A3 and A2B-nitrocorroles: synthesis and antiviral activity · 2020. 5. 19. · 1 #08/11/19...

1

#08/11/19

SUPPORTING INFORMATION

A3 and A2B-nitrocorroles: synthesis and antiviral activity

evaluation against Human Cytomegalovirus Infection Léo Bucher, Sandrine Kappler-Gratias, Nicolas Desbois, Kerstin Bystricky,

Franck Gallardo, and Claude P. Gros

Table of contents

Fig. S1 MALDI/TOF LRMS of 5,10,15-tris(5’-fluoro-2’-nitrophenyl)corrole 1 p. 6

Fig. S2 ESI HRMS of 5,10,15-tris(5’-fluoro-2’-nitrophenyl)corrole 1 p. 7

Fig. S3 1H NMR spectrum (500 MHz, CDCl3 + one drop of hydrazine 64%) of

5,10,15-tris(5’-fluoro-2’-nitrophenyl)corrole 1

p. 8

Fig. S4 19F NMR (470 MHz, THF-d8 + one drop of hydrazine 64%) of 5,10,15-

tris(5’-fluoro-2’-nitrophenyl)corrole 1

p. 9

Fig. S5 HPLC chromatogram of 5,10,15-tris(5’-fluoro-2’-nitrophenyl)corrole 1 p. 10

Fig. S6 MALDI/TOF LRMS of 5,10,15-tris(5’-chloro-2’-nitrophenyl)corrole 2 p. 11

Fig. S7 ESI HRMS of 5,10,15-tris(5’-chloro-2’-nitrophenyl)corrole 2 p. 12

Fig. S8 1H NMR spectrum (500 MHz, THF-d8 + one drop of hydrazine 64%) of

5,10,15-tris(5’-chloro-2’-nitrophenyl)corrole 2

p. 13

Fig. S9 HPLC chromatogram of 5,10,15-tris(5’-chloro-2’-nitrophenyl)corrole 2 p. 14





p. 17



p. 18


Fig. S15 MALDI/TOF LRMS of 5,10,15-tris(2’-nitro-4’-trifluoromethyl)corrole 4 p. 20

Fig. S16 ESI HRMS of 5,10,15-tris(2’-nitro-4’-trifluoromethyl)corrole 4 p. 21

Electronic Supplementary Material (ESI) for RSC Medicinal Chemistry.This journal is © The Royal Society of Chemistry 2020

2


5,10,15-tris(2’-nitro-4’-trifluoromethyl)corrole 4

p. 22


tris(2’-nitro-4’-trifluoromethyl)corrole 4

p. 23

Fig. S19 HPLC chromatogram of 5,10,15-tris(2’-nitro-4’-trifluoromethyl)corrole 4 p. 24

Fig. S20 MALDI/TOF LRMS of 5,10,15-tris(4’-dimethylamino-2’-

nitrophenyl)corrole 5

p. 25

Fig. S21 ESI HRMS of 5,10,15-tris(4’-dimethylamino-2’-nitrophenyl)corrole 5 p. 26

Fig. S22 1H NMR spectrum (500 MHz, DMSO-d6 + one drop of hydrazine 64%) of

5,10,15-tris(4’-dimethylamino-2’-nitrophenyl)corrole 5

p. 27

Fig. S23 HPLC chromatogram of 5,10,15-tris(4’-dimethylamino-2’-

nitrophenyl)corrole 5 p. 28





p. 31



p. 32



Fig. S30 ESI HRMS of 5,10,15-tris(4’-Fluoro-3’-nitrophenyl)corrole 7 p. 35


5,10,15-tris(4’-Fluoro-3’-nitrophenyl)corrole 7

p. 36


tris(4’-Fluoro-3’-nitrophenyl)corrole 7

p. 37

Fig. S33 HPLC chromatogram of 5,10,15-tris(4’-Fluoro-3’-nitrophenyl)corrole 7 p. 38





p. 41



p. 42


3

Fig. S39 MALDI/TOF LRMS of of 5,10,15-tris(2’-fluoro-5’-nitrophenyl)corrole 9 p. 44

Fig. S40 ESI HRMS of of 5,10,15-tris(2’-fluoro-5’-nitrophenyl)corrole 9 p. 45


5,10,15-tris(2’-fluoro-5’-nitrophenyl)corrole 9 p. 46



p. 47

Fig. S43 HPLC chromatogram of of 5,10,15-tris(2’-fluoro-5’-nitrophenyl)corrole 9 p. 48

Fig. S44 MALDI/TOF LRMS of 5,10,15-tris(2’,6’-difluoro-3’-nitrophenyl)

corrole 10

p. 49

Fig. S45 ESI HRMS of 5,10,15-tris(2’,6’-difluoro-3’-nitrophenyl)corrole 10 p. 50

Fig. S46 1H NMR spectrum (500 MHz, CDCl3 + one drop of hydrazine 64%) of

5,10,15-tris(2’,6’-difluoro-3’-nitrophenyl)corrole 10 p. 51

Fig. S47 19F NMR (470 MHz, CDCl3 + one drop of hydrazine 64%) of 5,10,15-

tris(2’,6’-difluoro-3’-nitrophenyl)corrole 10 p. 52

Fig. S48 HPLC chromatogram of 5,10,15-tris(2’,6’-difluoro-3’-nitro-

phenyl)corrole 10

p. 53

Fig. S49 MALDI/TOF LRMS of 5,10,15-tris(4’-bromo-2’-fluoro-5’-nitro-

phenyl)corrole 11

p.54


5,10,15-tris(4’-bromo-2’-fluoro-5’-nitrophenyl)corrole 11

p. 55


tris(4’-bromo-2’-fluoro-5’-nitrophenyl)corrole 11

p. 56

Fig. S52 HPLC chromatogram of 5,10,15-tris(4’-bromo-2’-fluoro-5’-nitro-

phenyl)corrole 11

p. 57





p. 60



p.61



4


Fig. S60 1H NMR spectrum (500 MHz, CDCl3) of 5,10,15-tris(3’-fluoro-4’-


p. 65



p. 66

Fig. S62 HPLC chromatogram of 5,10,15-tris(3’-Fluoro-4’-nitrophenyl)corrole 13 p. 67

Fig. S63 MALDI/TOF LRMS of 5,15-bis(3’-nitrophenyl)-10-(phenyl)corrole 14 p. 68

Fig. S64 ESI HRMS of 5,15-bis(3’-nitrophenyl)-10-(phenyl)corrole 14 p. 69


5,15-bis(3’-nitrophenyl)-10-(phenyl)corrole 14

p. 70

Fig. S66 HPLC chromatogram of 5,15-bis(3’-nitrophenyl)-10-(phenyl)corrole 14 p. 71

Fig. S67 MALDI/TOF LRMS of 5,15-bis(3’-nitrophenyl)-10-(4’-fluoro-3’-nitro-

phenyl)corrole 15

p. 72

Fig. S68 ESI HRMS of 5,15-bis(3’-nitrophenyl)-10-(4’-fluoro-3’-nitrophenyl)-

corrole 15

p. 73

Fig. S69 1H NMR spectrum (500 MHz, DMSO-d6 + one drop of hydrazine 64%) of

5,15-bis(3’-nitrophenyl)-10-(4’-fluoro-3’-nitrophenyl)corrole 15

p. 74

Fig. S70 19F NMR (470 MHz, THF-d8 + one drop of hydrazine 64%) of 5,15-bis(3’-

nitrophenyl)-10-(4’-fluoro-3’-nitrophenyl)corrole 15

p. 75

Fig. S71 HPLC chromatogram of 5,15-bis(3’-nitrophenyl)-10-(4’-fluoro-3’-


p. 76

Fig. S72 MALDI/TOF LRMS of 5,15-bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-

2’-nitrophenyl)corrole 16

p. 77

Fig. S73 ESI HRMS of 5,15-bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-2’-


p. 78


5,15-bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-2’-nitrophenyl)-

corrole 16

p. 79


fluoro-5’-nitrophenyl)-10-(5’-fluoro-2’-nitrophenyl)corrole 16

p. 80

Fig. S76 HPLC chromatogram of 5,15-bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-


p. 81

5

Fig. S77 MALDI/TOF LRMS of 5,15-bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-


p. 82

Fig. S78 ESI HRMS of 5,15-bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-5’-nitro-

phenyl)corrole 17

p. 83


5,15-bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-5’-nitrophenyl)-

corrole 17

p. 84


fluoro-2’-nitrophenyl)-10-(3’-fluoro-5’-nitrophenyl)corrole 17

p. 85

Fig. S81 HPLC chromatogram of 5,15-bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-


p. 86

Fig. S82 Example of the algorithm used to detect and measure infection parameters p. 87

Miscellaneous precursors syntheses p. 88

Fig. S83 1H NMR spectrum of 5-(3’-fluoro-5’-nitrophenyl)-dipyrromethane p. 89

Fig. S84 ESI HRMS of 5-(3’-fluoro-5’-nitrophenyl)-dipyrromethane p. 89

Fig. S85 1H NMR spectrum of 5-(5’-fluoro-2’-nitrophenyl)-dipyrromethane p. 90

Fig. S86 ESI LRMS of 5-(5’-fluoro-2’-nitrophenyl)-dipyrromethane p. 91

Fig. S87 1H NMR spectrum of 2-fluoro-3-nitrobenzyl alcohol p. 92

Fig. S88 1H and 19F NMR spectra of 2-fluoro-3-nitrobenzaldehyde p. 93

Fig. S89 13C NMR spectrum of 2-fluoro-3-nitrobenzaldehyde p. 94

6

Chemical Formula: C37H20F3N7O6

Exact Mass: 715.1427 Molecular Weight: 715.6052

Figure S1: MALDI/TOF LRMS of 5,10,15-tris(5’-fluoro-2’-nitrophenyl)corrole 1.

18VIRCO_LB008

HN

NNH

NH

F

NO2

NO2

FO2N

F

7

Chemical Formula [M+H]+: C37H21F3N7O6

Exact Mass: 716.14980 Experimental: 716.14999

d (ppm) = 0.26

Figure S2: ESI HRMS of 5,10,15-tris(5’-fluoro-2’-nitrophenyl)corrole 1.

18VIRCO_LB008

HN

NNH

NH

F

NO2

NO2

FO2N

F

8

Figure S3: 1H NMR spectrum (500 MHz, CDCl3 + one drop of hydrazine 64%) of 5,10,15-

tris(5’-fluoro-2’-nitrophenyl)corrole 1. 18VIRCO_LB008

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

3.1

0

3.9

1

9.9

8

2.0

0

2.8

4 N

H2

NH

2

7.2

6 C

DC

l3

7.58.08.59.0

3.1

0

3.9

1

9.9

8

2.0

0

7.5

4

7.9

5

8.0

8

8.3

4

8.4

7

8.5

4

8.5

7

8.6

2

8.9

0

8.9

2

8.9

6

8.9

7

9

Figure S4: 19F NMR (470 MHz, THF-d8 + one drop of hydrazine 64%) of 5,10,15-tris(5’-

fluoro-2’-nitrophenyl)corrole 1. 18VIRCO_LB008

-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100

3.00

-109.86

-109.26

-109.24

-108.58

-108.09

-110.5-109.5-108.5-107.5

3.00

-109.86

-109.26

-109.24

-108.58

-108.09

10

Figure S5: HPLC chromatogram of 5,10,15-tris(5’-fluoro-2’-nitrophenyl)corrole 1. 18VIRCO_LB008

Instrument:HPLC Sequence:seq_2019 Page 1 of 2

Default/IntegrationChromeleon (c) Dionex

Version 7.2.3.7553

Chromatogram and Results

InjectionˇDetailsInjection Name: 18VIRCO_LB008 Run Time (min): 10.00Vial Number: RB8 Injection Volume: 5.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 420Instrument Method: Standard_CHCl3_modified Bandwidth: 4Processing Method: Standard Processing Method Dilution Factor: 1.0000Injection Date/Time: 24/mai/19 15:49 Sample Weight: 1.0000

Chromatogram

IntegrationˇResultsNo. Peak Name Retention Time Area Height Relative Area Relative Height Amount

min mAU*min mAU % % n.a.1 3.333 8.657 26.627 100.00 100.00 n.a.Total: 8.657 26.627 100.00 100.00

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0-5.0

0.0

5.0

10.0

15.0

20.0

25.0

30.0

1 - 3.333

seq_2019 #34 [manually integrated] 18VIRCO_LB008 UV_VIS_2 WVL:420 nm

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

413.61

577.11

nm

%

Apex Peak #1 100% at 3.33 min Apex

11

Chemical Formula: C37H20Cl3N7O6


Figure S6: MALDI/TOF LRMS of 5,10,15-tris(5’-chloro-2’-nitrophenyl)corrole 2.

18VIRCO_LB042

HN

NNH

NH

Cl

Cl

Cl

NO2

O2N

NO2

12

Chemical Formula [M+H]+: C37H21Cl3N7O6


d (ppm) = 0.81

Figure S7: ESI HRMS of 5,10,15-tris(5’-chloro-2’-nitrophenyl)corrole 2. 18VIRCO_LB042

HN

NNH

NH

Cl

Cl

Cl

NO2

O2N

NO2

13

Figure S8: 1H NMR spectrum (500 MHz, THF-d8 + one drop of hydrazine 64%) of 5,10,15-

tris(5’-chloro-2’-nitrophenyl)corrole 2.

18VIRCO_LB042

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

3.2

7

10

.23

2.1

3

2.0

0

1.7

3 T

HF

2.8

8 N

H2N

H2

3.5

8 T

HF

7.77.87.98.08.18.28.38.48.58.68.78.88.99.09.1

7.9

2

8.2

4

8.3

0

8.3

1

8.4

5

8.5

2

8.5

8

8.9

5

14

Figure S9: HPLC chromatogram of 5,10,15-tris(5’-chloro-2’-nitrophenyl)corrole 2.

18VIRCO_LB042



Version 7.2.3.7553


InjectionˇDetailsInjection Name: 18VIRCO_LB042 Run Time (min): 10.00Vial Number: BB1 Injection Volume: 2.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 420Instrument Method: MeOH_3%_modified Bandwidth: 4Processing Method: Standard Processing Method Dilution Factor: 1.0000Injection Date/Time: 28/mai/19 20:05 Sample Weight: 1.0000

Chromatogram


min mAU*min mAU % % n.a.1 3.820 323.752 980.291 87.30 95.32 n.a.2 5.450 47.077 48.128 12.70 4.68 n.a.Total: 370.829 1028.419 100.00 100.00

0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0-100

0

125

250

375

500

625

750

875

1000

1100

1 - 3.820

2 - 5.450


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

420.15

365.20 581.38 619.26

nm

%

Peak #1 at 3.82 min Peak #1



Version 7.2.3.7553

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

419.44

nm

%


15




19VIRCO_LB074

HN

NNH

NH

NO2

O2N

NO2

F

F

F

16



d (ppm) = 1.941

Figure S11: ESI HRMS of 5,10,15-tris(4’-fluoro-2’-nitrophenyl)corrole 3. 19VIRCO_LB074

HN

NNH

NH

NO2

O2N

NO2

F

F

F

17



0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

3.2

8

12

.16

2.0

0

1.7

2 T

HF

2.8

6 N

H2

NH

2

3.5

7 T

HF

7.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.2

7.7

5

8.0

8

8.3

1

8.5

0

8.9

2

18



-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40

3.00

-114.12

-113.98

-113.65

-113.64

-115.0-114.5-114.0-113.5-113.0

3.00

-114.12

-113.98

-113.65

-113.64

19

Figure S14: HPLC chromatogram of 5,10,15-tris(4’-fluoro-2’-nitrophenyl)corrole 3.

19VIRCO_LB074



Version 7.2.3.7553


InjectionˇDetailsInjection Name: 18VIRCO_LB074 Run Time (min): 10.00Vial Number: RD2 Injection Volume: 2.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 420Instrument Method: MeOH_3%_modified Bandwidth: 4Processing Method: Standard Processing Method Dilution Factor: 1.0000Injection Date/Time: 28/mai/19 16:34 Sample Weight: 1.0000

Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0-50

0

100

200

300

400

500

550

1 - 3.820

2 - 6.017


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

411.86

577.32610.11

nm

%




Version 7.2.3.7553

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

410.67

nm

%


20



Figure S15: MALDI/TOF LRMS of 5,10,15-tris(2’-nitro-4’-trifluoromethyl)corrole 4.

18VIRCO_LB072

HN

NNH

NH

NO2

O2N

NO2

CF3

F3C CF3

21



d (ppm) = 1.362 Figure S16: ESI HRMS of 5,10,15-tris(2’-nitro-4’-trifluoromethyl)corrole 4.

18VIRCO_LB072

HN

NNH

NH

NO2

O2N

NO2

CF3

F3C CF3

22

Figure S17: 1H NMR (500 MHz, THF-d8 + one drop of hydrazine 64%) of 5,10,15-tris(2’-

nitro-4’-trifluoromethyl)corrole 4.

18VIRCO_LB072

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

5.0

3

2.2

4

4.0

0

4.1

6

1.9

0

1.7

2 T

HF

2.9

5 N

H2

NH

2

3.5

7 T

HF

8.18.28.38.48.58.68.78.88.99.0

8.2

6

8.2

9

8.3

9

8.4

2

8.4

9

8.6

2

8.6

7

8.9

2

8.9

3

8.9

5

8.9

6

23


nitro-4’-trifluoromethyl)corrole 4.

18VIRCO_LB072

-220-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-1001020

-65.06

-64.87

-64.86

-64.83

-64.82

-64.81

-64.94-64.90-64.86-64.82-64.78-64.74

9.00

-64.87

-64.86

-64.83

-64.82

-64.81

24

Figure S19: HPLC chromatogram of 5,10,15-tris(2’-nitro-4’-trifluoromethyl)corrole 4. 18VIRCO_LB072



Version 7.2.3.7553


InjectionˇDetailsInjection Name: 18VIRCO_LB072 Run Time (min): 10.00Vial Number: RD3 Injection Volume: 2.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 420Instrument Method: MeOH_3%_modified Bandwidth: 4Processing Method: Standard Processing Method Dilution Factor: 1.0000Injection Date/Time: 28/mai/19 17:11 Sample Weight: 1.0000

Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0-20

0

20

40

60

80

100

120

1 - 3.883

2 - 5.380


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

414.44

360.27 582.78357.11352.11347.90

nm

%




Version 7.2.3.7553

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

414.52

nm

%


25

Chemical Formula: C43H38N10O6


Figure S20: MALDI/TOF LRMS of 5,10,15-tris(4’-dimethylamino-2’-nitrophenyl)corrole 5. 18VIRCO_LB021

NH

N HN

HN

NO2

O2N

NO2

N

N N

26

Chemical Formula [M+H]+: C43H39N10O6


d (ppm) = 0.16

Figure S21: ESI HRMS of 5,10,15-tris(4’-dimethylamino-2’-nitrophenyl)corrole 5. 18VIRCO_LB021

NH

N HN

HN

NO2

O2N

NO2

N

N N

27

Figure S22: 1H NMR (500 MHz, DMSO-d6 + one drop of hydrazine 64%) of 5,10,15-tris(4’-

dimethylamino-2’-nitrophenyl)corrole 5. 18VIRCO_LB021

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

18.4

6

3.5

4

3.1

2

1.9

0

2.9

8

2.0

9

2.1

5

2.0

0

2.5

1 D

MS

O

3.2

1

3.2

8 N

H2N

H2

7.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.0

3.5

4

3.1

2

1.9

0

2.9

8

2.0

9

2.1

5

2.0

0

7.3

1

7.4

8

7.9

3

7.9

5

8.1

0

8.2

1

8.2

2

8.2

4

8.2

4

8.3

1

8.3

5

8.3

6

8.7

8

28

Figure S23: HPLC chromatogram of 5,10,15-tris(4’-dimethylamino-2’-nitrophenyl)corrole 5.

18VIRCO_LB021



Version 7.2.3.7553


InjectionˇDetailsInjection Name: 18VIRCO_LB021 Run Time (min): 10.00Vial Number: BA1 Injection Volume: 2.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 420Instrument Method: MeOH_3%_modified Bandwidth: 4Processing Method: Standard Processing Method Dilution Factor: 1.0000Injection Date/Time: 28/mai/19 18:23 Sample Weight: 1.0000

Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0-10.0

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

1 - 3.833

2 - 6.373


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

406.38

362.30353.37 627.87348.85346.01

nm

%


29



Figure 24: MALDI/TOF LRMS of 5,10,15-tris(2’-fluoro-3’-nitrophenyl)corrole 6. 19VIRCO_LB080

HN

NNH

NH

F

F

F NO2

NO2

O2N

30



d (ppm) = 0.461 Figure S25: ESI HRMS of 5,10,15-tris(2’-fluoro-3’-nitrophenyl)corrole 6.

19VIRCO_LB080

HN

NNH

NH

F

F

F NO2

NO2

O2N

31

Figure S26: 1H NMR (500 MHz, THF-d8 + one drop of hydrazine 64%) of 5,10,15-tris(2’-


0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

3.1

9

12

.00

1.7

3

1.7

2 T

HF

2.9

5 N

H2

NH

2

3.5

7 T

HF

7.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.2

7.6

9

7.7

1

8.3

4

8.3

7

8.3

9

8.4

1

8.4

2

8.4

9

8.5

7

8.9

6

8.9

6

8.9

7

8.9

8

8.9

9

32


fluoro-3’-nitrophenyl)corrole 6.

19VIRCO_LB080

33


19VIRCO_LB080

Instrument:HPLC-MS Sequence:VIRCO-171018 Page 1 of 2

uv/IntegrationChromeleon (c) Dionex

Version 7.2.4.8179

ChromatogramˇandˇResults

InjectionˇDetailsInjection Name: 19VIRCO_LB080 Run Time (min): 12.00Vial Number: RB1 Injection Volume: 10.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 400.0Instrument Method: Corroles-LB-Kinetex Bandwidth: 4Processing Method: no integration Dilution Factor: 1.0000Injection Date/Time: 27/Feb/19 11:34 Sample Weight: 1.0000

Chromatogram



34




18VIRCO_LB047

NH

N HN

HN

NO2

NO2

O2N

F

FF

35


18VIRCO_LB047

C:\Xcalibur\data\2019\lb\19VIRCO_LB047_1 5/20/2019 5:30:37 PMDCM/MeOH

710 720 730 740 750 760 770

m/z

0

20

40

60

80

100

0

20

40

60

80

100

Re

lativ

e A

bu

nd

an

ce

71

6.1

48

67

z=1

73

0.1

27

35

z=1

71

7.1

51

60

z=1

73

1.1

30

44

z=1

71

5.1

40

93

z=1

71

8.1

54

80

z=1

71

4.1

34

24

z=1

74

8.1

38

01

z=1

71

6.1

49

99

71

7.1

53

35

71

8.1

56

70

NL:5.22E5

19VIRCO_LB047_1#1-14 RT: 0.01-0.28 AV: 14 T: FTMS + p ESI Full ms [200.00-2000.00]

NL:6.43E5

C 37 H 20 F 3 N 7 O 6 +H: C 37 H 21 F 3 N 7 O 6

pa Chrg 1

36





0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

3.1

8

12

.12

2.0

0

1.7

2 T

HF

2.7

5 N

H2

NH

2

3.5

7 T

HF

8.08.18.28.38.48.58.68.78.88.99.09.19.29.39.4

8.1

8

8.5

1

8.8

2

8.9

1

8.9

9

9.3

6

NH

N HN

HN

NO2

NO2

O2N

F

FF

37



38

Figure S33: HPLC chromatogram of 5,10,15-tris(4’-fluoro-3’-nitrophenyl)corrole 7. 18VIRCO_LB047



Version 7.2.3.7553



Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0-50

0

50

100

150

200

250

1 - 3.773

2 - 4.113


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

417.68

577.92360.42357.28352.96349.45 614.23nm

%




Version 7.2.3.7553

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

416.89

nm

%


39



Figure S34: MALDI/TOF LRMS of 5,10,15-tris(3’-fluoro-5’-nitrophenyl)corrole 8. 18VIRCO_LB013

NH

N HN

HN

F

F

F

NO2

NO2

O2N

40



d (ppm) = 0.22


18VIRCO_LB013

NH

N HN

HN

F

F

F

NO2

NO2

O2N

41





0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

1.7

2 T

HF

2.9

7 N

H2

NH

2

3.5

7 T

HF

8.18.28.38.48.58.68.78.88.99.09.1

2.0

0

2.2

7

2.2

6

2.1

6

2.1

8

2.2

3

1.0

0

4.1

1

8.2

3

8.2

5

8.3

3

8.4

3

8.4

3

8.4

6

8.4

8

8.6

2

8.6

3

8.7

4

8.7

5

8.8

7

9.0

1

NH

N HN

HN

F

F

F

NO2

NO2

O2N

42



Figure S37: 19F NMR spectrum (470 MHz, THF-d8 + one drop of hydrazine 64%) of 5,10,15-


NH

N HN

HN

F

F

F

NO2

NO2

O2N

43


18VIRCO_LB013



Version 7.2.3.7553



Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time [min]

-50

0

50

100

150

200

250

300

350

Abs

orba

nce

[mA

U]

1 - 3.937


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

419.92

581.89349.43

nm

%


44




17VIRCO_LB002

NH

N HN

HN

NO2

F

F

O2N F

NO2

45

Chemical Formula[M+H]+: C37H21F3N7O6


d (ppm) = 0.39


17VIRCO_ 2

NH

N HN

HN

NO2

F

F

O2N F

NO2

46





0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

3.0

3

2.0

0

2.0

5

5.0

0

5.0

0

1.3

9 B

HT

1.7

2 T

HF

2.2

0 B

HT

2.9

4 N

H2N

H2

3.5

7 T

HF

6.9

1 B

HT

7.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.29.3

7.7

2

8.3

4

8.3

5

8.5

0

8.5

1

8.5

9

9.0

3

NH

N HN

HN

NO2

F

F

O2N F

NO2

47



Figure S42: 19F NMR spectrum (470 MHz, THF-d8 + one drop of hydrazine 64%) of 5,10,15-tris(2’-fluoro-5’-nitrophenyl)corrole 9. 17VIRCO_LB002

NH

N HN

HN

NO2

F

F

O2N F

NO2

48


17VIRCO_LB002

Instrument:HPLC-MS Sequence:VIRCO-010218 Page 1 of 2


Version 7.2.4.8179


InjectionˇDetailsInjection Name: VIRCO_002_t0 Run Time (min): 12.00Vial Number: GC2 Injection Volume: 10.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 400.0Instrument Method: Corroles-LB-Kinetex Bandwidth: 4Processing Method: no integration Dilution Factor: 1.0000Injection Date/Time: 04/Sep/18 09:41 Sample Weight: 1.0000

Chromatogram



49



Figure S44: MALDI/TOF LRMS of 5,10,15-tris(2’,6’-difluoro-3’-nitrophenyl)corrole 10. 18VIRCO_LB041

NH

N HN

HN

NO2

O2N

NO2

F

F

F

F

F

F

50



d (ppm) = 0.54

Figure S45: ESI HRMS of 5,10,15-tris(2’,6’-difluoro-3’-nitrophenyl)corrole 10. 18VIRCO_LB041

NH

N HN

HN

NO2

O2N

NO2

F

F

F

F

F

F

51



Figure S46: 1H NMR spectrum (500 MHz, CDCl3 + one drop of hydrazine 64%) of 5,10,15-

tris(2’,6’-difluoro-3’-nitrophenyl)corrole 10. 18VIRCO_LB041

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

2.9

8

7.1

2

2.0

0

2.0

0

2.2

9 N

H2

NH

2

7.2

6 C

DC

l3

7.47.67.88.08.28.48.68.89.09.29.42

.98

7.1

2

2.0

0

2.0

0

7.5

2

8.5

3

8.5

7

8.7

1

9.0

7

NH

N HN

HN

NO2

O2N

NO2

F

F

F

F

F

F

52

Figure S47: 19F NMR spectrum (470 MHz, CDCl3 + one drop of hydrazine 64%) of 5,10,15-

tris(2’,6’-difluoro-3’-nitrophenyl)corrole 10. 18VIRCO_LB041

-117-115-113-111-109-107-105-103-101-99-97-95-93-912.88

3.00

-110.39

-110.31

-109.49

-109.39

-96.41

-96.30

-95.30

53

Figure S48: HPLC chromatogram of 5,10,15-tris(2’,6’-difluoro-3’-nitrophenyl)corrole 10. 18VIRCO_LB041

Instrument:HPLC-MS Sequence:VIRCO-project Page 1 of 2


Version 7.2.4.8179


InjectionˇDetailsInjection Name: VIRCO_041 Run Time (min): 12.00Vial Number: GD5 Injection Volume: 10.00Injection Type: Unknown Channel: UV_VIS_3Calibration Level: Wavelength: 440.0Instrument Method: Corroles-LB-Kinetex Bandwidth: 4Processing Method: no integration Dilution Factor: 1.0000Injection Date/Time: 25/Sep/18 09:51 Sample Weight: 1.0000

Chromatogram



54

Chemical Formula: C37H17Br3F3N7O6


Figure S49: MALDI/TOF LRMS of 5,10,15-tris(4’-bromo-2’-fluoro-5’-nitrophenyl)-

corrole 11.

18VIRCO_LB022

HN

NNH

NH

F

BrNO2

F

Br

NO2F

Br

O2N

55

Chemical Formula: C37H17Br3F3N7O6


Figure 50: 1H NMR spectrum (500 MHz, THF-d8 + one drop of hydrazine 64%) of 5,10,15-

tris(4’-bromo-2’-fluoro-5’-nitrophenyl)corrole 11.

18VIRCO_LB022

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

3.2

8

2.2

4

1.9

4

2.2

3

3.4

1

2.0

0

1.7

2 T

HF

2.9

5 N

H2N

H2

3.5

7 T

HF

7.87.98.08.18.28.38.48.58.68.78.88.99.09.1

8.0

2

8.0

6

8.0

8

8.3

6

8.5

0

8.5

1

8.5

9

8.8

0

8.9

5

8.9

5

HN

NNH

NH

F

BrNO2

F

Br

NO2F

Br

O2N

56


tris(4’-bromo-2’-fluoro-5’-nitrophenyl)corrole 11. 18VIRCO_LB022

-220-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-1001020

-105.5-104.5-103.5-102.5-101.5

2.42

1.00

-104.04

-102.82

57

Figure S52: HPLC chromatogram of 5,10,15-tris(4’-bromo-2’-fluoro-5’-nitrophenyl)-

corrole 11. 18VIRCO_LB022



Version 7.2.3.7553


InjectionˇDetailsInjection Name: 18VIRCO_LB022 Run Time (min): 10.00Vial Number: BA4 Injection Volume: 5.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 420Instrument Method: MeOH_10% Bandwidth: 4Processing Method: Standard Processing Method Dilution Factor: 1.0000Injection Date/Time: 31/mai/19 11:25 Sample Weight: 1.0000

Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0-50

0

50

100

150

200

250

300

1 - 3.617


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

424.48

579.91615.35

nm

%


58



Figure 53: MALDI/TOF LRMS of 5,10,15-tris(2’-fluoro-4’-nitrophenyl)corrole 12. 18VIRCO_LB050

HN

NNH

NH

F

F

F

O2N

NO2

NO2

59



680 700 720 740 760 780 800

m/z

0

20

40

60

80

100

0

20

40

60

80

100

Re

lativ

e A

bu

nd

an

ce

71

6.1

50

57

z=1

71

7.1

52

61

z=1

73

0.1

27

68

z=1

71

5.1

43

98

z=1

73

1.1

30

53

z=1

71

6.1

49

99

71

7.1

53

35

71

8.1

56

70

NL:2.34E6


NL:6.43E5

C 37 H 20 F 3 N 7 O 6 +H: C 37 H 21 F 3 N 7 O 6

pa Chrg 1

60





0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

11

.20

2.0

72

.01

2.0

0

0.8

70

.89

Hep

tan

e0

.90

1.2

8 H

epta

ne

1.7

2 T

HF

2.9

4 N

H2

NH

2

3.5

7 T

HF

7.98.08.18.28.38.48.58.68.78.88.99.09.1

8.3

9

8.5

08

.51

8.5

1

8.5

9

8.9

58

.95

8.9

68

.97

HN

NNH

NH

F

F

F

O2N

NO2

NO2

61




tris(2’-fluoro-4’-nitrophenyl)corrole 12.

18VIRCO_LB050

HN

NNH

NH

F

F

F

O2N

NO2

NO2

62


18VIRCO_LB050



Version 7.2.4.8179


InjectionˇDetailsInjection Name: VIRCO_050 Run Time (min): 12.00Vial Number: GD1 Injection Volume: 10.00Injection Type: Unknown Channel: UV_VIS_2Calibration Level: Wavelength: 400.0Instrument Method: Corroles-LB-Kinetex Bandwidth: 4Processing Method: no integration Dilution Factor: 1.0000Injection Date/Time: 10/Sep/18 11:09 Sample Weight: 1.0000

Chromatogram


min mAU*min mAU % % n.a.1 6.527 12.115 325.099 95.31 95.43 n.a.2 6.627 0.169 5.037 1.33 1.48 n.a.3 6.753 0.225 6.057 1.77 1.78 n.a.4 6.867 0.202 4.459 1.59 1.31 n.a.Total: 12.711 340.653 100.00 100.00

63




18VIRCO_LB053

NH

N HN

HN

F

F

F

NO2

NO2O2N

64


C:\Xcalibur\data\2019\lb\19VIRCO_LB053_1 5/21/2019 9:45:53 AMDCM/MeOH

690 700 710 720 730 740 750 760 770 780 790

m/z

0

20

40

60

80

100

0

20

40

60

80

100

Re

lativ

e A

bu

nd

an

ce

71

6.1

50

28

z=1

71

7.1

52

37

z=1

71

5.1

43

35

z=1

73

0.1

27

37

z=1

71

6.1

49

99

71

7.1

53

35

71

8.1

56

70

NL:2.47E6


NL:6.43E5

C 37 H 20 F 3 N 7 O 6 +H: C 37 H 21 F 3 N 7 O 6

pa Chrg 1

65



Figure S60: 1H NMR spectrum (500 MHz, CDCl3) of 5,10,15-tris(3’-fluoro-4’-

nitrophenyl)corrole 13.

18VIRCO_LB053

2.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

1.2

2

4.1

5

5.2

6

2.2

5

1.1

8

2.1

9

2.0

0

7.2

6 C

DC

l3

8.1

6

8.1

7

8.3

2

8.3

4

8.5

1

8.5

9

8.7

0

8.8

8

8.9

8

9.1

0

8.08.18.28.38.48.58.68.78.88.99.09.19.2

1.2

2

4.1

5

5.2

6

2.2

5

1.1

8

2.1

9

2.0

0

8.1

6

8.1

7

8.3

2

8.3

4

8.5

1

8.5

9

8.7

0

8.8

8

8.9

8

9.1

0

NH

N HN

HN

F

F

F

NO2

NO2O2N

66





NH

N HN

HN

F

F

F

NO2

NO2O2N

67

Figure 62: HPLC chromatogram of 5,10,15-tris(3’-fluoro-4’-nitrophenyl)corrole 13.

18VIRCO_LB053



Version 7.2.4.8179


InjectionˇDetailsInjection Name: VIRCO_053 Run Time (min): 12.00Vial Number: GC5 Injection Volume: 10.00Injection Type: Unknown Channel: UV_VIS_3Calibration Level: Wavelength: 440Instrument Method: Corroles-LB-Kinetex Bandwidth: 4Processing Method: no integration Dilution Factor: 1.0000Injection Date/Time: 24/Sep/18 14:30 Sample Weight: 1.0000

Chromatogram



68



Figure S63: MALDI/TOF LRMS of 5,15-bis(3’-nitrophenyl)-10-(phenyl)corrole 14. 18VIRCO_LB009

HN

NNH

NH

O2N

NO2

69

Chemical Formula [M+H]+: C37H25N6O4


d (ppm) = 1.12

Figure S64: ESI HRMS of 5,15-bis(3’-nitrophenyl)-10-(phenyl)corrole 14.

18VIRCO_LB009

HN

NNH

NH

O2N

NO2

70



Figure S65: 1H NMR spectrum (500 MHz, THF-d8 + one drop of hydrazine 64%) of 5,15-

bis(3’-nitrophenyl)-10-(phenyl)corrole 14.

18VIRCO_LB009

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

3.2

0

2.1

2

2.0

8

4.1

2

2.0

7

2.1

9

2.0

4

2.0

3

2.0

0

1.7

2 T

HF

2.7

5 N

H2N

H2

3.5

7 T

HF

7.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.2

3.2

0

2.1

2

2.0

8

4.1

2

2.0

7

2.1

9

2.0

4

2.0

3

2.0

0

7.7

0

7.7

1

7.9

9

8.0

1

8.0

3

8.1

7

8.1

8

8.5

2

8.5

3

8.5

7

8.5

8

8.7

2

8.7

3

8.7

7

8.7

8

9.0

1

9.0

2

9.1

7

HN

NNH

NH

O2N

NO2

71

Figure S66: HPLC chromatogram of 5,15-bis(3’-nitrophenyl)-10-(phenyl)corrole 14.

18VIRCO_LB009



Version 7.2.3.7553



Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0-100

0

100

200

300

400

500

600

700

800

9001 - 3.670

2 - 4.607


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

418.05

576.60619.62 643.57

nm

%




Version 7.2.3.7553

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

417.00

nm

%


72

Chemical Formula: C37H22FN7O6


Figure S67: MALDI/TOF LRMS of 5,15-bis(3’-nitrophenyl)-10-(4’-fluoro-3’-

nitrophenyl)corrole 15. 18VIRCO_LB018

HN

NNH

NH

O2N

NO2

F

NO2

73

Chemical Formula [M+H]+: C37H23FN7O6


d (ppm) = 0.26 Figure S68: ESI HRMS of 5,15-bis(3’-nitrophenyl)-10-(4’-fluoro-3’-nitrophenyl)corrole 15.

18VIRCO_LB018

HN

NNH

NH

O2N

NO2

F

NO2

74

Figure S69: 1H NMR spectrum (500 MHz, DMSO-d6i + one drop of hydrazine 64%) of 5,15-

bis(3’-nitrophenyl)-10-(4’-fluoro-3’-nitrophenyl)corrole 15.

18VIRCO_LB018

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

2.5

0 D

MS

O

3.8

8 N

H2N

H2

7.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.2

1.0

3

2.0

7

1.0

3

1.9

8

2.1

3

2.1

3

0.9

9

4.1

8

4.0

0

7.9

5

7.9

6

8.0

7

8.0

9

8.1

1

8.3

1

8.3

3

8.4

6

8.4

7

8.5

0

8.5

1

8.5

2

8.5

3

8.5

7

8.5

8

8.6

3

8.6

3

8.6

9

8.7

0

8.7

2

8.7

4

9.0

1

9.0

3

9.0

4

9.0

5

75

Figure S70: 19F NMR spectrum (470 MHz, THF-d8 + one drop of hydrazine 64%) of 5,15-

bis(3’-nitrophenyl)-10-(4’-fluoro-3’-nitrophenyl)corrole 15.

18VIRCO_LB018

76

Figure S71: HPLC chromatogram of 5,15-bis(3’-nitrophenyl)-10-(4’-fluoro-3’-




Version 7.2.3.7553



Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time [min]

-50

0

50

100

150

200

250

300

Abs

orba

nce

[mA

U]

1 - 3.780seq_2019 #88 [manually integrated] 18VIRCO_LB018 UV_VIS_2 WVL:420 nm

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

418.77

579.51360.96 615.11349.80

nm

%


77



Figure 72: MALDI/TOF LRMS of 5,15-bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-2’-


18VIRCO_LB035

HN

NNH

NH

O2N

NO2F

F

F

NO2

78



d (ppm) = 0.06

Figure S73: ESI HRMS of 5,15-bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-2’-


18VIRCO_LB035

HN

NNH

NH

O2N

NO2F

F

F

NO2

79



Figure S74: 1H NMR spectrum (500 MHz, THF-d8 + one drop of hydrazine 64%) of 5,15-

bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-2’-nitrophenyl)corrole 16. 18VIRCO_LB035

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

1.0

3

1.0

4

1.9

6

3.0

2

2.0

6

2.0

4

2.0

5

1.9

2

1.9

9

1.7

2 T

HF

2.8

7 N

H2

NH

2

3.5

7 T

HF

7.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.19.2

7.6

7

8.0

2

8.0

3

8.0

4

8.0

5

8.2

8

8.3

0

8.3

7

8.3

8

8.4

8

8.5

0

8.6

4

8.6

5

8.7

5

8.7

6

9.0

2

9.0

3

9.0

4

HN

NNH

NH

O2N

NO2F

F

F

NO2

80

Figure S75: 19F NMR spectrum (470 MHz, THF-d8 + one drop of hydrazine 64%) of 5,15-

bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-2’-nitrophenyl)corrole 16.

18VIRCO_LB035

81

Figure S76: HPLC chromatogram of 5,15-bis(3’-fluoro-5’-nitrophenyl)-10-(5’-fluoro-2’-




Version 7.2.3.7553



Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time [min]

-50

0

50

100

150

200

250

300

350

400

Abs

orba

nce

[mA

U]

1 - 3.887

2 - 4.557


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

421.28

583.51619.42

nm

%




Version 7.2.3.7553

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

420.45

386.90

583.33

nm

%


82



Figure S77: MALDI/TOF LRMS of 5,15-bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-5’-


19VIRCO_LB081

HN

NNH

NH

F

F

F

NO2

NO2

NO2

83



d (ppm) = 0.880 Figure S78: ESI HRMS of 5,15-bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-5’-


19VIRCO_LB081

HN

NNH

NH

F

F

F

NO2

NO2

NO2

84



Figure 79: 1H NMR spectrum (500 MHz, THF-d8 + one drop of hydrazine 64%) of 5,15-

bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-5’-nitrophenyl)corrole 17.

19VIRCO_LB081

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

2.1

4

2.1

7

8.3

9

2.1

1

2.9

8

1.1

8 A

cO

Et

1.7

2 T

HF

1.9

3 A

cO

Et

2.8

1 N

H2

NH

2

3.5

7 T

HF

4.0

4 A

cO

Et

7.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.1

2.1

4

2.1

7

8.3

9

2.1

1

2.9

8

7.6

4

8.1

0

8.4

1

8.5

9

8.9

2

HN

NNH

NH

F

F

F

NO2

NO2

NO2

85



Figure 80: 19F NMR spectrum (470 MHz, THF-d8 + one drop of hydrazine 64%) of 5,15-

bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-5’-nitrophenyl)corrole 17. 19VIRCO_LB081

HN

NNH

NH

F

F

F

NO2

NO2

NO2

86

Figure S81: HPLC chromatogram of 5,15-bis(5’-fluoro-2’-nitrophenyl)-10-(3’-fluoro-5’-




Version 7.2.3.7553



Chromatogram



0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time [min]

-100

0

100

200

300

400

500

600

Abs

orba

nce

[mA

U]

1 - 3.900

2 - 5.463


345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

418.77

578.77 616.90350.56

nm

%




Version 7.2.3.7553

345 400 450 500 550 600 650 700 750 8000.0

10.0

20.0

30.0

40.0

50.0

56.0

418.43

nm

%


87

Figure S82: example of the algorithm used to detect and measure infection parameters. The spot detector algorithm on a cellInsight CX7 microscope was used. On top, raw images acquired by the microscope. Bottom, overlay of the algorithm result, where total nuclei are represented in brown, selected nuclei (infected cells) in blue and hCMV replication center detected in green. The integrated intensity of the green signal is used to calculate replication rate.

88

Miscellaneous precursors syntheses.

Synthesis of 5-(3’-fluoro-5’-nitrophenyl)-dipyrromethane 18

3-Fluoro-5-nitrobenzaldehyde (1.53 g, 9.05 mmol), purchased from Fluorochem, was added to

pyrrole (67.8 mL, 904.74 mmol) in a round-bottom flask. Magnesium bromide (833.1 mg, 4.53

mmol) was introduced afterwards, then the reaction was left stirring in the dark at room

temperature for 2 h. This solution was stirred one more hour after addition of sodium hydroxide

in powder (1.81 g, 45.25 mmol). The mixture was filtrated over a Dicalite® plug and evaporated

to dryness. The oily residue was purified with a SiO2 plug (heptane/ethyl acetate 8:2) and

subsequent washings with heptane (20 mL) and pentane (20 mL) to afford the dipyrromethane

as a yellow solid with 71.0% yield (1.83 g). 1H NMR (500 MHz, CDCl3) δ (ppm): 8.01 (se 2H), 7.92 (m, 1H), 7.82 (m, 1H), 7.26 (m, 1H),

6.76 (m, 2H), 6.18 (m, 2H), 5.58 5.88 (m, 2H), 5.57 (s, 1H).

HR-MS (ESI) m/z = 286.0970 [M+H]+, 286.0986 calcd for C15H13FN3O2.

NH

HNNH

1) , MgBr2

rt, 2 h

2) NaOH rt, 1 h

NO2F

O

NO2F

89

Figure S83: 1H (500 MHz) NMR spectrum (CDCl3) of 5-(3’-fluoro-5’-nitrophenyl)-

dipyrromethane

Figure S84: ESI HRMS mass spectrum of 5-(3’-fluoro-5’-nitrophenyl)-dipyrromethane

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0

1.0

0

1.9

8

2.0

0

2.0

4

0.4

80

.52

1.0

41

.06

1.8

9

0.8

9 h

epta

ne

1.2

7 h

epta

ne

1.5

7 H

2O

2.1

7 A

ceto

ne

5.3

0 D

CM

5.65.86.06.26.46.66.87.07.27.47.67.88.0

5.5

7

5.8

8

6.1

86

.19

6.7

6

7.2

57

.26

CD

Cl3

7.2

7

7.8

17

.82

7.9

28

.01


282 283 284 285 286 287 288 289 290 291 292

m/z

0

50

100

0

50

100

Re

lativ

e A

bu

nd

an

ce

0

50

100

28

4.0

82

16

z=1

28

5.0

86

02

z=1

28

6.0

96

95

z=1

28

4.0

82

98

28

5.0

86

34

28

6.0

98

63

28

7.1

01

99

NL:3.06E6


NL:8.36E5

C 15 H 11 FN 3 o 2: C 15 H 11 F 1 N 3 O 2

pa Chrg 1

NL:8.36E5

C 15 H 12 FN 3 o 2 +H: C 15 H 13 F 1 N 3 O 2

pa Chrg 1

90

Synthesis of 5-(5’-fluoro-2’-nitrophenyl)-dipyrromethane 18SPA285

This compound was synthesized following a modified procedure described in the literature

(Wu, Yanping et al., Chemistry - An Asian Journal, 2017, 12 (17), 2216-2220).

5-Fluoro-2-nitrobenzaldehyde (5.00 g, 29.57 mmol) supplied by Fluorochem was added to

pyrrole (205.1 mL, 2.96 mol) in a round-bottom flask. Magnesium bromide (2.72 g, 14.79

mmol) was introduced afterwards, then the reaction was left stirring in the dark at room

temperature for 2 h. This solution was stirred one more hour after addition of sodium hydroxide

in powder (5.91 g, 147.85 mmol). The mixture was filtrated over a Dicalite® plug and

evaporated to dryness. The oily residue was purified with a SiO2 plug (heptane/ethyl acetate

8:2) and recrystallization in heptane to afford the dipyrromethane as a yellow solid with 70.4%

yield (5.96 g). 1H NMR (500 MHz, CDCl3) δ (ppm): 8.14 (s, 2H), 7.98 (m, 1H), 7.06 (m, 1H), 6.92 (m, 1H),

6.73 (m, 2H), 6.29 (s, 1H), 6.16 (m, 2H), 5.87 (m, 2H).

LR-MS (ESI) m/z = 283.86 [M-H]-, 284.08 calcd for C15H11FN3O2.

Figure S85: 1H (500 MHz) NMR spectrum (CDCl3) of 5-(5’-fluoro-2’-nitrophenyl)-

dipyrromethane 18SPA285

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

2.0

12

.02

1.0

02

.00

1.0

21

.03

1.0

22

.00

5.8

75

.87

6.1

66

.16

6.2

96

.73

6.7

46

.92

6.9

26

.94

6.9

47

.06

7.2

67

.96

7.9

77

.98

7.9

98

.14

5.86.06.26.46.66.87.07.27.47.67.88.08.28.4f1 (ppm)

5.8

75

.87

6.1

66

.16

6.2

9

6.7

36

.74

6.9

26

.92

6.9

46

.94

7.0

67

.26

7.9

67

.97

7.9

87

.99

8.1

4

91

Figure S86: ESI LRMS mass spectrum of 5-(5’-fluoro-2’-nitrophenyl)-dipyrromethane

18SPA285

Synthesis of 2-fluoro-3-nitrobenzyl alcohol 19VIRCO_LB078 – for 19VIRCO_LB079

This compound was synthesized following a slightly modified procedure described in the

literature (Ashton, Susan Elizabeth et al. PCT Int. Appl., 2008104754, 04 Sep 2008).

2-Fluoro-3-nitrobenzoic acid (3.00 g, 16.21 mmol) from Fluorochem was introduced in a

round-bottom flask. After vacuum/argon cycles, dry THF (25 mL) was added and the solution

was cooled down to 0 °C. A borane tetrahydrofuran solution (1 M in THF, 81.05 mL, 81.05

mmol) was dropwisely added at this temperature over 1 h. The mixture was left freely warming

up overnight (for 14 hours), then was cooled down again to 0 °C before quenching with

methanol (10 mL) then water (100 mL). The product was extracted with ethyl acetate (3x100

mL), washed with water (100 mL) and dried over MgSO4 before evaporation to dryness. The

crude compound was purified with a SiO2 plug (ethyl acetate/heptane 5:5) to afford the expected

alcohol derivative as a yellow oil with 99.7% yield (2.77 g). 1H NMR (500 MHz, CDCl3) δ (ppm): 7.96 (m, 1H), 7.79 (m, 1H), 7.30 (t, 3J = 8.0 Hz, 1H),

4.86 (s, 2H).

COOHF F

NO21) BF3–THF, THF, 0 °C, 1 h

2) rt, 18 h

NO2

HO

92

Figure S87: 1H NMR spectrum (500 MHz, CDCl3) of 2-fluoro-3-nitrobenzyl alcohol

Synthesis of 2-fluoro-3-nitrobenzaldehyde 19VIRCO_LB079 – for 19VIRCO_LB080

This compound was synthesized following a modified procedure described in the literature

(Kanno, Hideo et al. Chemical & Pharmaceutical Bulletin, 1992, 40 (8), 2049-2054).

2-Fluoro-3-nitrobenzyl alcohol (2.77 g, 16.17 mmol) was added to a round-bottom flask with

manganese(II) oxide (11.6 g, 113.17 mmol)) and ethyl acetate (100 mL). The mixture was left

refluxing for 2.5 h, and was directly filtrated over a Dicalite® plug in order to remove insoluble

materials. After evaporation to dryness, the crude compound was purified with a SiO2 plug

(ethyl acetate/heptane 5:5) to give the aldehyde as a yellow sticky solid with 85.4% yield

(2.34 g). 1H NMR (500 MHz, CDCl3) δ (ppm): 10.41 (s, 1H), 8.31 (m, 1H), 8.17 (m, 1H), 7.47 (t, 3J =

8.0 Hz, 1H). 19F NMR (470 MHz, CDCl3) δ (ppm): -128.99 (t, 4JF-H = 7.0 Hz, 1F). 13C (125 MHz, CDCl3) δ (ppm): 184.9, 158.6, 156.4, 134.1, 131.6, 126.3, 124.9.

CHOFF

NO2

AcOEt, reflux, 25 h

NO2

HO

MnO2

93

Figure S88. 1H (500 MHz, CDCl3) and 19F (470 MHz, CDCl3) NMR spectra

of 2-fluoro-3-nitrobenzaldehyde

94

Figure S89. 13C (125 MHz, J-mode, CDCl3) NMR spectrum of 2-fluoro-3-nitrobenzaldehyde

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