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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: lhotakp@vscht.cz
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
Compound 4
1H NMR spectrum of compound 4 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 4 (CDCl3, 298K, 100 MHz)
Compound 4
IR (ATR) spectrum of compound 4
HRMS (ESI+) spectrum of compound 4
Compound 6
1H NMR spectrum of compound 6 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 6 (CDCl3, 298K, 100 MHz)
Compound 6
IR (ATR) spectrum of compound 6
HRMS (ESI+) spectrum of compound 6
Compound 7a
1H NMR spectrum of compound 7a (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 7a (CDCl3, 298K, 100 MHz)
Compound 7a
IR (ATR) spectrum of compound 7a
HRMS (ESI+) spectrum of compound 7a
Compound 7b
1H NMR spectrum of compound 7b (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 7b (CDCl3, 298K, 100 MHz)
Compound 7b
IR (ATR) spectrum of compound 7b
HRMS (ESI+) spectrum of compound 7b
Compound 8
1H NMR spectrum of compound 8 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 8 (CDCl3, 298K, 100 MHz)
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
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)
Compound 9
1H NMR spectrum of compound 9 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 9 (CDCl3, 298K, 100 MHz)
Compound 9
IR (ATR) spectrum of compound 9
HRMS (ESI+) spectrum of compound 9
Compound 17
1H NMR spectrum of compound 17 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 17 (CDCl3, 298K, 100 MHz)
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
28
68
29
15
29
55vz orek JM427
0,00
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
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
Compound 18
1H NMR spectrum of compound 18 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 18 (CDCl3, 298K, 100 MHz)
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
Compound 10
HRMS (ESI+) spectrum of compound 10
Compound 11
HRMS (ESI+) spectrum of compound 11
Compounds 13 and 14
HRMS (ESI+) spectrum of compounds 13 and 14
Compound 19
1H NMR spectrum of compound 19 (CDCl3, 298K, 400 MHz)
13C NMR (APT) spectrum of compound 19 (CDCl3, 298K, 100 MHz)
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
0,10
0,15
0,20
0,25
0,30
0,35
0,40
0,45
0,50
0,55
0,60
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
Compound 20
1H NMR spectrum of compound 20 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 20 (CDCl3, 298K, 100 MHz)
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
29
31
29
61
34
33
vz orek JM415_3
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)
Compound 21
1H NMR spectrum of compound 21 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 21 (CDCl3, 298K, 100 MHz)
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)
Compound 22
1H NMR spectrum of compound 22 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 22 (CDCl3, 298K, 100 MHz)
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
0,25
0,30
0,35
0,40
0,45
Ab
so
rba
nc
e
500 1000 1500 2000 2000 3000
Wav enumbers ( cm-1)
Compound 23
1H NMR spectrum of compound 23 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 23 (CDCl3, 298K, 100 MHz)
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)
Compound 24
1H NMR spectrum of compound 24 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 24 (CDCl3, 298K, 100 MHz)
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)
Compound 25
1H NMR spectrum of compound 25 (CDCl3, 298K, 400 MHz)
13
C NMR (APT) spectrum of compound 25 (CDCl3, 298K, 100 MHz)
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)
Compound 26
HRMS (ESI+) spectrum of compound 26
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..
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