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Denitrative Imino-Diaza-Nazarov Cyclization: Synthesis of Pyrazoles
Balakrishna Aegurla, Nisha Jarwal and Rama Krishna Peddinti*
Department of Chemistry, Indian Institute of Technology Roorkee
Roorkee-247667, Uttarakhand, India
SUPPLEMENTARY INFORMATION
Table of Contents ………………………………………………………………….. S-1
Figure S1: ORTEP plot of crystal structure of 7c…………………………………… S-2
Figure S2. Monitoring reaction of 1a and 2a by 1H NMR analysis…………………. S-3
Scheme S1: Plausible reaction mechanism…………………………………………. S-4
Prototropic tautomers……………………………………………………………… S-4
1H and 13C NMR and DEPT spectra of substituted pyrazoles……………………… S-5–S-25
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2020
2
Figure S1. ORTEP plot of crystal structure of 7c (numbering is arbitrary).
3
Figure S2. Monitoring reaction of 1a and 2a by 1H NMR analysis.
OH or NH
Hb a
decomposition of
benzaldehyde hydrazone
reaction
after 10 min
reaction
after 1 h
after 2 h;
isolated 3a
reaction
after 10 min
4
Scheme S1: Plausible reaction mechanism.
Prototropic tautomers:
The NMR spectra of the products 3b & 4a are identical. Similarly, each product of the other two
sets 3c & 5a, 4c & 5b have identical spectral data. This indicates that most likely, the proton in the
pyrazole ring is delocalized between the two nitrogen atoms of the heterocycle. Though the
position of the proton in the pyrazole ring is shown in the structures on one nitrogen atom, in
principle, it can be on either of the two nitrogen atoms due to prototropic tautomerism.
5
6
7
8
9
abun
dan
ce
00.
020.
040.
060.
080.
10.
120.
140.
160.
180.
20.
220.
240.
260.
28
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
16
3.4
22
16
0.9
78
12
7.7
25
12
7.0
61
12
6.9
97
11
5.5
05
11
5.2
91
98
.97
5
77
.32
2
77
.19
3
77
.00
0
76
.67
8
40
.46
7
40
.21
0
40
.01
7
39
.80
3
39
.58
8
BS-2F
10
abun
dan
ce
00.
020.
040.
060.
080.
10.
120.
140.
160.
180.
20.
220.
240.
260.
280.
30.
32
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
16
3.6
36
16
1.1
71
15
9.4
56
14
8.7
15
14
7.4
50
12
7.9
83
12
7.1
89
12
7.1
04
12
6.7
39
12
3.1
80
11
5.6
12
11
5.3
98
11
4.0
69
98
.89
0
77
.32
2
77
.00
0
76
.67
8
55
.15
3
BS-NFM
11
abun
danc
e
00.
10.
20.
30.
40.
50.
60.
7
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
159.
370
148.
865
147.
921
131.
606
128.
626
127.
790
126.
825
125.
517
123.
845
114.
047
99.1
25
77.3
22
77.0
00
76.7
00
55.1
32BS-919
12
abun
dan
ce
00.
10.
20.
30.
4
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
16
3.4
22
16
0.9
78
15
9.2
63
14
8.2
64
14
7.0
85
12
8.2
83
12
7.0
82
12
7.0
18
12
6.6
53
12
3.5
02
11
5.4
41
11
5.2
26
11
3.9
40
98
.61
1
77
.32
2
77
.00
0
76
.67
8
55
.04
6
40
.42
4
40
.21
0
39
.97
4
39
.76
0
39
.54
5
BS-917-OMF
13
abun
danc
e
00.
10.
20.
30.
40.
50.
6
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
159.
156
147.
986
126.
654
124.
295
113.
897
98.2
46
77.3
22
77.0
00
76.6
78
55.0
46
40.5
10
40.2
74
40.0
60
39.8
46
39.6
31
Bs-920
14
abun
dan
ce
00.
10.
20.
30.
4
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
13
4.1
57
12
9.6
76
12
8.4
76
12
7.7
04
12
7.2
54
12
5.1
74
12
3.3
52
99
.40
4
77
.32
2
77
.19
3
77
.00
0
76
.67
8
40
.33
9
40
.08
1
39
.88
9
39
.67
4
39
.46
0
BS-930
15
abun
danc
e
00.
10.
20.
30.
4
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
163.
636
161.
171
134.
479
133.
557
129.
891
127.
618
127.
447
127.
211
127.
125
125.
453
123.
523
115.
698
115.
484
99.5
97
77.3
22
77.0
00
76.6
78
40.5
96
40.3
60
40.1
24
39.9
10
39.7
17
16
abun
dan
ce
00.
10.
20.
30.
4
X : parts per Million : Carbon13
200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
15
9.2
41
14
8.0
50
14
6.4
63
13
4.2
00
12
9.6
76
12
7.2
54
12
6.5
89
12
5.2
81
12
3.4
16
12
3.2
66
11
3.9
40
98
.82
5
77
.32
2
77
.00
0
76
.67
8
55
.02
5
40
.40
3
40
.16
7
39
.95
3
39
.73
8
39
.52
4
BS-932
17
abun
dan
ce
00.
10.
20.
30.
40.
50.
60.
70.
80.
91.
01.
1
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
14
8.5
64
13
8.2
09
13
1.2
84
13
0.9
63
12
8.6
04
12
8.5
19
12
7.7
90
12
6.2
46
12
5.5
17
12
2.6
87
99
.72
6
77
.32
2
77
.00
0
76
.67
8
21
.25
8
BS-928-3M
18
abun
danc
e
00.
020.
040.
060.
080.
10.
120.
140.
160.
180.
20.
220.
240.
260.
280.
3
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
163.
744
161.
278
148.
565
147.
964
138.
424
130.
491
128.
948
128.
669
127.
833
127.
189
126.
203
122.
623
115.
677
99.6
61
77.3
22
77.0
00
76.6
78
21.3
01
BS-3MF
19
abun
danc
e
00.
10.
20.
30.
40.
50.
60.
70.
80.
91.
01.
1
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
159.
220
148.
908
147.
964
138.
102
131.
392
128.
454
126.
804
126.
246
123.
888
122.
666
113.
940
98.9
97
77.3
22
77.0
00
76.7
00
55.0
46
21.2
36
BS-3MOM
20
abun
dan
ce
00.
10.
20.
30.
40.
50.
60.
70.
80.
9
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
13
1.8
20
13
1.3
49
13
0.4
48
13
0.2
34
12
9.8
27
12
9.2
48
12
8.7
33
12
8.0
90
12
6.9
97
12
5.6
46
10
3.6
06
77
.32
2
77
.00
0
76
.67
8
BS-POCL
21
abun
dan
ce
00.
10.
20.
30.
40.
50.
6
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
14
6.3
13
14
4.4
48
13
5.2
51
13
0.3
84
12
8.5
19
12
7.7
90
12
7.2
54
12
5.2
60
12
4.1
67
12
3.4
80
99
.40
4
77
.32
2
77
.00
0
76
.67
8
40
.36
0
40
.12
4
39
.91
0
39
.69
6
39
.48
1
BS-931-CLF
22
abun
dan
ce
00.
10.
20.
3
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
16
3.0
57
16
0.6
13
12
7.0
39
12
6.8
04
12
6.7
18
12
3.9
52
12
3.2
45
11
5.1
83
11
4.9
69
98
.91
1
77
.32
2
77
.21
4
77
.00
0
76
.67
8
40
.08
1
39
.84
6
39
.63
1
39
.41
7
39
.22
4
38
.96
7
BS-941-SF
23
abun
danc
e
00.
10.
20.
30.
4
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
150.
029
147.
885
132.
685
128.
633
127.
732
125.
696
100.
955
77.3
07
77.0
07
76.6
85
31.7
27
29.2
19
29.0
04
26.3
67
22.6
15
14.0
61
BS-912-OC
24
25
abun
danc
e
00.
10.
20.
30.
40.
5
X : parts per Million : Carbon13
190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
159.
284
149.
529
148.
114
126.
911
125.
410
113.
983
100.
347
77.3
22
77.0
00
76.7
00
55.2
39
31.7
42
29.2
55
29.0
40
26.4
67
22.6
08
14.0
54
B-923
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