Synergetic effects of naturally sourced metal oxides in organic synthesis: A greener approach for synthesis

of pyrano[2,3-c]pyrazoles and pyrazolyl-4H-chromenesSachin K. Shinde1, Megha U. Patil1, Shashikant A. Damate1, Suresh S. Patil1

1 Synthetic Research Laboratory, PG Department of Chemistry, PDVP College, Tasgaon, Dist-Sangli 416312 (MS) India (Affiliated to

Shivaji University, Kolhapur).

Supporting Information

INDEX

Sr. No. Title

1. Experimental Section

2. Analytical and spectral data of unreported compounds

i Compound (5j)

ii Compound (5l)

iii Compound (5n)

iv Compound (5q)

v Compound (11)

vi Compound (7h)

vii Compound (7m)

viii Compound (7n)

3. Spectra of unreported compounds

i

6-amino-4-[4-(diethoxymethyl)phenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5j)

1H-NMR (Fig.1)

13C-NMR (Fig.2)

ii

6-amino-4-(3-ethoxy-4-hydroxyphenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5l)

1H-NMR (Fig.3)

12C-NMR (Fig.4)

iii

6-amino-4-(3-bromo-4-fluorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5n)

1H-NMR (Fig.5)

12C-NMR (Fig.6)

iv

6-amino-4-(2-bromo-5-fluorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5q)

1H-NMR (Fig.7)

12C-NMR (Fig.8)

v 4,4'-(thiophene-2,5-diyl)bis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile) 14

FT-IR (Fig.9)

1H-NMR (Fig.10)

12C-NMR (Fig.11)

vi

2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-8-methoxy-4H-chromene-3-carbonitrile (7h)

FT-IR (Fig.12)

1H-NMR (Fig. 13)

13C-NMR (Fig. 14)

vii

2-amino-8-bromo-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile (7m)

FT-IR (Fig.15)

1H-NMR (Fig. 16)

13C-NMR (Fig. 17)

viii

3-amino-1-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-1H-benzo[f]chromene-2-carbonitrile (7n)

FT-IR (Fig.18)

1H-NMR (Fig. 19)

13C-NMR (Fig. 20)

4. Some spectra of other synthesized compounds

Fig. 1.FT-IR Spectra of 6-amino-4-(phenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5a)

Fig. 2.1H-NMR spectra of 6-amino-4-(phenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5a)

Fig. 3.13C-NMR spectra of 6-amino-4-(phenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5a)

Fig. 4. Mass spectra of 6-amino-4-(phenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5a)

Fig. 5. FT-IR spectra of 6-amino-4-[4-chlorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5b)

Fig. 6.1H-NMR spectra of 6-amino-4-[4-chlorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5b)

Fig. 7.13C-NMR spectra of 6-amino-4-[4-chlorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5b)

Fig. 8.Mass spectra of 6-amino-4-[4-chlorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5b)

Fig. 9. FT-IR spectra of 6-amino-4-[4-nitrophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5e)

Fig. 10.1H-NMR spectra of 6-amino-4-[4-nitrophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5e)

Fig. 11.13C-NMR spectra of 6-amino-4-[4-nitrophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5e)

Fig. 12.Mass spectra of 6-amino-4-[4-nitrophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5e)

Fig. 13.FT-IR spectra of 6-amino-4-[4-hydroxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5g)

Fig. 14.1H-NMR spectra of 6-amino-4-[4-hydroxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5g)

Fig. 15.13C-NMR spectra of 6-amino-4-[4-hydroxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5g)

Fig. 16.Mass spectra of 6-amino-4-[4-hydroxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5g)

Fig. 17.1H-NMR spectra of 6-amino-4-[4-methoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5f)

Fig. 18.13C-NMR spectra of 6-amino-4-[4-methoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5f)

Fig. 19.1H-NMR spectra of 6-amino-4-[4-bromoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5c)

Fig. 20.13C-NMR spectra of 6-amino-4-[4-bromoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5c)

Fig. 21.1H-NMR spectra of 6-amino-4-[4-hyroxy-3-methoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5m)

Fig. 22.13C-NMR spectra of 6-amino-4-[4-hyroxy-3-methoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5m)

Fig. 23.1H-NMR spectra of 6-amino-4-[4-fluorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5d)

Fig. 24.13C-NMR spectra of 6-amino-4-[4-fluorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5d)

Fig. 25.1H-NMR spectra of 4,4'-(1,4-phenylene)bis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile)

Fig. 26.13C-NMR spectra of 4,4'-(1,4-phenylene)bis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile)

Fig. 27.1H-NMR spectra of 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 28.13C-NMR spectra of 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 29.1H-NMR spectra of 2-amino-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 30.13C-NMR spectra of 2-amino-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 31.1H-NMR spectra of 2-amino-6-bromo-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 32.13C-NMR spectra of 2-amino-6-bromo-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

1. Experimental section

Materials and methods

All chemicals were of reagent grade and procured from Sigma–Aldrich Pvt. Ltd, and were used without any further

purification. Analytical thin-layer chromatography (TLC) was carried out on precoated Merck silicagel 60 F254 aluminum plates.

Melting points were recorded on DBK programmable melting point apparatus and are uncorrected. IR spectra were obtained using

potassium bromide pellets on Bruker ALPHA FT-IR spectrometer. The 1H NMR and 13C NMR spectra of synthesized compounds

were recorded on a Bruker AC (300 MHz for 1H NMR and 75 MHz for 13C NMR) spectrometer using CDCl3 and DMSO as a solvent.

Chemical shifts (δ) are expressed in parts per million (ppm) values with tetramethylsilane (TMS) as the internal reference and

coupling constants are expressed in hertz (Hz). Mass spectra were recorded on a Shimadzu QP2010 GCMS with an ion source

temperature of 280 °C. SHIMADZU AA-7000 atomic absorption spectrophotometer (AAS) was used for elemental analysis by flame

emission method. The thermal gravimetric analysis (TGA) curves were obtained using the instrument TA SDT Q600 V20.9 Build 20

in the presence of static air at a linear heating rate of 10 °C min -1 from 25 °C to 1000 °C. XRD was taken using a Brucker D2 Phaser. It

was obtained in reflection mode with Cu Ka radiation (λ=1.5418Ao) at 30 kV, 10 mA, a scan speed of 1.0 degree min, -1 and a scan

range of 10-90o. The data was analysed in the 2θ/degree range from 2o to 70o with the scanning step of 0.5 per sec. A JEOL (Tokyo,

Japan) JSM-5200 scanning electron microscope was used for SEM analysis.

2. Analytical and spectral data of unreported compounds

6-amino-4-[4-(diethoxymethyl)phenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5j)

Pale yellow solid; MP (oC): 284-286; IR (KBr): 3498, 3390, 3106, 2961, 2183, 1648, 1618, 1510,

1302, 1100, 758 cm-1. 1H NMR (300 MHz, CDCl3+DMSO-d6) δH: 1.11 (t, 6H CH3), 1.76 (s, 3H, CH3)

3.50 (m, 4H, CH2), 4.58 (s, 1H, CH), 5.43 (s, 1H, CH), 6.88 (s, 2H, NH2), 7.14 (d, 2H, J=7.5 Hz, Ar-H),

7.32 (d, 2H, J=7.5 Hz, Ar-H), 12.10 (s, 1H, NH) ppm; 13C NMR (75 MHz, CDCl3+DMSO-d6) δC: 9.81,

15.20, 36.01, 57.08 60.88, 97.60, 100.97, 120.86, 126.63, 127.24, 128.37, 130.02, 135.68, 137.76,

144.42, 154.77, 160.93 ppm; MS/EI m/z: 354.1 (M+).

6-amino-4-(3-ethoxy-4-hydroxyphenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5l)

Yellow solid; MP (oC): 192-194; IR (KBr): 3568, 3465, 3390, 3000, 2946, 2177, 1654, 1615, 1536,

1406, 1130 cm-1. 1H NMR (300 MHz, CDCl3+DMSO-d6) δH: 0.96 (t, 3H, J=6.5 Hz, CH3) 1.94 (s, 3H,

CH3), 3.65 (q, 3H, J=6.5 Hz, CH2), 5.49 (s, 1H, CH), 6.62 (s, 2H, NH2), 6.72 (d, 1H, J=2.1 Hz, Ar-H),

6.88 (d, 1H, J=8.2 Hz, Ar-H), 7.16 (dd, 1H, J=8.2, 2.1 Hz, Ar-H), 9.43 (bs, 1H, OH), 12.14 (s, 1H, NH)

ppm; 13C NMR (75 MHz, CDCl3+DMSO-d6) δC: 9.90, 14.80, 29.64, 35.84, 57.71, 63.93, 97.97,

113.11, 115.57, 119.88,135.41, 145.58, 146.43, 154.80, 160.73, 169.71 ppm; MS/EI m/z: 312.1

(M+).

6-amino-4-(3-bromo-4-fluorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5n)

Brown solid; MP (oC): 224-226; IR (KBr): 3458, 3310, 3084, 2938, 2195, 1644, 1618, 1510, 1483,

1170 cm-1. 1H NMR (300 MHz, CDCl3+DMSO-d6) δH:1.79 (s, 3H, CH3), 4.67 (s, 1H, CH), 6.97 (s, 2H,

NH2), 7.21 (dd, 1H, J=8.5 Hz, Ar-H), 7.32 (dd, 1H, J=8.5, 2.3 Hz, Ar-H), 7.48 (d, 1H, J=2.3 Hz, Ar-H),

12.17 (s, 1H, NH) ppm; 13C NMR (75 MHz, CDCl3+DMSO-d6) δC:9.82, 35.15, 56.44, 97.01, 115.81,

117.68, 120.68, 128.95, 132.18, 135.89, 142.76, 155.49, 158.72, 161.03 ppm; MS/EI m/z: 348.0

(M+).

6-amino-4-(2-bromo-5-fluorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5q)

Yellow solid; MP (oC): 251-253; IR (KBr): 3464, 3326, 3104, 2942, 2184, 1654, 1608, 1505, 1443,

1158 cm-1. 1H NMR (300 MHz, CDCl3+DMSO-d6) δH:1.77 (s, 3H, CH3), 5.04 (s, 1H, CH), 7.02 (s, 2H,

NH2), 7.06 (d, 1H, J=2.1 Hz, Ar-H), 7.11 (dd, 1H, J=8.2, 2.1 Hz, Ar-H), 7.63 (d, 1H, J=8.2 Hz, Ar-H),

12.28 (s, 1H, NH) ppm; 13C NMR (75 MHz, CDCl3+DMSO-d6) δC: 9.72, 36.27, 55.26, 96.37, 116.33,

117.55, 120.28, 134.56, 135.61, 144.99, 154.91, 160.15, 161.42, 163.40 ppm; MS/EI m/z: 348.0

(M+).

4,4'-(thiophene-2,5-diyl)bis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile) 14

Brown solid; MP (oC): Above 310; IR (KBr): 3589, 3354, 3245, 2922, 2139, 1640, 1558, 1503,

1289, 973 cm-1. 1H NMR (300 MHz, excess DMSO-d6) δH: 1.72 (s, 3H, CH3), 2.02 (s, 3H, CH3), 4.55

(s, 1H, CH), 4.57 (s, 1H, CH), 6.85 (s, 1H, Ar-H), 6.96 (s, 1H, Ar-H), 7.09 (s, 4H, NH2), 12.11 (s, 2H,

NH) ppm; 13C NMR (75 MHz, CDCl3+DMSO-d6) δC: 9.73(2C), 11.01(2C), 35.96(2C), 57.14(2C),

97.77(2C), 120.86(2C), 126.70(2C), 126.69(2C), 135.65(2C), 142.80(2C), 154.72(2C), 160.90(2C)

ppm; MS/EI m/z: 432.1 (M+).

2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-8-methoxy-4H-chromene-3-carbonitrile 7h

White solid; MP (oC): ; IR (KBr): 3422,3365, 2919, 2198, 1665, 1611, 1525, 1402, 1332,

1250cm-1. 1H NMR (300 MHz, DMSO-d6) δH: 1.94 (s, 3H, CH3), 3.77 (s, 3H, OCH3), 4.58 (s, 1H, CH),

6.68 (s, 2H, NH2),6.94 (d, 1H, J= 3.6 Hz, Ar-H), 7.13 (dd, 1H ,J=8, 0.8 Hz, Ar-H), 7.28 (t, 1H ,J=8Hz

Ar-H ), 10.11 (br s, 1H, NH), 10.88 (br s, 1H, OH)ppm; 13C NMR (75 MHz, DMSO-d6) δC: 162.84,

160.10, 146.74, 137.91, 136.52, 124.34, 123.95, 120.11, 118.37, 110.11, 105.02, 55.92, 54.95,

28.83, 9.94 ppm; MS/EI m/z: 299.11 (M+).

2-amino-8-bromo-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile 7m

White solid; MP (oC): 244-246; IR (KBr): 3455, 3333, 2917, 2190, 1658, 1609, 1520, 1412, 1402,

825cm-1. 1H NMR (300 MHz, DMSO-d6) δH: 2.04 (s, 3H, CH3), 4.65 (s, 1H, NH2), 6.90 (s, 2H), 7.00

(s, 1H Ar-H), 7.61 (s, 1H, Ar-H), 9.78 (br s, 1H, NH), 11. 31(bs, 1H, OH) ppm; 13C NMR (75 MHz,

DMSO-d6) δC:159.51, 159.14, 144.68, 136.67, 130.41, 128.00, 127.91, 127.15, 120.22, 109.98,

104.33, 55.17, 29.43, 9.84 ppm; MS/EI m/z: 379.97 (M+).

3-amino-1-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-1H-benzo[f]chromene-2-carbonitrile 7n

White solid, MP (oC): 232-234; IR (KBr): 3441,3294, 3169, 2182, 1661, 1584, 1405, 1224, 1085,

807cm-1; 1H NMR (300 MHz, DMSO-d6) δH: 1.87 (s, 3H CH3), 5.05 (s, 1H, CH), 6.75 (s, 2H, NH2),

7.21 (d, 1H, J=8.8 Hz), 7.49-7.38 (m, 2H, Ar-H),7.88 (d, 1H, J=7.6 Hz, Ar-H), 7.92(d, 1H, J=8.4 Hz,

Ar-H), 10.01 (br s, 1H, NH), 11.27 (br s, 1H, OH) ppm; 13C NMR (75 MHz, DMSO-d6) δC:159.65,

158.2, 146.44, 130.68, 130.53, 128.80, 128.45, 126.88, 124.75, 123.38, 120.96, 116.57, 115.17,

105.29, 56.40, 26.73, 9.71 ppm; MS/EI m/z: 319.11 (M+).

3. Spectra of unreported compounds

Fig.1.1H-NMR spectra of 6-amino-4-[4-(diethoxymethyl)phenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5j)

Fig.2.13C-NMR spectra of 6-amino-4-[4-(diethoxymethyl)phenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5j)

Fig.3.1H-NMR spectra of 6-amino-4-(3-ethoxy-4-hydroxyphenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5l)

Fig.4.13C-NMR spectra of 6-amino-4-(3-ethoxy-4-hydroxyphenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5l)

Fig.5.1H-NMR spectra of 6-amino-4-(3-bromo-4-fluorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5n)

Fig.6.13C-NMR spectra of 6-amino-4-(3-bromo-4-fluorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5n)

Fig. 7.1H-NMR spectra of 6-amino-4-(2-bromo-5-fluorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5q)

Fig. 8.13C-NMR spectra of 6-amino-4-(2-bromo-5-fluorophenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5q)

Fig. 9. FT-IR spectra of 4,4'-thiene-2,5-diylbis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (14)

Fig. 10.1H-NMR spectra of 4,4'-thiene-2,5-diylbis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (14)

Fig. 11.13C-NMR spectra of 4,4'-thiene-2,5-diylbis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (14)

Fig. 12. FT-IR spectra of 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-8-methoxy-4H-chromene-3-carbonitrile 7h

Fig. 13.1H-NMR spectra of 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-8-methoxy-4H-chromene-3-carbonitrile 7h

Fig. 14.13C-NMR spectra of 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-8-methoxy-4H-chromene-3-carbonitrile 7h

Fig. 15.1H-NMR spectra of 2-amino-8-bromo-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile 7m

Fig. 16.1H-NMR spectra of 2-amino-8-bromo-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile 7m

Fig. 17.13C-NMR spectra of 2-amino-8-bromo-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile 7m

Fig. 18. FT-IR spectra of 3-amino-1-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-1H-benzo[f]chromene-2-carbonitrile 7n

Fig. 19.1H-NMR spectra of 3-amino-1-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-1H-benzo[f]chromene-2-carbonitrile 7n

Fig. 20.13C-NMR spectra of 3-amino-1-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-1H-benzo[f]chromene-2-carbonitrile 7n

4. Some spectra of other synthesized compounds

Fig. 1.FT-IR Spectra of 6-amino-4-(phenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5a)

Fig. 2.1H-NMR spectra of 6-amino-4-(phenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5a)

Fig. 3.13C-NMR spectra of 6-amino-4-(phenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5a)

Fig. 4.Mass spectra of 6-amino-4-(phenyl)-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5a)

Fig. 5. FT-IR spectra of 6-amino-4-[4-chlorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5b)

Fig. 6.1H-NMR spectra of 6-amino-4-[4-chlorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5b)

Fig. 7.13C-NMR spectra of 6-amino-4-[4-chlorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5b)

Fig. 8.Mass spectra of 6-amino-4-[4-chlorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5b)

Fig. 9.FT-IR spectra of 6-amino-4-[4-nitrophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5e)

Fig. 10.1H-NMR spectra of 6-amino-4-[4-nitrophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5e)

Fig. 11.13C-NMR spectra of 6-amino-4-[4-nitrophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5e)

Fig. 12.Mass spectra of 6-amino-4-[4-nitrophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5e)

Fig. 13.FT-IR spectra of 6-amino-4-[4-hydroxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5g)

Fig. 14.1H-NMR spectra of 6-amino-4-[4-hydroxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5g)

Fig. 15.13C-NMR spectra of 6-amino-4-[4-hydroxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5g)

Fig. 16.Mass spectra of 6-amino-4-[4-hydroxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5g)

Fig. 17.1H-NMR spectra of 6-amino-4-[4-methoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5f)

Fig. 18.13C-NMR spectra of 6-amino-4-[4-methoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5f)

Fig. 19.1H-NMR spectra of 6-amino-4-[4-bromoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5c)

Fig. 20.13C-NMR spectra of 6-amino-4-[4-bromoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5c)

Fig. 21.1H-NMR spectra of 6-amino-4-[4-hyroxy-3-methoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5m)

Fig. 22.13C-NMR spectra of 6-amino-4-[4-hyroxy-3-methoxyphenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5m)

Fig. 23.1H-NMR spectra of 6-amino-4-[4-fluorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5d)

Fig. 24.13C-NMR spectra of 6-amino-4-[4-fluorophenyl]-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile (5d)

Fig. 25.1H-NMR spectra of 4,4'-(1,4-phenylene)bis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile) 13

Fig. 26.13C-NMR spectra of 4,4'-(1,4-phenylene)bis(6-amino-3-methyl-2,4-dihydropyrano[2,3-c]pyrazole-5-carbonitrile) 13

Fig. 27. FT-IR spectra of 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 28.1H-NMR spectra of 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 29.13C-NMR spectra of 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 30. FT-IR spectra of 2-amino-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 31. 1H-NMR spectra of 2-amino-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 32.13C-NMR spectra of 2-amino-6-chloro-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 33. FT-IR spectra of 2-amino-6-bromo-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 34.1H-NMR spectra of 2-amino-6-bromo-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile

Fig. 35.13C-NMR spectra of 2-amino-6-bromo-4-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-4H-chromene-3-carbonitrile