Supporting information · 2019-08-26 · S1 Supporting information Pyrazolofused 4-azafluorenones...
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S1 Supporting information Pyrazolofused 4-azafluorenones as key reagents for the synthesis of fluorescent dicyanovinilydene-substituted derivatives Jessica Orrego-Hernández, a Carolina Lizarazo, a Justo Cobo, b and Jaime Portilla* ,a a Bioorganic Compounds Research Group, Department of Chemistry, Universidad de los Andes, Carrera 1 No. 18A-10, Bogotá, Colombia b Departamento de Química Orgánica e Inorgánica, Universidad de Jaén, 23071 Jaén, Spain *E-mail: [email protected]; Tel: +57 1 3394949. Ext. 2080 Contents 1. Overview of Substrates, Intermediates and Products Numbering……………………….........S2 2. Experimental procedures and characterization data………………………………………......S4 3. Supplementary Analytical Data (Identification of intermediate 5a).………….….….………S16 4. Photophysical studies……………………………………………………………..…...….....S17 5. Computational calculations………………………….………………...…………..….…......S18 6. Fluorescent chemosensors 7a-d for detection of cyanide…………………………...….........S23 7. Copies of NMR spectra……………………………………………………...………….…...S25 8. ORTEP Drawing for Structure 7b……………………...........................................................S54 9. HRMS analysis data of the final products 7a-d……………………………………………..S55 10. References………………………………………………………………………………S60 Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2019
Transcript of Supporting information · 2019-08-26 · S1 Supporting information Pyrazolofused 4-azafluorenones...
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Supporting information
Pyrazolofused 4-azafluorenones as key reagents for the synthesis of fluorescent
dicyanovinilydene-substituted derivatives
Jessica Orrego-Hernández,a Carolina Lizarazo,a Justo Cobo,b and Jaime Portilla*,a
a Bioorganic Compounds Research Group, Department of Chemistry, Universidad de los Andes,
Carrera 1 No. 18A-10, Bogotá, Colombia
bDepartamento de Química Orgánica e Inorgánica, Universidad de Jaén, 23071 Jaén, Spain
*E-mail: [email protected]; Tel: +57 1 3394949. Ext. 2080
Contents
1. Overview of Substrates, Intermediates and Products Numbering……………………….........S2
2. Experimental procedures and characterization data………………………………………......S4
3. Supplementary Analytical Data (Identification of intermediate 5a).………….….….………S16
4. Photophysical studies……………………………………………………………..…...….....S17
5. Computational calculations………………………….………………...…………..….…......S18
6. Fluorescent chemosensors 7a-d for detection of cyanide…………………………...….........S23
7. Copies of NMR spectra……………………………………………………...………….…...S25
8. ORTEP Drawing for Structure 7b……………………...........................................................S54
9. HRMS analysis data of the final products 7a-d……………………………………………..S55
10. References………………………………………………………………………………S60
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2019
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1. Overview of Substrates Intermediates and Products Numbering
1.1. Substrates 1, 2a-h, 3a-e, and intermediates 6h and 5a
Indan-1,3-dione 1, 4-R-benzaldehydes 2a-h and 3-alkyl-5-amino-1-aryl-1H-pyrazoles 3a-e
1.2. Products 4a-x and final products 7a-d
4-Aryl-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-ones 4a-h and 4-Aryl-3-
(tert-butyl)-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-ones 4i-o.
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Aryl-3-(tert-butyl)-1-(4-chlorophenyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-ones 4p-v, 1-
(4-chlorophenyl)-3-methyl-4-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one 4w 3-(tert-
butyl)-1-(4-nitrophenyl)-4-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one 4x, and 2-(4-
aryl-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-ylidene)malononitrile 7a-d.
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2. Experimental procedures and characterization data
2.1. General information. All reagents were purchased from commercial sources and used without
further purification, unless otherwise noted. All starting materials were weighed and handled in
air at room temperature. The reactions were monitored by TLC and were visualized by UV (254
nm). Column and Flash chromatography was performed on silica gel (230-400 mesh or 70-230
mesh, respectively). All reactions under microwave (MW) irradiation were performed using a
sealed reaction vessel (10 mL, max pressure = 300 psi) containing a Teflon coated stirring bar
(obtained from CEM). MW-assisted reactions were performed in a CEM Discover focused
microwave (ν = 2.45 GHz) reactor, equipped with a built-in pressure measurement sensor, and
with a vertically focused IR temperature sensor; controlled temperature, power, and time settings
were used for all reactions. NMR spectra were recorded at 400 MHz (1H) and 100 MHz (13C) at
298 K using tetramethylsilane (0 ppm) as the internal reference. NMR spectroscopic data were
recorded in CDCl3 and DMSO-d6 using as internal standards the residual non-deuterated signal for
1H NMR and the deuterated solvent signal for 13C NMR spectroscopy. DEPT spectra were used
for the assignment of carbon signals. Chemical shifts (δ) are given in ppm and coupling constants
(J) are given in Hz. The following abbreviations are used for multiplicities: s = singlet, d = doublet,
t = triplet, and m = multiplet. Melting points were collected using a Stuart SMP10 melting point
apparatus, and the acquired data are uncorrected. The mass spectra were recorded on a Hewlett
Packard HP Engine-5989 spectrometer (equipped with a direct inlet probe) and operating at 70
eV, and the High Resolution Mass Spectra (HRMS) by electron impact were recorded on a
Micromass AutoSpec-Ultima, magnetic sector mass spectrometer at 70 eV. HPLC-HRMS data
were obtained on an Agilent Technologies Q-TOF 6520 spectrometer via an electrospray
ionization (ESI, 4000 V). X-ray diffraction intensities were collected on a Bruker D8 Venture
diffractometer. Crystallographic data were recorded on a diffractometer using graphite-
monochromated Mo Kα radiation (λ= 0.71073 Å). Structures were solved using an interactive
algorithm,1 subsequently completed by a difference Fourier map, and refined using the program
SHELXL20142 and the graphic material was prepared using the Mercury 3.10 software.3 The
electronic absorption spectra were measured on Varian Cary 100 Conc (Agilent Technologies)
spectrophotometer in a quartz cuvette having a path length of 1 cm. The fluorescence emission
spectra were recorded by using a CARY Eclipse (Agilent Technologies) fluorescence
spectrophotometer in a quartz cell (1 cm path length). UV-vis and fluorescence measurements
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were performed at room temperature (20 °C). For fluorescence measurements, both the excitation
and emission slit widths were 5 nm.
2.2. Synthesis and characterization
2.2.1. General Procedure for the synthesis of 3-alkyl-1,4-bis(aryl)indeno[1,2-b]pirazolo[4,3-
e]pyridin-5(1H)-ones 4a-x and 2-(4-dimethylaminobenzylidene)indene-1,3(2H)-dione (6h). A
mixture of equimolar quantities (0.25 mmol of each component) of indan-1,3-dione (1, 1, 37 mg),
4-R-benzaldehyde 2, and 3-alkyl-5-amino-1H-pyrazole 3 in water:triethylamine (0.7 ml, 15:1 v/v)
was placed in a reaction tube of a CEM Discover, containing a magnetic stirring bar. The tube was
sealed with a plastic MW septum and was irradiated at 80 °C (100 W, monitored by an IR
temperature sensor) and maintained at this temperature for 10-25 min. The reaction mixture was
cooled to 50 °C by airflow and then was partitioned between dichloromethane and water. The
organic layer was washed with water and dried over anhydrous sodium sulfate. Subsequently,
solvent was removed by rotary evaporation under reduced pressure and the residue was purified
by flash chromatography on silica gel (eluent: CH2Cl2) to give the expected indenopirazolopyridin-
5-ones 4a-x and the intermediate 6h.
3-Methyl-1,4-diphenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4a). By following the
general procedure for 15 min, 4a was obtained as yellow crystals (81.3 mg, 84%). Mp 225-227 °C
(Lit.4 220-221 °C). 1H NMR (CDCl3): δ = 2.05 (s, 3H), 7.35 (t, J = 7.5 Hz, 1H), 7.40-7.47 (m, 3H),
7.50-7.62 (m, 7H), 7.96 (d, J = 7.4 Hz, 1H), 8.31 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3): δ = 14.8
(CH3), 115.6 (C), 120.0 (C), 121.4 (CH), 121.5 (CH), 123.4 (CH), 126.3 (CH), 128.0 (CH), 128.6
(CH), 129.0 (CH), 129.2 (CH), 131.4 (CH), 132.8 (C), 134.6 (CH), 137.4 (C), 139.0 (C), 142.4
(C), 145.8 (C), 145.9 (C), 152.8 (C), 165.1 (C), 189.9 (C); MS (EI) m/z 387 (M+, 100%), 386 45),
372 (5), 345 (5). HRMS (IE) m/z calcd. for C26H17N3O [M]+: 387.1372; found 387.1366.
4-(4-Methoxyphenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4b). By
following the general procedure for 15 min, 4b was obtained as yellow crystals (77.3 mg, 74%).
Mp 244-246 °C (Lit.4 224-225 °C). 1H NMR (CDCl3): δ = 2.12 (s, 3H), 3.91 (s, 3H), 7.06 (d, J =
8.9 Hz, 2H), 7.34 (t, J = 7.4 Hz, 1H), 7.41 (m, 3H), 7.52-7.62 (m, 4H), 7.95 (d, J = 7.5 Hz, 1H),
8.31 (d, J = 8.8 Hz, 2H); 13C NMR (CDCl3): δ = 15.2 (CH3), 55.3 (CH3), 113.4 (CH), 115.8 (C),
120.0 (C), 121.4 (CH), 121.6 (CH), 123.4 (CH), 124.6 (C), 129.0 (CH), 130.5 (CH), 131.4 (CH),
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134.6 (CH), 137.4 (C), 139.0 (C), 142.4 (C), 146.0 (C), 146.1 (C), 152.8 (C), 160.5 (C), 165.2 (C),
190.0 (C); MS (EI) m/z 417 (M+, 100%), 402 (4), 386 (15). HRMS (IE) m/z calcd. for C27H19N3O2
[M]+: 417.1477; found 417.1476.
3-Methyl-1-phenyl-4-(4-(trifluoromethyl)phenyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one
(4c). By following the general procedure for 10 min, 4c was obtained as white powder (104.8 mg,
92%). Mp 265-267 °C (Lit.4 280-281 °C). 1H NMR (CDCl3): δ = 2.05 (s, 3H), 7.37 (t, J = 7.4 Hz,
1H), 7.45 (t, J = 7.4 Hz, 1H), 7.54-7.63 (m, 6H), 7.80 (d, J = 8.1 Hz, 2H), 7.99 (d, J = 7.3 Hz, 1H),
8.30 (d, J = 8.6 Hz, 2H); 13C NMR (CDCl3): δ = 14.9 (CH3), 115.1 (C), 119.9, 122.7, 125.4, 128.1
(CF3, q, J = 367.5 Hz), 120.0 (C), 121.6 (CH), 121.7 (CH), 123.6 (CH), 125.1 (CH, q, J = 3.7 Hz),
126.6 (CH), 129.1 (CH), 129.2 (CH), 130.8, 131.2, 131.5, 131.8 (C-CF3, q, J = 33.7 Hz), 131.7
(CH), 135.0 (CH), 136.6 (C), 137.3 (C), 138.8 (C), 143.8 (C), 145.5 (C), 152.8 (C), 165.0 (C),
189.8 (C); MS (EI) m/z 455 (M+, 100%), 440 (6), 413 (6), 386 (5). HRMS (IE) m/z calcd. for
C27H16F3N3O [M]+: 455.1245; found 455.1241.
4-(4-(Dimethylamino)phenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one
(4d). By following the general procedure for 25 min, 4d was obtained as orange crystals (90.4 mg,
84%). Mp 223-225 °C (Lit.4 242-244 °C). 1H NMR (CDCl3): δ = 2.22 (s, 3H), 3.07 (s, 6H), 6.83
(d, J = 8.9 Hz, 2H), 7.33 (t, J = 7.5 Hz, 1H), 7.40 (m, 3H), 7.55 (m, 3H), 7.62 (d, J = 7.4 Hz, 1H),
7.95 (d, J = 7.4 Hz, 1H), 8.32 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3): δ = 15.6 (CH3), 40.3 (CH3),
111.0 (CH), 115.8 (C), 119.4 (C), 119.8 (C), 121.2 (CH), 121.6 (CH), 123.3 (CH), 126.2 (CH),
129.0 (CH), 130.8 (CH), 131.2 (CH),134.4 (CH), 137.6 (C), 139.1 (C), 142.4 (C), 146.2 (C), 147.4
(C), 151.1 (C), 153.0 (C), 165.4 (C), 190.1 (C); MS (EI) m/z 430 (M+, 100%), 415 (5), 386 (7).
HRMS (IE) m/z calcd. for C28H22N4O [M]+: 430.1778; found 430.1794.
3-Methyl-1-phenyl-4-(p-tolyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4e). By following
the general procedure for 15 min, 4e was obtained as pale-yellow crystals (78.3 mg, 78%). Mp
300 °C (Lit.4 217-218 °C). 1H NMR (CDCl3): δ = 2.09 (s, 3H), 2.49 (s, 3H), 7.32-7.36 (m, 5H),
7.42 (t, J = 7.5 Hz, 1H), 7.53-7.62 (m, 4H), 7.96 (d, J = 7.4 Hz, 1H), 8.31 (d, J = 8.6 Hz, 2H); 13C
NMR (CDCl3): δ = 15.0 (CH3), 21.6 (CH3), 115.7 (C), 120.1 (C), 121.4 (CH), 121.6 (CH), 123.4
(CH), 126.3 (CH), 128.7 (CH), 129.0 (CH), 129.7 (C), 131.4 (CH), 134.6 (CH), 137.4 (C), 139.0
(C), 139.1 (C), 142.4 (C), 146.0 (C), 146.3 (C), 152.8 (C), 165.1 (C), 189.9 (C); MS (EI) m/z 401
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(M+, 100%), 386 (41), 324 (8). HRMS (IE) m/z calcd. for C27H19N3O [M]+: 401.1528; found
401.1517.
4-(4-Chlorophenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4f). By
following the general procedure for 10 min, 4f was obtained as yellow crystals (93.9 mg, 89%).
Mp 268-270 °C (Lit.4 269-270 °C). 1H NMR (CDCl3): δ = 2.08 (s, 3H), 7.35 (t, J = 7.4 Hz, 1H),
7.38-7.44 (m, 3H), 7.50-7.61 (m, 6H), 7.95 (d, J = 7.4 Hz, 1H), 8.29 (d, J = 8.9 Hz, 2H); 13C NMR
(CDCl3): δ = 15.0 (CH3), 115.3 (C), 120.0 (C), 121.5 (CH), 121.6 (CH), 123.5 (CH), 126.5 (CH),
128.3 (CH), 129.1 (CH), 130.2 (CH), 131.1 (C), 131.6 (CH), 134.8 (CH), 135.4 (C), 137.3 (C),
139.0 (C), 142.3 (C), 144.4 (C), 145.6 (C), 152.7 (C), 165.0 (C), 189.8 (C); MS (EI) m/z 423/421
(M+, 37/100%), 406 (5), 386 (10). HRMS (IE) m/z calcd. for C26H16ClN3O [M]+: 421.0982; found
421.0978.
4-(4-Bromophenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4g). By
following the general procedure for 10 min, 4g was obtained as pale-yellow crystals (107.3 mg,
92%). Mp 264-265 °C (Lit.4 274-276 °C). 1H NMR (CDCl3): δ = 2.10 (s, 3H), 7.33-7.38 (m, 3H),
7.50-7.64 (m, 5H), 7.67 (d, J = 8.9 Hz, 2H), 7.98 (d, J = 7.4 Hz, 1H), 8.29 (d, J = 8.9 Hz, 2H); 13C
NMR (CDCl3): δ = 15.0 (CH3), 115.2 (C), 119.9 (C), 121.5 (CH), 121.6 (CH), 123.6 (CH), 123.7
(C), 126.5 (CH), 129.1 (CH), 130.4 (CH), 131.3 (CH), 134.8 (CH), 135.8 (C), 138.9 (C), 142.4
(C), 144.3 (C), 145.6 (C), 152.8 (C), 165.1 (C), 189.8 (C); MS (EI) m/z 467/465 (M+, 97/100%),
450 (5), 386 (15). HRMS (IE) m/z calcd. for C26H16BrN3O [M]+: 465.0477; found 465.0494.
3-Methyl-4-(4-nitrophenyl)-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4h). By
following the general procedure for 10 min, 4h was obtained as pale-yellow crystals (77.8 mg,
72%). Mp 245-246 °C (Lit.4 >300 °C). 1H NMR (CDCl3): δ = 2.05 (s, 3H), 7.38 (t, J = 7.4 Hz,
1H), 7.46 (t, J = 7.4 Hz, 1H), 7.57 (t, J = 7.6 Hz, 1H), 7.64 (m, 4H), 8.00 (d, J = 7.9 Hz, 1H), 8.29
(d, J = 7.6 Hz, 2H), 8.41 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3): δ = 14.9 (CH3), 114.7 (C), 119.9
(C), 121.7 (CH), 123.3 (CH), 123.7 (CH), 126.7 (CH), 131.8 (CH), 135.1 (CH), 137.2 (C), 138.7
(C), 139.6 (C), 142.3 (C), 142.5 (C), 145.1 (C), 148.4 (C), 152.8 (C), 165.0 (C), 189.7 (C); MS
(EI) m/z 432 (M+, 100%), 417 (3), 386 (9), 345 (5). HRMS (IE) m/z calcd. for C26H16N4O3 [M]+:
432.1222; found 432.1231.
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3-(tert-Butyl)-1,4-diphenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4i). By following the
general procedure for 15 min, 4i was obtained as yellow crystals (83.8 mg, 78%). Mp 230-232 °C;
1H NMR (CDCl3): δ = 1.15 (s, 9H), 7.36 (m, 3H), 7.42 (t, J = 7.4 Hz, 1H), 7.49-7.61 (m, 7H), 7.99
(d, J = 7.4 Hz, 1H), 8.37 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3): δ = 30.2 (CH3), 34.2 (C), 114.8
(C), 121.0 (C), 121.3 (CH), 122.0 (CH), 123.4 (CH), 126.1 (CH), 127.9 (CH), 128.7 (CH), 128.8
(CH), 129.0 (CH), 131.4 (CH), 134.6 (CH), 136.2 (C), 137.6 (C), 139.2 (C), 142.1 (C), 146.2 (C),
153.6 (C), 157.0 (C), 163.9 (C), 190.0 (C); MS (EI) m/z 429 (M+, 73%), 414 (100), 399 (23), 384
(24). HRMS (IE) m/z calcd. for C29H23N3O [M]+: 429.1841; found 429.1843.
3-(tert-Butyl)-1-phenyl-4-(p-tolyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4j). By
following the general procedure for 15 min, 4j was obtained as pale-yellow crystals (85.4 mg,
77%). Mp 207-208 °C; 1H NMR (CDCl3): δ = 1.16 (s, 9H), 2.50 (s, 3H), 7.24 (d, J = 8.6 Hz, 2H),
7.32-7.39 (m, 3H), 7.41 (t, J = 7.4 Hz, 1H), 7.54-7.61 (m, 4H), 7.98 (d, J = 7.4 Hz, 1H), 8.37 (d, J
= 8.6 Hz, 2H); 13C NMR (CDCl3): δ = 21.6 (CH3), 30.3 (CH3), 34.3 (C), 115.1 (C), 121.2 (C),
121.3 (CH), 122.0 (CH), 123.4 (CH), 126.3 (CH), 128.5 (CH), 128.6 (CH), 128.9 (CH), 131.4
(CH), 133.2 (C), 134.6 (CH), 137.6 (C), 138.6 (C), 139.2 (C), 142.1 (C), 146.6 (C), 153.5 (C),
157.1 (C), 163.9 (C), 190.1 (C); MS (EI) m/z 443 (M+, 70%), 428 (100), 413 (25), 398 (28). HRMS
(IE) m/z calcd. for C30H25N3O [M]+: 443.1998; found 443.2004.
3-(tert-Butyl)-4-(4-chlorophenyl)-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4k).
By following the general procedure for 10 min, 4k was obtained as yellow crystals (96.1 mg, 83%).
Mp 235-237 °C; 1H NMR (CDCl3): δ = 1.16 (s, 9H), 7.30 (d, J = 8.5 Hz, 2H), 7.36 (t, J = 7.5 Hz,
1H), 7.42 (t, J = 7.4 Hz, 1H), 7.51 (d, J = 8.6 Hz, 1H), 7.54-7.62 (m, 4H), 7.98 (d, J = 7.4 Hz, 1H),
8.36 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3): δ = 30.4 (CH3), 34.2 (C), 114.6 (C), 120.9 (C), 121.4
(CH), 122.0 (CH), 123.5 (CH), 126.4 (CH), 128.3 (CH), 129.0 (CH), 130.2 (CH), 131.6 (CH),
134.6 (C), 134.8 (CH), 135.0 (C), 137.5 (C), 139.1 (C), 142.0 (C), 144.7 (C), 153.5 (C), 156.8 (C),
163.8 (C), 190.0 (C); MS (EI) m/z 465/463 (M+, 23/65%), 450/448 (36/100), 435/433 (6/18).
HRMS (IE) m/z calcd. for C29H22ClN3O [M]+: 463.1451; found 463.1458.
4-(4-Bromophenyl)-3-(tert-butyl)-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4l).
By following the general procedure for 10 min, 4l was obtained as yellow crystals (119.5 mg,
94%). Mp 233-235 °C; 1H NMR (CDCl3): δ = 1.16 (s, 9H), 7.24 (d, J = 8.1 Hz, 2H), 7.36 (t, J =
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7.5 Hz, 1H), 7.42 (t, J = 7.4 Hz, 1H), 7.54-7.61 (m, 4H), 7.65 (d, J = 8.2 Hz, 1H), 7.97 (d, J = 7.4
Hz, 1H), 8.35 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3): δ = 30.4 (CH3), 34.2 (C), 114.5 (C), 121.4
(C), 122.0 (CH), 123.1 (C), 123.5 (CH), 126.4 (CH), 129.0 (CH), 130.5 (CH), 131.2 (CH), 131.6
(CH), 134.8 (CH), 135.1 (C), 137.4 (C), 139.1 (C), 142.0 (C), 144.6 (C), 153.5 (C), 156.8 (C),
163.8 (C), 189.9 (C); MS (EI) m/z 509/507 (M+, 79/69%), 494/492 (100/87), 398 (50). HRMS
(IE) m/z calcd. for C29H22BrN3O [M]+: 507.0946; found 507.0945.
3-(tert-Butyl)-1-phenyl-4-(4-(trifluoromethyl)phenyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-
5(1H)-one (4m). By following the general procedure for 10 min, 4m was obtained as pale-yellow
crystals (112.0 mg, 90%). Mp 250-252 °C; 1H NMR (CDCl3): δ = 1.13 (s, 9H), 7.38 (t, J = 7.4 Hz,
1H), 7.43 (t, J = 7.5 Hz, 1H), 7.51 (d, J = 8.0 Hz, 1H), 7.56-7.62 (m, 4H), 7.79 (d, J = 7.9 Hz, 2H),
7.99 (d, J = 7.4 Hz, 1H), 8.36 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3): δ = 30.3 (CH3), 34.2 (C),
114.3 (C), 120.7 (C), 121.5 (CH), 122.1 (CH), 123.5 (CH), 125.0 (CH, q, J = 3.7 Hz,), 126.5 (CH),
129.0 (CH), 129.4 (CH), 130.6, 131.0, 131.3, 131.6 (C-CF3, q, J = 33.0 Hz), 131.7 (CH), 134.9
(CH), 137.4 (C), 139.1 (C), 140.1 (C), 142.0 (C), 144.2 (C), 153.5 (C), 156.7 (C), 163.8 (C), 189.89
(C); MS (EI) m/z 497 (M+, 58%), 482 (100), 455 (18). HRMS (IE) m/z calcd. for C30H22F3N3O
[M]+: 497.1715; found 497.1718.
3-(tert-Butyl)-4-(4-methoxyphenyl)-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one
(4n). By following the general procedure for 10 min, 4n was obtained as orange crystals (89.5 mg,
78%). Mp 228-230 °C; 1H NMR (CDCl3): δ = 1.17 (s, 9H), 3.92 (s, 3H), 7.05 (d, J = 8.7 Hz, 2H),
7.27 (d, J = 8.7 Hz, 2H), 7.35 (t, J = 7.4 Hz, 1H), 7.54-7.61 (m, 4H), 7.98 (d, J = 7.3 Hz, 1H), 8.37
(d, J = 8.7 Hz, 2H); 13C NMR (CDCl3): δ = 30.3 (CH3), 34.3 (C), 55.3 (CH3), 113.4 (CH), 115.3
(C), 121.3 (CH), 121.4 (C), 122.0 (CH), 123.4 (CH), 126.3 (CH), 128.3 (C), 129.0 (CH), 130.0
(CH), 131.4 (CH), 134.6 (CH), 137.6 (C), 139.2 (C), 142.1 (C), 146.4 (C), 153.6 (C), 157.1 (C),
160.0 (C), 163.9 (C), 190.2 (C); MS (EI) m/z 459 (M+, 79%), 444 (100), 429 (36), 414 (21). HRMS
(IE) m/z calcd. for C30H25N3O2 [M]+: 459.1947; found 459.1931.
3-(tert-Butyl)-4-(4-nitrophenyl)-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4o).
By following the general procedure for 10 min, 4o was obtained as pale-orange crystals (89.0 mg,
75%). Mp 270-272 °C; 1H NMR (CDCl3): δ = 1.14 (s, 9H), 7.39 (t, J = 7.4 Hz, 1H), 7.45 (t, J =
7.5 Hz, 1H), 7.56-764 (m, 6H), 8.00 (d, J = 7.4 Hz, 1H), 8.35 (d, J = 8.6 Hz, 2H), 8.40 (d, J = 8.7
S10
Hz, 2H); 13C NMR (CDCl3): δ = 30.4 (CH3), 34.2 (C), 113.8 (C), 120.5 (C), 121.6 (CH), 122.1
(CH), 123.3 (CH), 123.6 (CH), 126.7 (CH), 129.0 (CH), 130.2 (CH), 131.8 (CH), 135.0 (CH),
137.3 (C), 139.0 (C), 142.0 (C), 143.0 (C), 143.2 (C), 148.2 (C), 156.5 (C), 163.8 (C), 189.8 (C);
MS (EI) m/z 474 (M+, 53%), 459 (100), 432 (15), 398 11). HRMS (IE) m/z calcd. for C29H22N4O3
[M]+: 474.1692; found 474.1696.
3-(tert-Butyl)-1-(4-chlorophenyl)-4-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4p).
By following the general procedure for 15 min, 4p was obtained as yellow crystals (99.7 mg, 86%).
Mp 233-235 °C (Lit.5 237-238 °C); 1H NMR (CDCl3): δ = 1.14 (s, 9H), 7.35 (d, J = 8.7 Hz, 2H),
7.43 (t, J = 7.5 Hz, 1H), 7.49-762 (m, 7H), 7.96 (d, J = 7.5 Hz, 1H) and 8.35 (d, J = 8.9 Hz, 2H);
13C NMR (CDCl3): δ = 30.2 (CH3), 34.3 (C), 115.0 (C), 121.1 (C), 121.3 (CH), 122.9 (CH), 123.5
(CH), 127.9 (CH), 128.7 (CH), 128.9 (CH), 129.0 (CH), 131.5 (C), 131.6 (CH), 134.7 (CH), 136.0
(C), 137.5 (C), 137.8 (C), 141.9 (C), 146.3 (C), 153.5 (C), 157.3 (C), 164.0 (C), 189.8 (C); MS
(EI) m/z 465/463 (M+, 21/71%), 450/448 (37/100), 435/433 (6/14), 420/418 (19/21). HRMS (IE)
m/z calcd. for C29H22ClN3O [M]+: 463.1451; found 463.1469. The characterization data for 4p
match previously reported data by us.5
3-(tert-Butyl)-1-(4-chlorophenyl)-4-(p-tolyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one
(4q). By following the general procedure for 15 min, 4q was obtained as yellow crystals (88.0 mg,
78%). Mp 213-215 °C; 1H NMR (CDCl3): δ = 1.15 (s, 9H), 2.50 (s, 3H), 7.23 (d, J = 8.0 Hz, 2H),
7.33 (d, J = 7.9 Hz, 2H), 7.42 (t, J = 7.4 Hz, 1H), 7.52 (d, J = 9.0 Hz, 2H), 7.56-761 (m, 2H), 7.96
(d, J = 7.5 Hz, 1H), 8.38 (d, J = 8.9 Hz, 2H); 13C NMR (CDCl3): δ = 21.6 (CH3), 30.2 (CH3), 34.3
(C), 115.2 (C), 121.2 (CH), 121.3 (C), 122.9 (CH), 123.5 (CH), 128.5 (CH), 128.6 (CH), 129.0
(CH), 129.7 (C), 131.5 (CH), 133.0 (C), 134.6 (CH), 137.6 (C), 137.8 (C), 138.7 (C), 141.9 (C),
146.7 (C), 153.5 (C), 157.4 (C), 164.0 (C), 189.9 (C); MS (EI) m/z 479/477 (M+, 27/76%), 464/462
(38/100), 449/447 (9/27), 434/432 (27/32). HRMS (IE) m/z calcd. for C30H24ClN3O [M]+:
447.1608; found 447.1605.
3-(tert-Butyl)-1,4-bis(4-chlorophenyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4r). By
following the general procedure for 15 min, 4r was obtained as yellow crystals (99.7 mg, 80%).
Mp 260-262 °C; 1H NMR (CDCl3): δ = 1.15 (s, 9H), 7.29 (d, J = 8.7 Hz, 2H), 7.43 (t, J = 7.5 Hz,
1H), 7.49-762 (m, 6H), 7.97 (d, J = 7.4 Hz, 1H), 8.36 (d, J = 9.0 Hz, 2H); 13C NMR (CDCl3): δ =
30.3 (CH3), 34.3 (C), 114.8 (C), 121.1 (C), 121.4 (CH), 122.9 (CH), 123.6 (CH), 128.3 (CH),
S11
129.0 (CH), 130.2 (CH), 131.6 (CH), 131.7 (C), 134.5 (C), 134.8 (CH), 135.1 (C), 137.4 (C), 137.7
(C), 141.8 (C), 144.8 (C), 153.5 (C), 157.1 (C), 163.9 (C), 189.8 (C); MS (EI) m/z
501/500/499/497 (M+, 7/10/52/68%), 484/483/482/467/457 (75/11/100/13/23). HRMS (IE) m/z
calcd. for C29H21Cl2N3O [M]+: 497.1062; found 497.1056.
4-(4-Bromophenyl)-3-(tert-butyl)-1-(4-chlorophenyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-
5(1H)-one (4s). By following the general procedure for 15 min, 4s was obtained as pale-yellow
crystals (124.8 mg, 92%). Mp 252-254 °C; 1H NMR (CDCl3): δ = 1.15 (s, 9H), 7.23 (d, J = 8.4
Hz, 2H), 7.43 (t, J = 7.5 Hz, 1H), 7.52 (d, J = 9.0 Hz, 2H), 7.57-763 (m, 2H), 7.66 (d, J = 8.3 Hz,
2H), 7.97 (d, J = 7.5 Hz, 1H), 8.36 (d, J = 8.9 Hz, 2H); 13C NMR (CDCl3): δ = 30.3 (CH3), 34.3
(C), 114.7 (C), 121.0 (C), 121.4 (CH), 123.0 (CH), 123.2 (C), 123.6 (CH), 129.1 (CH), 130.5 (CH),
131.2 (CH), 131.7 (CH), 131.8 (C), 134.9 (CH), 135.0 (C), 135.1 (C), 137.4 (C), 137.7 (C), 141.8
(C), 144.7 (C), 153.5 (C), 157.1 (C), 163.9 (C), 189.8 (C); MS (EI) m/z 545/544/543/541 (M+,
21/20/100/68%), 530/529/528/526/513 (14/17/98/70/15). HRMS (IE) m/z calcd. for
C29H21BrClN3O [M]+: 541.0557; found 541.0541.
3-(tert-Butyl)-1-(4-chlorophenyl)-4-(4-(trifluoromethyl)phenyl)indeno[1,2-b]pirazolo[4,3-
e]pyridin-5(1H)-one (4t). By following the general procedure for 15 min, 4t was obtained as
yellow crystals (126.4 mg, 95%). Mp 226-227 °C; 1H NMR (CDCl3): δ = 1.12 (s, 9H), 7.44 (t, J =
7.4 Hz, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.53 (d, J = 8.9 Hz, 2H), 7.57 (d, J = 7.4 Hz, 1H), 7.62 (t, J
= 7.5 Hz, 1H), 7.79 (d, J = 8.1 Hz, 2H), 7.98 (d, J = 7.4 Hz, 1H), 8.36 (d, J = 9.0 Hz, 2H); 13C
NMR (CDCl3): δ = 30.2 (CH3), 34.2 (C), 114.4 (C), 120.0, 122.7, 125.4, 128.1 (CF3, q, J = 272.2
Hz), 120.9 (C), 121.5 (CH), 123.0 (CH), 123.6 (CH), 125.0 (CH, q, J = 3.7 Hz), 129.1 (CH), 129.4
(CH), 130.7, 131.0, 131.4, 131.7 (C-CF3, q, J = 32.3 Hz), 131.7 (CH), 131.8 (C), 135.0 (CH),
137.4 (C), 137.7 (C), 139.9 (C), 141.8 (C), 144.2 (C), 153.5 (C), 157.0 (C), 163.9 (C), 189.7 (C);
MS (EI) m/z 533/531 (M+, 27/68%), 518/516 (35/100), 489/487 (6/16). HRMS (IE) m/z calcd. for
C30H21ClF3N3O [M]+: 531.1325; found 531.1304.
3-(tert-Butyl)-1-(4-chlorophenyl)-4-(4-methoxyphenyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-
5(1H)-one (4u). By following the general procedure for 20 min, 4u was obtained as pale-orange
crystals (105.0 mg, 79%). Mp 225-227 °C (Lit.5 230-231 °C); 1H NMR (CDCl3): δ = 1.16 (s, 9H),
3.92 (s, 3H), 7.05 (d, J = 8.7 Hz, 2H), 7.26 (d, J = 8.7 Hz, 2H), 7.42 (t, J = 7.4 Hz, 1H), 7.51 (d, J
S12
= 8.9 Hz, 2H), 7.56-761 (m, 2H), 7.96 (d, J = 7.4 Hz, 1H), 8.37 (d, J = 9.0 Hz, 2H); 13C NMR
(CDCl3): δ = 30.2 (CH3), 34.4 (C), 55.3 (CH3), 113.4 (CH), 115.5 (C), 121.3 (CH), 121.5 (C),
122.9 (CH), 123.5 (CH), 128.1 (CH), 129.0 (CH), 130.0 (CH), 131.4 (C), 131.5 (CH), 134.7 (CH),
137.6 (C), 137.8 (C), 138.7 (C), 141.9 (C), 146.5 (C), 153.5 (C), 157.4 (C), 164.0 (C), 190.0 (C);
MS (EI) m/z 495/493 (M+, 28/77%), 480/478 (36/100), 465/463 (11/37). HRMS (IE) m/z calcd.
for C30H24ClN3O2 [M]+: 493.1557; found 493.1544. The characterization data for 4p match
previously reported data by us.5
3-(tert-Butyl)-1-(4-chlorophenyl)-4-(4-nitrophenyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-
one (4v). By following the general procedure for 15 min, 4v was obtained as yellow crystals (99.2
mg, 78%). Mp 288-290 °C; 1H NMR (CDCl3): δ = 1.14 (s, 9H), 7.45 (t, J = 7.4 Hz, 1H), 7.51-758
(m, 5H), 7.63 (t, J = 7.4 Hz, 1H), 7.99 (d, J = 7.5 Hz, 1H), 8.36 (d, J = 9.1 Hz, 1H), 8.40 (d, J =
8.7 Hz, 1H); 13C NMR (CDCl3): δ = 30.4 (CH3), 34.2 (C), 114.0 (C), 120.6 (C), 121.6 (CH), 123.0
(CH), 123.3 (CH), 123.7 (CH), 129.1 (CH), 130.2 (CH), 131.9 (CH), 132.0 (C), 135.1 (CH), 137.3
(C), 137.6 (C), 141.8 (C), 143.0 (C), 148.3 (C), 153.5 (C), 156.8 (C), 163.9 (C), 189.6 (C); MS
(EI) m/z 510/508 (M+, 23/67%), 495/493 (36/100), 468/466 (5/14). HRMS (IE) m/z calcd. for
C29H21ClN4O3 [M]+: 508.1302; found 508.1300.
1-(4-Chlorophenyl)-3-methyl-4-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4w). By
following the general procedure for 15 min, 4w was obtained as yellow crystals (84.4 mg, 80%).
Mp 240-242 °C; 1H NMR (CDCl3): δ = 2.04 (s, 3H), 7.40-7.46 (m, 3H), 7.48-7.55 (m, 5H), 7.58-
7.63 (m, 2H), 7.96 (d, J = 7.5 Hz, 1H), 8.32 (d, J = 8.9 Hz, 2H); 13C NMR (CDCl3): δ = 14.8 (CH3),
115.7 (C), 120.2 (C), 121.4 (CH), 122.4 (CH), 123.5 (CH), 128.0 (CH), 128.6 (CH), 129.1 (CH),
129.2 (CH), 131.6 (CH), 132.6 (C), 134.8 (CH), 137.3 (C), 137.6 (C), 142.3 (C), 145.9 (C), 146.2
(C), 152.8 (C), 165.2 (C), 189.8 (C); MS (EI) m/z 423/421 (M+, 36/100%). HRMS (IE) m/z calcd.
for C26H16ClN3O [M]+: 421.0982; found 421.0988.
3-(tert-Butyl)-1-(4-nitrophenyl)-4-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4x).
By following the general procedure for 15 min, 4x was obtained as yellow crystals (89.0 mg, 75%).
Mp 245-247 °C; 1H NMR (DMSO-d6, 120 °C): δ = 1.11 (s, 9H), 7.39 (d, J = 7.9 Hz, 2H), 7.47-
756 (m, 6H), 8.05 (d, J = 7.4 Hz, 1H), 8.42 (d, J = 9.2 Hz, 2H), 8.71 (d, J = 9.1 Hz, 2H); 13C NMR
(DMSO-d6, 120 °C): δ = 29.2 (CH3), 33.4 (C), 114.7 (C), 120.0 (C), 120.5 (CH), 120.7 (CH),
122.1 (CH), 124.0 (CH), 126.9 (CH), 128.1 (CH), 128.2 (CH), 131.4 (CH), 134.4 (CH), 134.8 (C),
S13
135.0 (C), 136.4 (C), 140.4 (C), 143.0 (C), 144.4 (C), 145.6 (C), 157.6 (C), 163.2 (C), 187.5
(C);MS (EI) m/z 474 (M+, 30%), 459 (100), 444 (33), 429 (17). HRMS (IE) m/z calcd. for
C29H22N4O3 [M]+: 474.1692; found 474.1692.
2-(4-(Dimethylamino)benzylidene)-1H-indene-1,3(2H)-dione 6h. By following the general
procedure for 10 min, 6h was obtained as bright-orange crystals (65.8 mg, 95%). Mp 192-193 °C
(Lit. [37] 203 °C). 1H NMR (CDCl3): δ = 3.13 (s, 6H), 6.73 (d, J = 9.2 Hz, 2H), 7.71 (m, 2H), 7.77
(s, 1H), 7.91 (m, 2H), 8.52 (d, J = 9.0 Hz, 2H); 13C NMR (CDCl3): δ = 40.0 (CH3), 111.4 (CH),
122.0 (C), 122.4 (CH), 123.0 (C), 134.0 (CH), 134.3 (CH), 137.9 (CH), 139.9 (C), 142.2 (C), 147.5
(CH), 153.9 (C), 189.9 (C), 191.7 (C); MS (EI) m/z 277 (M+, 100%), 260 (7), 233 (10). HRMS
(IE) m/z calcd. for C18H15NO2 [M]+: 277.1103; found 277.1096.
2.2.2. General procedure for the synthesis of 2-(4-aryl-3-methyl-1-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-ylidene)malononitrile 7a-d. A mixture of the appropiate ketone
4a-d (0.22 mmol) and malononitrile (27 mg, 2.2 mmol) in 20 mL of chlorobenzene was added
pyridine (0.36 mL, 4.4 mmol) and TiCl4 (0.24 mL, 2.2 mmol) under argon atmosphere. The
mixture was stirred at room temperature for 15 min and it was heated at reflux for 20 h. Then,
equal amounts of pyridine and TiCl4 was added and the final mixture was heated at reflux for 4 h.
The resulting crude was added 20 mL of water and partitioned with DCM. The organic layer was
washed with water and dried over anhydrous Na2SO4. Later, the solvent was removed under
vacuum and the residue was purified by flash chromatography (eluent: CH2Cl2:MeOH 50:1 v/v)
to give the pure products 7a-d as orange solids.
2-(3-Methyl-1,4-diphenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-ylidene)malononitrile (7a).
By following the general procedure, 7a was obtained as orange powder (96.0 mg, 96%). Mp. 235-
237 °C. 1H NMR (CDCl3): δ = 2.10 (s, 3H), 7.37 (t, J = 7.4 Hz, 1H), 7.48-7.65 (m, 9H), 8.05 (d, J
= 7.0 Hz, 1H), 8.26 (d, J = 8.5 Hz, 2H), 8.49 (d, J = 7.8 Hz, 1H); 13C NMR (CDCl3): δ = 16.1
(CH3), 111.7 (C), 114.8 (C), 115.7 (C), 121.7 (CH), 121.8 (C), 122.4 (CH), 125.9 (CH), 126.7
(CH), 128.7 (C), 129.2 (CH), 129.6 (CH), 129.9 (CH), 130.6 (CH), 131.5 (CH), 134.1 (CH), 134.2
(C), 138.6 (C), 138.7 (C), 139.9 (C), 146.0 (C), 147.7 (C), 152.3 (C), 160.0 (C), 162.1 (C). HRMS
(ESI+) m/z calcd. for C29H18N5 [M+H]+: 436.1562; found 436.1548.
S14
2-(4-(4-Methoxyphenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-
ylidene)malononitrile (7b). By following the general procedure, 7b was obtained as orange powder
(100.0 mg, 98%). Mp. 244-246 °C. Recrystallization of 7b from DMF afforded crystals of suitable
size and quality for single-crystal X-ray diffraction analysis. 1H NMR (CDCl3): δ = 2.19 (s, 3H),
3.93 (s, 3H), 7.14 (d, J = 8.7 Hz, 2H), 7.37 (t, J = 7.4 Hz, 1H), 7.43 (d, J = 8.7 Hz, 2H), 7.49 (t, J
= 7.6 Hz, 1H), 7.56 (t, J = 7.8 Hz, 2H), 7.61 (t, J = 7.5 Hz, 1H), 8.04 (d, J = 7.0 Hz, 1H), 8.26 (d,
J = 7.4 Hz, 2H), 8.48 (d, J = 7.9 Hz, 1H); 13C NMR (CDCl3): δ = 16.4 (CH3), 55.5 (CH3), 111.9
(C), 114.9 (C), 115.2 (CH), 115.9 (C), 121.7 (CH), 122.0 (C), 122.4 (CH), 125.8 (CH), 126.3 (C),
126.6 (CH), 128.3 (C), 129.2 (CH), 131.3 (CH), 131.4 (CH), 134.0 (CH), 138.9 (C), 139.9 (C),
146.0 (C), 160.4 (C), 161.5 (C), 161.9 (C). HRMS (ESI+) m/z calcd. for C30H20N5O [M+H]+:
466.1668; found 466.1647. Crystal data for 7b were deposited at CCDC (1886021): Chemical
formula C30H19N5O, Mr 187.20, Monoclinic, C2/c, 100 K, cell dimensions a, b, c (Å) 14.878(7),
12.149(6), 27.262(12) A α, β, γ (º) 90, 96.052(12), 90. V (Å3) 4900 (4), Z = 8, F(000)= 1936, Dx
(Mg m-3) = 1.262, Mo Kα, μ (mm-1)= 0.080, Crystal size (mm) = 0.307 x 0.200 x 0.180. Data
collection: Diffractometer Bruker D8 Venture (APEX 3), Monochromator multilayer mirror, CCD
rotation images, thick slices φ & θ scans, Mo INCOATEC high brilliance microfocus sealed tube
(= 0.71073 Å), multiscan absorption correction (SADABS-2016/2), Tmin, Tmax 0.6907 0.7456.
No. of measured, independent and observed [I > 2σ(I)] reflections 70658, 5639, 4245, Rint= 0.091
(0.041), θ values (°): θmax = 27.5, θmin = 2.25; Range h = -19→19, k = -15→15, l = -35→35,
Refinement on F2:R[F2 > 2σ(F2)]= 0.0637, wR(F2)= 0.0915, S=1.149. No. of reflections 4245, No.
of parameters 327, No. of restraints 0. Weighting scheme: w = 1/σ2(Fo2) + (0.0346P)2 + 13.4077P
where P = (Fo2 + 2Fc2)/3. (∆/σ) < 0.001, Δρmax, Δρmin (e Å-3) 0.310, -0.350.
2-(3-Methyl-1-phenyl-4-(4-(trifluoromethyl)phenyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-
ylidene)malononitrile (7c). By following the general procedure, 7c was obtained as orange powder
(111.0 mg, 95%). Mp. 272-273 °C. 1H NMR (CDCl3): δ = 2.07 (s, 3H), 7.38 (t, J = 7.4 Hz, 1H),
7.49-7.58 (m, 3H), 7.61-7.66 (m, 3H), 7.88 (d, J = 8.0 Hz, 2H), 8.06 (d, J = 7.1 Hz, 1H), 8.25 (d,
J = 8.7 Hz, 2H), 8.49 (d, J = 7.9Hz, 1H); 13C NMR (CDCl3): δ = 16.2 (CH3), 111.9 (C), 114.4 (C),
115.2 (C), 121.7 (CH), 122.4 (C), 122.5 (CH), 125.2 (C), 126.0 (CH), 126.6 (CHo-CF3, q, J = 3.7
Hz), 126.9 (CH), 129.2 (CH), 130.4 (CH), 131.7 (CH), 132.6 (Ci-CF3 q, J = 67 Hz), 134.3 (CH),
S15
137.9 (C), 138.5 (C), 138.6 (C), 139.7 (C), 145.5 (C), 145.6 (C), 152.2 (C), 159.8 (C), 162.2 (C).
HRMS (ESI+) m/z calcd. for C30H27F3N5 [M+H]+: 504.1436; found 504.1419.
2-(4-(4-(Dimethylamino)phenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-
ylidene)malononitrile (7d). By following the general procedure, 7d was obtained as green powder
(53.2 mg, 50%). Mp. >300 °C. 1H NMR (CDCl3): δ = 2.29 (s, 3H), 3.10 (s, 6H), 6.88 (d, J = 8.7
Hz, 2H), 7.33-7.37 (m, 3H), 7.48 (t, J = 7.6 Hz, 1H), 7.53-7.61 (m, 3H), 8.01 (d, J = 7.1 Hz, 1H),
8.26 (d, J = 8.4 Hz, 2H), 8.44 (d, J = 7.9 Hz, 1H); 13C NMR (CDCl3): δ = 16.8 (CH3), 40.2 (CH3),
112.0 (C), 112.6 (CH), 115.1 (C), 115.9 (C), 121.0 (C), 121.7 (CH), 122.0 (CH), 122.2 (CH), 125.6
(CH), 126.5 (CH), 129.1 (CH), 131.1 (CH), 131.2 (CH), 133.7 (CH), 138.8 (C), 139.9 (C), 146.2
(C), 149.1 (C), 151.7 (C), 152.6 (C), 161.1 (C), 161.8 (C). HRMS (ESI+) m/z calcd. for C31H23N6
[M+H]+: 479.1984; found 479.1969.
2.3. Photophysical properties. The solvochromic studies of compounds 7a-d were carried out with
50 μM solutions in toluene (PhMe), dichloromethane (DCM), acetonitrile (ACN), acetone, and
dimethyl sulfoxide (DMSO). Fluorescence response in photographs was at an excitation of 365
nm using a UV lamp. The relative quantum yields were obtained using quinine sulfate (ϕF = 0.59
in 0.15 M HClO4 ) [38] as reference and calculated according to the following equation6-8
where x and st indicate the sample and standard solution, respectively, ϕ is the quantum yield, F is
the integrated area of the emission, A is the absorbance at the excitation wavelength, and η is the
index of refraction of the solvents.
2.4. Computation details. Theoretical calculations were obtained using DFT performed using
Gaussian 09.9 The DFT calculations employed the B3LYP hybrid functional and the 6-311G+(d,p)
basis set. All geometries were optimized in the ground state without solvent effects. Time-
dependent (TD-DFT) calculations were performed on optimized geometries. The visual software
used in this work was Avogadro 1.2.0 to analyze the output files performed in the calculations.10
S16
3. Supplementary Analytical Data (Identification of intermediate 5a)
Fig. S 1. Identification by 1H NMR (CDCl3) of the intermediates 5a'-5a" versus 1H NMR of 4a
Fig. S2. HPLC-HRMS of the mixture of 5a', 5a" and 4a
Ha
5a' Hb
5a''
CH3
4a
CH3
5a''
Ar
4aAr
5a''
(a) Initial mixture
(b) After 1 month
(c) Pure product 4a
Ha
5a''
DCM
CH3
5a'
(a)
(b) (c)[M+H]+[M+H]+
S17
4. Photophysical studies
Fig. S3. UV-vis spectra of 7a-d (10 µM). (a) DMF, (b) ACN, (c) acetone, (d) DCM, and (e) toluene.
Photograph of compounds 7a-d in DMSO under natural.
Fig. S4. Fluorescence spectra of 7a-d (10 µM). (a) DMF, (b) ACN, (c) acetone, (d) DCM, and (e)
toluene. Photograph under a hand-held UV lamp at long wavelength λ = 365 nm.
S18
Table S1. Photophysical properties of compounds 7a-d
Compound Solventa λab
(nm) ε (L mol-1 cm-1)
λex
(nm)
λem
(nm) Stokes shift (nm) ϕF
b
7a
DMSO 309 16970
340
519 210 0.030
ACN 306 23633 490 184 0.011
Acetona 334 14523 491 157 0.028
DCM 307 25934 482 175 0.010
Tolueno 310 22642 382 72 0.009
7b
DMSO 304 25793
345
475 171 0.133
ACN 305 27142 482 177 0.013
Acetona 336 16433 485 149 0.082
DCM 305 40837 476 171 0.027
Tolueno 305 25049 417 112 0.010
7c
DMSO 308 21140
350
453 145 0.114
ACN 305 23535 486 181 0.015
Acetona 335 17885 485 150 0.012
DCM 307 49177 475 168 0.050
Tolueno 308 23044 465 157 0.011
7d
DMSO 297 22544 350 406 109 0.002
ACN 260 20342 345 550 290 0.181
Acetona 339 22311
350
507 168 0.003
DCM 294 42680 462 168 0.026
Tolueno 291 23195 430 139 0.006 a50 µM. bRelative quantum yields were taken by using quinine sulfate as a reference (ϕF = 0.59 in 0.15 M HClO4).
5. Computational calculations
Fig. S5. Frontier Orbitals of compounds 7a-d
S19
Table S2. Theoretical data of 7a-d.TD-DFT calculations at B3LYP/6-31G(d,p) theory level
Compound Wavelength (nm) Excitation
energy (eV)
Oscillator
strength (f) Transitions
Theoreticala Experimentalb
7a
477 434 2.6922 0.6964 HOMO-1 LUMO+1 (100%)
368 ------ 3,648 0.0628 HOMO-4 LUMO (22%)
HOMO LUMO+1 (30%)
344 344 3.6019 0.2363 HOMO-5 LUMO (33%)
HOMO-2 LUMO (17%)
295 310 4.1959 0.5933 HOMO-1 LUMO+1 (43%)
HOMO-6 LUMO (31%)
291 285 4.2543 0.2476
HOMO-8 LUMO (30%)
HOMO-4 LUMO+1 (24%)
HOMO-2 LUMO+1 (24%)
7b
498 -------- 2.4875 0.0902 HOMO-1 LUMO (35%)
HOMO LUMO (65%)
464 -------- 2.6707 0.0886
HOMO-2 LUMO (36%)
HOMO-1 LUMO (44%)
HOMO LUMO (20%)
457 445 2.7156 0.0507
HOMO-2 LUMO (49%)
HOMO-1 LUMO (31%)
HOMO- LUMO (20%)
362 -------- 3.4225 0.0835
HOMO-5 LUMO (39%)
HOMO-3 LUMO (43%)
HOMO- LUMO+1 (18%)
339 347 3.6538 0.2224
HOMO-5 LUMO (18%)
HOMO-3 LUMO (16%)
HOMO-1 LUMO+1 (38%)
300 305 4.1259 0.1098 HOMO-8 LUMO (43%)
HOMO-3 LUMO+1 (46%)
294 300 4.2079 0.6188 HOMO-6 LUMO (34%)
HOMO-2 LUMO+1 (52%)
7c
480 436 2.5802 0.1984 HOMO LUMO (100%)
351 355 3.5284 0.1925 HOMO-4 LUMO (44%)
HOMO-2 LUMO (25%)
312 307 3.9615 0.1059
HOMO-8 LUMO (14%)
HOMO-7 LUMO (22%)
HOMO-6 LUMO (17%)
HOMO-1 LUMO+1 (23%)
298 285 4.1572 0.4470 HOMO-6 LUMO (28%)
HOMO-1 LUMO+1 (32%)
7d
644 -------- 1.9259 0.0333 HOMO LUMO (100%)
471 550 2.6337 0.1850 HOMO-2 LUMO (24%)
HOMO-1 LUMO (76%)
416 400 2.9792 0.1479 HOMO LUMO+1 (100%)
343 343 3.6133 0.2563 HOMO-5 LUMO (31%)
HOMO-3 LUMO (28%)
297 290 4.1821 0.5251
HOMO-9 LUMO (16%)
HOMO-6 LUMO (28%)
HOMO-2 LUMO+1 (56%) a Data calculated on gas phase. b Experimental data in toluene
S20
Fig. S6. Frontier molecular orbitals of compound 7a
Fig. S7. Frontier molecular orbitals of compound 7b
Fig. S8. Frontier molecular orbitals of compound 7c
S21
Fig. S9. Frontier molecular orbitals of compound 7d
3.1 Coordinates of the optimized structure for 7a calculated at the B3LYP/6-31+G(d, p) level theory
SCF Energy: -1389.11581695 a. u.
Num. Imaginary Frequencies: 0
HOMO energy: -0.23473 eV
LUMO energy: -0.12464 eV
Atom X Y Z
N 1.45067 1.05228 -0.06115
N 2.93430 -0.85397 -0.10439
N 2.81572 -2.21531 0.02142
C 0.73524 -1.31264 -0.03590
C 1.69947 -0.26744 -0.11266
C -0.92496 0.39808 -0.07878
C 0.16340 1.33793 -0.01690
C -0.64523 -0.97957 -0.00566
C -0.38103 2.68195 0.19209
C 4.22996 -0.26664 -0.14104
C 1.52897 -2.51266 0.07449
C -2.46838 -1.96681 1.38915
H -2.34449 -1.13953 2.08207
C -1.67088 -2.03054 0.23438
C -3.41449 0.82459 -0.58075
C -1.79060 2.59313 0.22454
C -2.17148 1.19402 -0.11203
C -3.40051 -2.96977 1.66134
H -4.00432 -2.91244 2.56215
C 5.31001 -0.97708 0.40023
H 5.13823 -1.95245 0.83787
C 4.43129 0.99071 -0.72558
H 3.59583 1.53485 -1.14522
C -4.54912 1.69716 -0.52359
C -2.77383 -4.10471 -0.37847
H -2.90490 -4.92216 -1.08085
Atom X Y Z
C -1.83445 -3.10994 -0.64568
H -1.25158 -3.14857 -1.56033
C 0.28379 3.88625 0.38859
H 1.36762 3.92419 0.35233
C 1.13823 -3.94931 0.24177
H 0.70276 -4.36325 -0.67265
H 0.40005 -4.07391 1.03851
H 2.03183 -4.52724 0.48791
C -3.69689 -0.37531 -1.30600
C -0.48059 5.03090 0.64312
H 0.01230 5.98450 0.80679
C -3.55541 -4.04107 0.77777
C 5.71659 1.53469 -0.75255
H 5.86840 2.50928 -1.20706
C -1.87670 4.95288 0.69750
C -2.54655 3.74129 0.48285
H -3.62665 3.71669 0.53297
C 6.79950 0.83572 -0.21409
H 7.79666 1.26431 -0.24273
C 6.58855 -0.42226 0.35767
H 7.42197 -0.97726 0.77809
N -5.50273 2.36420 -0.47466
N -4.00121 -1.26535 -1.99246
H -2.45743 5.84527 0.90946
H -4.28696 -4.81645 0.98454
S22
3.2. Coordinates of the optimized structure for 7b calculated at the B3LYP/6-31+G(d, p) level theory
SCF Energy: -1503.64623840 a. u.
Num. Imaginary Frequencies: 0
HOMO energy: -0.22997 eV
LUMO energy: -0.12229 eV
Atom X Y Z
O -5.56390 -2.83286 0.93302
N 2.14749 0.73038 -0.03815
N 2.89209 -1.56622 -0.11815
N 2.31501 -2.80779 -0.02855
C 0.66709 -1.24873 -0.08563
C 1.93086 -0.59364 -0.12463
C -0.30730 0.92656 -0.09768
C 1.03415 1.43721 0.00106
C -0.51895 -0.46546 -0.05627
C 0.97573 2.88294 0.23336
C 4.31058 -1.45516 -0.12639
C 1.00307 -2.64890 0.00347
C -2.61700 -0.75081 1.27820
H -2.23947 -0.01518 1.98252
C -1.84638 -1.09571 0.15038
C -2.48602 2.18466 -0.64517
C -0.38007 3.28026 0.23719
C -1.20609 2.09976 -0.13822
C -3.84405 -1.35345 1.51877
H -4.43405 -1.09661 2.39233
C 5.07426 -2.50461 0.40264
H 4.57246 -3.37310 0.81043
C 4.93909 -0.32800 -0.67204
H 4.34683 0.47910 -1.08189
C -3.25228 3.39404 -0.60163
C -3.59594 -2.66011 -0.50877
H -3.96967 -3.37569 -1.23072
C -2.35729 -2.05728 -0.72814
Atom X Y Z
H -1.80263 -2.31211 -1.62545
C 2.00578 3.78487 0.47080
H 3.03832 3.45157 0.45527
C 0.14417 -3.86980 0.13214
H -0.37496 -4.10445 -0.80222
H -0.61812 -3.74332 0.90533
H 0.78102 -4.71862 0.39127
C -3.14347 1.16161 -1.39847
C 1.67085 5.11730 0.73903
H 2.45484 5.84260 0.93510
C -4.34638 -2.31007 0.62152
C 6.33313 -0.25502 -0.67293
H 6.81597 0.62026 -1.09745
C 0.33089 5.51959 0.76557
C -0.70603 4.61290 0.50889
H -1.73091 4.95734 0.53787
C 7.10334 -1.29471 -0.14666
H 8.18722 -1.23167 -0.15461
C 6.46591 -2.41868 0.38653
H 7.05250 -3.23494 0.79769
C -6.15981 -3.76465 0.03417
H -6.31386 -3.31782 -0.95508
H -7.12477 -4.02088 0.47225
H -5.55064 -4.67193 -0.06075
N -3.91899 4.34858 -0.56659
N -3.72040 0.43991 -2.10736
H 0.08377 6.55287 0.98880
3.3. Coordinates of the optimized structure for 7c calculated at the B3LYP/6-31+G(d, p) level theory
SCF Energy: -1726.17280429a. u.
Num. Imaginary Frequencies: 0
HOMO energy: -0.23934 eV
LUMO energy: -0.13124 eV
Atom X Y Z
N 2.63874 0.49576 -0.01517
N 2.98752 -1.89033 -0.15076
N 2.20502 -3.01669 -0.13722
C 0.84973 -1.19928 -0.19616
C 2.20726 -0.76868 -0.15778
C 0.25782 1.11204 -0.16780
C 1.66198 1.38196 0.00316
C -0.18235 -0.22389 -0.18933
C 1.83916 2.80675 0.29413
C 4.40393 -2.02242 -0.09110
C 0.93852 -2.63892 -0.15308
C -2.33419 -0.25222 1.07950
H -1.86228 0.36697 1.83619
C -1.60664 -0.63875 -0.05748
C -1.65446 2.74365 -0.72427
C 0.57097 3.42903 0.27122
C -0.42686 2.42391 -0.18410
C -3.65148 -0.67184 1.25674
C 4.95124 -3.19494 0.44654
H 4.29058 -3.97256 0.80898
C 5.23886 -1.00914 -0.57948
H 4.81231 -0.10725 -0.99777
C -2.21081 4.06135 -0.64668
C -3.54975 -1.85730 -0.85327
C -2.23108 -1.44307 -1.02044
H -1.69564 -1.71485 -1.92366
C 2.99703 3.51008 0.60312
Atom X Y Z
H 3.95812 3.00640 0.60623
C -0.11895 -3.69977 -0.11752
H -0.64619 -3.78399 -1.07254
H -0.86788 -3.49651 0.65282
H 0.35745 -4.65925 0.09508
C -2.43973 1.87336 -1.54294
C 2.88199 4.86931 0.91699
H 3.76903 5.44273 1.16867
C -4.25957 -1.47652 0.28883
C 6.62353 -1.17327 -0.51365
H 7.26784 -0.38608 -0.89381
C 1.62920 5.49289 0.91824
C 0.46462 4.78685 0.59006
H -0.48739 5.30011 0.60217
C 7.17966 -2.33724 0.02206
H 8.25765 -2.45888 0.06582
C 6.33656 -3.34589 0.49712
H 6.75618 -4.25638 0.91444
N -2.70926 5.11218 -0.58609
N -3.09064 1.26880 -2.29577
H 1.55199 6.54413 1.17779
H -4.02988 -2.45924 -1.61669
H -4.20258 -0.37184 2.14141
C -5.66492 -1.97575 0.50370
F -6.31555 -2.20143 -0.66169
F -6.41453 -1.10589 1.22323
F -5.67617 -3.15439 1.18869
S23
3.4. Coordinates of the optimized structure for 7d calculated at the B3LYP/6-31+G(d, p) level theory
6. Fluorescent chemosensors 7a-d for detection of cyanide
Fig. S10. Normalized UV-vis spectra of 50 µM acetonitrile solutions of 7a-d with different equiv of CN-
SCF Energy: -1523.09554001 a. u.
Num. Imaginary Frequencies: 0
HOMO energy: -0.20749 eV
LUMO energy: -0.11791 eV
Atom X Y Z
N 2.42350 0.61107 -0.01552
N 2.98590 -1.73488 -0.12002
N 2.31170 -2.92852 -0.07156
C 0.79189 -1.24355 -0.15041
C 2.10356 -0.68968 -0.13753
C -0.00441 1.00354 -0.13853
C 1.36900 1.40340 0.00794
C -0.33121 -0.36875 -0.13230
C 1.41934 2.84608 0.26191
C 4.40764 -1.73496 -0.07689
C 1.01560 -2.66710 -0.07676
C -2.50453 -0.45211 1.10261
H -2.10515 0.27010 1.80925
C -1.70818 -0.88368 0.02791
C -2.05287 2.43957 -0.74533
C 0.10027 3.35092 0.22871
C -0.80379 2.24450 -0.19231
C -3.78844 -0.94304 1.30456
H -4.35079 -0.58046 2.15571
C 5.06858 -2.85141 0.45378
H 4.48654 -3.68622 0.82352
C 5.14143 -0.64951 -0.57391
H 4.62853 0.20963 -0.98476
C -2.72027 3.70603 -0.71176
C -3.55505 -2.31277 -0.67410
H -3.94747 -3.00383 -1.40905
C -2.26858 -1.82462 -0.85006
H -1.70580 -2.14464 -1.72116
C 2.50970 3.65929 0.54540
H 3.51233 3.24440 0.55627
Atom X Y Z
C 0.06385 -3.82151 0.00543
H -0.43821 -4.00705 -0.94904
H -0.71408 -3.64737 0.75324
H 0.62687 -4.71819 0.27444
C -2.76231 1.48088 -1.53558
C 2.27363 5.01067 0.82449
H 3.10619 5.66809 1.05661
C -4.35424 -1.89426 0.41893
C 6.53601 -0.68557 -0.52432
H 7.10022 0.15793 -0.91129
C 0.96986 5.51857 0.81572
C -0.12711 4.70151 0.51118
H -1.12170 5.12666 0.51204
C 7.20402 -1.79260 0.00430
H 8.28914 -1.81411 0.03578
C 6.46237 -2.87402 0.48851
H 6.96861 -3.74188 0.90092
N -3.31040 4.71023 -0.68466
N -3.37238 0.82029 -2.27582
H 0.79868 6.56527 1.04764
N -5.62777 -2.39295 0.61388
C -6.48526 -1.80384 1.63232
H -6.69844 -0.74155 1.43956
H -7.43222 -2.34421 1.65638
H -6.03176 -1.88819 2.62655
C -6.23972 -3.22897 -0.40970
H -6.35954 -2.70075 -1.36733
H -5.64511 -4.13231 -0.58739
H -7.22537 -3.54600 -0.06717
S24
Fig. S11. Fluorescence spectra of 50 µM acetonitrile solutions of 7a-d with different equiv of CN-
Table S3. Photophysical properties of compounds 7a-d with different equivalents of CN-
Compounda Equiv CN- λab (nm) λex (nm) λem (nm) Stokes shift
(nm) ϕF
b
7a
0 306
340
488 182 0.011
1 306 489 183 0.026
10 272 621 349 0.073
7b
0 305
340
480 175 0.013
1 278 613 335 0.041
10 274 623 349 0.079
7c
0 305
345
486 181 0.015
1 305 477 172 0.027
10 273 625 352 0.063
7d
0 260
345
550 290 0.181
1 260 555 295 0.166
10 260 560 300 0.161
100 260 585 325 0.023
a50 µM. bRelative quantum yields were taken by using quinine sulfate as a reference (ϕF = 0.59 in 0.15 M HClO4).
S25
7. Copies of NMR spectra
1H and 13C{1H} NMR spectra of 3-methyl-1,4-diphenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one
(4a)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
7.30 3.222.07
TMS
CH3
Chloroform-d
CH
CH
CH
CH
CH
CH
CH
CH
CHCH
2.0
5
7.4
27
.46
7.4
77.5
37.5
57
.60
7.9
67
.978.3
08
.32
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
7.30 3.162.07 1.051.00
Chloroform-dCH
CHCH
CH
CH
CH
CHCHCH
CH
7.2
6
7.3
37.3
57
.36
7.4
07.4
27
.42
7.4
37
.44
7.4
47
.45
7.4
67
.47
7.5
27
.53
7.5
47.5
5
7.5
77
.58
7.5
87
.60
7.6
2
7.9
67
.978.3
08
.30
8.3
28
.33
145 140 135 130 125ppm
C
C
C C CCH
CCH
CH
CH
CH CH
CH CH
CH
CH
14
5.92
14
5.84
14
2.40
13
8.99
13
7.37
13
4.65
13
2.76
13
1.44
12
9.15 12
9.03
12
8.64
12
7.97
12
6.32
12
3.43 12
1.53
12
1.40
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C C CC
C
C
C
C
CH
C CH
CH
CH
CH
CH
CH
CH
CH
C
C
Chloroform-d
CH3
TMS
18
9.85
16
5.05
15
2.75
14
5.92
14
5.84
14
2.40 1
34.
651
31.
441
29.
151
29.
031
28.
641
27.
971
23.
431
21.
531
21.
401
20.
021
15.
57
77
.35
77
.03
76
.71
14
.80
0.0
0
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.66
13
1.44
12
9.15 12
9.03
12
8.64
12
7.97
12
1.53
12
1.40
14
.80
S26
1H and 13C{1H} NMR spectra of 4-(4-methoxyphenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4b)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
4.15 3.10 3.082.052.01
CH CH
CH
CH
CH
CH
CH
CH
Chloroform-d
CH
CH3
CH3
TMS
8.3
18
.30
7.5
6 7.5
47
.527
.42
7.4
07
.25 7
.07
7.0
4
3.9
1
2.1
2
1.5
9 0.0
0
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 7.0ppm
4.15 3.04 2.052.01 1.071.00
CH
CH CH CH
CHCH
CH
CHChloroform-d
CH
8.3
28
.31
8.3
08
.29
7.9
67
.94
7.6
27
.60
7.5
97
.59 7.5
77
.57
7.5
6 7.5
47
.52
7.4
37
.42
7.4
0
7.3
67
.34
7.3
2
7.2
5
7.0
77
.07
7.0
47
.04
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C CC
CC
C
C C
C
CH
CH
CH
CH
CH
C
CH
CH
C
C
CH
Chloroform-d
CH3 CH3
TMS
19
0.0
2
16
5.1
8
16
0.4
6
15
2.8
2
14
6.0
91
45.9
7
14
2.3
7
13
7.4
21
34.6
11
31.4
01
30.4
81
29.0
31
26.3
0
12
3.3
91
21.5
61
21.3
61
20.0
2
11
5.7
71
13.4
0
77
.36
77
.03
76
.71
55
.32
15
.17
0.0
0
145 140 135 130 125ppm
C
C
C C CCH CH
CH CH
CH
CCH
CH
CH
14
6.0
91
45.9
7
14
2.3
7
13
9.0
2
13
7.4
2
13
4.6
1
13
1.4
0 13
0.4
8
12
9.0
3
12
6.3
0
12
4.6
0
12
3.3
9 12
1.5
61
21.3
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.6
1
13
0.4
81
29.0
31
26.3
01
23.3
9 12
1.5
71
21.3
6
11
3.3
9
55
.32
15
.17
S27
1H and 13C{1H} NMR spectra of 3-methyl-1-phenyl-4-(4-(trifluoromethyl)phenyl)indeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4c)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
6.08 3.072.02
CHCH CH
CH
CH
CH
CH
Chloroform-d
ch3
TMS
8.3
1
7.8
17
.79
7.6
37
.62
7.6
0 7.5
87
.45
7.2
6
2.0
5
1.5
6 0.0
0
8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
6.082.062.02 1.03 1.021.02
CH
CH
CH
CH
CH
CH
CH CH
Chloroform-d
8.3
1 8.3
18
.29
8.2
9
8.0
07
.98
7.8
1 7.7
9
7.6
3 7.6
27
.60
7.5
97
.58
7.5
67
.55
7.5
4
7.4
77
.47 7.4
57
.43
7.4
37
.39
7.3
9 7.3
77
.35
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C C C C
C
CCC
CH
C-CF3
CH
CH
CF3
CH
CF3
CH
CF3
CH
CH
C
CF3
C
Chloroform-d
CH3
TMS
18
9.7
9
16
5.0
4
15
2.7
9
14
5.4
81
43.7
61
38.8
41
37.2
71
34.9
71
31.7
2 12
9.1
21
26.5
91
23.6
2
12
1.6
71
21.6
01
20.0
01
15.1
3
77
.35
77
.03
76
.71
14
.89
0.0
0
137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121 120ppm
C C
CH C-CF3
CH
C-CF3
C-CF3
C-CF3
CH
CH
CF3
CH CF3
CH-C-CF3
CH
CF3
CH
CH
C
CF3
13
7.2
7
13
6.5
8
13
4.9
7
13
1.8
1 13
1.7
21
31.4
9
13
1.1
5
13
0.8
3
12
9.1
91
29.1
2
12
8.1
0
12
6.5
9
12
5.3
91
25.1
21
25.0
91
25.0
51
25.0
1
12
3.6
2
12
2.6
8
12
1.6
71
21.6
0
12
0.0
0
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
14
.891
21.6
61
23.6
21
26.5
912
9.1
11
31.7
21
34.9
6
S28
1H and 13C{1H} NMR spectra of 4-(4-(dimethylamino)phenyl)-3-methyl-1-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4d)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
6.133.20 3.112.102.03
TMS
CH3
N(CH3)2
CHCH
CH
CH
CH
CH
CH
CHCH
0.0
0
1.6
1
2.2
2
3.0
7
6.8
26
.84
7.3
8
7.4
07
.41
7.5
27.5
47
.56
7.9
47
.96
8.3
18
.33
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 7.0 6.9 6.8ppm
3.20 3.13 2.102.03 1.071.041.01
CH
Chloroform-d
CHCHCHCHCH
CHCHCH
6.8
26
.84
7.2
6
7.3
27.3
37
.35
7.3
77
.38
7.4
07
.41
7.4
17
.427.5
27.5
47
.56
7.5
87.6
17
.63
7.9
47
.968.3
18
.33
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C CC
C
C
C
C C
C
CH
CH
CH
CH
CH
CH
CH
C
C
C
CH Chloroform-d N(CH3)2
CH3
TMS
19
0.10
16
5.39
15
2.95
15
1.12
14
7.40
14
6.19
14
2.39
13
7.56 13
4.39
13
1.23
13
0.77
12
8.99
12
6.17
12
1.59
12
1.22
11
9.75
11
5.82
11
0.95
77
.35
77
.03
76
.71
40
.26
15
.57
0.0
0
131 130 129 128 127 126 125 124 123 122 121 120 119ppm
CH
CH CH
CH CH
CH
CH
C C
13
1.23 1
30.
77
12
8.99
12
6.17
12
3.26 1
21.
59
12
1.22
11
9.75
11
9.35
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.37
13
1.21 1
30.
751
28.
97
12
3.24
12
1.57
12
1.20 1
10.
94
40
.25
15
.57
119.5ppm
CC
11
9.35
11
9.75
S29
1H and 13C{1H} NMR spectra of 3-methyl-1-phenyl-4-(p-tolyl)indeno[1,2-b]pyrazolo[4,3-e]pyridin-
5(1H)-one (4e)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
5.06 3.022.00
TMS
CH3
CH3Chloroform-d
CH,CH,CH
CH
CH
CH
CH
CHCH
0.0
1
1.5
9
2.0
9
2.4
9
7.2
67
.33
7.3
5
7.5
57
.57
7.5
87
.60
7.9
78
.30
8.3
2
8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
5.064.132.00 1.081.00
Chloroform-d
CH,CH,CH
CHCHCHCHCHCH
7.2
6
7.3
27
.33
7.3
37
.35
7.3
67
.40
7.4
07
.42
7.4
27
.43
7.4
4
7.5
37
.537.5
57
.56
7.5
67
.57
7.5
87
.58
7.6
07
.60
7.6
2
7.9
5
7.9
7
8.3
08.3
08
.30
8.3
28.3
28
.32
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
TMS
CH3CH3
Chloroform-d
C
C
CH
CH
CH
CH
CH
C
CH
CH
C
C
C
CC
C
CCC
0.0
0
14
.98
21
.55
76
.71
77
.03
77
.35
11
5.6
91
20.0
81
21.3
71
21.5
5
12
6.2
91
28.6
91
29.0
31
31.4
01
34.6
11
37.4
21
39.1
41
42.4
01
46.0
21
46.2
71
52.7
8
16
5.1
2
18
9.9
3
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
14
.98
21
.55
12
1.3
71
21.5
41
23.4
11
26.2
91
28.6
81
29.0
3
13
4.6
1
145 140 135 130 125 120ppm
C
CH
CH
CHCH
CH
CH
CCHCH
CC
C
CC
C
12
0.0
8
12
1.3
71
21.5
5
12
3.4
1
12
6.2
9
12
8.6
91
29.0
3
12
9.6
6
13
1.4
0
13
4.6
1
13
7.4
2
13
9.0
21
39.1
4
14
2.4
0
14
6.0
21
46.2
7
S30
1H and 13C{1H} NMR spectra of 4-(4-chlorophenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4f)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
6.21 3.132.03
CH CH
CH
CH
CH
CH
CH
CH
CH
Chloroform-d CH3
TMS
8.3
08
.28
7.6
07
.57
7.5
57
.53 7
.52 7
.50
7.4
17
.39
7.3
57
.26
2.0
8
1.5
8 0.0
0
8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
6.21 3.112.03 1.091.00
CH
CH CHCH
CH
CH CH
CH
CHChloroform-d
8.3
08
.30
8.2
8
7.9
67
.94
7.6
1
7.6
0 7.6
07
.58 7.5
77
.55
7.5
37
.52
7.5
2
7.5
07
.44
7.4
4 7.4
27
.42 7
.41
7.4
07
.39
7.3
87
.37 7.3
57
.33
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C C CC
C
C C
C
C
CH C
CH
CH
CH
CH CH
CH
C
C
Chloroform-d
CH3
TMS
18
9.8
1
16
5.0
4
15
2.7
41
45.6
1
14
2.3
21
37.2
81
35.4
31
34.8
11
31.5
81
30.2
01
29.0
71
28.3
41
26.4
6
12
1.5
81
19.9
6
11
5.3
2
77
.35
77
.03
76
.71
15
.01
0.0
0
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.8
21
31.5
81
30.2
01
29.0
71
28.3
41
23.5
21
21.5
8
15
.01
145 140 135 130 125ppm
C C C C C CCH CH
C
CH CH CHCH CH
CH
CH
14
5.6
1
14
4.3
6
14
2.3
2
13
8.8
9
13
7.2
8
13
5.4
3
13
4.8
1
13
1.5
8
13
1.0
9 13
0.2
0
12
9.0
7
12
8.3
4
12
6.4
6
12
3.5
2
12
1.5
8
S31
1H and 13C{1H} NMR spectra of 4-(4-bromophenyl)-3-methyl-1-phenylindeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4g)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
5.18 3.082.01
CH
CH CH
CH
CH
CH
CH
CH
Chloroform-d
CH3
TMS
8.3
08
.28
8.2
87
.99
7.9
7 7.6
87
.66
7.5
17
.35
7.3
37
.26
2.1
0
1.6
1
0.0
0
8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
5.18 3.052.032.01 1.00
CH
CH
CH
CH CHCH
CH
CH
CH
Chloroform-d
8.3
18
.30
8.2
88
.28
8.2
8 7.9
9
7.9
7
7.6
97
.68
7.6
77
.66
7.6
47
.62
7.6
07
.60
7.5
7 7.5
57
.54 7
.53
7.5
17
.51
7.5
0 7.3
8 7.3
67
.35
7.3
47
.33
7.3
3
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C C C C
C
C
C
C
C
CH
CH
CH
CH
CH
CH
C
CH
CH
C
C
Chloroform-d
CH3
TMS
18
9.8
3
16
5.0
8
15
2.7
71
45.6
31
44.3
41
42.3
51
38.8
71
35.7
61
34.8
41
31.7
2 13
1.2
91
30.4
21
29.0
81
26.4
9 12
1.6
31
19.9
3
11
5.2
5
77
.34
77
.03
76
.71
15
.02
0.0
0
131.5 131.0 130.5 130.0 129.5 129.0 128.5 128.0 127.5 127.0 126.5 126.0 125.5 125.0 124.5 124.0 123.5 123.0 122.5 122.0 121.5ppm
CHCH CH CH
CHC
CH CH
CH
13
1.7
2
13
1.2
9
13
0.4
2
12
9.0
8
12
6.4
9
12
3.6
91
23.5
5
12
1.6
31
21.5
1
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.8
41
31.7
21
31.2
91
30.4
21
29.0
81
26.4
81
23.5
51
21.6
2
15
.02
S32
1H and 13C{1H} NMR spectra of 3-methyl-4-(4-nitrophenyl)-1-phenylindeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4h)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
4.08 3.202.07
CH
CH
CH
CH
CH
CH
CH
CH
Chloroform-d
CH3
TMS
8.4
28
.40
8.2
88
.01
7.6
77
.64
7.6
37
.57
7.4
8
7.2
6
2.0
5
1.5
6
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
4.08 2.182.072.02 1.13 1.071.02
CHCH
CH
CH
CH
CHCH CH
Chloroform-d
8.4
2
8.4
0
8.3
08
.28
8.0
17
.99 7
.67
7.6
47
.63
7.6
17
.59 7.5
77
.55
7.4
87
.46
7.4
5
7.4
07
.38
7.3
6
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
TMS
CH3
Chloroform-d
C
CCH
CH
CH
CH
CH
CH
CH
C
C
C
C
C
CCCC
0.0
0
14
.92
76
.71
77
.02
77
.34
11
4.7
4
11
9.8
81
21.7
01
23.3
31
23.7
31
29.1
51
29.9
01
31.8
41
35.1
1
13
9.6
51
42.3
31
42.5
31
45.1
41
48.4
01
52.7
6
16
4.9
7
18
9.6
7
143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123ppm
CH
CHCH
CHCH
CHCHCCCCC
12
3.3
3
12
3.7
3
12
6.7
2
12
9.1
5
12
9.9
0
13
1.8
4
13
5.1
1
13
7.1
8
13
8.7
4
13
9.6
5
14
2.3
31
42.5
3
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
14
.92
12
1.7
01
23.3
3
12
6.7
212
9.1
41
29.9
01
31.8
41
35.1
1
S33
1H and 13C{1H} NMR spectra of 4-(4-(dimethylamino)phenyl)-3-methyl-1-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4i)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.207.392.00
CHCH CH
CH
CH
CH
CH
CH
CH
CH
Chloroform-d
(CH3)3
TMS
8.3
98
.38
8.3
7
7.5
97
.58
7.5
77
.54
7.5
2
7.3
87
.36 7.2
6
1.5
4
1.1
5
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
7.39 3.062.00 1.051.01
CHCH
CH
CH
CH
CH
CH
CH
CH
CH Chloroform-d
8.3
98
.38
8.3
78
.36
8.0
07
.98
7.6
1 7.5
9 7.5
97
.57 7
.57
7.5
77
.55 7.5
47
.52
7.4
47
.43 7.4
27
.42 7
.38
7.3
87
.36
7.3
6
7.3
4
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
TMS
(CH3)3
C-(CH3)3
Chloroform-d
C
C
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
C
C
C
CCCCCC
0.0
0
30
.25
34
.24
76
.70
77
.01
77
.33
11
4.8
41
20.9
812
1.3
21
22.0
21
23.4
31
27.9
11
28.7
41
28.9
61
31.4
21
34.6
11
36.2
31
39.2
11
42.0
61
46.1
9
15
3.5
5
15
6.9
9
16
3.8
5
18
9.9
8
129.0 128.5 128.0 127.5 127.0 126.5 126.0 125.5 125.0 124.5 124.0 123.5 123.0 122.5 122.0 121.5 121.0ppm
CCH
CHCHCH
CHCH
CH
CH
12
0.9
8
12
1.3
2
12
2.0
2
12
3.4
3
12
6.3
1
12
7.9
1
12
8.7
41
28.8
31
28.9
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
30
.25
12
1.3
212
2.0
2
12
6.3
112
7.9
11
28.7
51
28.9
61
31.4
21
34.6
1
S34
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-1-phenyl-4-(p-tolyl)indeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4j)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.444.12 3.082.01
TMS
(CH3)3
CH3
CH
CH
CH
CH
CH
CH
CHCH
0.00
1.16
1.55
2.50
7.23
7.26
7.327.56
7.58
7.59
7.978.36
8.38
8.39
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2ppm
4.12 3.14 2.642.01 1.111.01
CH
Chloroform-d
CHCHCH
CH
CH
CH
CHCH
7.23
7.26
7.32
7.34
7.36
7.37
7.39
7.397.
417.
417.
437.
437.54
7.55
7.56
7.58
7.59
7.59
7.60
7.617.
977.
998.36
8.38
8.39
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
TMS
CH3
(CH3)3
C-(CH3)3
Chloroform-d
C
C
CH
CH
CH
CH
CH
CH
CH
C
CH
C
C
C
CC
CC
CC
0.0
0
21
.58
30
.29
34
.27
76
.70
77
.02
77
.34
11
5.0
71
21.1
61
21.2
91
22.0
11
23.4
0
12
8.6
11
28.9
41
31.3
71
34.5
71
37.6
21
38.5
71
39.2
41
42.0
71
46.6
41
53.5
41
57.0
7
16
3.8
6
19
0.0
8
129.0 128.5 128.0 127.5 127.0 126.5 126.0 125.5 125.0 124.5 124.0 123.5 123.0 122.5 122.0 121.5 121.0ppm
CCH
CH
CHCH
CH
CH
CH
12
1.1
6
12
1.2
9
12
2.0
1
12
3.4
0
12
6.2
7
12
8.6
1
12
8.9
4
129.0ppm
CH
CH
CH
12
8.5
91
28.6
1
12
8.9
5
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
21
.58
30
.29
12
1.3
012
2.0
11
23.4
012
8.5
91
28.9
5
13
4.5
7
S35
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-4-(4-chlorophenyl)-1-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4k)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.444.112.01
CH CHCH
CH
CH
CH
CH
CH
CH
(CH3)3
8.3
78
.35
7.9
97
.97
7.5
87
.58 7
.57
7.5
27
.49
7.3
27
.29
7.2
5
1.5
5
1.1
6
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
4.11 2.04 2.042.01 1.051.051.00
CHCH
CHCH
CH
CH
CH CH
CH
8.3
78
.37
8.3
58
.34
7.9
97
.97
7.6
27
.61
7.6
07
.59 7.5
8 7.5
77
.55 7.5
4 7.5
2
7.4
97
.49
7.4
47
.44
7.4
27
.42
7.4
17
.38
7.3
67
.35
7.3
27
.31 7
.29
7.2
5
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C CC
CC C C
C C
CH
CCH
CH
CH
CH
CH CH
CH
C
C
Chloroform-d
C-(CH3)3
(CH3)3
TMS
18
9.9
5
16
3.8
2
15
6.8
21
53.5
4
14
4.7
11
42.0
11
39.1
11
37.5
01
34.9
91
34.7
81
30.2
41
28.9
91
28.3
11
26.4
3
12
2.0
51
21.4
21
20.9
41
14.6
2
77
.34
77
.03
76
.71
34
.24
30
.35
0.0
0
135 134 133 132 131 130 129 128 127 126 125 124 123 122 121ppm
CCH
C
CH
CH CH CH
CH CH
CH
CH
C
13
4.9
91
34.7
81
34.6
4
13
1.5
5 13
0.2
4
12
8.9
9
12
8.3
1
12
6.4
3
12
3.4
9 12
2.0
5
12
1.4
2
12
0.9
4
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.7
81
30.2
41
28.9
91
28.3
0
12
3.4
9 12
2.0
51
21.4
2
30
.35
S36
1H and 13C{1H} NMR spectra of 4-(4-bromophenyl)-3-(tert-butyl)-1-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4l)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.404.132.02
CHCH CH
CH
CH
CH
CH
Chloroform-d
CH
(CH3)3
8.3
68
.34
8.3
47
.98
7.9
6 7.6
67
.64
7.5
87
.56 7.2
57
.23
7.2
2
1.5
6
1.1
6
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2ppm
4.13 2.542.052.02 1.09 1.051.00
CHCH
CH
CH
CH
CH
CHCH
Chloroform-d
CH
8.3
68
.36
8.3
48
.34
7.9
87
.96
7.6
77
.66
7.6
47
.61 7.5
97
.59 7
.58 7
.56
7.5
4
7.4
47
.44
7.4
27
.42
7.4
07
.40
7.3
87
.36
7.3
4
7.2
67
.25
7.2
37
.22
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C CC
CC C C
CC
CH
CH
CH
CH
CH
CH
C
CH
CH
C
C
Chloroform-d
C-(CH3)3
(CH3)3
TMS
18
9.9
2
16
3.8
0
15
6.8
11
53.5
3
14
4.6
41
41.9
9
13
7.4
81
35.1
31
34.7
81
31.2
31
30.4
91
28.9
81
26.4
3
12
2.0
51
21.4
11
20.8
61
14.5
1
77
.34 77
.02
76
.70
34
.23
30
.35
0.0
0
135 134 133 132 131 130 129 128 127 126 125 124 123 122 121ppm
CCH CH
CH CH CH
CH CHC
CH
CHC
13
5.1
3
13
4.7
8
13
1.5
5
13
1.2
3
13
0.4
9
12
8.9
8
12
6.4
3
12
3.4
9
12
3.1
3 12
2.0
5
12
1.4
1
12
0.8
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.7
81
31.5
5 13
1.2
21
30.4
91
28.9
8
12
3.4
9 12
2.0
41
21.4
1
30
.35
S37
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-1-phenyl-4-(4-(trifluoromethyl)phenyl)indeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4m)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.344.162.00
CH CH
CH
CH
CH
CH
CH
CH
Chloroform-d
(CH3)3
TMS
8.3
78
.35
7.8
07
.78
7.5
97
.57
7.5
67
.52 7
.26
1.1
3
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
4.162.06 2.032.00 1.05 1.031.00
CH CHCH
CH
CH CHCH CH
Chloroform-d
8.3
78
.37
8.3
58
.35
8.0
07
.98
7.8
0
7.7
8
7.6
27
.61
7.6
17
.59
7.5
97
.59
7.5
87
.57
7.5
77
.56
7.5
57
.52
7.5
07
.45
7.4
57
.43
7.4
37
.42
7.4
17
.39
7.3
87
.36
7.2
6
131 130 129 128 127 126 125 124 123 122 121ppm
CH
C-CF3
C-CF3
C-CF3
C-CF3
CH CH
CHCH-C-CF3
CH
CH
CH
C
13
1.6
51
31.6
11
31.2
9
13
0.9
6
13
0.6
4
12
9.4
0
12
9.0
1
12
6.5
2
12
4.9
91
24.9
51
24.9
2
12
3.5
3 12
2.0
9
12
1.4
8
12
0.7
1
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
30
.29
12
1.4
912
2.0
9
12
6.5
212
9.0
11
29.4
01
31.6
51
34.8
8
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
(CH3)3
C-(CH3)3
C
C
CH
CH
CH
CH
CH
CH
C-CF3
C-CF3
C-CF3
C-CF3
CH
CH
C
C
C
CCCCCC
0.0
0
30
.29
34
.16
76
.70
77
.02
77
.33
11
4.2
71
20.7
112
1.4
81
22.0
9
12
6.5
21
29.0
11
29.4
01
31.6
51
34.8
71
37.4
31
39.0
6
14
2.0
01
44.1
5
15
3.5
41
56.7
0
16
3.8
0
18
9.8
6
S38
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-4-(4-methoxyphenyl)-1-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4n)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.094.12 3.092.082.02
CH CHCH
CH
CH
CH
CH
CH
Chloroform-d
CH
CH3
(CH3)3
TMS
8.3
88
.36
7.9
8 7.5
87
.58
7.5
67
.54
7.4
3 7.2
87
.26
7.2
67
.06
7.0
4
3.9
2
1.5
6
1.1
7
0.0
0
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 7.0ppm
4.12 2.66 2.082.02 1.11 1.041.02
CH
CH
CH
CH
CH
CHCH
CH
Chloroform-d
CH
8.3
88
.38
8.3
68
.36
7.9
87
.97
7.6
17
.60
7.5
8
7.5
77
.56
7.5
67
.54
7.4
37
.43 7.4
17
.40
7.3
9
7.3
77
.35
7.3
47
.28 7.2
67
.26
7.0
77
.06
7.0
4
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C CC C
C CC C
C
CH
CH
CH
C
CH
CH
CH
C
CH
C
CH
Chloroform-d
CH3
C-(CH3)3
(CH3)3
TMS
19
0.1
8
16
3.8
8
16
0.0
11
57.0
91
53.5
5
14
6.4
11
42.0
7
13
7.6
21
34.5
91
31.3
91
30.0
11
28.9
51
26.2
71
22.0
11
21.3
1
11
5.3
01
13.3
8
77
.34
77
.03
76
.71
55
.28
34
.32
30
.31
0.0
0
131.5131.0 130.5 130.0 129.5 129.0 128.5 128.0 127.5 127.0 126.5 126.0 125.5 125.0 124.5 124.0 123.5 123.0 122.5 122.0 121.5 121.0ppm
CH
CH CH
CCH CH
CH
C
CH
13
1.3
9 13
0.0
1
12
8.9
5
12
8.3
2
12
6.2
7
12
3.4
0 12
2.0
1
12
1.3
61
21.3
1
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.6
01
31.3
9 13
0.0
11
28.9
6
12
3.4
1 12
2.0
11
21.3
1 11
3.3
8
55
.29
30
.31
S39
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-4-(4-nitrophenyl)-1-phenylindeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4o)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.366.092.00
CH
CH
CH
CH
CH
CH
CH
CH
CH
Chloroform-d
(CH3)3
TMS
8.4
2 8.4
18
.39
8.3
68
.34
8.0
17
.60 7
.58
7.5
67
.40
7.2
6
1.5
9
1.1
4
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
6.092.002.00 1.08 1.041.01
CHCH
CH CH
CH
CH
CH
CH CH
Chloroform-d
8.4
28
.41
8.4
0 8.3
98
.39 8.3
68
.36
8.3
48
.34
8.0
17
.99
7.6
47
.64
7.6
27
.62
7.6
07
.58
7.5
7 7.5
6
7.4
77
.46
7.4
57
.44
7.4
37
.43
7.4
17
.40
7.3
97
.37
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C C C C C C
C
C
C
C
CH
CH
CH
CH
CH CH
CH
C
C
Chloroform-d
C-(CH3)3
(CH3)3
TMS
18
9.7
7
16
3.7
7
15
6.4
8
14
8.2
21
43.1
91
42.9
91
41.9
71
38.9
51
35.0
41
31.7
71
30.1
71
29.0
51
23.6
3 12
3.2
91
22.1
41
21.5
81
20.4
81
13.7
8
77
.34
77
.02
76
.71
34
.16
30
.40
0.0
0
143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122ppm
C
C
C C CCH CH
CH CH
CHCH
CH
CH
CH
14
3.1
91
42.9
9
14
1.9
7
13
8.9
5
13
7.3
4
13
5.0
4
13
1.7
7
13
0.1
7
12
9.0
5
12
6.6
6
12
3.6
31
23.2
9
12
2.1
4
12
1.5
8
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
5.0
41
31.7
7 13
0.1
71
29.0
41
23.6
21
23.2
91
22.1
31
21.5
8
30
.40
S40
1H and 13C{1H} NMR spectra of 3-(tert-Butyl)-1-(4-chlorophenyl)-4-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4p)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.055.092.00
CHCH
CH
CH
CH
CH
CH
CH
CH
Chloroform-d
(CH3)3
TMS
8.3
68
.34
7.9
77
.58
7.5
47
.52
7.5
07
.36
7.3
47
.26
1.5
4
1.1
4
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
5.092.09 2.032.00 1.021.01
CHCH CH
CH CH
CH
CH
CHCH
Chloroform-d
8.3
6
8.3
4
7.9
77
.95
7.6
2
7.6
07
.58
7.5
6
7.5
4 7.5
2
7.5
07
.49
7.4
57
.43
7.4
1 7.3
6
7.3
4
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
CC
C C C C
C
C
CHC
CH
CH
CH
CH CH
CH
CH
C
C
Chloroform-dC-(CH3)3
(CH3)3
TMS
18
9.8
2
16
3.9
5
15
7.2
8
15
3.5
4
14
6.2
71
41.9
01
37.8
11
36.0
51
34.6
81
31.5
51
29.0
21
28.7
11
27.9
31
23.5
0
12
2.9
01
21.3
01
21.1
11
15.0
0
77
.34
77
.03
76
.71
34
.28
30
.19
0.0
0
138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121ppm
C C CCH CH
C CH
CH
CH
CH
CH
CH
CH
C
13
7.8
1
13
7.5
3
13
6.0
5
13
4.6
8
13
1.5
51
31.4
7 12
9.0
21
28.9
01
28.7
1
12
7.9
3
12
3.5
0
12
2.9
0
12
1.3
01
21.1
1
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.6
91
31.5
5 12
9.0
31
28.7
11
27.9
4
12
2.9
01
21.3
0
30
.19
S41
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-1-(4-chlorophenyl)-4-(p-tolyl)indeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4q)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.493.122.512.021.00
CH CH CH
CH
CH
CH
CH
Chloroform-d
CH
CH3
(CH3)3
TMS
8.3
98
.37
7.5
97
.58 7
.53
7.5
1
7.3
27
.26
7.2
47
.22
2.5
0
1.5
5
1.1
5
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2ppm
2.512.08 2.032.02 2.011.061.00
CH
CH CH
CH CH
CHCH
Chloroform-d
CH
8.3
9
8.3
7
7.9
77
.95
7.6
17
.60
7.5
97
.58
7.5
77
.56
7.5
37
.52
7.5
1
7.4
47
.44
7.4
27
.42
7.4
0 7.3
3 7.3
2 7.2
67
.24
7.2
2
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C C C C CC C
C
C
CH
C
C
CH
CH
CH
CH
CH
C
CH
C
Chloroform-d
C-(CH3)3
(CH3)3
CH3
TMS
189.
93
163.
97
157.
37
153.
52
146.
7214
1.91
138.
66
137.
57 134.
6513
1.51
129.
0212
8.55
123.
4712
2.89
121.
27
115.
23
77.3
477
.02
76.7
1
34.3
1
30.2
3
21.5
8
0.00
138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122ppm
C CCH
CCH
C
CH CH
CH
CH
CH
C
CH
137.
84
137.
57
134.
65
133.
02
131.
51
129.
69 129.
0212
8.63
128.
55
123.
47
122.
89
121.
3012
1.27
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
134.
6413
1.51 12
9.01
128.
5512
3.47 12
2.89
121.
27
30.2
3
21.5
8
S42
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-1,4-bis(4-chlorophenyl)indeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4r)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.534.052.04
CH CH CH
CH
CH
CH
CH
CH
Chloroform-d
(CH3)3
TMS
8.3
78
.35
7.6
07
.58 7.5
37
.52
7.5
17
.49
7.3
07
.28
1.5
5
1.1
5
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
4.05 2.252.092.04 1.061.00
CH
CHCH
CH CH
CH
CH
CH
Chloroform-d
8.3
88
.37
8.3
58
.35
8.3
4 7.9
87
.96
7.6
27
.62 7.6
17
.60
7.5
87
.57
7.5
47
.53
7.5
27
.51
7.4
97
.49
7.4
57
.45
7.4
37
.43
7.4
17
.41
7.3
17
.30
7.2
87
.28
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C CC
CC C
C
C
C
C
C
CH
CH
CH
CH CH
CH
CH
C
C
Chloroform-d
C-(CH3)3
(CH3)3
TMS
18
9.7
9
16
3.9
3
15
7.1
01
53.5
21
44.7
91
41.8
4
13
7.4
41
35.0
71
34.8
4
13
1.6
81
30.2
01
29.0
51
28.3
31
23.5
51
22.9
31
21.3
91
21.0
81
14.7
8
77
.34
77
.02
76
.70
34
.28
30
.29
0.0
0
137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121ppm
C C C
CH
CC
CH CH CH CH
CH
CH
CH
C
13
7.7
1
13
7.4
4
13
5.0
71
34.8
4
13
4.4
6
13
1.7
11
31.6
8
13
0.2
0
12
9.0
5
12
8.3
3
12
3.5
5 12
2.9
3
12
1.3
9
12
1.0
8
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.8
51
31.6
81
30.2
11
29.0
61
28.3
3
12
2.9
31
21.3
9
30
.29
S43
1H and 13C{1H} NMR spectra of 4-(4-bromophenyl)-3-(tert-butyl)-1-(4-chlorophenyl)indeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4s)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.022.472.01 2.00
CH CHCH
CH
CH
CH
CH
Chloroform-d
CH
(CH3)3
TMS
8.3
78
.35
7.9
6 7.6
77
.65
7.5
9 7.5
37
.51
7.2
47
.22
1.5
4
1.1
5
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2ppm
2.472.012.012.01 2.00 1.091.02
CH
CH
CH
CH
CH CH
CH
Chloroform-d
CH
8.3
78
.35
8.3
5
7.9
87
.96
7.6
87
.67
7.6
57
.63
7.6
17
.61
7.5
97
.57
7.5
37
.51
7.5
1
7.4
67
.45
7.4
47
.43
7.4
27
.42
7.2
67
.24
7.2
2
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C CC
CC C
C
C
C
CH
C
CH
CH
C
CH
CH
C
C
Chloroform-d
C
(CH3)3
TMS
18
9.7
8
16
3.9
3
15
7.1
0
15
3.5
3
14
4.7
41
41.8
51
37.7
11
37.4
41
34.8
61
31.2
51
30.4
61
29.0
6
12
3.5
71
22.9
51
21.4
01
21.0
11
14.6
9
77
.34
77
.02
76
.71
34
.27
30
.30
0.0
0
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.8
61
31.7
0 13
1.2
61
30.4
61
29.0
71
23.5
8 12
2.9
51
21.4
0
30
.30
137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121ppm
C CC
CH
C
CH
CHC
CH
CH
C
13
7.7
11
37.4
4
13
4.9
51
34.8
6
13
1.7
31
31.7
0 13
1.2
5
13
0.4
6
12
9.0
6
12
3.5
7
12
3.2
2 12
2.9
5
12
1.4
0
12
1.0
1
S44
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-1-(4-chlorophenyl)-4-(4-(trifluoromethyl)phenyl)-
indeno[1,2-b]pyrazolo[4,3-e]pyridin-5(1H)-one (4t)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.334.042.00
CHCH
CH
CH
CH
CH
CH
CH
Chloroform-d
(CH3)3
TMS
8.3
78
.35
7.9
77
.80
7.7
8 7.5
47
.52
7.5
17
.49
7.2
6
1.1
2
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
4.042.042.00 1.05 1.05 1.051.03
CH
CHCH
CH CH
CH CH
CH
Chloroform-d
8.3
78
.35
8.3
5
7.9
97
.97
7.8
0
7.7
8
7.6
47
.63
7.6
27
.61
7.6
07
.60
7.5
87
.56
7.5
47
.52
7.5
27
.51
7.4
97
.46
7.4
67
.44
7.4
47
.42
7.4
2
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C C CC
CC
CC
C
C
CH
C-CF3
C-CF3
C-CF3
C-CF3
CH
CH
CF3
CF3
CH
CF3
CH
C
CF3
C
Chloroform-d
C
(CH3)3
TMS
18
9.7
1
16
3.9
2
15
7.0
0
15
3.5
4
14
4.2
41
41.8
51
37.6
61
37.3
81
34.9
61
31.7
9 12
9.3
81
29.0
91
24.9
91
22.9
91
21.4
71
20.8
51
20.0
01
14.4
4
77
.35
77
.03
76
.71
34
.21
30
.24
0.0
0
137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121 120ppm
C C
CH C
CH
C-CF3
C-CF3
C-CF3
CH
CH
CF3
CF3
CH-CCF3
CH
CH
CF3
CH
CCF3
13
7.6
61
37.3
8
13
4.9
6
13
1.8
21
31.7
91
31.7
01
31.3
71
31.0
5
13
0.7
2
12
9.3
8
12
9.0
9
12
8.1
1
12
5.4
11
25.0
31
24.9
9
12
3.6
1 12
2.9
91
22.7
1 12
1.4
7
12
0.8
5
12
0.0
0
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.9
61
31.7
9 12
9.3
81
29.0
91
24.9
5
12
2.9
91
21.4
7
30
.24
S45
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-1-(4-chlorophenyl)-4-(4-methoxyphenyl)indeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4u)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.423.112.432.031.00
TMS
(CH3)
CH3
CHCH
CH
CH
CH
CH
CH
0.0
0
1.1
6
1.5
6
3.9
2
7.0
47
.06
7.2
57
.27
7.5
07
.52
7.5
67
.59
7.9
58.3
68
.38
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 7.0ppm
2.43 2.062.052.03 2.03 1.041.00
CHCH
Chloroform-d
CH
CH
CH
CH
CH
CH
7.0
47
.06
7.2
47
.25
7.2
67
.27
7.4
07
.407.4
27
.42
7.4
37
.44
7.5
07
.52
7.5
67
.57
7.5
87
.59
7.5
97
.61
7.6
17.9
57
.97
8.3
68
.38
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
TMS
(CH3)3
C-(CH3)3
CH3
Chloroform-d
CH
C
CH
C
CH
CH
CH
CH
CH
C
CH
CH
C
C
CCC
CCCC
0.0
0
30
.24
34
.35
55
.28
76
.71
77
.03
77
.34
11
3.3
91
15.4
612
1.2
7
12
2.8
81
23.4
7
12
8.1
11
29.0
11
29.9
81
31.5
2
13
4.6
6
13
7.5
51
37.8
31
41.9
0
14
6.5
0
15
3.5
3
15
7.3
71
60.0
6
16
3.9
8
19
0.0
2
142 141 140 139 138 137 136 135 134 133 132 131 130 129 128 127 126 125 124 123 122 121ppm
CH
C
CHCH
CH
CHCHC
CH
CH
CCC
12
1.2
71
21.4
812
2.8
8
12
3.4
7
12
8.1
1
12
9.0
1
12
9.9
8
13
1.4
91
31.5
2
13
4.6
6
13
7.5
5
13
7.8
3
14
1.9
0
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
30
.24
55
.28
11
3.3
9
12
1.2
712
2.8
81
23.4
6
12
9.0
11
29.9
81
31.5
01
34.6
6
S46
1H and 13C{1H} NMR spectra of 3-(tert-butyl)-1-(4-chlorophenyl)-4-(4-nitrophenyl)indeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-one (4v)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.124.984.00
CH
CH
CH
CH
CH
CH
CH
CH
Chloroform-d
(CH3)3
TMS8
.41
8.3
98
.37
8.3
4
7.9
87
.63 7
.57
7.5
7 7.5
47
.52
7.4
57
.26
1.5
7
1.1
4
0.0
0
8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
4.984.00 1.12 1.091.09
CHCH
CH CH
CH
CH
CH
CH
Chloroform-d
8.4
28
.41
8.4
18
.39
8.3
88
.37
8.3
68
.34
8.3
4 8.0
07
.98
7.6
57
.65 7.6
37
.63
7.6
17
.58
7.5
7
7.5
77
.55
7.5
47
.54
7.5
27
.51
7.4
77
.47
7.4
57
.45
7.4
37
.43
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
CC C
CC
C
C
C
C
C
CHC
CH
CH
CH
CH
CH
CH
CH
C
C
Chloroform-d C-(CH3)3
(CH3)3
TMS
18
9.6
1
16
3.8
8
15
6.7
61
53.5
3
14
8.2
7
14
2.9
91
41.8
1
13
5.1
21
31.9
01
30.1
51
29.1
2
12
3.7
01
23.3
11
23.0
21
21.5
61
20.6
2
11
3.9
5
77
.36
77
.03
76
.71
34
.20
30
.35
0.0
0
137 136 135 134 133 132 131 130 129 128 127 126 125 124 123ppm
C CCH C
CH CH CH
CH
CHCH
13
7.5
5
13
7.2
8
13
5.1
2
13
1.9
61
31.9
0 13
0.1
5
12
9.1
2
12
3.7
0 12
3.3
1
12
3.0
2
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
5.1
21
31.9
1 13
0.1
51
29.1
21
23.7
0 12
3.3
11
23.0
21
21.5
7
30
.35
S47
1H and 13C{1H} NMR spectra of 1-(4-chlorophenyl)-3-methyl-4-phenylindeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4w)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
5.35 3.072.01
CH CHCH
CH
CH
CH
Chloroform-d
CH3
TMS
8.3
38
.33
8.3
07
.97
7.9
5
7.6
17
.54
7.5
17
.48
7.4
47
.43
7.2
6
2.0
4
1.5
9
0.0
0
8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
5.35 3.262.162.01 1.00
CH
CH CH
CHCH
CHChloroform-d
8.3
38
.33
8.3
18
.30
8.3
0 7.9
77
.95
7.6
3
7.6
17
.60
7.5
87
.55
7.5
4
7.5
37
.52
7.5
17
.50
7.4
87
.48
7.4
57
.45
7.4
47
.43
7.4
37
.42
7.4
17
.40
7.2
6
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C CC
C
C
C C
C
CH
CCH
CH
CH
CH
CH
CH
CH
C
C
Chloroform-d
CH3
TMS
18
9.7
5
16
5.1
8
15
2.7
6
14
6.2
2
14
2.2
61
37.6
11
37.3
4 13
4.7
51
31.6
01
29.1
1
12
8.0
21
23.5
41
22.3
81
21.4
01
20.1
7
11
5.7
3
77
.34
77
.03
76
.71
14
.81
0.0
0
146 145 144 143 142 141 140 139 138 137 136 135 134 133 132 131 130 129 128ppm
C C C C CCH
CCH
CH
CH
CH CH
14
6.2
2
14
5.9
2
14
2.2
6
13
7.6
11
37.3
4
13
4.7
5
13
2.6
0
13
1.6
0
12
9.2
51
29.1
1
12
8.6
1
12
8.0
2
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
13
4.7
51
31.6
11
29.1
21
28.6
21
28.0
3
12
3.5
41
22.3
91
21.4
0
14
.81
S48
1H and 13C{1H} NMR spectra of 3-(tert-Butyl)-1-(4-nitrophenyl)-4-phenylindeno[1,2-b]pyrazolo[4,3-
e]pyridin-5(1H)-one (4x)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.106.342.04
CH
CH
CHCH
CH
CH
CH
CH
CH
DMSO-d6
TMS
8.7
28
.70
8.4
38
.41
8.0
6 7.5
57
.54
7.5
17
.50
7.4
07
.38
3.3
2
2.4
82
.47
1.1
1
0.0
0
8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4ppm
6.342.04 2.032.03 1.04
CH CH
CH
CH
CH
CH
CH
CH
CH
8.7
2 8.7
0
8.4
3
8.4
1
8.0
68
.04
7.5
67
.55 7.5
47
.52
7.5
17
.50
7.4
87
.48
7.4
77
.40
7.4
07
.38
7.3
8
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
(CH3)3
C-(CH3)3
DMSO-d6
C
C
CH
CH
CH
CH
CH
CH
CH
CH
CH
C
C
C
CC
C
CCCC 29
.19
33
.37
38
.87
39
.08
39
.2939
.50
39
.70
39
.92
40
.13
11
4.7
11
20.0
112
0.5
2
12
4.0
11
26.9
31
28.2
21
31.4
21
34.4
11
34.8
41
35.0
51
36.3
51
43.0
01
44.4
21
45.6
0
15
7.5
5
16
3.1
9
18
7.5
3
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
29
.19
12
0.5
1
12
4.0
11
26.9
412
8.2
31
31.4
31
34.4
1
145 140 135 130 125 120ppm
C
CH
CH
CHCH
CHCH
CH
CHCHC
C
CCCCC
12
0.0
1
12
0.5
21
20.6
8
12
2.0
7
12
4.0
1
12
6.9
3
12
8.2
2
13
1.4
2
13
4.4
1
13
4.8
41
35.0
5
13
6.3
5
14
0.4
4
14
3.0
0
14
4.4
2
14
5.6
0
128.2ppm
12
8.2
0
12
8.2
2
S49
1H and 13C{1H} NMR spectra of 2-(4-(Dimethylamino)benzylidene)-1H-indene-1,3(2H)-dione (6h)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
6.222.072.032.02
CH
CH
=CH
CH
Chloroform-d
CH
N(CH3)2
TMS
8.53
8.51
7.91
7.91
7.77
7.72
7.71
7.70 7.26 6.74
6.72
3.13
1.66
0.00
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 7.0 6.9 6.8 6.7ppm
2.072.032.02 2.00 1.02
CH CH
=CH
CH Chloroform-d
CH
8.53
8.51
7.93
7.93
7.92 7.
917.
917.
917.
90 7.90
7.77
7.72 7.72
7.72 7.
717.
707.
70 7.26
6.74
6.72
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
C
CC
CH
C
C
CH
CH
CH
C
CH
CCH Chloroform-d
N(CH3)2
TMS
19
1.6
91
89.9
4
15
3.9
3
14
7.4
6
14
2.2
11
39.8
61
37.9
4
13
4.3
31
34.0
5
12
2.9
91
22.4
41
21.9
8
11
1.3
6
77
.31
77
.00
76
.67
40
.02
0.0
0
135 134 133 132 131 130 129 128 127 126 125 124 123 122ppm
CHCH
C
CH
C
13
4.3
3
13
4.0
5
12
2.9
9 12
2.4
4
12
1.9
8
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
CH CH
CHCH
CH
N(CH3)2
14
7.4
6
13
7.9
41
34.3
31
34.0
5
12
2.4
3
11
1.3
6
40
.02
S50
1H and 13C{1H} NMR spectra of 2-(3-Methyl-1,4-diphenylindeno[1,2-b]pyrazolo[4,3-e]pyridin-
5(1H)-ylidene)malononitrile (7a)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
9.57 3.232.02
TMSH2O
CH3
Chloroform-d
CH
CH
CH
CH
CH CH
CH
CH
CH
CH
0.0
0
1.5
6
2.1
0
7.2
67
.377.5
07
.52
7.5
67.6
17
.62
7.6
3
8.2
58
.27
8.4
88
.50
8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
9.572.02 1.02 1.011.00
CHCH
CH
CH
CH CH
CH
CHCH
CH
7.2
6
7.3
57
.37
7.3
9
7.4
87.5
07
.50
7.5
17.5
27
.54
7.5
67
.58
7.6
07
.61
7.6
2
7.6
37
.64
7.6
5
8.0
48
.06
8.2
5
8.2
7
8.4
88
.50
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
TMS
CH3
Chloroform-d
CC
C
CH
C
CH
CH
CH
C
CH
CH
CH
CH
CH
CH
C
C
C
C
C
C
CCC
16
.11
76
.74
77
.05
77
.37
77
.55
11
1.7
41
14.7
81
15.6
71
21.6
6
12
2.4
21
25.9
3
12
9.1
61
29.6
01
29.8
61
30.5
61
31.4
71
34.0
81
34.2
21
38.6
61
38.7
41
39.8
41
46.0
21
47.7
11
52.2
81
60.0
11
62.1
0
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0ppm
CH3
CH
CH
CHCH
CH
CH
CH
CH
CH
16
.1212
1.6
61
22.4
2
12
6.6
81
29.1
61
29.6
01
29.8
51
30.5
61
31.4
71
34.0
8
130 125ppm
CH
C
CHCHCHC
CHCH
CH
CHCHCH
C
12
1.6
61
21.7
6
12
2.4
2
12
5.9
3
12
6.6
8
12
8.6
612
9.1
6
12
9.6
01
29.8
6
13
0.5
6
13
1.4
7
13
4.0
81
34.2
2
S51
1H and 13C{1H} NMR spectra of 2-(4-(4-methoxyphenyl)-3-methyl-1-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-ylidene)malononitrile (7b)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
3.21 3.102.102.02
TMSH2O
CH3
CH3
CH
Chloroform-d
CH
CH
CH
CH
CH
CH
CH
0.0
0
1.5
5
2.1
93.9
3
7.1
27
.12
7.1
57
.26
7.4
27
.44
7.5
67
.61
8.0
38.2
58
.27
8.4
78
.49
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 7.1ppm
2.10 2.042.02 2.00 1.061.031.011.01 1.00
CH
Chloroform-d
CH
CH
CHCH
CHCHCH
CH
7.1
27
.12
7.1
57
.15
7.2
67
.35
7.3
57.3
77
.38
7.3
87
.39
7.4
17
.42
7.4
4
7.4
97
.49
7.5
17
.54
7.5
57
.56
7.5
87
.59
7.6
17
.61
7.6
37
.63
8.0
38
.05
8.2
48.2
58
.25
8.2
78
.27
8.4
78
.49
7.60 7.55 7.50 7.45 7.40 7.35ppm
2.102.00 1.061.031.01
CH
CH
CHCHCH
7.3
47
.35
7.3
5
7.3
7
7.3
87
.38
7.3
9
7.4
1
7.4
2
7.4
3
7.4
47.4
4
7.4
5
7.4
77
.48
7.4
97
.49
7.5
17
.51
7.5
37.5
47
.54
7.5
57
.56
7.5
6
7.5
7
7.5
8
7.5
97
.59
7.6
17
.61
7.6
37
.63
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0ppm
CH3CH3
CHCH
CH
CH
CHCH
CH
CH
16
.41
55
.5311
5.1
8
12
1.6
91
22.3
91
25.8
51
26.6
412
9.1
51
31.3
51
33.9
8
134 133 132 131 130 129 128 127 126 125 124 123 122 121 120 119 118 117 116 115ppm
C
CH
C
CH
CCHCH
CCH
C
CHCH
CH
CH
11
4.8
6
11
5.1
8
11
5.8
8
12
1.6
9
12
2.0
3
12
2.3
8
12
5.8
5
12
6.3
0
12
6.6
4
12
8.2
9
12
9.1
5
13
1.3
51
31.3
9
13
3.9
8
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
CH3CH3
Chloroform-d
CC
CH
C
CH
C
CH
CH
CCCH
CH
CH
C
C
CC
C
C
16
.41
55
.53
76
.7377
.05
77
.36
11
1.8
71
14.8
611
5.1
81
15.8
812
1.6
9
12
2.3
81
26.6
4
12
9.1
51
31.3
51
33.9
8
13
9.8
8
14
6.0
3
16
0.4
11
61.5
31
61.9
4
S52
1H and 13C{1H} NMR spectra of 2-(3-Methyl-1-phenyl-4-(4-(trifluoromethyl)phenyl)indeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-ylidene)malononitrile (7c)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
3.05 3.052.02
CH3
Chloroform-d
CH
CH
CH
CH
CH
CH
CH
CH
CH
1.5
5
2.0
7
7.2
6
7.5
47
.56
7.5
87
.63
7.6
37
.66
7.8
77
.89
8.2
48
.26
8.4
88
.50
8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3ppm
3.053.022.02 2.011.011.00 1.00
Chloroform-d
CHCH
CHCHCH
CH
CH
CH
CH
7.2
6
7.3
67
.36
7.3
67.3
8
7.4
07
.40
7.4
97
.51
7.5
17
.53
7.5
37
.54
7.5
47
.56
7.5
67
.58
7.6
17.6
37
.63
7.6
47
.66
7.8
7
7.8
9
8.0
58
.06
8.2
38
.24
8.2
4
8.2
68
.26
8.4
88
.50
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
TMS
CH3
Chloroform-d
CC
C
CH
C
C
CH
CH
CH
CH
CH
Ci-CF3
CH
C
C
C
C
C
C
CCC
0.0
0
16
.17
76
.73
77
.05
77
.37
11
1.8
81
14.4
21
15.2
01
21.6
91
22.5
41
26.8
81
29.2
11
30.3
81
31.7
11
34.3
11
38.5
01
39.6
61
45.4
91
45.5
81
52.2
1
15
9.7
81
62.1
8
145 140 135 130 125ppm
CH
C
CCH
CoCF3
CH
CHCH
CH
Ci-CF3
CHCC
C
CC
C1
21.6
9
12
2.4
41
22.5
4
12
5.1
6
12
6.0
41
26.5
61
26.6
11
26.6
41
26.8
812
9.2
1
13
0.3
8
13
1.7
11
32.1
51
32.4
81
32.8
01
33.1
3
13
4.3
1
13
7.8
9
13
8.5
01
38.6
2
13
9.6
6
14
5.4
91
45.5
8
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0ppm
CH3
CH
CH
CH
CHo-CF3
CHCH
CH
CH
16
.171
21.7
01
22.5
41
26.0
31
26.8
812
9.2
11
30.3
81
31.7
11
34.3
2
S53
1H and 13C{1H} NMR spectra of 2-(4-(4-(Dimethylamino)phenyl)-3-methyl-1-phenylindeno[1,2-
b]pyrazolo[4,3-e]pyridin-5(1H)-ylidene)malononitrile (7d)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1ppm
6.253.15 3.102.08 2.05
TMS
CH3
(CH3)2
CH
CH CH
CH
CH
CH
CH
CH
CH
0.0
0
1.5
5
2.2
9
3.1
0
6.8
76
.897.2
67
.34
7.3
77
.53
7.5
57
.57
7.5
98
.00
8.2
58
.27
8.4
38
.45
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 7.0 6.9ppm
3.15 3.122.08 2.051.06 1.031.01
CH
Chloroform-d
CH CH
CH
CHCHCH
CH
CH
6.8
76
.89
7.2
6
7.3
37
.34
7.3
47
.37
7.3
7
7.4
77
.48
7.4
97
.507.5
37
.55
7.5
77
.58
7.5
97
.60
7.6
1
8.0
08
.028.2
58
.25
8.2
78
.27
8.4
38
.45
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10ppm
TMS
CH3
(CH3)2
Chloroform-d
C
CH
C
C
C
CH
C
CH
CH
CH
CH
CH
CH
C
C
CCC
C
C
C
0.0
0
16
.824
0.2
3
76
.74
77
.05
77
.38
11
1.9
81
12.5
71
15.1
3
12
1.0
51
21.6
81
25.6
41
26.4
81
29.1
01
31.1
71
33.7
1
13
8.8
21
39.8
9
14
6.1
71
49.0
71
51.7
01
52.5
7
16
1.1
01
61.8
1
160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0ppm
CH3
(CH3)2CH
CH
CH
CH
CH
CH
CH
CH
16
.824
0.2
3
11
2.5
7
12
1.6
81
22.2
4
12
6.4
812
9.1
01
31.1
71
33.7
2
127 126 125 124 123 122 121 120 119 118 117 116 115 114 113 112ppm
C
CH
CCC
CH
CCHCHCH
11
1.9
811
2.5
7
11
5.1
3
11
5.8
8
12
1.0
512
1.6
8
12
1.9
9
12
2.2
4
12
5.6
4
12
6.4
8
S54
8. ORTEP Drawing for Structure 7b
Fig. S12. ORTEP drawing for structure 7b. Displacement ellipsoids are drawn at the 70% probability level
and hydrogen atoms are shown as small spheres of arbitrary radius.
S55
9. HRMS analysis data of the final products 7a-d
S56
S57
S58
S59
S60
10. References
1 L. Palatinus and G. Chapuis, J. Appl. Cryst., 2007, 40, 786-790
2 G. M. Sheldrick, Acta Cryst., 2015, C71, 3-8.
3 C. F. Macrae, I. J. Bruno, J. A. Chisholm, P. R. Edgington, P. McCabe, E. Pidcock, L. Rodriguez-
Monge, R. Taylor, J. van de Streek and P. A. Wood, J. Appl. Cryst., 2008, 41, 466-470.
4 J. Quiroga, D. Cobo, B. Insuasty, R. Abonía, S. Cruz, M. Nogueras and J. Cobo, J. Heterocycl.
Chem., 2008, 45, 155–159.
5 J. Portilla, C. Lizarazo, J. Cobo and C. Glidewell, Acta Cryst., 2011, C67, 479–483.
6 C. Würth, M. Grabolle, J. Pauli, M. Spieles and U. Resch-Genger, Nat. Protoc., 2013, 8, 1535–
1550.
7 U. Resch-Genger and K. Rurack, Pure Appl. Chem., 2013, 85, 2005–2026.
8 G. A. Crosby and J. N. Demas, J. Phys. Chem., 1971, 75, 991–1024.
9 M. D. Hanwell, D. E. Curtis, D. C. Lonie, T. Vandermeersch, E. Zurek and G. R. Hutchison, J.
Cheminform., 2012, 4, 1–17.
10 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G.
Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. Marenich, J. Bloino, B.
G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L.
Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone,
T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada,
M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H.
Nakai, T. Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J.
Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K.
Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene,
C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman and
D. J. Fox, Gaussian 09, Revision A.1. Wallingford CT, 2009.
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