69451 weinheim, germany - wiley- · pdf filecl no2 ipr 6b white crystalline ... 394.1893,...
TRANSCRIPT
![Page 1: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/1.jpg)
Supporting Information
© Wiley-VCH 2007
69451 Weinheim, Germany
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Reaction of “Huisgen Zwitterion” with Chalcones and Dienones: Efficient Strategy
for the Synthesis of Pyrazoline and Pyrazolopyridazine Derivatives
Vijay Nair;*a
Smitha C. Mathew;a A. T. Biju
a and Eringathodi Suresh
b
Dedicated with best regards to Professor C. N. R. Rao
[a] Dr. V. Nair, S. C. Mathew, A. T. Biju
Organic Chemistry Section
Regional Research Laboratory, CSIR
Trivandrum 695019 (India)
Fax: +91 471-2491712
E-mail: [email protected]
[b] Dr. E. Suresh
Analytical Sciences Discipline
Central salt and Marine Chemicals Research Institute,
CSIR, Bhavnagar 364002 (India)
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General
All reactions were conducted in oven-dried glassware sealed with rubber septa under a positive
pressure of deoxygenated argon from a manifold. Solvents used for the experiments were distilled or
dried as specified. Diisopropyl azodicarboxylate (DIAD), diethyl azodicarboxylate (DEAD) and di-tert-
butyl azodicarboxylate (DTAD) were purchased from Aldrich and used as received. The chalcones and
dienones were prepared by standard procedures. All other reagents were purchased from local suppliers
and used without purification. All reactions were monitored by TLC, visualization was effected with UV
and/or by developing in iodine. Chromatography refers to open column chromatography on silica gel
(100-200 mesh).
Melting points were recorded on a Buchi melting point apparatus and are uncorrected. NMR
spectra were recorded at 300 (1H) and 75 (
13C) MHz respectively on a Brucker Advance DPX-300 MHz.
Chemical shifts are reported in δ (ppm) relative to TMS (1H) or CDCl3 (
13C) as internal standards. IR
spectra were recorded on Bomem MB series FT-IR spectrometer; absorbencies are reported in cm-1
.
High resolution mass spectra were recorded under EI / HRMS (at 5000 resolution) using JOEL JMS 600
H Mass Spectrometer.
General Procedure for the synthesis of functionalized pyrazoline:
To a stirred solution of chalcone 4 (0.33 mmol) in toluene (5 mL) under an atmosphere of Ar, was
added DIAD 2 (0.49 mmol) and the reaction mixture was stirred under reflux. To the refluxing solution
was added triphenylphosphine (128 mg, 0.49 mmol) in 2 mL toluene dropwise. The reaction mixture was
kept stirring under reflux for 3 h. The reaction mixture cooled and the solvent was removed under
reduced pressure on a rotary evaporator. The residue was subjected to column chromatography on silica
gel (100-200 mesh) using 85:15 petroleum ether-ethyl acetate as eluent to afford the corresponding
product (6a-6m).
Functionalized Pyrazoline 6a
N N
CO2iPr
O2C
Br
F6a
iPr
White crystalline solid Mp. 105-107°C
IR (KBr) ννννmax: 2982, 2934, 1716, 1508, 1367, 1294, 1226, 1100, 832, 749 cm-1
.
1H NMR δ: 7.49 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 7.33-7.29 (m, 2H), 7.02 (t, J = 8.6 Hz, 2H),
5.85 (d, J = 3.1 Hz, 1H), 5.75 (d, J = 3.3 Hz, 1H), 5.12-5.05 (m, 1H), 4.87-4.79 (m, 1H), 1.35-1.31 (m,
6H), 1.13 (d, J = 6.2 Hz, 3H), 1.02 (d, J = 6.2 Hz, 3H).
![Page 4: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/4.jpg)
13C NMR δ: 162.7 (d, JCF = 245.3 Hz), 155.7, 143.5, 134.9, 132.2, 131.7, 131.4, 130.6, 129.9, 128.9,
128.5, 123.1, 115.8 (d, JCF = 21.5 Hz), 111.9, 71.0, 70.8, 65.8, 22.3, 22.2, 21.8, 21.6.
LRMS (FAB) for C23H24BrFN2O4: calcd. (M+): 490.09, found: 490.8.
Crystal structure of compound 6a has been deposited at the Cambridge Crystallographic Data Center and
allocated the reference no. CCDC 616377.
Single crystal X-ray structure of 6a
Functionalized Pyrazoline 6b
N N
CO2iPr
O2C
Cl
NO2
iPr
6b
White crystalline solid Mp. 114-116 °C
IR (KBr) ννννmax: 2987, 2939, 1717, 1596, 1523, 1460, 1372, 1343, 1294, 1177, 1095, 847, 749, 696 cm-1
.
1H NMR δ: 8.19 (d, J = 8.7 Hz, 2H), 7.64 (d, J = 8.7 Hz, 2H), 7.58-7.55 (m, 1H), 7.42-7.38 ( m, 2H),
7.27-7.24 (m, 1H), 6.23 (d, J = 3.2 Hz, 1H), 6.15 (d, J = 3.3 Hz, 1H), 5.14- 5.07 (m, 1H), 5.05-4.94
(m,1H), 1.38-1.31 (m, 6H), 1.21-1.17 (m, 6H).
13C NMR δ: 156.7, 154.9, 147.6, 141.1, 137.5, 136.1, 131.2, 130.6, 129.8, 129.2, 129.1, 128.1, 127.5,
126.9, 123.9, 114.0, 73.0, 71.9, 65.5, 22.0, 21.6, 21.5, 21.2.
LRMS (FAB) for C23H24ClN3O6: calcd. (M+): 473.14, found: 473.1.
Functionalized Pyrazoline 6c
N N
CO2
iPr
O2C
OMe
MeO
iPr
6c
Yellow viscous oil.
IR (film) ννννmax: 2982, 2934, 1716, 1596, 1508, 1377, 1251, 1173, 1105, 1027, 822 cm-1
.
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1H NMR δ: 7.46 (d, J = 8.7 Hz, 2H), 7.26 (d, J = 8.6 Hz, 2H), 6.88-6.83 ( m, 4H), 5.8 (d, J = 2.9 Hz, 1H)
5.64 (d, J = 3.2 Hz, 1H), 5.1-5.03 (m, 1H), 4.87-4.79 (m, 1H), 3.81(s, 3H), 3.78 (s, 3H), 1.32-1.28 (m,
6H), 1.13 (d, J = 6.2 Hz, 3H), 1.01 (d, J = 6.2 Hz, 3H).
13C NMR δ: 159.3, 155.7, 143.7, 131.5, 130.6, 130.0, 128.5, 127.8, 124.2, 119.5, 114.3, 113.9, 113.4,
109.9, 70.2, 70.1, 65.7, 55.3, 55.2, 22.1, 21.9, 21.6, 21.5.
LRMS (FAB) for C25H30N2O6: calcd. (M+): 454.21, found: 454.8.
Functionalized Pyrazoline 6d
N N
CO2
iPr
O2C
Cl
iPr
6d
Colorless viscous oil
IR (film) ννννmax: 2981, 2934, 1713, 1484, 1372, 1289, 1100, 1007, 754, 691 cm-1
.
1H NMR δ: 7.53-7.56 (m, 2H), 7.35-7.25 (m, 7H), 5.85 (d, J = 3.0 Hz, 1H), 5.72 (d, J = 3.3 Hz, 1H), 5.09
(m, 1H), 4.83 (m, 1H), 1.34 (t, J = 5.7 Hz, 6H), 1.09 (d, J = 6.0 Hz, 3H), 1.01 (d, J = 6.3 Hz, 3H.)
13C NMR δ: 155.4, 144.3, 137.8, 133.7, 131.4, 128.9, 128.8, 127.9, 127.4, 127.2, 110.7, 70.5, 70.4, 65.5,
22.1, 22.0, 21.6, 21.5.
HRMS (EI) for C23H25ClN2O4: calcd. (M+): 428.1503, found: 428.1518.
Functionalized Pyrazoline 6e
N N
CO2
iPr
O2C
Br
F3C
iPr
6e
Colorless viscous oil
IR (film) ννννmax: 2985, 2933, 1714, 1460, 1377, 1315, 1161, 1104, 1012, 831cm-1
.
1H NMR δ: 7.61 (d, J = 8.1 Hz, 2H), 7.48 (d, J = 8.7 Hz, 4H), 7.38 (d, J = 8.4 Hz, 2H), 5.95 (d, J = 2.7
Hz, 1H), 5.77 (d, J = 3.6 Hz, 1H), 5.13-5.04 ( m, 1H), 4.89-4.81 (m, 1H), 1.36-1.32 (m, 6H), 1.13 (d, J =
6.3 Hz, 3H), 1.06 (d, J = 6.3 Hz, 3H).
13C NMR δ: 155.4, 155.2, 143.5, 132.1, 131.5, 131.2, 130.2, 129.8, 128.8, 128.3, 127.6, 126.6, 125.8,
125.2, 110.9, 71.7, 70.9, 65.8, 64.9, 22.1, 21.9, 21.6, 21.3.
HRMS (EI) for C24H24BrF3N2O4: calcd (M+): 540.0872, found: 540.0898.
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Functionalized Pyrazoline 6f
N N
CO2
iPr
O2C
Br
Cl
iPr
6f
Colorless viscous oil
IR (film) ννννmax: 2979, 2932, 1728, 1591, 1468, 1378, 1303, 1104, 1010, 916, 840 cm-1
.
1H NMR δ: 7.53-7.37 (m, 8H), 5.86 (d, J = 3.2 Hz, 1H), 5.76 (d, J = 3.3 Hz, 1H), 5.12-5.06 (m, 1H),
4.88-4.84 (m, 1H), 1.36-1.32 (m, 6H), 1.15 (d, J = 6.5 Hz, 3H), 1.09 (d, J = 6.2 Hz, 3H).
13C NMR δ: 157.5, 155.4, 141.4, 134.3, 132.5, 131.2, 130.2, 129.8, 129.3, 129.4, 128.0, 126.6, 124.6,
111.2, 71.0, 70.7, 65.7, 22.1, 21.7, 21.5, 21.4.
HRMS (EI) for C23H24BrClN2O4: calcd (M+): 506.0608, found: 506.0604.
Functionalized Pyrazoline 6g
N N
CO2
iPr
O2C
6g
iPr
Colorless viscous oil.
IR (film) ννννmax: 2985, 2930, 1716, 1490, 1454, 1371, 1284, 1103, 949, 758, 691 cm-1
.
1H NMR δ: 7.54- 7.51 (m, 2H), 7.37-7.26 (m, 8H), 5.88 (d, J = 3.2 Hz, 1H), 5.76 (d, J = 3.3 Hz, 1H),
5.12-5.03 (m, 1H), 4.87-4.81 (m, 1H), 1.38-1.31 (m, 6H), 1.1 (d, J = 6.2 Hz, 3H), 0.99 (d, J = 6.2 Hz,
3H).
13C NMR δ: 155.4, 143.8, 139.1, 131.6, 128.6, 127.8, 127.7, 127.1, 126.3, 125.9, 111.3, 70.1, 70.0, 66.2,
22.1, 21.6, 21.4, 21.0.
HRMS (EI) for C23H26N2O4: calcd. (M+): 394.1893, found: 394.1843.
Functionalized Pyrazoline 6h
N N
CO2
iPr
O2C
Cl
6h
iPr
White crystalline solid Mp. 147-149 °C
IR (KBr) ννννmax: 2985, 2938, 1714, 1593, 1490, 1377, 1299, 1176, 1103, 769 cm-1
.
1H NMR δ: 8.25 (d, J = 8.3 Hz, 1H), 7.88 (d, J = 7.6 Hz, 1H), 7.78 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 7.1
Hz, 1H), 7.59-7.51 (m, 2H), 7.42 (d, J = 8.4 Hz, 3H), 7.31-7.24 (m, 2H), 6.63 (d, J = 2.6 Hz, 1H), 5.93 (d,
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J = 3.2 Hz ,1H), 5.15-5.09 (m, 1H), 4.93-4.88 (m, 1H), 1.36-1.31 (m, 6H), 1.14 (d, J = 6.2 Hz, 3H), 1.06
(d, J = 6.2 Hz, 3H).
13C NMR δ: 155.4, 142.5, 134.6, 134.2, 134.1, 130.2, 128.9, 128.5, 128.2, 126.4, 125.8, 125.7, 123.3,
123.2, 112.4, 70.7, 64.4, 22.2, 22.1, 21.7, 21.6.
HRMS (EI) for C27H27ClN2O4: calcd. (M+): 478.1659, found: 478.1683.
Functionalized Pyrazoline 6i
N N
CO2
iPrO2C
Cl
iPr
6i
Colorless viscous oil
IR (film) ννννmax: 2980, 2933.73, 1714.1, 1588.7, 1377.7, 1295.2, 1094.3, 836.7, 754.4cm-1
.
1H NMR δ: 8.44 (s,1H), 8.32 (d, J = 9.5 Hz, 2H), 7.99-7.96 ( m, 2H), 7.49-7.44 (m, 8H), 7.33 (d, J = 8.5
Hz, 2H), 5.69 (d, J = 3.2 Hz,1H), 5.01-4.94 (m, 2H), 1.3-1.18 (m, 9H), 0.99 (d, J = 6.2 Hz, 3H).
13C NMR δ: 162.3, 155.5, 141.8, 134.6, 133.9, 131.7, 130.8, 130.3, 129.5, 129.4, 128.9, 128.8, 128.2,
127.4, 127.2, 126.1, 124.7, 123.9, 120.9, 113.3, 71.1, 69.9, 63.2, 22.1, 21.9, 21.7, 21.6.
HRMS (EI) for C31H29ClN2O4: calcd. (M+): 528.1816, found: 528.1811.
Functionalized Pyrazoline 6j
N N
CO2EtEtO2C
6jCl
Colorless viscous oil
IR (film) ννννmax: 2981, 1734, 1689, 1595, 1521, 1489, 1413, 1377, 1319, 1238, 1093, 1062, 1012, 829,
759, 692 cm-1
.
1H NMR δ: 7.54-7.51 (m, 2H), 7.36-7.31 (m, 7H), 5.87 (d, J = 3.3 Hz, 1H), 5.73 (d, J = 3.3 Hz, 1H),
4.36-4.27 (m, 2H), 4.11-4.02 (m, 2H), 1.35 (t, J = 7.1Hz, 3H), 1.02 (t, J = 7.1 Hz, 3H).
13C NMR δ: 157.4, 155.8, 144.2, 137.6, 134.2, 131.2, 128.9, 127.9, 127.8, 127.2, 126.7, 110.8, 65.7,
63.7, 14.6, 13.9.
LRMS (FAB) for C21H21ClN2O4: calcd. (M+): 400.12, found: 400.6.
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Functionalized Pyrazoline 6k
N N
CO2EtEtO2C
Cl
NO2
6k
Colorless viscous oil
IR (film) ννννmax: 3053, 2983, 1724, 1598, 1524, 1469, 1375, 1309, 1265, 1174, 1109, 902, 771cm-1
.
1H NMR δ: 8.21 (d, J = 8.8 Hz, 2H), 7.66 (d, J = 8.8 Hz, 2H), 7.57-7.54 (m, 1H), 7.43-7.40 (m, 1H),
7.29-7.24 (m, 2H), 5.24 (d, J = 3.3 Hz, 1H), 5.15 (d, J = 3.4 Hz, 1H), 4.39-4.16 (m, 4H), 1.38-1.33 (m,
3H), 1.17-1.12 (m, 3H).
13C NMR δ: 157.1, 155.6, 147.8, 141.1, 137.4, 135.9, 131.3, 129.9, 129.3, 128.1, 127.7, 126.9, 123.3,
114.2, 65.7, 63.3, 14.2, 14.0.
HRMS (EI) for C21H20ClN3O6: calcd. (M+): 445.1041, found: 445.1004.
Functionalized Pyrazoline 6l
N N
CO2EtEtO2C
Cl
6lO
Colorless viscous oil
IR (film) ννννmax: 3053, 2985, 1722, 1591, 1469, 1404, 1377, 1328, 1261, 1178, 1097, 1060, 1012, 1012,
916, 792 cm-1
.
1H NMR δ: 8.11 (d, J = 8.5 Hz, 2H), 7.61 (d, J = 3.2Hz, 1H), 7.47 (d, J = 8.6 Hz, 2H), 7.05 (s. 1H), 6.72
(s, 1H), 6.29 (d, J = 4.9 Hz, 1H), 5.90 (s, 1H), 5.71 (bs, 1H), 4.35-4.16 (m, 4H), 1.41-1.22 (m, 6H).
13C NMR δ: 160.2, 140.8, 136.5, 132.5, 130.9, 129.3, 64.2, 63.7, 50.7, 14.5, 14.3.
LRMS (FAB) for C19H19ClN2O5: calcd. (M+): 390.10, found: 390.8.
Functionalized Pyrazoline 6m
N N
CO2
tBu
O2C
F
Br
6m
tBu
Colorless viscous oil
IR (film) ννννmax: 3053, 2985, 1720, 1604, 1546, 1510, 1421, 1269, 1155, 894, 762cm-1
.
1H NMR δ: 7.53 (d, J = 6Hz, 2H), 7.40-7.31 (m, 4H), 7.05-6.99 (m, 2H), 5.74 (s, 1H), 5.65 (m, 1H),
1.24-1.18 (m, 18H).
13C NMR δ: 162.3 , (d, JCF = 244.6 Hz), 160.7, 154.5, 143.9, 135.2, 131.8, 128.2, 127.9, 127.1, 126.4,
124.7, 122.5, 115.4 , (d, JCF = 21.3 Hz) 110.7, 82.1, 81.9, 65.2, 28.1, 27.5.
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LRMS (FAB) for C25H28BrFN2O4: calcd. (M+): 518.12, found: 518.6.
Polycyclic pyrazoline derivative 11
NN
O2CCO2
iPr
Ph
iPr
11
Colorless viscous oil
IR (film) ννννmax: 3065, 2982, 2939, 1728, 1707, 1459, 1377, 1304, 1187, 1104, 1022, 939, 759, 696 cm-1
.
1H NMR δ: 7.45 (d, J = 7.4 Hz, 1H), 7.37-7.29 (m, 5H), 7.25-7.1 (m, 3H), 5.5 (s, 1H), 5.08-4.93 (m,
2H), 3.06-2.93 (m, 1H), 2.82-2.75 (m, 1H), 2.5-2.36 (m, 1H), 2.25-2.17 (m, 1H), 1.33-1.27 (m, 6H), 1.23
(d, J = 6.3 Hz, 3H), 1.1 (d, J = 6.2 Hz, 3H).
13C NMR δ: 156.8, 139.1, 137.2, 134.8, 129.6, 128.9, 128.5, 128.4, 128.1, 127.8, 127.4, 126.4, 125.4,
120.4, 71.2, 70.6, 68.2, 66.2, 29.4, 28.8, 22.3, 21.9, 21.6, 20.9.
LRMS (EI) for C25H28N2O4, calcd (M+): 420.20, found 420.2.
Procedure for the synthesis of pyrazolopyridazine:
To a stirred solution of dienone 12 (0.42 mmol) in toluene (5 mL) under an atmosphere of Ar, was
added DIAD (1.0 mmol) and the reaction mixture was stirred under reflux. To the refluxing solution was
added triphenylphosphine (0.58 mmol) in 2 mL toluene dropwise. The reaction mixture was kept stirring
under reflux for 12 h. The reaction mixture cooled and the solvent was removed under reduced pressure
on a rotary evaporator. The residue was subjected to column chromatography on silica gel (100-200
mesh) using 70:30 petroleum ether-ethyl acetate as eluent to afford the corresponding product (13a-13m).
Pyrazolopyridazine derivative 13a
NN
N N
O2CCO2
iPr
O2C CO2
iPr
H
iPr
iPr
S
13a
White crystalline solid Mp.105-107 °C
IR (KBr) ννννmax: 2987, 2939, 1733, 1716, 1705, 1650, 1542, 1455, 1377, 1294, 1231, 1177, 1105, 1036,
924, 827, 754, 696 cm-1
.
1H NMR δ: 7.56 (s, 1H), 7.38-7.23 (m, 6H), 6.95-6.93 (m, 1H), 6.39 (s, 1H), 6.19 (d, J = 11.4 Hz, 2H),
5.06-4.99 (m, 4H), 4.73 (s, 1H), 4.44 (s, 1H), 1.33-1.27 (m, 20 H), 1.12 (s, 4H).
13C NMR δ: 156.6, 154.6, 154.1, 152.9, 141.8, 138.5, 134.7, 128.3, 127.9, 127.3, 126.6, 126.4, 125.7,
125.3, 125.1, 71.0, 70.9, 70.6, 69.8, 65.9, 59.4, 55.8, 22.1, 22.0, 21.9, 21.4.
LRMS (FAB) for C31H40N4O8S: calcd. (M+1): 629.26, found: 629.4.
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Crystal structure of compound 13a has been deposited at the Cambridge Crystallographic Data Center
and allocated the reference no. CCDC 616376.
Single-crystal X-ray structure of 13a
Pyrazolopyridazine derivative 13b
NN
N N
CO2
iPr
O2C CO2
iPr
H
F3CF3CO2C
iPr
iPr
13b
White crystalline solid Mp. 134-136°C
IR (KBr) ννννmax: 3070, 2987, 2939, 1732, 1716, 1606, 1455, 1372, 1319, 1231, 1104, 1041, 924, 832, 769,
735 cm-1
.
1H NMR δ: 7.92 (s, 1H), 7.71-7.34 (m, 9H), 5.86 (s, 1H), 5.57 (s, 1H), 5.13-5.07 (m, 4H), 4.86 (s, 1H),
3.94 (s, 1H), 1.35-1.20 (m, 24H).
13C NMR δ: 156.6, 154.9, 151.1, 140.4, 139.8, 137.2, 132.9, 131.9, 128.9, 128.2, 127.7, 127.4, 126.4,
122.7, 122.5, 107.9, 71.4, 70.9, 70.5, 69.9, 59.8, 55.7, 22.1, 21.8.
LRMS (FAB) for C35H40F6N4O8: calcd. (M+Na): 781.28, found: 781.1.
Pyrazolopyridazine derivative 13c
NN
N N
O2CCO2
iPr
O2C CO2iPr
H
FF
iPr
iPr
13c Colorless viscous oil
![Page 11: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/11.jpg)
IR (film) ννννmax: 2982, 2944, 1747, 1733, 1716, 1704, 1537, 1484, 1372, 1309, 1231, 1182, 1095, 1031,
929, 759 cm-1
.
1H NMR δ: 7.56-7.45 (m,2H), 7.28 (bs, 2H), 7.16-6.99 (m, 4H), 4.79 (bs, 1H), 4.58 (s, 1H), 1.31-1.08
(m, 24H).
13C NMR δ: 162.4, 158.9, 156.4, 154.4, 135.2, 131.6, 130.9, 129.5, 129.4, 129.4, 129.3, 127.7, 125.7,
123.7, 115.5, 115.3, 70.7, 69.5, 59.9, 50.5, 21.8, 21.7, 21.6, 21.4.
LRMS (FAB) for C33H40F2N4O8: calcd. (M+): 658.28, found: 658.9.
Pyrazolopyridazine derivative 13d
NN
N N
O2C
CO2
iPr
O2C CO2
iPr
H
iPr
iPr
13d
F
Yellow viscous oil
IR (film) ννννmax: 2979, 1749, 1734, 1717, 1697, 1557, 1540, 1455, 1304, 1226, 1178, 1100, 1027, 920,
832, 749 cm-1
.
1H NMR δ: 7.59-7.57 (m, 2H), 7.4-7.25 ( m, 5H), 7.05-6.98 (m, 2H), 5.96 (d, J = 12 Hz, 2H), 5.08-4.94
(m, 4H), 4.7 (bs, 1H), 4.38-4.33 (m, 1H), 1.34-1.25 (m, 24H).
13C NMR δ: 162.1 (d, JCF = 244.1 Hz), 156.8, 154.4, 153.9, 141.3, 138.4, 135.3, 134.6, 129.7, 128.8,
128.2, 127.8, 127.2, 126.8, 126.2, 115.0 (d, JCF = 25.2 Hz), 71.9, 71.7, 70.9, 69.7, 66.3, 61.3, 55.59, 21.9,
21.8, 21.7, 21.6, 21.5, 21.2, 20.8.
LRMS (FAB) for C33H41FN4O8: calcd. (M+1): 641.29, found: 641.5.
Pyrazolopyridazine derivative 13e
NN
N N
O2CCO2
iPr
O2C CO2
iPr
H
iPr
iPr
F
13e
F
Colourless viscous oil
IR (film) ννννmax: 2987, 2944, 1732, 1716, 1606, 1508, 1459, 1372, 1304, 1231, 1177, 1100, 1012, 905,
832, 749 cm-1
.
1H NMR δ: 7.57 (bs, 2H), 7.36 (bs, 2H), 7.07-6.99 (m, 4H), 6.32 (bs, 1H), 5.95 (s, 1H), 5.10-4.97 (m,
4H), 4.7 (bs, 1H), 4.31 (bs, 1H), 1.35-1.25 (m, 24 H).
13C NMR δ: 162.5 , (d, JCF = 245.8 Hz), 162.2(d, JCF = 244.7 Hz) , 156.8, 154.4, 154.0, 152.5, 136.6,
135.2, 134.5, 134.4, 132.5, 131.9, 130.2, 129.8, 128.9, 127.8, 115.9, 115.3, 72.1, 71.8, 71.0, 70.8, 66.5,
55.1, 54.0, 22.1, 22.0, 21.8, 21.6, 21.5, 21.3.
![Page 12: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/12.jpg)
LRMS (FAB) for C33H40F2N4O8: calcd. (M+): 658.28, found: 658.9.
Pyrazolopyridazine derivative 13f
NN
N N
O2C
CO2
iPr
O2C CO2iPr
H
iPr
iPr
S
13f
S
Yellow viscous oil
IR (film) ννννmax: 2982, 2939, 1748, 1732, 1716, 1705, 1698, 1649, 1542, 1513, 1455, 1377, 1309, 1231,
1182, 1109, 1041, 934, 832, 769, 705 cm-1
.
1H NMR δ7.23 (bs, 3H), 7.03-6.93 (m, 2H), 6.01 (bs, 2H), 5.03-4.99 (m, 4H), 4.78 (bs, 1H), 4.44 (s, 1H),
1.33-1.26 (m, 24H).
13C NMR δ: 156.6, 154.0, 152.6, 144.3, 141.4, 135.5, 134.9, 126.5, 126.3, 125.8, 125.6, 125.1, 112.4,
71.3, 71.0, 70.9, 69.9, 65.9, 59.2, 51.8, 50.7, 22.1, 22.0, 21.9, 21.4.
LRMS (FAB) for C29H38N4O8S: calcd. (M+1): 635.21, found: 635.1.
Pyrazolopyridazine derivative 13g
NN
N N
O2C
CO2
iPr
O2C CO2
iPr
H
iPr
iPr
13g
Cl
Yellow viscous oil
IR (film) ννννmax: 2982, 2939, 1746, 1732, 1716, 1705, 1635, 1558, 1472, 1373, 1311, 1233, 1180, 1105,
920, 754, 691 cm-1
.
1H NMR δ: 7.59 (d, J = 7.2 Hz, 2H), 7.5-7.3 (m, 7H), 5.96 (bs, 2H), 5.06-4.97 (m, 4H), 4.76 (bs, 1H),
4.36 (bs, 1H), 1.32-1.3 (m, 24 H).
13C NMR δ: 156.9, 154.5, 154.0, 152.3, 140.9, 135.5, 134.3, 129.5, 129.1, 128.6, 128.2, 127.9, 127.3,
126.9, 126.3, 126.1, 125.6, 111.3, 71.9, 71.0, 70.8, 69.9, 66.8, 60.9, 54.6, 22.0, 21.9, 21.8, 21.6, 21.3.
LRMS (FAB) for C33H41ClN4O8: calcd. (M+): 656.26, found: 656.9.
Pyrazolopyridazine derivative 13h
NN
N N
O2CCO2
iPr
O2C CO2iPr
H
iPr
iPr
BrBr
13h
Yellow viscous oil
![Page 13: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/13.jpg)
IR (film) ννννmax: 2987, 2939, 1733, 1716, 1508, 1464, 1382, 1309, 1265, 1236, 1182, 1032, 910, 832, 759
cm-1
.
1H NMR δ: 7.65-7.55 (m, 3H), 7.33- 7.13 (m, 5H), 5.99 (s, 1H), 5.74 (s, 1H), 5.12-4.96 (m, 4H), 4.94 (s,
1H), 4.29 (s, 1H), 1.45- 1.25 (m, 24H).
13C NMR δ: 156.5, 154.7, 151.7, 151.5, 138.9, 136.3, 133.3, 133.1, 132.4, 130.1, 129.2, 128.9, 128.4,
127.7, 127.4, 122.5, 72.3, 72.0, 70.9, 70.5, 70.1, 63.5, 57.6, 22.0, 21.9, 21.7, 20.1.
LRMS (FAB) for C33H40Br2N4O8: calcd. (M+2): 780.12, found (M+2): 780.6.
Pyrazolopyridazine derivative 13i
N N
NN
CO2CO2
iPr
H
F
F
CO2
iPr
O2CF
F
iPr
iPr
13i
Yellow viscous oil.
IR (film) ννννmax: 3070, 2987, 2944, 1732, 1716, 1620, 1591, 1469, 1377, 1304, 1221, 1177, 1100, 1002,
919, 788, 735 cm-1
.
1H NMR δ: 7.29-7.22 (m, 2H), 6.92-6.83 (m, 4H), 6.03 (s, 1H), 5.84 (d, J = 5.8 Hz, 1H), 5.08-4.88 (m,
4H), 4.79-4.76 (m, 2H), 1.35-1.19 (m, 24H).
13C NMR δ: 163.0, 160.2, 159.9, 156.3, 130.2, 130.0, 129.3, 115.3, 111.8, 111.6, 111.5, 111.3, 71.1,
70.6, 69.7, 60.3, 54.9, 21.9, 21.7, 21.6, 21.4.
LRMS (FAB) for C33H38F4N4O8: calcd. (M+1): 695.26, found: 695.1.
Pyrazolopyridazine derivative 13j
NN
N N
O2CCO2
iPr
O2C CO2iPr
H
F3C
iPr
iPr
13j
Colorless viscous oil
IR (film) ννννmax: 2987, 2943, 1730, 1714, 1624, 1465, 1326, 1104, 1017, 919, 841 cm-1
.
1H NMR δ: 7.75 (d, J = 7.9 Hz, 1H), 7.58-7.57 (m, 4H), 7.38-7.26 (m, 4H), 5.99 (bs, 2H), 5.09-4.96 (m,
4H), 4.71 (bs, 1H), 4.39 (s, 1H), 1.35- 1.08 (m, 24 H).
13C NMR δ: 157.1, 154.7, 154.2, 152.5, 150.2, 143.1, 140.9, 138.7, 136.0, 131.1, 130.7, 130.3, 129.6,
128.5, 128.1, 127.8, 126.5, 125.9, 122.4, 72.2, 71.1, 70.1, 67.1, 61.6, 55.6, 22.2, 22.1, 22.0, 21.9.
LRMS (FAB) for C34H41F3N4O8: calcd. (M+1): 691.29, found: 691.1.
Pyrazolopyridazine derivative 13k
![Page 14: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/14.jpg)
NN
N N
CO2Et
EtO2C CO2Et
H
FFEtO2C
13k
Yellow viscous oil
IR (Film) ννννmax: 3012, 2935, 1724, 1616, 1589, 1490, 1415, 1377, 1315, 1222, 1099, 1045, 927, 765 cm-1
.
1H NMR δ: 7.47 (bs, 2H), 7.36-7.23 (m, 2H), 7.14-7.01 (m, 4H), 6.19 (s, 1H), 6.00 (s, 1H), 4.35-4.15 (m,
8H), 3.90 (bs, 2H), 1.30-1.21 (m, 12H).
13C NMR δ: 162.4, 159.1, 156.7, 154.9, 135.0, 129.7, 129.6, 129.5, 127.7, 125.6, 123.9, 115.8, 115.5,
114.9, 63.9, 62.9, 62.2, 14.4, 14.3, 14.2.
LRMS (FAB) for C29H32F2N4O8: calcd. (M+): 602.22, found: 602.9.
Pyrazolopyridazine derivative 13l
NN
N N
CO2Et
EtO2C CO2Et
H
F3CF3CEtO2C
13l
Yellow viscous oil
IR (Film) ννννmax: 2983, 2937, 1734, 1712, 1608, 1583, 1452, 1398, 1373, 1313, 1228, 1163, 1126, 1058,
1039, 866, 842, 769, 711, 657, 603 cm-1
.
1H NMR δ: 7.72-7.35 (m, 8H), 6.78 (bs, 1H), 5.91 (bs, 1H), 5.62 (bs, 1H), 4.38-4.23 (m, 8H), 4.01 (bs,
1H), 1.36-1.27 (m, 12H).
13C NMR δ: 156.9, 155.6, 151.5, 150.8, 139.9, 136.9, 132.9, 132.2, 128.6, 128.3, 127.8, 127.4, 126.8,
126.4, 122.7, 108.9, 64.3, 64.1, 62.9, 62.6, 55.8, 14.6, 14.5, 14.3.
LRMS (FAB) for C31H32F6N4O8: calcd. (M+1): 703.21, found: 703.5.
Pyrazolopyridazine derivative 13m
NN
N N
CO2
tBu
O2C CO2
tBu
H
F3CF3CO2C
13m
tBu
tBu
White crystalline solid, Mp. 212-214°C
IR (Film) ννννmax: 2980, 1737, 1716, 1454, 1392, 1369, 1313, 1251, 1157, 1128, 1035, 854, 767 cm-1
.
1H NMR δ: 7.77-7.33 (m, 4H), 6.86 (s, 1H), 5.81 (s, 1H), 5.49 (s, 1H), 3.90 (s, 1H), 1.53-1.49 (m, 27H),
1.33 (s, 9H).
![Page 15: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/15.jpg)
13C NMR δ:155.2, 150.0, 140.9, 140.3, 137.1, 132.7, 131.6, 128.6, 127.7, 127.3, 126.2, 122.6, 107.5,
82.9, 82.3, 81.5, 69.6, 59.4, 55.2, 53.3, 28.2, 28.0.
Vinyl pyrazoline derivative 15
NN
O2C CO2
iPri
Pr
S
15
Yellow viscous oil
IR (Film) ννννmax: 2982, 2934, 1713, 1601, 1460, 1367, 1299, 1177, 1100, 905, 759, 696.cm-1
.
1H NMR δ: 7.45 (d, J = 6.9 Hz, 1H), 7.34-7.19 (m, 4H), 7.02-6.93 (m, 3H), 6.04 (bs, 1H), 5.74 (bs, 1H),
5.07-4.91 (m, 2H), 1.34-1.13 (m, 12H).
13C NMR δ: 155.5, 143.2, 142.6, 136.3, 133.1, 128.9, 128.6, 126.9, 125.5, 124.9, 119.2, 109.9, 70.6,
70.4, 61.2, 22.7, 21.8, 21.7, 21.6.
LRMS (FAB) for C23H26N2O4S: calcd. (M+1): 427.16, found: 427.0.
Indazole derivative 17
NN
N
H
OO
O2CCO2
iPr
F3CF3C
iPr
17
Yellow viscous oil
IR (Film) ννννmax: 3231, 3080, 2987, 2939, 1748, 1732, 1716, 1698, 1649, 1537, 1533, 1372, 1304, 1158,
1105, 1036, 764 cm-1
.
1H NMR δ: 8.56 (s, 1H), 7.74-7.26 (m, 8H), 6.54 (s, 1H), 6.03 (s, 1H), 5.17-5.09 (m, 1H), 5.01-4.99 (m,
1H), 3.89 (bs, 1H), 3.62 (bs, 1H), 3.32 (m, 1H), 2.84 (bs, 1H), 1.37-1.25 (m, 12H).
13C NMR δ: 176.6, 175.8, 156.2, 153.7, 139.5, 137.6, 132.5, 131.6, 129.4, 128.8, 127.5, 126.3, 126.2,
125.9, 114.1, 106.9, 71.3, 71.2, 63.1, 59.3, 47.1, 41.9, 36.1, 22.2, 21.8, 21.7.
LRMS (FAB) for C31H29F6N3O6: calcd. (M+Na): 676.20, found: 676.2.
![Page 16: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/16.jpg)
Spectra of Compounds
1H NMR Spectrum of Functionalized pyrazoline 6a
N N
CO2iPr
O2C
Br
F6a
iPr
![Page 17: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/17.jpg)
13C NMR Spectrum of Functionalized pyrazoline 6a
N N
CO2iPr
O2C
Br
F6a
iPr
![Page 18: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/18.jpg)
1H NMR Spectrum of Functionalized pyrazoline 6b
N N
CO2iPr
O2C
Cl
NO2
iPr
6b
![Page 19: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/19.jpg)
13C NMR Spectrum of Functionalized pyrazoline 6b
N N
CO2iPr
O2C
Cl
NO2
iPr
6b
![Page 20: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/20.jpg)
1H NMR Spectrum of Functionalized pyrazoline 6c
N N
CO2
iPr
O2C
OMe
MeO
iPr
6c
![Page 21: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/21.jpg)
13C NMR Spectrum of Functionalized pyrazoline 6c
N N
CO2
iPr
O2C
OMe
MeO
iPr
6c
![Page 22: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/22.jpg)
1H NMR Spectrum of Functionalized pyrazoline 6d
N N
CO2
iPr
O2C
Cl
iPr
6d
![Page 23: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/23.jpg)
13C NMR Spectrum of Functionalized pyrazoline 6d
N N
CO2
iPr
O2C
Cl
iPr
6d
![Page 24: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/24.jpg)
1H NMR Spectrum of Functionalized pyrazoline 6j
N N
CO2EtEtO2C
Cl
6j
![Page 25: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/25.jpg)
13C NMR Spectrum of Functionalized pyrazoline 6j
N N
CO2EtEtO2C
Cl
6j
![Page 26: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/26.jpg)
1H NMR Spectrum of polycyclic pyrazoline 11
NN
O2CCO2
iPr
Ph
iPr
11
![Page 27: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/27.jpg)
13C NMR Spectrum of polycyclic pyrazoline 11
NN
O2CCO2
iPr
Ph
iPr
11
![Page 28: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/28.jpg)
1H NMR Spectrum Pyrazolopyridazine derivative 13a
NN
N N
O2CCO2
iPr
O2C CO2
iPr
H
iPr
iPr
S
13a
![Page 29: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/29.jpg)
13C NMR Spectrum of Pyrazolopyridazine derivative 13a
NN
N N
O2CCO2
iPr
O2C CO2
iPr
H
iPr
iPr
S
13a
![Page 30: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/30.jpg)
1H NMR Spectrum Pyrazolopyridazine derivative 13b
NN
N N
O2CCO2
iPr
O2C CO2iPr
H
iPr
iPr
13b
F3C
F3C
![Page 31: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/31.jpg)
13C NMR Spectrum of Pyrazolopyridazine derivative 13b
NN
N N
O2CCO2
iPr
O2C CO2iPr
H
iPr
iPr
13b
F3C
F3C
![Page 32: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/32.jpg)
1H NMR Spectrum of Pyrazolopyridazine derivative 13c
NN
N N
O2CCO2
iPr
O2C CO2
iPr
H
FF
iPr
iPr
13c
![Page 33: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/33.jpg)
13C NMR Spectrum of Pyrazolopyridazine derivative 13c
NN
N N
O2CCO2
iPr
O2C CO2
iPr
H
FF
iPr
iPr
13c
![Page 34: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/34.jpg)
1H NMR Spectrum of Pyrazolopyridazine derivative 13d
NN
N N
O2C
CO2
iPr
O2C CO2iPr
H
iPr
iPr
13d
F
![Page 35: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/35.jpg)
13C NMR Spectrum of Pyrazolopyridazine derivative 13d
NN
N N
O2C
CO2
iPr
O2C CO2
iPr
H
iPr
iPr
13d
F
![Page 36: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/36.jpg)
1H NMR Spectrum Vinyl pyrazoline derivative 15
NN
O2C CO2iPri
Pr
S
15
![Page 37: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/37.jpg)
13C NMR Spectrum Vinyl pyrazoline derivative 15
NN
O2C CO2iPri
Pr
S
15
![Page 38: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/38.jpg)
1H NMR Spectrum of Indazole derivative 17
NN
N
H
OO
O2CCO2
iPr
F3CF3C
iPr
17
![Page 39: 69451 Weinheim, Germany - Wiley- · PDF fileCl NO2 iPr 6b White crystalline ... 394.1893, found: 394.1843. Functionalized Pyrazoline 6h N N CO2 iPr O2C Cl 6h iPr ... 7.78 (d, J = 8.2](https://reader031.vdocument.in/reader031/viewer/2022030422/5aa9aba27f8b9a72188d3488/html5/thumbnails/39.jpg)
13C NMR Spectrum of Indazole derivative 17
NN
N
H
OO
O2CCO2
iPr
F3CF3C
iPr
17