO CN
NH2
CN
Cl
Cl
5c
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CNNH2
CN
Cl
Cl
O
O
5c
ppm (t1)050100150
0
50000
10000
15000
162.
842
148.
821
147.
134
139.
538
132.
386
132.
362
129.
632
129.
487
129.
212
128.
659
126.
187
121.
604
120.
251
112.
415
111.
671
97.5
36
92.9
32
60.6
50
11.3
86
Figure 3 X-ray crystallographic structure of 1c
1d mp201~202℃ . 1H NMR (600MHz, CDCl3) δ(ppm) 7.27~7.25 (m, 1H,
m-ClC6H4), 7.22~7.16 (m, 2H, m-ClC6H4), 7.10~7.04 (m, 2H, m-ClC6H4), 6.95 (s, 2H,
m-ClC6H4), 6.78 (s, 1H, m-ClC6H4), 5.44 (s, 2H, NH2), 4.13 (q, J = 8.4Hz, 2H, CH2),
1.03 (t, J = 8.4Hz, 3H, CH3). 13C NMR (600MHz, CDCl3) δ(ppm) 150.9, 148.9, 137.1,
137.1, 134.4, 134.4, 129.9, 129.7, 129.3, 129.2, 128.3, 128.2, 127.4, 114.4, 113.8,
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99.6, 62.8, 16.5.
ppm (t1)0.01.02.03.04.05.06.07.08.0
0
50
100
150
200
250
7.27
07.
256
7.24
07.
220
7.20
57.
189
7.17
37.
156
7.10
07.
084
7.06
97.
037
6.94
56.
783
5.43
8
4.15
04.
135
4.12
14.
107
1.04
01.
026
1.01
2
3.00
2.00
1.002.002.002.011.00
2.00
ppm (t1)050100150
0
500
150.
935
148.
909
137.
146
137.
116
134.
386
134.
354
129.
940
129.
711
129.
310
129.
181
128.
276
128.
146
127.
355
114.
399
113.
790
99.6
02
77.2
4676
.992
76.7
38
62.8
07
13.5
13
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
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1e mp252~253�. 1H NMR (CDCl3, 600 MHz) δ 7.419 (d, J = 8.4 Hz, 2H,
p-BrC6H4), 7.315 (d, J = 8.4 Hz, 2H, p-BrC6H4), 6.926 (d, J = 8.4 Hz, 2H, p-BrC6H4),
6.797 (d, J = 8.4 Hz, 2H, p-BrC6H4), 5.423 (s, 2H, NH2), 4.129 (q, J = 7.2 Hz, 2H,
CH2), 1.052 (t, J = 7.2 Hz, 3H, CH3); 13C NMR (CDCl3, 600 MHz) δ(ppm) 163.31,
149.48, 147.33, 140.08, 135.93, 131.43, 130.72, 129.57, 128.39, 127.97, 127.26,
125.61, 125.30, 120.85, 120.50, 112.85, 112.25, 96.16, 93.67, 61.30, 12.03; IR(KBr)
ν3469, 3352, 3243, 2221, 1742, 1639, 1558, 1445, 1376, 1305, 1262, 1219, 1025,
785, 734;Found: C,52.49; H,2.68; N,7.87. C23H15Br2N3O2 requires C,52.60; H,2.88;
N,8.00.
ppm (t1)0.01.02.03.04.05.06.07.0
0
10000
20000
30000
40000
50000
60000
7.42
97.
415
7.32
57.
311
6.93
66.
923
6.80
56.
792
5.44
8
4.13
64.
124
1.04
6
2.00
2.002.00
3.00
2.00
2.00
2.00
O
O CNNH2
CN
Br
Br
5d
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CNNH2
CN
Br
Br
O
O5d
ppm (t1)050100150
0
50000
10000
15000
163.
306
149.
476
147.
332
140.
077
135.
926
131.
431
130.
719
129.
571
128.
391
127.
970
127.
259
126.
609
126.
295
120.
850
120.
501
112.
854
112.
254
98.1
63
93.6
73
61.3
04
12.0
36
1f mp187~188�. 1H NMR (CDCl3, 600 MHz) δ 7.437 (d, J = 8.4 Hz, 1H,
m-BrC6H4), 7.340 (d, J = 7.2 Hz, 1H, m-BrC6H4), 7.214 (s, 1H, m-BrC6H4), 7.163
(q, J = 7.8 Hz, 2H, m-BrC6H4), 7.028 (q, J = 7.8 Hz, 2H, m-BrC6H4), 6.846 (s, 1H,
m-BrC6H4), 5.450 (s, 2H, NH2),4.154(q, J = 7.2 Hz, 2H, CH2), 1.060 (t, J = 7.2 Hz,
3H, CH3); 13C NMR (CDCl3, 600 MHz) δ(ppm) 165.05, 150.55, 150.15, 141.18,
138.22, 136.81, 132.53, 132.40, 129.40, 126.69, 126.36, 126.06, 114.63, 113.73,
99.42, 93.70, 61.91, 20.75, 20.61, 12.97; IR(KBr)ν3464, 3348, 3238, 2223, 1728,
1636, 1563, 1448, 1384, 1275, 1232, 1029, 775, 682; Found: C,52.47; H,2.68; N,7.87.
C23H15Br2N3O2 requires C,52.60; H,2.88; N,8.00.
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ppm (t1)0.01.02.03.04.05.06.07.08.0
0
10000
20000
30000
40000
500007.44
47.
430
7.34
67.
334
7.26
07.
214
7.17
67.
163
7.15
07.
139
7.05
37.
041
7.02
87.
014
6.84
2
5.45
0
4.17
24.
160
4.14
84.
136
1.07
21.
060
1.04
8
3.00
1.001.001.002.002.001.00
2.00
2.00
O
O CNNH2
CN
BrBr
5e
CNNH2
CN
O
O
BrBr
ppm (t1)050100150
0
50000
10000
15000
20000
165.
065
150.
554
150.
156
141.
184
138.
219
136.
809
132.
632
132.
403
129.
389
128.
693
128.
368
128.
057
114.
628
113.
734
99.4
18
93.6
95
61.9
12
20.7
5720
.610
12.9
74
5e
1g mp171~172℃. 1H NMR (600MHz, CDCl3) δ(ppm) 7.52 (d, J = 9.6Hz, 1H,
o-BrC6H4), 7.39 (d, J = 8.4Hz, 1H, o-BrC6H4), 7.16~7.10 (m, 3H, o-BrC6H4),
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7.06~6.99 (m, 3H, o-BrC6H4), 5.48 (s, 2H, NH2), 4.10 (q, J = 8.4Hz, 2H, CH2), 0.99 (t,
J = 8.4Hz, 3H, CH3).13CNMR (600MHz,CDCl3) δ(ppm) 164.4, 150.9, 149.2, 140.9,
136.0, 135.8, 133.4, 133.1, 132.6, 131.6, 130.5, 129.5, 129.4, 126.5, 126.1, 124.5,
123.0, 114.4, 114.2, 101.2, 95.9, 62.6, 13.3 . C23H15Br2N3O2 (Mw= 525.19, M+ =
525.95)
ppm (t1)1.02.03.04.05.06.07.08.0
0
50
100
150
200
250
300
7.52
87.
511
7.39
57.
380
7.24
07.
160
7.14
57.
126
7.11
07.
095
7.05
87.
045
7.02
37.
006
6.98
8
5.48
3
4.14
04.
133
4.12
64.
119
4.10
44.
101
4.08
74.
079
4.07
24.
065
1.00
60.
992
0.97
8
3.00
1.001.00
3.003.00
2.00
2.00
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
16
ppm (t1)50100150
-500
0
500
1000
1500
2000
2500
3000
3500164.
373
150.
944
149.
157
140.
962
135.
991
135.
825
133.
398
133.
057
132.
624
131.
642
130.
459
129.
485
129.
384
126.
513
126.
116
124.
547
123.
039
114.
367
114.
173
101.
189
95.9
65
77.2
4876
.993
76.7
39
62.5
95
13.3
38
1h mp187-188℃.1H NMR (600MHz, CDCl3) δ(ppm) 7.25 (d, J = 9.6Hz, 2H,
p-(CH3)3CC6H4), 7.16 (d, J = 8.4Hz, 2H, p-(CH3)3CC6H4), 6.99 (d, J = 9.6Hz, 2H,
p-(CH3)3CC6H4), 6.84 (d, J = 9.6Hz, 2H, p-(CH3)3CC6H4), 5.44 (s, 2H, NH2), 4.13 (q,
J = 8.4Hz, 2H, CH2), 1.28 (s, 9H, (CH3)3C), 1.25 (s, 9H, (CH3)3C), 0.95 (t, J = 8.4Hz,
3H, CH3). 13C NMR (600MHz, CDCl3) δ(ppm) 165.7, 151.7, 151.2, 150.5, 141.3,
132.9, 129.6, 129.0, 124.3, 124.5, 115.2, 114.3, 99.5, 93.9, 62.3, 34.5, 34.4, 31.1, 31.1,
13.3. C31H33N3O2 (Mw = 479.26, M+ = 479.61)
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ppm (t1)1.02.03.04.05.06.07.0
0
500
7.31
1
7.25
77.
240
7.16
37.
149
7.00
06.
984
6.84
86.
831
5.43
9
4.15
14.
137
4.12
24.
108
1.27
91.
253
0.96
00.
946
0.93
2
3.00
2.002.00
2.002.00
2.00
2.00
9.009.00
ppm (t1)050100150
0
5000
165.
656
151.
698
151.
184
150.
445
141.
302
132.
902
129.
627
129.
033
124.
769
124.
477
115.
180
114.
327
99.5
04
93.9
1493
.908
77.2
4776
.994
76.7
39
62.3
34
34.5
2434
.359
31.1
0731
.054
13.3
03
F (Ar = p-(CH3)3CC6H4) Yield: 22%; Mp: 180-182. 1H NMR (600MHz, CDCl3) δ(ppm)
7.39 (d, J = 9.6Hz, 2H, p-(CH3)3CC6H4), 7.26 (t, J = 8.4Hz, 4H, p-(CH3)3CC6H4), 6.97
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(d, J = 9.6Hz, 2H, p-(CH3)3CC6H4), 5.47 (s, 2H, NH2), 4.31 (s, 1H, CH), 4.07 (q, J =
7.2Hz, 2H, CH2), 1.29 (s, 9H, (CH3)3C), 1.24 (s, 9H, (CH3)3C), 0.91 (t, J = 8.4Hz, 3H,
CH3). 13C NMR (600MHz, CDCl3) δ(ppm) 165.1, 153.4, 151.9, 142.3, 134.7, 133.5,
129.1, 126.9, 126.5, 125.7, 125.3, 124.9, 115.0, 111.9, 110.7, 80.2, 61.8, 53.1, 42.4,
34.7, 31.1, 13.3.C32H34N4O2 (Mw = 506.65, M+ = 507.27)
ppm (f1)0.01.02.03.04.05.06.07.0
0
100
200
300
400
500
6007.39
67.
379
7.27
47.
257
7.24
47.
240
6.98
16.
964
5.47
3
4.31
04.
089
4.07
74.
063
4.06
04.
048
1.29
2
1.24
10.
921
0.90
70.
893
3.00
9.009.00
2.00
2.004.00
2.00
2.00
1.00
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
19
ppm (t1)050100150
-1000
0
1000
2000
3000
4000
5000
600016
5.07
8
153.
357
151.
869
142.
303
134.
742
133.
482
129.
097
126.
913
126.
491
125.
656
125.
340
124.
881
115.
011
111.
919
110.
656
80.1
51
77.2
4776
.993
76.7
38
61.7
63
53.1
22
42.3
56
34.7
1834
.602
31.1
30
13.3
36
General procedure for the synthesis of cyclopropane derivatives
A mixture of pyridine (20.0mmol, 1.58g), ethyl α-bromoacetate (5.0mmol,
0.835g), aromatic aldehyde (5.0mmol), malononitrile (5.mmol, 0.330g) and
triethylamine (1.0mL) in acetonitrile (20mL) was refluxed for 12 hours. The solvent
was removed by evaporation and the residue was titrated with ethanol (10mL) to give
the crude product, which is recrystallized in ethanol to give light yellow solid D
D1 (Ar = p-ClC6H4): yield 84.8%,mp: 175~176�。1H NMR (600MHz, CDCl3) δ
(ppm) 7.43 (d, J = 8.4Hz, 2H, C6H4), 7.26 (d, J = 8.4Hz, 2H, C6H4), 4.71 (q, J =
7.2Hz, 2H, CH2), 3.66 (d, J = 7.2Hz,1H, CH), 3.11 (d, J = 7.2Hz, 1H, CH), 1.39 (t, J
= 7.2Hz,3H, CH3).
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
20
D2 (Ar = o-BrC6H4): yield: 75.2% mp: 191-193�. 1H NMR (600MHz, CDCl3) δ(ppm)
7.77 (d, J = 9.6Hz, 1H, o-BrC6H4), 7.44~7.36 (m, 2H, o-BrC6H4), 7.23 (d, J = 8.4Hz,
1H, o-BrC6H4), 4.43 (q, J = 8.4Hz, 2H, CH2), 3.74 (d, J = 7.2Hz, 1H, CH), 3.17 (d, J
= 9.6Hz, 1H, CH), 1.44 (t, J = 8.4Hz, 3H, CH3). 13C NMR (600MHz, CDCl3) δ(ppm)
164.5, 133.5, 133.5, 131.3, 131.3, 129.6, 129.6, 129.3, 129.3, 127.9, 127.9, 126.2,
126.207, 111.5, 111.3, 63.4, 39.2, 34.5, 14.0. C14H11BrN2O2 (M+ 318.93, 320.93)
ppm (t1)0.01.02.03.04.05.06.07.0
0
10000
20000
30000
40000
7.43
37.
419
7.26
47.
250
4.38
84.
377
4.36
54.
354
3.66
83.
655
3.11
83.
105
1.39
91.
388
1.37
6
3.00
1.00
2.002.00
2.00
1.00
Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008
21
ppm (t1)0.01.02.03.04.05.06.07.08.0
0
100
200
300
400
500
7.77
37.
757
7.43
87.
423
7.40
87.
386
7.37
17.
356
7.30
4
7.24
07.
225
4.45
14.
437
4.42
34.
409
3.75
23.
736
3.17
93.
163
1.45
61.
442
1.42
8
3.00
1.00
2.001.00
2.00
1.00
0.95
ppm (t1)050100150
0
5000
164.
545
133.
498
133.
486
131.
326
131.
314
129.
604
129.
591
129.
348
129.
335
127.
951
127.
939
126.
219
126.
207
111.
481
111.
336
77.2
5276
.998
76.7
44
63.4
14
39.1
86
34.4
64
14.0
47