Application of photoclick chemistry for the synthesis of pyrazoles via 1,3‐dipolar cycloaddition between alkynes and nitrilimines generated in situ

Index

1

HNMR,

13

CNMR spectra of 1a

S4

1

HNMR,

13

CNMR spectra of 1b

S6

1

HNMR,

13

CNMR spectra of 1c

S8

1

HNMR,

13

CNMR spectra of 1d

S10

1

HNMR,

13

CNMR spectra of 1e

S12

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1f

S14

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1g

S18

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1h

S22

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1i

S26

1

HNMR,

13

CNMR and IR spectra of 1j

S30

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1k

S33

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1l

S37

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1m

S41

1

HNMR spectra of 1n

S45

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1o

S46

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1p

S50

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1q

S54

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1r

S58

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1s

S62

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 1t

S66

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3a

S70

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3b

S74

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3b’

S78

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3c

S82

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3c’

S86

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3d

S90

1

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3f

S98

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3f’

S102

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3h/3h’

S106

1

HNMR,

13

CNMR, IR and MALDI-TOF spectra of 3i/3i’

S110

1

HNMR and

13

CNMR spectra of 3j

S114

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3k/3k’

S116

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3l

S120

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3l’

S124

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3m/3m’

S128

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3o

S132

1

HNMR spectrum of 3o/3o’

S136

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3p

S137

1

HNMR, IR and ESI-HRMS spectra of 3p/3p’

S141

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3q/3q’

S144

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3s

S148

1

HNMR, IR and ESI-HRMS spectra of 3s/3s’

S152

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3t

S155

1

HNMR, IR and ESI-HRMS spectra of 3t/3t’

S159

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3u/3u’

S162

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3v

S166

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3v’

S170

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3w

S174

1

HNMR,

13

CNMR, IR and ESI-HRMS spectra of 3x

S178

1

_HNMR,

13

_{CNMR, IR and ESI-HRMS spectra of 3y}

_S182

1

HNMR,

13

CNMR and IR spectra of 4

S186

5 methyl 2H tetrazole

RR199Fi_001000fid 10.0 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 2.50 2.51 2.52 2.52

N

N

N

H

N

S4

5 methyl 2H tetrazole

RR199Fi_002000fid 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 8.37 38.68 38.96 39.23 39.51 39.79 40.07 40.35 129.41

N

N

N

H

N

5 phenyl 2H tetrazole

RR200Fi_001000fid 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 NormalizedIntensity 2.99 2.00 2.49 2.49 2.50 2.51 2.51 3.57 3.59 7.58 7.58 7.59 7.59 7.60 7.61 7.61 7.63 7.63 8.02 8.03 8.04 8.05

N

N

N

H

N

S6

5 phenyl 2H tetrazole

RR200Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 38.68 38.96 39.23 39.51 39.79 40.07 40.35 124.15 126.99 129.47 131.31

N

N

N

H

N

5 methyl 2 trityl 2H tetrazole

RR201Fi_001000fid 9.5 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 0 Chemical Shift (ppm) 0 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 NormalizedIntensity 3.00 6.32 9.93 2.58 7.11 7.14 7.14 7.32 7.34 7.36 7.37 7.38

N

N

N

N

S8

5 methyl 2 trityl 2H tetrazole

RR201Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 NormalizedIntensity 11.22 76.57 77.00 77.42 82.60 127.74 130.17 141.40 161.97

N

N

N

N

5 phenyl 2 trityl 2H tetrazole

RR202Fi_001000fid 9.5 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 6.02 3.07 2.00 1.56 7.16 7.17 7.20 7.20 7.27 7.35 7.37 7.37 7.45 7.46 7.47 7.48 7.49 8.15 8.15 8.18 8.18

N

N

N

N

S10

5 phenyl 2 trityl 2H tetrazole

RR202Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) -0.05 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 76.58 77.00 77.42 83.12 127.04 127.76 130.31 141.40

N

N

N

N

2 benzyl 5 phenyl 2H tetrazole

RR214Fi_001000fid 10.0 9.5 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 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 NormalizedIntensity 2.00 7.93 1.94 5.82 7.27 7.37 7.38 7.40 7.47 7.47 7.48 7.49 7.49 7.50 7.51 7.52 8.13 8.14 8.15 8.17 8.18

N

N

N

N

S12

2 benzyl 5 phenyl 2H tetrazole

RR214Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 NormalizedIntensity 56.76 76.58 77.00 77.42 126.83 128.33 128.79 130.26 133.34

N

N

N

N

2 5-diphenyl-2H-tetrazole

RR221_1FI_001000FID.ESP 10.0 9.5 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 6.30 1.04 7.27 7.48 7.49 7.51 7.52 7.53 7.59 7.59 7.62 7.62 7.62 8.19 8.20 8.21 8.23 8.26 8.27 8.29 8.30 RR221_1FI_001000FID.ESP 8.45 8.40 8.35 8.30 8.25 8.20 8.15 8.10 8.05 8.00 Chemical Shift (ppm) 0 0.25 0.50 0.75 1.00 NormalizedIntensity 1.04 0.98 1.99 8.19 8.20 8.21 8.21 8.22 8.23 8.23 8.24 8.25 8.26 8.27 8.27 8.28 8.29 8.29 8.30 8.30

N

N

N

N

S14

2 5-diphenyl-2H-tetrazole

RR221_1Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) -0.05 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 76.58 77.00 77.42 119.83 127.03 128.92 129.63 130.52 136.89 165.18

N

N

N

N

5- 4-methoxyphenyl)-2-phenyl-2H-tetrazole

RR221_2Fi_002000fid 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 55.37 76.58 77.00 77.42 114.33 119.78 128.55 129.60 136.94 161.43 165.07

N

N

N

N

O

5- 2-bromophenyl)-2-phenyl-2H-tetrazole

RRtet1e_8_001000fid 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 1.04 2.05 1.02 2.00 M06(m) M05(m) M07(m) M02(dd) M03(dd) M01(m) 7.29 7.36 7.36 7.37 7.38 7.39 7.49 7.49 7.58 7.60 7.60 7.79 7.79 7.81 7.99 8.00 8.02 8.23 8.23 8.25 8.25 RRtet1e_8_001000fid 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 Chemical Shift (ppm) 0 0.25 0.50 NormalizedIntensity 1.04 2.07 2.05 1.00 1.02 2.00 M06(m) M05(m) M07(m) M02(dd) M03(dd) M01(m) 7.29 7.37 7.38 7.39 7.47 7.49 7.49 7.51 7.52 7.54 7.55 7.58 7.58 7.60 7.62 7.62 7.79 7.79 7.81 7.81 7.99 8.00 8.01 8.02 8.23 8.23 8.23 8.25 8.25 8.25

N

N

N

N

Br

S22

5- 2-bromophenyl)-2-phenyl-2H-tetrazole

RRtet1e_8_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) -0.05 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 76.69 77.00 77.32 119.88 122.11 127.45 129.64 131.68 134.19 136.79 164.16

N

N

N

N

Br

                      



































:DYHQXPEHUFP











7UDQVPLWWDQFH>@

&?8VHUV?UHP\U?'HVNWRS?,5GHFHPEUH

55WHWH

'DWH





S24

4- 2-phenyl-2H-tetrazol-5-yl)benzonitrile

RRTETK_001000FID.ESP 9.5 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 1.04 2.06 2.02 M05(m) M04(m) M01(m) M03(d) M02(m) 7.27 7.50 7.50 7.52 7.54 7.56 7.58 7.60 7.78 7.80 8.16 8.18 8.18 8.33 8.35

N

N

N

N

NC

S26

4- 2-phenyl-2H-tetrazol-5-yl)benzonitrile

RRTETK_002000FID.ESP 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 NormalizedIntensity M04(s) M07(s) M05(s) M06(s) M08(s) M10(s) M09(s) M02(s) M03(s) M01(s) 76.68 77.00 77.31 113.93 118.19 119.75 127.37 129.68 129.97 131.16 132.65 136.50 163.43

N

N

N

N

NC

5- 4-nitrophenyl)-2-phenyl-2H-tetrazole

RR247FINAL2_002000FID.ESP 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity M08(s) M01(s) M07(s) M09(s) M04(s) M06(s) M05(s) M02(s) M03(s) 76.58 77.00 77.42 119.93 124.27 127.85 129.81 130.15 133.02 136.62 149.02 163.33

N

N

N

N

O

2

N

2-methoxy-6-(2-phenyl-2H-tetrazol-5-yl)phenyl acetate

RRTETL_001000FID.ESP 9.5 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 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 NormalizedIntensity 3.12 3.14 1.09 1.18 2.10 1.21 2.12 M04(d) M03(m) M01(d) M05(t) M06(d) M02(d) M07(s) M08(s) 2.47 3.92 7.13 7.15 7.27 7.38 7.51 7.57 7.58 7.60 7.89 7.91 8.15 8.17

N

N

N

N

OMe

OAc

2-methoxy-6-(2-phenyl-2H-tetrazol-5-yl)phenyl acetate

RRTETL_002000FID.ESP 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity M02(s) M03(s) M08(s) M09(m) M11(s) M07(s) M05(s) M01(s) M04(s) M12(s) M13(s) M06(m) 20.93 56.20 76.68 77.00 77.31 114.07 119.84 121.06 121.45 126.87 129.67 136.85 137.98 152.33 162.26 169.18

N

N

N

N

OMe

OAc

S34

5- 5-methylfuran-2-yl)-2-phenyl-2H-tetrazole

RRtet1g_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) -0.05 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 NormalizedIntensity 13.79 76.69 77.00 77.32 108.07 113.13 119.88 129.58 136.68 140.90 154.99 158.48

N

N

N

N

O

S38

ethyl 2-phenyl-2H-tetrazole-5-carboxylate

RRtet1m_13_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) -0.05 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 NormalizedIntensity 14.08 62.66 76.69 77.00 77.32 120.17 127.02 128.81 129.71 130.50 136.25 157.66

N

N

N

N

O

O

S42

2- 4-fluorophenyl)-5-phenyl-2H-tetrazole

RRTETH_002000FID.ESP 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 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 0.80 0.85 NormalizedIntensity M07(s) M06(s) M09(s) M08(s) M10(s) M11(s) M04(s) M03(s) M01(s) M02(s) M05(s) 76.68 77.00 77.31 116.55 116.78 121.76 121.84 127.01 127.03 128.95 130.61 161.73 164.22 165.31

N

N

N

N

F

2- 3-chlorophenyl)-5-phenyl-2H-tetrazole

RRTETI_002000FID.ESP 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 NormalizedIntensity M05(s) M04(s) M08(s) M06(s) M07(s) M09(s) M10(s) M03(s) M01(s) M02(s) M11(s) 76.68 77.00 77.31 117.81 120.07 126.82 127.07 128.95 130.72 135.55 137.56 165.36

N

N

N

N

Cl

2- benzo[d][1,3]dioxol-5-yl)-5-phenyl-2H-tetrazole

RRTETJ_002000FID.ESP 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 NormalizedIntensity M02(s) M03(s) M12(s) M08(s) M07(s) M09(s) M11(s) M04(s) M06(s) M10(s) M05(s) M01(s) 76.68 77.31 101.65 102.19 108.46 113.77 126.97 128.89 130.45 131.41 148.50 148.68 164.94

N

N

N

N

O

O

2- 4-methoxyphenyl)-5- o-tolyl)-2H-tetrazole

RRTETE_002000FID.ESP 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 NormalizedIntensity M08(s) M05(s) M09(s) M06(s) M07(s) M11(s) M04(s) M10(s) M12(s) M02(s) M03(s) M01(s) M13(s) 21.76 55.63 76.69 77.00 77.32 114.65 121.31 126.01 129.52 129.96 131.38 137.55 160.42 165.36

N

N

N

N

OMe

2-phenyl-5- 2- prop-2-yn-1-yloxy)phenyl)-2H-tetrazole

RR336_1TETRAZJUSTINE_002000FID.ESP 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 NormalizedIntensity M06(s) M05(s) M07(s) M08(s) M04(s) M01(s) M09(s) M10(s) M11(s) M12(s) M03(s) M13(s) M02(s) M14(s) 53.45 53.72 54.00 54.27 54.54 57.56 76.20 79.03 115.11 117.99 120.43 122.54 130.13 130.23 132.16 137.58 156.23 163.61

N N

N

N

O

5-phenyl-2- 2- prop-2-yn-1-yl)phenyl)-2H-tetrazole

RR339P1_002000FID.ESP 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 NormalizedIntensity M07(s) M09(s) M04(s) M11(s) M05(s) M10(m) M08(s) M14(s) M06(s) M03(s) M13(s) M12(s) M02(s) 22.10 71.39 76.69 77.00 77.32 79.89 125.21 127.02 128.97 130.58 130.69 135.59 165.08

N

N

N

N

1,3-diphenyl-5-(thiophen-2-yl)-1H-pyrazole and 1,3-diphenyl-4-(thiophen-2-yl)-1H-pyrazole

RR653_2P2_001000FID.ESP 10.0 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 NormalizedIntensity 0.05 2.20 0.52 0.18 M10(d) M01(d) M09(d) M04(m) M02(d) M03(m) M05(m) M12(s) M13(dd) M06(m) _M11(dd) M07(m) 1.27 1.57 6.86 6.87 6.87 6.89 6.97 6.98 7.16 7.22 7.27 7.30 7.43 7.44 7.47 7.47 7.48 7.49 7.49 7.53 7.55 7.90 7.90 7.91 7.93 8.07 RR653_2P2_001000FID.ESP 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 Chemical Shift (ppm) 0 0.25 0.50 0.75 NormalizedIntensity 0.05 2.17 2.20 8.61 1.34 0.52 2.21 0.18 M10(d) M01(d) M09(d) M04(m) M02(d) M03(m) _M05(m) M12(s) M13(dd) M06(m) M11(dd) M08(m) 6.86 6.86 6.87 6.87 6.89 6.96 6.97 6.97 6.98 7.16 7.21 7.22 7.26 7.27 7.30 7.31 7.41 7.41 7.42 7.43 7.44 7.44 7.45 7.47 7.47 7.48 7.53 7.55 7.57 7.85 7.86 7.86 7.90 7.90 7.91 7.93 7.93 8.05 8.06 8.07 8.08

N N

S

N N

S

S110

1,3-diphenyl-5-(thiophen-2-yl)-1H-pyrazole and 1,3-diphenyl-4-(thiophen-2-yl)-1H-pyrazole

RR653_2P2_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 NormalizedIntensity M12(s) M17(s) M11(s) M15(s) M16(s) M10(s) M07(s) M13(s) M14(s) M20(s) M18(s) M08(s) M04(m) M06(s) M03(s) M01(s) M02(s) 76.68 77.00 77.31 104.97 125.80 126.22 128.62 129.01 131.34 132.80 134.83 138.17 139.86 151.88

N N

S

N N

S







   







 



























:DYHQXPEHUFP

















7UDQVPLWWDQFH>@

&?8VHUV?UHP\U?'HVNWRS

55B)L

'DWH





S112

ethyl 3-(2-bromophenyl)-1-phenyl-1H-pyrazole-5-carboxylate

RR348_1Fi1_002000fid 10.0 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 3.33 2.00 0.96 4.60 0.95 1.26 1.28 1.30 1.55 4.26 4.28 4.29 4.31 7.23 7.24 7.25 7.25 7.27 7.38 7.48 7.49 7.51 7.54 7.68 7.79 7.79 7.81 7.81 RR348_1Fi1_002000fid 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 Chemical Shift (ppm) 0 0.25 0.50 NormalizedIntensity 0.96 1.03 4.60 0.95 0.93 0.95 7.23 7.23 7.23 7.24 7.25 7.27 7.35 7.37 7.38 7.39 7.47 7.47 7.49 7.49 7.51 7.54 7.68 7.68 7.70 7.70 7.79 7.79 7.81 7.81

N

N

Br

CO

₂

Et

S120

ethyl 3-(2-bromophenyl)-1-phenyl-1H-pyrazole-5-carboxylate

RR348_1Fi1_003000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 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 NormalizedIntensity 14.05 61.25 76.69 77.00 77.32 113.25 122.06 126.09 128.56 131.18 133.57 133.74 140.25 150.56 159.13

N

N

Br

CO

2

Et

ethyl 3-(2-bromophenyl)-1-phenyl-1H-pyrazole-4-carboxylate

RR348_1Fi2_001000fid 9.5 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 Chemical Shift (ppm) 0 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 NormalizedIntensity 3.10 1.90 1.04 0.95 1.00 1.15 1.16 1.18 1.27 1.28 1.55 4.17 4.19 4.21 4.23 7.27 7.37 7.50 7.50 7.52 7.66 7.68 7.78 7.78 7.80 7.80 7.80 8.53 RR348_1Fi2_001000fid 7.9 7.8 7.7 7.6 7.5 7.4 7.3 Chemical Shift (ppm) 0 0.1 0.2 0.3 NormalizedIntensity 1.04 1.96 2.98 0.95 1.90 7.27 7.30 7.30 7.31 7.37 7.39 7.40 7.40 7.47 7.47 7.48 7.49 7.50 7.50 7.50 7.52 7.66 7.66 7.68 7.68 7.78 7.78 7.80 7.80 7.80

N

N

Br

CO

2

Et

S124

ethyl 3-(2-bromophenyl)-1-phenyl-1H-pyrazole-4-carboxylate

RR348_1Fi2_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 NormalizedIntensity 13.95 60.31 76.68 77.00 77.31 119.57 124.22 126.90 127.53 129.57 129.97 132.38 134.30 139.24 153.31

N

N

Br

CO

2

Et

ethyl 3-(4-cyanophenyl)-1-phenyl-1H-pyrazole-5-carboxylate and ethyl

3-(4-cyanophenyl)-1-phenyl-1H-pyrazole-4-carboxylate

RR533_4P1_001000fid 9.5 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 Chemical Shift (ppm) 0 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 NormalizedIntensity 3.33 2.07 1.00 0.60 1.97 0.53 0.05 1.26 1.28 1.29 1.35 4.26 4.27 4.29 4.31 7.27 7.27 7.38 7.50 7.61 7.70 7.72 7.84 7.98 8.00 8.06 8.19 8.20 8.22 8.38 8.40 8.40 8.53 RR533_4P1_001000fid 9.0 8.5 8.0 7.5 7.0 6.5 Chemical Shift (ppm) 0 0.1 0.2 0.3 0.4 NormalizedIntensity 1.00 5.22 2.82 1.97 0.53 0.51 0.05 7.27 7.27 7.27 7.38 7.48 7.50 7.59 7.61 7.63 7.70 7.72 7.82 7.84 7.84 7.98 8.00 8.06 8.08 8.19 8.20 8.22 8.38 8.40 8.40 8.53

N

N

CO

₂

Et

NC

N

N

CO

₂

Et

NC

S128

ethyl 3-(4-cyanophenyl)-1-phenyl-1H-pyrazole-5-carboxylate and ethyl

3-(4-cyanophenyl)-1-phenyl-1H-pyrazole-4-carboxylate

RR533_4P1_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity _13.97 14.25 60.62 61.40 76.68 77.00 77.32 109.84 111.65 114.02 118.77 119.87 125.96 126.12 128.63 128.98 129.75 130.05 132.55 132.74 135.24 136.48 140.05 149.40 158.70 163.55

N

N

CO

₂

Et

NC

N

N

CO

2

Et

NC

ethyl 3-(2-acetoxy-3-methoxyphenyl)-1-phenyl-1H-pyrazole-5-carboxylate

RR537P1_001000fid 9.5 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 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 NormalizedIntensity 3.28 3.12 3.18 2.13 1.05 1.24 1.21 1.24 1.26 1.28 2.34 3.88 4.24 4.26 4.28 4.29 6.98 6.98 7.00 7.00 7.24 7.26 7.30 7.46 7.48 7.48 7.49 7.49 7.50 7.51 7.53 RR537P1_001000fid 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 Chemical Shift (ppm) 0 0.1 0.2 0.3 0.4 NormalizedIntensity 1.05 1.24 0.99 5.11 1.21 6.98 6.98 7.00 7.00 7.24 7.26 7.28 7.30 7.46 7.47 7.48 7.48 7.48 7.49 7.49 7.50 7.51 7.53

N

N

CO

2

Et

OAc

OMe

S132

ethyl 3-(2-acetoxy-3-methoxyphenyl)-1-phenyl-1H-pyrazole-5-carboxylate

RR537P1_002000fid 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 13.94 20.81 56.06 61.13 76.68 77.00 77.32 111.87 111.98 120.44 125.98 128.43 128.59 134.11 137.35 140.28 147.55 151.87 158.98 168.88

N

N

CO

2

Et

OAc

OMe

ethyl 3-(2-acetoxy-3-methoxyphenyl)-1-phenyl-1H-pyrazole-5-carboxylate and ethyl

3-(2-acetoxy-3-methoxyphenyl)-1-phenyl-1H-pyrazole-4-carboxylate

RR537P2_001000fid 10.0 9.5 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 3.83 2.00 3.00 1.93 3.23 1.32 0.65 0.87 0.87 0.89 0.91 1.18 1.19 1.21 1.23 1.27 1.40 1.42 1.43 2.13 2.33 3.86 3.87 3.88 4.22 4.24 4.25 4.27 4.29 5.41 5.42 5.44 6.98 7.04 7.05 7.06 7.07 7.22 7.24 7.24 7.27 7.29 7.35 7.47 7.48 7.48 7.50 7.52 7.75 7.77 7.78 8.50

N

N

CO

₂

Et

OMe

OAc

N

N

CO

2

Et

OAc

OMe

S136

ethyl 3-(5-methylfuran-2-yl)-1-phenyl-1H-pyrazole-5-carboxylate

RR350_1Fi1_001000fid 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 3.37 3.14 2.13 1.02 1.02 1.00 5.23 1.25 1.26 1.28 2.38 4.23 4.25 4.27 4.28 6.08 6.08 6.66 6.67 7.20 7.44 7.45 7.46 7.46 7.47 7.47 7.48

N

N

CO

₂

Et

O

ethyl 3-(5-methylfuran-2-yl)-1-phenyl-1H-pyrazole-5-carboxylate

RR350_1Fi1_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) -0.05 0 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 NormalizedIntensity 13.67 13.98 61.18 76.69 77.00 77.32 107.46 108.69 126.23 128.49 128.67 134.31 140.18 144.30 145.82 152.43 158.89

N

N

CO

2

Et

O

S138

ethyl 3-(5-methylfuran-2-yl)-1-phenyl-1H-pyrazole-5-carboxylate and ethyl

3-(5-methylfuran-2-yl)-1-phenyl-1H-pyrazole-4-carboxylate

RR350_1Fi2_001000fid 9.5 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 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 NormalizedIntensity 5.31 3.18 2.31 1.13 1.14 0.99 7.95 1.88 1.02 1.25 1.26 1.28 1.40 1.42 1.55 2.38 2.44 4.23 4.25 4.27 4.35 4.37 4.39 6.07 6.08 6.08 6.13 6.14 6.14 6.66 6.67 7.19 7.27 7.46 7.46 7.47 7.49 7.78 7.80 7.80 8.45

N

N

CO

₂

Et

O

N

N

CO

2

Et

O

diethyl 1-phenyl-1H-pyrazole-3,5-dicarboxylate and diethyl 1-phenyl-1H-pyrazole-3,4-dicarboxylate

RR565_3Fi_001000fid 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 3.03 1.98 2.12 5.02 0.07 1.23 1.25 1.37 1.39 1.41 1.44 1.46 4.22 4.24 4.26 4.29 4.34 4.43 4.45 4.48 4.48 7.27 7.42 7.45 7.45 7.45 7.46 7.52 8.38

N

N

CO

2

Et

O

O

N

N

CO

₂

Et

O

O

S144

diethyl 1-phenyl-1H-pyrazole-3,5-dicarboxylate and diethyl 1-phenyl-1H-pyrazole-3,4-dicarboxylate

RR565_3Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 NormalizedIntensity 13.91 14.31 61.36 61.48 76.57 77.00 77.42 114.57 120.08 126.16 128.55 129.28 129.57 134.87 139.74 143.72 158.37 161.52

N

N

CO

2

Et

O

O

N

N

CO

₂

Et

O

O

ethyl 1-(4-fluorophenyl)-3-phenyl-1H-pyrazole-5-carboxylate

RR533P1_001000fid 9.5 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 Chemical Shift (ppm) 0 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 0.80 0.85 NormalizedIntensity 3.09 2.05 2.04 4.21 2.00 1.28 1.29 1.31 1.32 4.26 4.27 4.28 4.30 4.32 7.15 7.15 7.17 7.17 7.27 7.34 7.44 7.47 7.49 7.50 7.51 7.87 7.89

N

N

CO

₂

Et

F

S148

ethyl 1-(4-fluorophenyl)-3-phenyl-1H-pyrazole-5-carboxylate

RR533P1_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 NormalizedIntensity 14.07 61.28 76.69 77.00 77.32 109.48 115.36 115.59 125.79 127.98 128.75 132.00 134.75 136.48 151.58 159.01 163.72

N

N

CO

2

Et

F

ethyl 1-(4-fluorophenyl)-3-phenyl-1H-pyrazole-5-carboxylate and ethyl

1-(4-fluorophenyl)-3-phenyl-1H-pyrazole-4-carboxylate

RR533P2_001000FID.ESP 9.5 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 6.25 4.00 3.92 0.89 2.09 1.00 1.20 1.22 1.29 1.31 1.32 1.34 3.48 3.50 4.26 4.28 4.30 4.32 4.33 7.15 7.17 7.18 7.19 7.20 7.27 7.34 7.44 7.44 7.46 7.48 7.50 7.75 7.76 7.86 7.87 7.88 7.89 7.89 8.45

N

N

CO

2

Et

F

N

N

CO

₂

Et

F

S152

ethyl 1-(3-chlorophenyl)-3-phenyl-1H-pyrazole-5-carboxylate

RR533_2P1_001000fid 9.5 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 3.00 2.03 1.06 1.00 1.93 1.29 1.31 1.33 4.28 4.30 4.32 4.33 7.27 7.35 7.43 7.45 7.56 7.88 7.90 7.90

N

N

CO

2

Et

Cl

ethyl 1-(3-chlorophenyl)-3-phenyl-1H-pyrazole-5-carboxylate

RR533_2P1_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 NormalizedIntensity 14.03 61.37 76.69 77.00 77.32 109.88 124.38 125.80 126.50 128.75 129.42 131.86 134.13 134.77 141.22 151.87 158.90

N

N

CO

₂

Et

Cl

S156

ethyl 1-(3-chlorophenyl)-3-phenyl-1H-pyrazole-5-carboxylate and ethyl

1-(3-chlorophenyl)-3-phenyl-1H-pyrazole-4-carboxylate

RR533_2P2_001000fid 10.0 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 0.85 NormalizedIntensity 8.12 4.83 2.59 1.43 5.68 1.00 1.22 1.24 1.26 1.27 1.28 1.29 1.31 1.33 1.35 1.37 1.39 4.28 4.30 4.31 4.32 4.33 4.34 7.26 7.27 7.27 7.35 7.42 7.44 7.46 7.56 7.56 7.66 7.67 7.69 7.86 7.87 7.87 7.89 7.90 8.50 8.51

N

N

CO

₂

Et

Cl

N

N

CO

₂

Et

Cl

ethyl 1-(benzo[d][1,3]dioxol-5-yl)-3-phenyl-1H-pyrazole-5-carboxylate and ethyl

1-(benzo[d][1,3]dioxol-5-yl)-3-phenyl-1H-pyrazole-4-carboxylate

RR533_3Fimix_001000fid 9.5 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 Chemical Shift (ppm) 0 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 0.80 NormalizedIntensity 3.15 2.08 2.07 1.01 1.00 2.05 0.11 1.30 1.32 1.34 4.27 4.29 4.31 4.33 6.04 6.05 6.87 6.87 6.88 6.90 6.97 6.99 7.27 7.31 7.44 7.45 7.46 7.87 7.87 7.88 7.90 7.90 8.39 RR533_3Fimix_001000fid 8.5 8.0 7.5 7.0 6.5 Chemical Shift (ppm) 0 0.25 0.50 NormalizedIntensity 1.01 1.73 1.00 2.16 2.05 0.11 6.88 6.88 6.90 6.90 6.90 6.97 6.99 6.99 7.27 7.31 7.37 7.42 7.43 7.44 7.45 7.46 7.87 7.87 7.87 7.88 7.90 7.90 8.39

N

N

CO

2

Et

O

O

N

N

CO

2

Et

O

O

S162

ethyl 1-(benzo[d][1,3]dioxol-5-yl)-3-phenyl-1H-pyrazole-5-carboxylate and ethyl

1-(benzo[d][1,3]dioxol-5-yl)-3-phenyl-1H-pyrazole-4-carboxylate

RR533_3Fimix_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 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 0.80 0.85 NormalizedIntensity 14.06 14.22 60.24 61.13 76.68 77.00 77.31 101.79 101.84 101.94 107.60 107.66 109.04 112.92 119.94 125.71 128.30 128.65 129.32 132.07 134.69 146.97 147.46 147.87 151.16 158.98 162.85

N

N

CO

2

Et

O

O

N

N

CO

2

Et

O

O

ethyl 1-(4-methoxyphenyl)-3-(o-tolyl)-1H-pyrazole-5-carboxylate

RR349_1Fi1_001000fid 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 NormalizedIntensity 3.00 2.97 2.98 1.99 1.99 0.94 1.96 1.00 1.28 1.30 1.32 1.59 2.55 3.87 4.26 4.28 4.30 4.32 6.98 7.00 7.17 7.28 7.28 7.29 7.43 7.45 7.64 7.65

N

N

CO

₂

Et

OMe

S166

ethyl 1-(4-methoxyphenyl)-3-(o-tolyl)-1H-pyrazole-5-carboxylate

RR349_1Fi1_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 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 0.80 0.85 NormalizedIntensity 14.10 21.22 55.50 61.09 76.69 77.00 77.32 112.11 113.64 125.87 127.24 129.29 130.85 133.52 136.11 151.54 159.29 159.58

N

N

CO

₂

Et

OMe

ethyl 1-(4-methoxyphenyl)-3-(o-tolyl)-1H-pyrazole-4-carboxylate

RR349_1Fi2_001000fid 10.0 9.5 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 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 NormalizedIntensity 2.76 2.65 2.83 1.83 1.93 1.54 1.79 0.90 1.15 1.17 1.19 1.56 2.28 3.87 3.87 4.16 4.17 4.19 4.21 6.99 7.01 7.26 7.27 7.28 7.30 7.35 7.67 7.69 8.43

N

N

CO

₂

Et

OMe

S170

ethyl 1-(4-methoxyphenyl)-3-(o-tolyl)-1H-pyrazole-4-carboxylate

RR349_1Fi2_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 NormalizedIntensity 14.05 20.04 55.61 60.06 76.68 77.00 77.32 114.61 114.72 121.05 125.12 128.49 129.71 130.91 132.48 137.28 153.98 158.88 162.84

N

N

CO

₂

Et

OMe

dimethyl 3-(4-nitrophenyl)-1-phenyl-1H-pyrazole-4,5-dicarboxylate

RR326Fi_001000fid 9.5 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 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 NormalizedIntensity 3.01 4.99 1.98 2.00 3.85 3.88 7.27 7.50 7.50 7.52 7.54 7.54 7.55 7.55 7.56 7.98 8.00 8.28 8.30

N

N

CO

₂

Me

CO

₂

Me

O

2

N

S174

dimethyl 3-(4-nitrophenyl)-1-phenyl-1H-pyrazole-4,5-dicarboxylate

RR326Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) 0 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 NormalizedIntensity 52.31 53.32 76.68 77.00 77.31 114.04 123.32 124.34 129.34 129.81 137.73 138.65 147.96 149.87 160.41 162.67

N

N

CO

2

Me

CO

2

Me

O

₂

N

2-phenyl-2 4-dihydrochromeno[4 3-c]pyrazole

RR343Fi_001000fid 10.0 9.5 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 Chemical Shift (ppm) 0 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 NormalizedIntensity 2.00 0.95 0.93 2.10 3.07 5.35 6.99 7.01 7.05 7.23 7.27 7.30 7.32 7.46 7.47 7.47 7.49 7.70 7.71 7.72 7.74 7.74 7.89 7.90 7.91 7.91 RR343Fi_001000fid 8.0 7.5 7.0 Chemical Shift (ppm) 0 0.25 0.50 0.75 NormalizedIntensity 0.95 1.07 0.93 2.10 3.07 0.98 6.98 6.99 7.01 7.01 7.05 7.06 7.07 7.23 7.23 7.25 7.25 7.27 7.30 7.32 7.32 7.32 7.45 7.47 7.47 7.49 7.50 7.70 7.71 7.72 7.74 7.74 7.89 7.90 7.91 7.91

N

N

O

S178

2-phenyl-2 4-dihydrochromeno[4 3-c]pyrazole

RR343Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) -0.05 0 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 0.80 0.85 0.90 NormalizedIntensity 63.25 76.68 77.00 77.32 114.28 117.19 119.07 121.60 122.69 126.39 129.44 129.60 140.12 145.07 154.31

N

N

O

2-phenyl-4H-pyrazolo[1 5-a]indole

RR342Fi_001000fid 10.0 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 2.00 0.93 1.03 3.10 0.98 1.90 1.27 1.56 3.94 5.32 5.32 6.64 6.64 6.65 7.20 7.21 7.22 7.22 7.35 7.41 7.41 7.43 7.43 7.45 7.49 7.51 7.64 7.66 7.89 7.89 7.89 7.91 7.92

N

N

S182

2-phenyl-4H-pyrazolo[1 5-a]indole

RR342Fi_002000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 Chemical Shift (ppm) -0.05 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 NormalizedIntensity 28.98 53.46 53.73 54.00 54.27 54.54 98.47 110.74 124.87 126.17 126.51 129.21 134.28 146.60

N

N

(Z)-N'-phenylbenzohydrazonoyl chloride

RR354Fi_003000fid 9.5 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 0 Chemical Shift (ppm) 0 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 0.80 0.85 0.90 0.95 1.00 NormalizedIntensity 1.00 2.05 2.99 1.96 1.54 5.32 5.32 6.94 6.96 6.98 7.20 7.20 7.22 7.33 7.41 7.44 7.46 7.46 7.93 7.94 7.94 7.96 8.11

N

NH

Cl

S186

(Z)-N'-phenylbenzohydrazonoyl chloride

RR354Fi_004000fid 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 Chemical Shift (ppm) -0.05 0 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 0.80 0.85 NormalizedIntensity 53.46 53.73 54.00 54.27 54.54 113.95 121.71 125.22 126.90 129.00 129.81 129.93 135.04 144.05

N

NH

Cl