Denitrative Imino-Diaza-Nazarov Cyclization: Synthesis of ... · 1 Denitrative Imino-Diaza-Nazarov...
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1 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 1 H NMR analysis…………………. S-3 Scheme S1: Plausible reaction mechanism…………………………………………. S-4 Prototropic tautomers……………………………………………………………… S-4 1 H and 13 C 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
Transcript of Denitrative Imino-Diaza-Nazarov Cyclization: Synthesis of ... · 1 Denitrative Imino-Diaza-Nazarov...
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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
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Figure S1. ORTEP plot of crystal structure of 7c (numbering is arbitrary).
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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.
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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
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12
7.7
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12
7.0
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6.9
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5.5
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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
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3.6
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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.
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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
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78
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9.2
63
14
8.2
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8.2
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7.0
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12
7.0
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12
6.6
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3.9
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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
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986
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39.8
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39.6
31
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20.
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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
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4.1
57
12
9.6
76
12
8.4
76
12
7.7
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7.2
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12
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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.
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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
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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
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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.
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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.
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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
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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
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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
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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
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529
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114
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410
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983
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347
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76.7
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31.7
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29.2
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29.0
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26.4
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22.6
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14.0
54
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