Unexpected Cleavage of Thiacalix[4]arene Sulfoxides · Unexpected Cleavage of Thiacalix[4]arene...
Transcript of Unexpected Cleavage of Thiacalix[4]arene Sulfoxides · Unexpected Cleavage of Thiacalix[4]arene...
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Unexpected Cleavage of Thiacalix[4]arene Sulfoxides
Jiří Mikšátko†, Václav Eigner,
§ and Pavel Lhoták
†*
†Department of Organic Chemistry, University of Chemistry and Technology, Prague (UCTP), Technická
5, 166 28 Prague 6, Czech Republic §Solid State Department, UCTP, 166 28 Prague 6, Czech Republic
E-mail: [email protected]
Supporting information
Table of Contents
Spectra of compounds p. 2-34
X-ray structure of compound 6 p. 35
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2017
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Compound 4
1H NMR spectrum of compound 4 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 4 (CDCl3, 298K, 100 MHz)
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Compound 4
IR (ATR) spectrum of compound 4
HRMS (ESI+) spectrum of compound 4
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Compound 6
1H NMR spectrum of compound 6 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 6 (CDCl3, 298K, 100 MHz)
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Compound 6
IR (ATR) spectrum of compound 6
HRMS (ESI+) spectrum of compound 6
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Compound 7a
1H NMR spectrum of compound 7a (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 7a (CDCl3, 298K, 100 MHz)
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Compound 7a
IR (ATR) spectrum of compound 7a
HRMS (ESI+) spectrum of compound 7a
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Compound 7b
1H NMR spectrum of compound 7b (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 7b (CDCl3, 298K, 100 MHz)
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Compound 7b
IR (ATR) spectrum of compound 7b
HRMS (ESI+) spectrum of compound 7b
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Compound 8
1H NMR spectrum of compound 8 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 8 (CDCl3, 298K, 100 MHz)
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Compound 8
IR (ATR) spectrum of compound 8
HRMS (ESI+) spectrum of compound 8
64
5
73
1
79
080
890
8
10
00
10
70
10
90
11
04
11
811
20
21
24
0
12
61
13
61
13
921
41
61
45
8
15
49
28
67
29
59
vz orek JM404_1
0,05
0,10
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0,55
0,60
0,65
0,70
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Ab
so
rba
nc
e
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Wav enumbers ( cm-1)
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Compound 9
1H NMR spectrum of compound 9 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 9 (CDCl3, 298K, 100 MHz)
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Compound 9
IR (ATR) spectrum of compound 9
HRMS (ESI+) spectrum of compound 9
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Compound 17
1H NMR spectrum of compound 17 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 17 (CDCl3, 298K, 100 MHz)
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Compound 17
IR (ATR) spectrum of compound 17
HRMS (ESI+) spectrum of compound 17
71
6
80
8
87
4 8
92
10
01
10
24
10
70
11
60
11
81
12
45
12
60
12
90
13
62
13
92
14
17
14
59
14
89
15
51
15
95
17
30
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68
29
15
29
55vz orek JM427
0,00
0,05
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0,15
0,20
0,25
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0,35
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0,45
0,50
0,55
0,60
0,65
Ab
so
rba
nc
e
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Wav enumbers ( cm-1)
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Compound 18
1H NMR spectrum of compound 18 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 18 (CDCl3, 298K, 100 MHz)
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806
1023
1066
1246
1290
1392
1439
1461
1488
2837
2866
2903
2956*vzo rek JM449
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
Compound 18
IR (ATR) spectrum of compound 18
HRMS (ESI+) spectrum of compound 18
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Compound 10
HRMS (ESI+) spectrum of compound 10
Compound 11
HRMS (ESI+) spectrum of compound 11
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Compounds 13 and 14
HRMS (ESI+) spectrum of compounds 13 and 14
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Compound 19
1H NMR spectrum of compound 19 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 19 (CDCl3, 298K, 100 MHz)
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Compound 19
IR (ATR) spectrum of compound 19
HRMS (ESI
+) spectrum of compound 19
64
5
70
0
73
47
90
80
8
87
4 8
91
91
0
99
9 1
02
3
10
70
10
90
11
08
11
63
12
42
12
62
13
6213
9214
17
14
59
14
91
15
49
17
25
28
68
29
60
34
89
vz orek JM415_1_B
0,05
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0,40
0,45
0,50
0,55
0,60
Ab
so
rba
nc
e
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Wav enumbers ( cm-1)
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Compound 20
1H NMR spectrum of compound 20 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 20 (CDCl3, 298K, 100 MHz)
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Compound 20
IR (ATR) spectrum of compound 20
HRMS (ESI
+) spectrum of compound 20
60
4
69
9
73
57
90
80
8
87
28
90
99
9
10
90
11
07
11
63
12
39
12
64
13
62
13
93
14
18
14
59
15
49
16
81
28
68
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29
61
34
33
vz orek JM415_3
0,05
0,10
0,15
0,20
0,25
0,30
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Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
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Compound 21
1H NMR spectrum of compound 21 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 21 (CDCl3, 298K, 100 MHz)
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Compound 21
IR (ATR) spectrum of compound 21
HRMS (ESI
+) spectrum of compound 21
59
96
45
69
9
73
37
60
80
8
90
8
99
7
10
23
10
70
10
90
11
12
11
60
11
80
12
45
12
62
13
62
13
931
41
81
45
9
14
90
15
49
15
95
28
67
29
60
30
27
30
6034
88
vz orek JM414_2
0,05
0,10
0,15
0,20
0,25
0,30
0,35
0,40
0,45
0,50
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
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Compound 22
1H NMR spectrum of compound 22 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 22 (CDCl3, 298K, 100 MHz)
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Compound 22
IR (ATR) spectrum of compound 22
HRMS (ESI
+) spectrum of compound 22
56
8
64
5
70
0
73
37
60
78
28
08
90
8
99
6
10
32
10
91
11
121
15
91
17
81
20
21
23
21
26
5
13
62
13
93
14
19
14
47
14
60
15
49
15
98
17
28
28
67
29
61
30
22
30
60
34
93
vz orek JM414_3
0,05
0,10
0,15
0,20
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0,30
0,35
0,40
0,45
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
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Compound 23
1H NMR spectrum of compound 23 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 23 (CDCl3, 298K, 100 MHz)
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Compound 23
IR (ATR) spectrum of compound 23
HRMS (ESI
+) spectrum of compound 23
73
2
79
1
87
5
10
00
10
92
11
40
12
59
13
64
13
93
14
18
14
60
15
49
17
27
29
60vz orek JM459_2
-0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
0,16
0,18
0,20
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
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Compound 24
1H NMR spectrum of compound 24 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 24 (CDCl3, 298K, 100 MHz)
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Compound 24
IR (ATR) spectrum of compound 24
HRMS (ESI
+) spectrum of compound 24
79
1
87
6
10
03
10
93
11
41
12
61
13
66 1
39
214
19
14
64
15
50
17
28
29
62vz orek JM459_3
0,00
0,05
0,10
0,15
0,20
0,25
0,30
0,35
0,40
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
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Compound 25
1H NMR spectrum of compound 25 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 25 (CDCl3, 298K, 100 MHz)
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Compound 25
IR (ATR) spectrum of compound 25
HRMS (ESI
+) spectrum of compound 25
64
4
73
0
80
8
90
7
99
9
10
70
10
90
12
60
13
62
13
92
14
17
14
59
15
49
15
93
16
92
28
68
29
60
vz orek JM420_1
0,05
0,10
0,15
0,20
0,25
0,30
0,35
0,40
0,45
0,50
0,55
0,60
0,65
0,70
0,75
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
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Compound 26
HRMS (ESI+) spectrum of compound 26
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X-ray structure
Finally, the structure of the corresponding linear oligophenol ether derivative 6 was determined unambiguously
using X-ray crystallography. This revealed that a monocrystal of 6 belonged to the monoclinic system, space group CC.
As shown in Fig. 1, the corresponding phenolic moieties are arranged in such a way that every succeeding unit is
almost perpendicular to the previous one. Thus, according to Fig 1a, the corresponding interplanar angles between
the succeeding aromatic subunits were 81.49°, 70.95°, and 71.83° (from the left to right).
a)
b)
Figure: Single crystal X-ray structure of oligophenol 6: (a) side-view, (b) front-view..