Zanco Journal of Pure and Applied Sciences
Vol.27, No.2, 2015
Synthesis and Spectroscopic Characterization of Some Diazodibenzyloxy Pyrazolines from Some Diazodibenzyloxy Chalcones pp.(53-60)
A.L.Mohammed K. Samad, Assist.Prof.Dr.Lana H. Chawishli, Dr. Awaz J. Hussein Department of Chemistry, College of Education, Salahaddin University - Erbil
[email protected]
Received: 08/02/2015 Accepted: 06/04/2015 Abstract 3-(4-chlorophenylazo)-4-(4-chlorobenzyloxy)benzaldehyde was prepared and reacted with different prepared substituted azo-benzoloxy acetophenones giving some chalcones which then treated with hydrazine hydrate to give the target compounds 3,5-disubstituted pyrazoline compounds which contain two different azo-linkages and two benzyloxy moiteis. The synthesized compounds were characterized by spectral methods FT-IR, 1HNMR,13C-NMR and DEPT-135. Keywords: Synthesis; coupling reaction; azo-linkage; chalcone; pyrazoline
1. Introduction zo compounds can be prepared generally by the diazotization of primary aromatic amines with nitrous acid, via the nitrosonium ion, giving relatively stable arenediazonium salts, which act as weak electrophiles to react only with strongly activated rings in diazo coupling reaction producing azo compounds. Azo compounds bring two substituted aromatic rings in conjugation with an azo group, are deep colored, and they use in making dyes, known as azo dyes(Wade 2013). In the case of the coupling agent containing formyl or acetyl along with hydroxyl group, the produced azo compound can be used as a new synthon for the preparation of α,β-unsaturated aromatic ketones, having azolinkages according to the Claisen-Schmidt condensation reaction(Hawiaz et al 2014, Deshpande & Chopde 2013). Further transformation gives different stable five and six membered heterocyclic rings as: pyrazolines (Trilleras et al 2013), pyridines (Mohamed et al 2008) and pyrimidines (Trivedi et al 2008). Recently, there are many concerns to prepare these kinds of such compounds and their uses for the industrial, medical and biological effectiveness, such as: Anti-Inflammatory (Nevagi 2014), antoxidant(Martins et al 2008), analgesic(Dohut, Kaishap and Chetia 2013) anti-fungal(Hassan 2013) and other antimicrobial activities(Chovatia et al 2010).
A
2. Experimental 2.1 Material and Methods Melting points were determined using an electro thermal melting point apparatus. IR spectra were recorded on IR affinity-1 spectrophotometer, using KBr disc. 1H-NMR, 13CNMR and 13C-DEPT-135 spectra were recorded on a Bruker (400MHz) with TMS as an internal reference. 2.2 Preparation of the starting material 3-(4-chlorophenylazo)-4-hydroxybenzaldehyde (1) In the first step, substituted aniline (0.05mol) was dissolved by heating gently in (40mL) of 3M HCl. The solution was cooled in an ice bath to 0 oC. Added slowly (50mL) of freshly prepared 1M sodium nitrite solution; in which the temperature remains 0-5 oC. The diazonium salt solution was kept in the ice bath and immediately preceded to the next step (Hawaiz and Samad 2012).
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In the second step, the coupling agent( substituted phenolic compounds) (0.05 mol) was dissolved in (100 mL) of 1M sodium hydroxide, then cooled with stirring in the ice bath and added slowly to the diazonium salt solution. The mixture allowed to stir for 15 min. until crystallization is completed. The solid azo dye was collected by vacuum filteration, washed several times with water, dried and recrystallized with ethaol, to give (orange) crystals of the azo compound: m.p.159-161, yield (12.61 gm, 97%). IR (cm-1): 3338, 1682, 1597, 1247. 2.3 General procedure for the benzylation of starting material (1) and five different azoacetophenones to give azobenzyloxy compounds (2 & 3a-f). According to the modified procedure (Hussein and Aziz 2011) A mixture of azo compounds (0.035 mol), benzyl chloride or 4-chlorobenzyl chloride (0.04 mol) and anhydrous K2CO3 (7.45gm, 0.054mol), in (70 mL) ethanol 96% was refluxed with stirring for 6hrs. The cooled solution poured into cold water (300mL), the solid material immediately was obtained. The product was filtered off, washed several times with cold water dried and recrystallized from xylene to give yellow-orange crystals of azobenzyloxy compounds (2 &3a-f). 3-(4-chlorophenylazo)-4-(4-chlorobenzyloxy)benzaldehyde (2): C20H14Cl2N2O2, m.p.121123oC, (13.20 gm, 97%). FTIR/cm-1: 3066: CH-Ar, 2721, 2816:C-H, aldehyde, 1693:C=O, 1597:C=C, 1257:C-O. 4-[4-benzyloxy-3-chlorophenylazo] acetophenone (3a): C21H17ClN2O2, m.p.138-140oC, yield 93%, FTIR/cm-1: 1670, 1589, 1249. 1H-NMR (ppm): 2.68(s, 3H, COCH3); 5.25(s, 2H, OCH2); 7.12-8.13(m 12H, Ar-H). 13C-NMR: 26.56, 71.16, 113.46, 122.86, 123.79, 124.46, 125.40, 127.25, 128.58, 128.96, 129.27, 135.92, 138.54, 146.90, 155.03, 157.07, 197.8. 3-(2-chlorophenylazo)-4-benzyloxyacetophenone (3b):C21H17ClN2O2, m.p.(133-134oC), yield 59%, FTIR/cm-1:1673, 1598, 1532, 1271. 1H-NMR (ppm):2.61 (s , 3H , COCH3); 5.39 (s , 2H , OCH2); 7.16-8.45 (m 12H, Ar-H). 13C-NMR: 26.38, 71.28, 116.91, 119.06, 126.13, 127.90, 128.48, 129.22, 129.59, 130.48, 131.08, 131.52, 132.83, 133.49, 135.39, 136.13, 142.14, 159.84, 196.7. Dept-135: 26.38, 71.28, 116.91, 119.06, 126.13. 3-(4-chlorophenylazo)-4-benzyloxy acetophenone(3c): C21H17ClN2O2, m.p.(123-125oC), yield 57%, FTIR/cm-1: 1669, 1598, 1532, 1260. 1H-NMR (ppm) :2.61(s , 3H , COCH3), 5.39 (s , 2H ,OCH2), 7.16-8.25(m , 12H , HAr).13C-NMR: 26.46, 71.34, 114.54, 117.71,124.4, 127.01, 128.17, 128.69, 129.39, 130.47, 132.34, 136.19, 137.19, 141.88, 151.29, 159.63, 196.60. Dept-135: 26.46, -71.34, 114.54, 117.71, 124.41, 127.01, 128.17, 128.69, 129.39, 132.34. 4-[4-(4-chloro-benzyloxy)-3-methyl-phenylazo] acetophenone(3d): C22H19ClN2O2, m.p. 136-138oC, 95%, FTIR/cm-1: 1684, 1594, 1250.1H-NMR (ppm): 2.30 (s, 3H, Ar-CH3); 2.65(s, 3H, COCH3); 5.14(s, 2H, OCH2); 6.85-8.10(m 11H, Ar-H`). 13C-NMR: 16.53, 26.81, 69.39, 112.56, 122.57, 124.21, 124.59, 128.08, 128.49, 128.85, 129.37, 133.89, 135.14, 137.84 , 146.92, 155.34, 159.83, 197.49.13C-DEPT: 16.53, 26.81, -69.39, 112.56, 122.57, 124.21, 124.59, 128.49, 128.85, 129.37. 4-[4-(4-chloro-benzyloxy)-2-methyl-phenylazo] acetophenone(3e): C22H19ClN2O2, o -1 1 m.p.139‐141 C, yield: 97%. FTIR/cm : 1683, 1597. H NMR: 2.30 (s, 3H, Ar‐CH3), 2.65 (s, 3H, COCH3), 5.14 (s, 2H, OCH2), 6.85‐8.10 (m, 11H, HAr). 13C NMR: 17.88, 26.55, 69.36, 113.28 116.41, 117.21, 122.72, 128.79, 128.87, 129.36, 134.01, 134.94, 137.75, 141.88, 145.39, 155.59. 13C-DEPT-135: 17.88, 26.55, 69.36, 113.28, 116.41, 117.21, 122.72, 128.79, 128.87, 129.36.
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2.4 Synthesis of chalcones (4a-e) Chalcones 4(a-g) were synthesized by dissolving 3-(4-chlorophenylazo)-4-benzyloxy benzaldehyde (0.91 gm, 0.0025 mol) in 30mL of 96% ethanol, and added to the solution of an appropriate prepared substituted azo acetophenones (0.0025 mol) in 96% ethanol (15 mL) and (4 mL) of 4% ethanolic sodium hydroxide. The mixture was refluxed for 1h. Chalcone crystals were separated by suction filteration, washed with ethanol, dried and purified by recrystallization from DMSO as a suitable solvent (Hawaiz 2014). 1-(4-(-(4-(benzyloxy)-3-chlorophenyl)diazenyl)phenyl)-3-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)prop-2-en-1-one(4a): C41H28Cl4N4O3, m.p.198-200, 85%. FTIR/ cm-1: C=O: 1655, C=C:1600. 1-(4-(benzyloxy)-3-(-(2-chlorophenyl)diazenyl)phenyl)-3-(4-(4-chlorobenzyloxy)-3--(4chlorophenyl)diazenyl)phenyl)prop-2-en-1-one(4b): C41H28Cl4N4O3, m.p. 235-237, 86%. FTIR/cm-1: C=O:1655, C=C: 1595, 1H-NMR(ppm):5.23 (s 2H -O-CH2-C32), 5.43 (s 2H -OCH2-C13), 6.76-8.41 ( m, 23H Ar-H and 2H of CH-α and CH-β). 13C-NMR(ppm): 70.93:OCH2-C13, 71.47:O-CH2-C32, 114.93:C5, 115.50:C24, 118.03:C21, 118.47:C2, 121.01:Cα, 124.28.04:C8,12, 124.42:C31, 127.06:C3, 127.34:C22, 127.96:C30, 128.15:C34,38, 128.27:C36, 128.43:C15,19, 128.56:C35,37, 128.59:C16,18, 128.69:C27, 128.86:C9,11, 129.33:C28, 129.38:C6, 130.22:C1, 130.70:C29, 131.49:C25, 131.85:C20, 132.17:C17, 133.04:C10, 140.47:C14, 142.33:C33, 143.61:Cβ, 148.21:C7, 153.76:C4, 156.33:C26, , 158.34:C23 ,189.78:C=O. 1-(4-(benzyloxy)-3-(-(4-chlorophenyl)diazenyl)phenyl)-3-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)prop-2-en-1-one(4c): C41H28Cl4N4O3, m.p.169-162, 89%. FTIR/cm-1: C=O: 1654, C=C:1595. 1H-NMR(ppm) :5.26 (s 2H -O-CH2-C32), 5.45 (s 2H -OCH2-C13), 7.09-8.45 ( m, 23H Ar-H and 2H of CH-α and CH-β). 13C-NMR(ppm): 71.34:OCH2-C13, 71.48:O-CH2-C32, 114.68:C5, 115.41:C24, 118.07:C2, 118.49.04:C21, 120.84:Cα, 127.31:C27,31, 128.09:C8,12, 128.15:C34,38, 128.23:C3,22,128.67:C36, 128.70:C15,19, 128.92:C35,37, 130.69:C16,18, 131.39:C1, 131.74:C28.30,131.8:C9,11, 132.5:C6, 133.04:C25,135.44:C20, 135.48:C17, 136.20:C10,136.44:C29, 142.34:C14, 142.89:C33, 143.78:Cβ, 149.15:C7, 149.19:C26, 158.02:C4, 159.54:C23,189.45:C=O. DEPT(ppm):71.34:O-CH2-C13, 71.48:O-CH2-C32, 114.68:C5, 115.41:C24, 118.07:C2, 118.49.04:C21, 120.81:Cα, 127.31:C27,31, 128.09:C8,12, 128.15:C34,38, 128.67: C36, 128.70:C15,19, 128.92:C35,37, 130.69:C16,18, 131.74:C28.30,131.8:C9,11, 132.5:C6, 133.04:C25, 143.78:Cβ. 1-(4-(-(4-(benzyloxy)-3-methylphenyl)diazenyl)phenyl)-3-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)prop-2-en-1-one(4d) C42H31Cl3N4O3, m.p. 213-215,87% FTIR/cm-1: C=O: 1660, C=C:1589. 1H-NMR (ppm): 2.25 (s, 3H –Ar-CH3-C32), 5.21 (s 2H -OCH2-C33), 5.35 (s, 2H -O-CH2-C13), 6.87-8.18 ( m, 22H Ar-H and 2H CH-α and CH-β). 13CNMR(ppm): 16.47:CH3-C32, 69.43:O-CH2-C13, 70.88:O-CH2-C33,111.17:C30, 112.77:C5, 114.93:C31, 122.56:Cα, 124.28:C2, 124.31:C22,24, , 124.4:C3, 124,48:C28, 128.48:C8,12, 128.60:C27, 128.78:C1, 128.84:C35,39, 128.90:C15,19, 128.94:C36,38, 129.28:C16,18, 129.35:C9,11, 129.42:C6, 129.47:C21,25, 134.43:C17,37, 135.17:C10, 137.87:C20, 140.26:C14,34, 142.86:Cβ, 146.89:C26, 149.37:C7, 150.29:C4, 155.37:C23.159.84:C29, 189.52:C=O. 1-(4-(-(4-(benzyloxy)-2-methylphenyl) diazenyl)phenyl)-3-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)prop-2-en-1-one(4e) C42H31Cl3N4O3, m.p. 154-156, 75% FTIR/cm-1: C=O: 1656, C=C:1599.
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2.5 Synthesis of pyrazolines (5a-e): A mixture of chalcones (4a-f) (0.5 mmoles), hydrazine hydrate (2.5 mmoles) and sodium hydroxide (5 mL, 0.4%) in ethanol (15mL) was refluxed with stirring for (6 hrs.). The ppt. was isolated by suction filteration, washed with ethanol, dried and purified by recrystallization from DMSO as suitable solvent (Siddiqui et al 2014). 3-(4-(-(4-(benzyloxy)-3-chlorophenyl)diazenyl)phenyl)-5-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)pyrazoline(5a): C41H30Cl4N6O2, m.p. 175-177, 90%. FTIR/cm-1: N-H:3313, C=N:1597. 1H-NMR(ppm): 3.06 (dd, 1H CH2-Ha), 3.47 (dd, 1H CH2Hb), 4.88 (dd, 1H CH2-Hx), 5.20 (s, 2H -O-CH2-C32), 5.56 (s 2H -O-CH2-C13), 5.91 (s 1H - NH), 6.89-7.98 (m 24H Ar-H). 3-(4-(benzyloxy)-3-(-(2-chlorophenyl)diazenyl)phenyl)-5-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)pyrazoline(5b):C41H31Cl3N6O2, m.p. 211-214, 91% FTIR/cm-1: NH:3339, C=N:1590. 1H-NMR(ppm): 3.16 (dd 1H CH2-Ha), 3.52 (dd 1H CH2Hb), 4.89 (dd 1H CH-Hx), 5.24 (s 2H -O-CH2-C32), 5.39 (s 2H -O-CH2-C13), 6.82-7.88 (m 23H Ar-H + 1H-N-H). 13C-NMR(ppm): 40.97:CH2 of pyra., 63.85:CH of pyra., 71.38:O-CH2C13, 71.73:O-CH2-C32, 114.80:C5, 115.43:C24, 116.22:C21, 118.29:C2, 124.42:C8,12, 124,47:C31, 126.35:C3, 127.07:C22, 127.28:C30, 127.97:C34,38, 128.15:C36, 128.47:C20, 128.69:C15,19, 128.74:C35,37, 128.86:C16,18, 129.33:C27, 129.72:C9,11, 130.25:C28, 130.69:C6, 131.54:C25, 131.87:C29, 134.78:C17, 135.93:C1, 136.93:C10, 141.85:C14, 142.64:C33, 149.20:C7, 150.62:C=N, 151.37:C4, 156.43:C26, 158.17:C23. 3-(4-(benzyloxy)-3-(-(4-chlorophenyl)diazenyl)phenyl)-5-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)pyrazoline(5c): C41H31Cl3N6O2, m.p. 110-112, 92%, FTIR/cm-1: N-H: 3346, C=N:1606. 1H-NMR(ppm): 3.08 (dd 1H CH2-Ha), 3.65 (dd 1H CH2Hb), 4.94 (dd 1H CH2-Hx), 5.37 (s 2H -O-CH2-C32), 5.49 (s 2H -O-CH2-C13), 6.11 (s 1H - NH), 6.85-7.98 (m 23H Ar-H). 13C-NMR(ppm): 41.30:CH2 of pyra., 63.83:CH of pyra., 71.67:O-CH2-C13, 71.81:O-CH2-C32, 113.04:C5, 115.69:C24, 116.21:C21, 118.04:C2, 126.35:C3,22, 127.10:C8,12,27,31, 127.27:C34,38, 127.92:C36, 127.97:C15,19, 128.58:C35,37, 128.60:C16,18, 130.30:C9,11,28,30, 130.55:C20, 130.61:C6, 131.52:C25, 135.27:C17, 135.71:C1, 136.73:C10, 136.89: C29, 142.61:C14, 142.79:C33, 149.17:C7,26, 150.72:C=N, 156.19:C4, 157.03:C23.DEPT(ppm): 41.30:CH2 of pyra., 63.83:CH of pyra., 71.67:O-CH2-C13, 71.81:OCH2-C32, 113.04:C5, 115.69:C24, 116.21:C21, 118.04:C2, 127.10:C8,12,27,31, 127.27:C34,38, 127.92:C36, 127.97:C15,19, 128.58:C35,37, 128.60:C16,18, 130.30:C9,11,28,30, 130.61:C6, 131.52:C25. 3-(4-(-(4-(benzyloxy)-3-methylphenyl)diazenyl)phenyl)-5-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)pyrazoline(5d): C42H33Cl3N6O2, m.p. 168-170, 90% FTIR/cm-1: N-H: 3335, C=N:1598. 1H-NMR(ppm): 2.27 (s 3H –Ar-CH3), 3.05 (dd 1H CH2Ha), 3.53 (dd 1H CH2-Hb), 4.95 (dd 1H CH-Hx), 5.24 (s 2H -O-CH2-C32), 5.48 (s 2H -O-CH2C13), 6.85-7.86 (m 22H Ar-H + 1H-N-H).13C-NMR(ppm): 16.49:CH3-C32, 41.01:CH2 of pyra., 6400:CH of pyra., 69.39:O-CH2-C13, 71.22: O-CH2-C33, 111.17:C30, 115.42:C5, 116.24:C31, 122.88:C2, 123.23:C22,24, 124.15:C8,12, 124,27:C28, 126.20:C3, 127.04:C27, 127.93:C35,39, 128.06:C15,19, 128.48:C36,38, 128.77:C16,18, 128.81:C9,11, 129.36:C21,25, 130.33:C6, 134.53:C20, 135.30:C37, 135.39:C17, 135.79:C1, 137.00:C10, 142.66:C14,34, 146.94:C26, 150.40:C7, 151.37:C=N, 152.70:C4, 155.70:C23, 159.30:C29. 3-(4-(-(4-(benzyloxy)-2-methylphenyl)diazenyl)phenyl)-5-(4-(4-chlorobenzyloxy)-3-(-(4chlorophenyl)diazenyl)phenyl)pyrazoline(5e): C42H33Cl3N6O2, m.p. 257-259, 87% FTIR/cm-1: N-H: 3332, C=N:1597, 1H-NMR (ppm): 2.27 (s 3H –Ar-CH3), 3.2 (dd 1H CH2-
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Ha), 3.52 (dd 1H CH2-Hb), 4.92 (dd 1H CH-Hx), 5.08 (s 2H -O-CH2-C32), 5.27 (s 2H -O-CH2C13), 6.82-7.49 (m 21H Ar-H) 6.04,s, 1H-N-H). 13C-NMR(ppm): 17.86:CH3-C32, 41.18:CH2 of pyra., 64.05:CH of pyra., 69.29:O-CH2-C13, 69.32:O-CH2-C33, 113.06:C30, 113.14;C28, 115.18:C5, 116.39:C2, 117.09:C31, 123.02:C22,24, 123.08:C8,12, 126,51:C3, 126.59:C15.19,35,39, 127.59:C16,18,36,38, 128.72:C9,11, 128.79:C21,25, 128.84:C6, 133.80:C27, 133.95:C37, 134.57:C17, 135.09:C20, 135.23:C1, 135.40:C10, 141.07:C14,34, 145.46:C26, 150.44:C7, 150.47:C=N, 152.95:C4, 158.20:C23, 160.94:C29. DEPT(ppm): 17.86:CH3-C32, 41.18:CH2 of pyra., 64.05:CH of pyra., 69.29:O-CH2-C13, 69.32:O-CH2-C33,113.06:C30,113.14;C28, 115.18:C5, 116.39:C2, 117.09:C31, 123.02:C22,24, 123.08:C8,12, 126.59: C15.19,35,39, 127.59:C16,18,36,38, 128.72:C9,11, 128.79:C21,25, 128.84:C6. 3. Results and discussion In this work, two types of starting materials, substituted acetophenones and substituted benzaldehyde both containing azo linkages and hydroxyl groups were prepared. After benzylation of the hydroxyl groups, the two types of starting materials were linked together through formyl and acetyl groups based on the Claisen-Schmidt condensation reaction to afford new types of α,β-unsaturated aromatic ketones(chalcones)(4a-e) containing azo groups and benzyloxy moieties at both sides. The synthesized chalcones have been treated with hydrazine hydrate giving the target heterocyclic compounds pyrazoline derivatives with two benzyloxy moieties and two azo linkages (5a-e), Scheme(1). Structure elucidation of the starting materials, intermediate chalcones (4a-e) and target pyrazoline compounds (5a-e) were characterized and confirmed according to their spectral data's FT-IR , 1H-NMR , 13C-NMR , and DEPT spectra. In the first the structure of the prepared starting material azobenzyloxy acetophenones and azobenzyloxy benzaldehydes were characyerized by the disappearance of the hydroxyl group band in IR and 1H-NMR spectra and appearing a distinct pick at 5.2,70 and -70ppm for 1H-NMR, 13C-NMR and DEPT for the CH2 signals of the benzyl groups, along with a characteristic bands for formyl and acetyl group for benzaldehyde and acetophenone respectively (Al–Douh, Hamid and Osman 2008). In the IR spectra of the synthesized chalcones, the shifting of the absorption band of carbonyl group of the two reactants substituted benzaldehyde and substituted acetophenones to lower wave numbers around 1655cm-1 consider as a good evidence for the formation of the conjugated enone of chalcones. Further structure elucidation are come from the 1H-NMR, 13 C-NMR and DEPT spectra for the most important features of Cα-H and Cβ-H of chalcones at a distinct region as described in experimental section (Asiri et al 2014). The IR spectra of azo-pyrazolines showed a sharp band at 3300 cm-1 for N-H stretching vibration and the disappearance of carbonyl group band at 1655 cm-1 for enone system which confirm the 2-pyrazolines formation(Sid et al 2013). In the 1H- NMR spectra of the azo-pyrazolines Figure (1) the three doublet to doublet (dd) signals appear approximately at δ 3 , 3.5 , 5 ppm for two geminal and one vicinal protons (ABX) spin system unequivocally prove a 2-pyrazoline structure (Kumar and Reddy 2013). Also signals for 13C- NMR, Figure(2) around (40) and (60)ppm along with downward signals at -40ppm for DEPT, Figure(3) spectrum corroborate the 2-pyrazoline ring(Lévai and Jekőb 2007). Finally the detail of structure elucidation of each compound was assigned in experimental part sections(2-3, 2-4 and 2-5).
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NH2
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N2Cl HNO2
Step1
0-5oC Cl N2Cl
O
Cl
H
O
Cl
Step2
NaOH
+
H
N N
(1)
HO Cl
O
OH H
K2CO3, EtOH
N
Comp.1 + 4-chlorobenzylchloride
Step3
Cl
N
reflux 6h. H2 C
O
Cl
(2) 9
7
Cl
Step4
Comp.2 +
24
N 3
NaOH,EtOH
11
reflux 1h.
16
R2
Cl
17
(3a-e) 18 9
R2 22
(4a-e)
5
H2 C
14
23 21
4
15
20
6
N
12
25
1
2
10
O
R1
O
8
R1
O
13
19
HN
8
N 25
Step5
7
NH2NH2.H2O NaOH, EtOH
Comp.(4a-e) +
Cl
10
N
11
N
12 16
18
26
30
R1
(5a-e)
O
R2
19
d
e
H
H
26
Cl
31 27
27
H
R1
5
N N
N N 31
23
13
c
b
H2 C
17
Ha 21 22
4 14
Cl
Hb
6
15
24
Hx
3
reflux 6h.
a
20
1
2
30
28
29
29
28
Cl
31 27
30
28 29
34
O Cl
34
O 32
26
26
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R2
N N
N N
N N 31
32 35
35
O 36
33
34
32
30
38 37
38 37
29
30
32
35
O 33
36
33
28
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37
34
35
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36
33
39 38
38 37
32 27
27
35
33
31
36 37
34 39 38
This numbering used particularly for interpretation of 1H &13C-NMR spectra Scheme(1)
4. Conclusion The results indicated that; preparation of two types of azo compounds one containing free formyl group and the other contain free acetyl group along with hydroxyl group in the coupling agent will react to give a huge chalcones containing azo linkages at both sides in high yields and short reaction times. The synthesized chalcones serve to use as a very useful intermediate for the synthesis of corresponding pyrazoline compounds.
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References Al–Douh, M. H., Hamid, S. A. and Osman , H.(2008) Benzylation and 1D NMR spectroscopic studies of some phenolic aldehydes. Univ. Aden J. Nat. and Appl. Sci., 12(3), pp. 531-547. Asiri, A. M., Marwan, H. M., Alamry, K. A., Al-Amoudi, M. S,. Khan, S. A. and El-Daly, S. A.(2014) Green Synthesis, Characterization, Photophysical and Electrochemical Properties of Bis-chalcones. Int. J. Electrochem. Sci., 9, pp. 799-809. Chovatia, Y. S., Ggandhi, S. P., Gorde, P. L. and Bagade, S. B.(2010) Synthesis and Antibacterial Activity of Some Pyrazoline Derivatives, Orient. J. Chem., 26(1), pp. 275-278. Deshpande, H. D. and Chopde, H.N. (2013) Synthesis, Characterization and Testing of Biological Activity of Some Novel Chalcones Derivatives of Coumarin. Chem Sci Trans., 2(2), pp. 621-627. Dohut, C., Kaishap, P. P. and Chetia, D.(2013) Synthesis and study of analgesic, anti-inflammatory activities of 3-methyl-5-pyrazolone derivatives. Int J Pharm Pharm Sci., 5(1), pp. 86-90. Hawaiz, F.E , Hussein, A. J. and Kreem, M S. (2014) One-pot three-component synthesis of some new azopyrazoline derivatives. European J Chem., 5(2), pp. 233‐236. Hawaiz, F. E. and Samad, M. K.(2012) Synthesis and Spectroscopic Characterization of Some New Biological Active Azo-Pyrazoline Derivatives. E-Journal of Chemistry, 9 (3), pp. 1613-1622. Hawaiz, F. E.(2014) Synthesis and Characterization of Some New 4,5-Dihydropyrazolyl Thiazoles. Chemical Science Transactions, 3 (4), pp. 1583-1589. Hassan , S. Y.(2013) Synthesis, Antibacterial and Antifungal Activity of Some New Pyrazoline and Pyrazole Derivatives. Molecules, 18, pp. 2683-2711. Hussein, A. J. and Aziz, H. J.(2011)Synthesis and spectroscopic characterization of some new azo-thiazolidinone derivatives. Der Chemica Sinica , 2(5), pp.136-146. Kumar, C. and Reddy, V.(2013) Synthesis, Characterization and Antimicrobial Screening on New 1,5Disubstituted Pyrazoline Derivatives Bearing P-Methoxy-M-Chloro Phenyl Moiety International Journal of Scientific and Research Publications, 3(5), pp. 1-7. Lévai, A., and Jekőb, J. (2007)Synthesis of carboxylic acid derivatives of 2-pyrazolines, ARKIVOC , (i), pp. 134-135. Martins, D. M., Torres, B. G., Spohr, P. R., Machado, P., Bonacorso ,H. G., Zanatta, N. M., Martins, A. P. and Emanuell, T.(2008) Antioxidant Potential of New Pyrazoline Derivatives to Prevent Oxidative Damage. Basic & Clinical Pharmacology & Toxicology , 104, pp. 107-112. Mohamed, S. F., Youssef, M. M., Amr, A. E. and Kotb, E. R.(2008) Antimicrobial Activities of some Synthesized Pyridines, Oxazines and Thiazoles from 3-Aryl-1-(2-naphthyl)prop-2-en-1-ones. Sci Pharm. 76, pp.279-303. Nevagi, R. J.(2014) Recent advances in bioactive pyrazole scaffold – Part II: Anti-Inflammatory agents. Der Pharmacia Lettre, 6 (5), pp. 274-284. Sid, A., Ziani, N., Debbih, O. D., Mokhtari, M. and Lamara, K.(2013) Synthesis, characterization and antimicrobial evaluation of 1‐((5,3‐diaryl)‐4,5‐dihydro‐1H‐pyrazol‐1‐yl)propan‐1‐one, European Journal of Chemistry, 4 (3), pp. 268-271. Siddiqui, A. A., Rahman, M. A., Shaharyar, M. and Mishra, R.(2010) Synthesis and anticonvulsant activity of some substituted 3, 5-diphenyl-2-pyrazoline-1-carboxamide derivatives. C Chemical Sciences Journal, 8, pp. 110. Trilleras, J., Polo, E., Quiroga, J., Cobo, J. and Nogueras, M. (2013) Ultrasonics Promoted Synthesis of 5(Pyrazol-4-yl)-4,5-Dihydropyrazoles Derivatives, Appl. Sci., 3, pp. 457-468. Trivedi, A. R., Odiy, D. K., Ravat, N. R. and Shah, V. H.(2008) Synthesis and biological evaluation of some new pyrimidines via a novel chalcone series, ARKIVOC, xi, pp. 131-141. Tran, T., Nguyen, T., Do, T., Huynh, T., Tran, C. and Thai, K.(2012) Synthesis and Antibacterial Activity of Some Heterocyclic Chalcone Analogues Alone and in Combination with Antibiotics. Molecules, 17, pp. 66846696. Wade, L.G. (2013) Organic Chemistry, 8th edn, Pearson Education, Inc, p.915.
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Figure(1)-1H- NMR Spectrum of compound (5e)
Figure(2)-13C- NMR Spectrum of compound (5e)
Figure(3)-13C- DEPT-NMR Spectrum of compound (5e)
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