Synthesis of novel benzimidazole derivatives and their platinum (II) complexes.

Plate 1: ¹H NMR spectrum of pyridyl[1,5-a]-4-phenylimidazolium chloride (4.3a)

10 9 8 7 6 5 4 3 2 1 ppm

0.981.05

2.98

2.97

0.950.95

1.00

7'

N⁺ N

2 1 3

4 5

6 7 8

9

10

11 12

10 11

Plate 1a:¹³C NMR spectrum of pyridyl[1,5-a]-4-phenylimidazolium chloride (4.3a)

130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135

136 ppm

Plate 1b: ¹³C Dept 135 NMR spectrum of pyridyl[1,5-a]-4-phenylimidazolium chloride (4.3a)

130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130

131 ppm

Plate 1c: IR spectrum of pyridyl[1,5-a]-4-phenylimidazolium chloride (4.3a)

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0

84.5 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99.3

cm-1

%T

vmz-53.4b (H)

3063.45

1614.82

1510.75

1075.14

759.63 693.24

Plate 1d: HRMS spectrum of pyridyl[1,5-a]-4-phenylimidazolium chloride (4.3a)

Plate 2: ¹H NMR spectrum of pyridyl[1,5-a]-4-phenylimidazolium chloride (4.3b)

10 9 8 7 6 5 4 3 2 1 ppm

1.021.042.04

2.99

0.961.09

1.00

7'

N⁺ N

F

2 1 3

4 5

6 7 8

9

10 11

12 10

11

Plate 2a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-(p-fluoro)phenylimidazolium chloride (4.3b)

10 20

30 40

50 60

70 80

90 100

110

120 ppm

115 120

125 130

135 140

145 150

155

160 ppm

Plate 2b: IR spectrum of pyridyl[1,5-a]-4-(p-fluoro)phenylimidazolium chloride (4.3b)

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400.0

30.1 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135.8

cm-1

%T

vmz-54.2b (F)

3353.39 3066.91

2059.16

1627.05 1545.76

1509.48

1344.80

1234.24 1163.57

1107.06 1081.88

1011.06

853.33

809.27 787.87

742.61

554.75 456.92

Plate 2c: HRMS spectrum of pyridyl[1,5-a]-4-(p-fluoro)phenylimidazolium chloride (4.3b)

Plate 3: ¹H NMR spectrum of pyridyl[1,5-a]-4-(p-chloro)phenylimidazolium chloride (4.3c)

10 9 8 7 6 5 4 3 2 1 ppm

0.981.05

1.993.06

0.951.05

1.00

7'

N⁺ N

Cl

2 1 3

4 5

6 7 8

9

10 11

12 10

11

Plate 3a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-(p-chloro)phenylimidazolium chloride (4.3c)

10 20

30 40

50 60

70 80

90 100

110 120

130 ppm

Plate 3b: IR spectrum of pyridyl[1,5-a]-4-(p-chloro)phenylimidazolium chloride (4.3c)

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0

80.06 80.5 81.0 81.5 82.0 82.5 83.0 83.5 84.0 84.5 85.0 85.5 86.0 86.5 87.0 87.5 88.0 88.5 89.0 89.5 90.0 90.5 91.0 91.5 92.0 92.5 93.0 93.32

cm-1

%T

vmz-69.2d (Cl)

3379.90

3056.80

1656.65

1546.87

1504.66 1421.01

1342.25

1211.82

1095.05 1071.89

1011.10

839.21

811.55 745.35

Plate 3c: HRMS spectrum of pyridyl[1,5-a]-4-(p-chloro)phenylimidazolium chloride (4.3c)

Plate 4: ¹H NMR spectrum of pyridyl[1,5-a]-4-(p-bromo)phenylimidazolium chloride (4.3d)

10 9 8 7 6 5 4 3 2 1 ppm

1.041.18

2.073.18

1.030.99

1.00

7'

N⁺ N

Br

2 1 3

4 5

6 7 8

9

10 11

12 10

11

Plate 4a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-(p-bromo)phenylimidazolium chloride (4.3d)

130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 4b: IR spectrum of pyridyl[1,5-a]-4-(p-bromo)phenylimidazolium chloride (4.3d)

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0

47.5 50 52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 84.1

cm-1

%T

vmz-55.2b (Br)

3369.56

3063.36

2075.76

1655.13 1545.11

1500.15 1416.78

1341.61 1260.72

1212.06 1120.61

1066.48 1008.67

948.27

835.75

805.73 744.21

711.62

Plate 4b: IR spectrum of pyridyl[1,5-a]-4-(p-bromo)phenylimidazolium chloride (4.3d)

Plate 5: ¹H NMR spectrum of pyridyl[1,5-a]-4-(o-methyl)phenylimidazolium chloride (4.3e)

10 9 8 7 6 5 4 3 2 1 ppm

3.17

1.031.081.063.00

1.07

0.97

1.03

1.00

7'

13 14

N⁺ 15

N

CH₃

2 1 3

4 5

6 7 8

9

10

11 12

Plate 5a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-(o-methyl)phenylimidazolium chloride (4.3e)

130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 6: ¹H NMR spectrum of pyridyl[1,5-a]-4-(m-methyl)phenylimidazolium chloride (4.3f)

10 9 8 7 6 5 4 3 2 1 ppm

3.25

0.991.040.991.031.021.011.09

1.011.08

1.00

7'

13 15 14

N

⁺

N

CH

₃

2 1 3

4 5

6 7 8

9

10

11 12

Plate 6a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-(m-methyl)phenylimidazolium chloride (4.3f)

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 7: ¹H NMR spectrum of pyridyl[1,5-a]-4-(p-methyl)phenylimidazolium chloride (4.3g)

10 9 8 7 6 5 4 3 2 1 ppm

3.37

1.011.062.062.071.11

0.981.06

1.00

7'

13

N⁺ N

CH₃

2 1 3

4 5

6 7 8

9

10

11 12 10

11

Plate 7a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-(p-methyl)phenylimidazolium chloride (4.3g)

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 8: ¹H NMR spectrum of pyridyl[1,5-a]-4-(p-anisy)phenylimidazolium chloride (4.3h)

10 9 8 7 6 5 4 3 2 1 ppm

3.32

3.111.18

2.051.12

1.021.07

1.00

7'

13

N⁺ N

O CH₃

2 1 3

4 5

6 7 8

9

10 11

12 10

11

Plate 9: ¹H NMR spectrum of pyridyl[1,5-a]-4-(p-nitro)phenylimidazolium chloride (4.3i)

10 9 8 7 6 5 4 3 2 1 ppm

0.951.04

1.11

1.93

2.921.08

1.00

7'

N⁺ N

NO₂

2 1 3

4 5

6 7 8

9

10 11

12 10

11

Plate 9a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-(p-nitro)phenylimidazolium chloride (4.3i)

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 10: ¹H NMR spectrum of pyridyl[1,5-a]-4-sulfanilamidylimidazolium chloride (4.3j)

10 9 8 7 6 5 4 3 2 1 ppm

1.021.10

1.05

4.02

2.18

1.00

7'

N⁺ N

S NH₂ O O

2 1 3

4 5

6 7 8

9

10 11

12 10

11

Plate 10a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-sulfanilamidylimidazolium chloride (4.3j)

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 10b: IR spectrum of pyridyl[1,5-a]-4-sulfanilamidylimidazolium chloride (4.3j)

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0

52.1 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 84 86 88 90 92 94.2

cm-1

%T

vmz-74.2e (SO2NH2)

3091.17

1656.60

1593.21 1546.52

1506.07 1424.95

1336.75 1285.84

1236.83 1193.35

1167.82 1097.43

1076.71

1020.30 922.31

836.19

799.91 736.05

Plate 10c: HRMS spectrum of pyridyl[1,5-a]-4-sulfanilamidylimidazolium chloride (4.3j)

Plate 11: ¹H NMR spectrum of pyridyl[1,5-a]-4-sulphapyridylimidazolium chloride (4.3k)

10 9 8 7 6 5 4 3 2 1 ppm

0.97

1.041.89

1.031.021.011.941.94

1.86

1.00

N⁺

N S NH

N O

1 O

2 3 4

5 6 7

8 9

10 11 12

13 15

14

16

17 18 20

19 7'

Plate 11a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-sulphapyridylimidazolium chloride (4.3k)

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 11b: IR spectrum of pyridyl[1,5-a]-4-sulphapyridylimidazolium chloride (4.3k)

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0

70.0 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96.0

cm-1

%T

vmz-76DS.d (SO2-pyridine)-2

3384.17

3057.28 2817.86

1614.41 1536.80

1509.47 1463.25

1427.43

1388.98

1347.56 1272.20

1244.98

1142.77 1107.87

1086.06 1007.94

986.85

962.56 849.17

785.90 768.98

747.07 729.52

715.12

Plate 11c: HRMS spectrum of pyridyl[1,5-a]-4-sulphapyridylimidazolium chloride (4.3k)

Plate 12: ¹H NMR spectrum of pyridyl[1,5-a]-4-(m-methyl)pheny-5-pyridylimidazolium chloride (4.4a)

3.0 3.5

4.0 4.5

5.0 5.5

6.0 6.5

7.0 7.5

8.0 8.5

9.0 ppm

3.19

1.961.154.111.08

1.20

1.06

0.90

0.911.00

7.4 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9

9.0 ppm

N⁺ N

CH₃ N

1 2 3

4 5

6 7 8

9

10

11 12

11'

10' 13

1' 3' 2'

4'

5' 6' 7'

H-2 H-2'

H-7

H-5

H-4'

H-3'

H-4,10,10',12

H-5' H-3,11

Plate 12a: ¹³C NMR spectrum of pyridyl[1,5-a]-4-(m-methyl)pheny-5-pyridylimidazolium chloride (4.4a)

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 13: ¹H NMR spectrum of pyridyl[1,5-a]-4-(p-N,N-Diethyl)pheny-5-pyridylimidazolium chloride (4.4b)

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

7.36

4.27

0.981.091.071.092.103.201.16

0.910.991.00

1 2 3

4 5

6 7 8

9 10 11 12

13 15

14

N⁺ N

N

N CH₃

C H₃

1' 3' 2'

4'

5' 6' 7'

Plate 13a: ¹³C Dept 135 NMR spectrum of pyridyl[1,5-a]-4-(p-N,N-Diethyl)pheny-5-pyridylimidazolium chloride (4.4b)

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

Plate 13b: IR spectrum of pyridyl[1,5-a]-4-(p-N,N-Diethyl)pheny-5-pyridylimidazolium chloride (4.4b)

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0

58.3 60 65 70 75 80 85 90 95 100 105 110 115 120 124.5

cm-1

%T

vmz-60.2c (NHEt2)

3372.20

2462.43

1653.06 1586.74

1516.71 1452.70

1422.69 1377.10

1358.68 1323.11 1276.71

1251.92 1192.44

1154.67 1020.56

916.28

842.55 787.51

744.74 680.43

Plate 13c: HRMS spectrum of pyridyl[1,5-a]-4-(p-N,N-Diethyl)pheny-5-pyridylimidazolium chloride (4.4b)