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..