INTRODUCTION:

Heterocyclic compounds containing nitrogen involved to sulfonamide moieties were received a huge attention in many reported papers. Sulfa drugs containing sulfonamide functional group which have extensive biological activities revolutionized the field of medical sciences¹

Heterocyclic sulfonamides are used as carbonic anhydrase inhibitors^2-4, antiseptic agents⁵, anticancer, anti-inflammatory and analgesic agents⁶, β3-adrenergic receptor agonists⁷, PC-1 inhibitors⁸, antifungal in addition to antiviral agents⁹. Azo dye, aromatic rings linked with azo (-N=N) chromophores, signify the prevalent classification of dyes adopted in textile processing and other productions as in foodstuff colorant, cosmetic, printing and pharmacological manufacturing^10-11. Chalcone products have α, β-unsaturated carbonyl moiety possess wide-ranging spectra of organic activity in pharmaceutical and medical areas as in antimicrobial¹², anti-inflammatory¹³, antitubercular¹⁴, antioxidant¹⁵ and anticancer¹⁶. In this paper, a sequence of 3-hydroxy-4-aminobenzene sulfonamide derivatives has deliberated with FT-IR spectrums and H-NMR results.

EXPERIMENTAL:

Each used chemical materials have been in maximum purity as delivered from the manufactures. Measurements melting points (m.p.) of produced compounds have been recorded in open capillary tube. Thin layer chromatography (T.L.C) has been accomplished on silica gel G for (T.L.C) besides spots that have been envisaged through Iodine vapors.

Preparation of Azo compounds (M):

3-hydroxy-4-aminobenzenesulfonamide (0.003mole) has been liquefied in (2 ml) of concentrated hydrochloric acid and (20 ml) of purified water. The solution has been under (0–5) ^ₒC in ice-water bath. About 0.003 mole of sodium nitrite has been liquefied in 10 ml of purified water with adding drop wise to the solution with stirring. Also, 0.003 mole of Acetyl acetone has been liquefied in 20 ml of ethanol and 5 ml (10 %) sodium hydroxide and cooled under (0–5)^ₒC with addition of diazonium solution in droppingly wise with stirring under (0–5) ^ₒC for two hours for getting the coupling agent. The resultant compound has been triggered, filtered and cleaned satisfactorily with ethanol.

4-((2,4-dioxopentan-3-yl) diazenyl-3-hydroxy benzene sulfonamide) M

yield 70.45 %, m. p 195-197°C, 1H-NMR (DMSO): δ 2.44 (s, 6H, COCH3), δ 7.19-8.20 (t,3H) for aromatic ring, δ 9.95 (s, 1H, OH), δ 3.39 (s, 1H) for (HC-C=O); 13C-NMR (DMSO): C13-NMR: 112.66, 114.15, 117.21, 120.21, 131.17, -132.80(C) Phenyl ring, 162.41, 168.41 C (C=O), 28.46-28.70 C(CH3), 50.04 C(CH-C=O); IR: (N-H) 3444.87cm−1, (C-H, aliphatic) 2950.89cm−1, (C-H, aromatic) 3053.46 cm−1, (N=N)1600.92, (C=O amide) 1653.00 cm−1, (C=O ketone) 1680.00 cm−1, (C=C aromatic) 1550.89 cm-1.

Fig 1: FT-IR Spectrum of Comp. M

Preparation of Chalcone derivative (M₁)

The prepared of chalcone (0.002 mole) of compounds (M) was dissolved in 30ml of absolute ethanol, and added to the solution of an appropriate p-chloro amino benzaldehyde (0.004 mole) and added (5 ml) of 10% sodium hydroxide. The mixture has been stirred for 1 to 6 hours under room temperature until chalcone formation. Subsequently, the solid crystals dehydrated and distilled by recrystallization using ethanol

Fig 2: FT-IR Spectrum of Comp. M1

4((1,7-bis(4-dimethylamino) phenyl-3,5-dioxohepta-1,6-dein-4-yl) diazenyl)-3-hydroxy benzene sulfonamide (M₁)

yield 72.53 %, m. p 285-287°C; 1H-NMR (DMSO): δ 6.54-8.08.61 (m,12H) for aromatic ring, δ 9.65 (s, 1H, OH), δ3.37 (s, 1H) for (HC-C=O ), 3.03-3.07(d,2H) for (CH=CH),7.18(d,2H,NH₂); 13C-NMR (DMSO): C13-NMR: 120.57,123.89,132.52,133.27,133.36,-135.58(C) Phenyl ring, 166.30 C (C=O), 115.13 -117.49 C(CH=CH), 49.57 C(CH-C=O); IR: (N-H) 3446.79cm−1, (C-H, aliphatic) 2925.18cm−1, (C-H, alkene) 3100.30 cm−1, (N=N ) 1604.06,(C=O amide ) 1654.92 cm−1, (C=O ketone) 1689.00 cm−1, (C=C aromatic) 1537.27 cm-1.

Preparation of Oxazine/ Pyrimidine/ Thiazine derivatives (M_2,M₃, M₄)

A mixture of chalcone (0.001 mole), urea / quinidine hydrochloride/thiourea (0.002 mole) have been liquefied in30 mL ethanolic sodium hydroxide solution with stirred for 7 hours. Afterward, it has been poured into 20 mL of icy water with uninterrupted stirring for one hour and left overnight. The formed precipitate has been cleaned and recrystallized by ethanol.

4-((bis(2-amino-6-(4-(dimethylamino)phenyl)-6H-1,3-oxazine-4-yl) methyl) diazenyl)-3-hydroxybenzene sulfonamide (M₂)

yield 77.28 %, m. p (153-155) °C; 1H-NMR (DMSO): δ 7.07-8.72 (m,11H) for aromatic ring, δ 9.67 (s, 1H, OH), δ 3.91 (s, 1H) for (CH-), δ5.44-5.93(d, 2H) for (CH=CH), δ6.02-6.91(d, 2H,NH₂); 13C-NMR (DMSO): C13-NMR: 113.1,114.09,114.3,128.1,128.4-132.7(C) Phenyl ring, 154.19 C(C=N) , 54.19 C(CH- ) IR: (N-H) 3421.72cm−1,(C-H, aliphatic) 2985.81cm−1, (OH) 3444 cm−1 ,(N=N ) 1600 (C=N ) 1670.00 cm−1, (C=C ) 1543 cm-1.

Fig 3: FT-IR Spectrum of Comp. M2

4-((bis(2-amino-6-(4-(dimethylamino)phenyl)-6H-1,3-oxazine-4-yl)methyl)diazenyl)-3-hydroxybenzene sulfonamide (M₃)

yield 80.23 %, m. p (224-226) °C; IR: (NH₂) 3161.33-3381.23cm−1, (C-H, aliphatic) 3053.32cm−1, (OH) 3450.85 cm−1, (N=N) 1571.99 cm−1 (C=N) 1666.50 cm−1, (C=C) 1552.70 cm-1.

Fig 4: FT-IR Spectrum of Comp. M3

4-((bis(2-amino-6-(4-(dimethylamino)phenyl)-6H-1,3-oxazine-4-yl)methyl)diazenyl)-3-hydroxybenzenes sulfonamide (M₄)

yield 73.88 %, m. p (178-180)°C, IR: (NH₂) 3244.27-3417.86cm−1, (C-H, aliphatic) 2924.09cm−1, (OH) 3330.00 cm−1, (N=N) 1618.23 cm−1 (C=N) 1680.23 cm−1, (C=C) 1550.77 cm-1.

Fig 5: FT-IR Spectrum of Comp. M4

Preparation of compound) M₅ andM₆):

Chalcone (M₁) (0.001 mole) and barbituric acid, Meldrum acid (0.002 mole) has been put in ethyl alcohol. Catalytic quantity of AcOH has been inserted and the reacting mixture has been refluxed for ten hours. Later to the reaction finishing point, the reaction mass has been cooled under room temperature, poured into crumpled ice and counterbalanced by NaHCO₃ solution. The separated out product was cleaned, dehydrated and recrystallized by means of ethanol

Fig 6: FT-IR Spectrum of Comp. M5

Fig 7: FT-IR Spectrum of Comp. M6

4-((1,7-bis(4-(dimethyl amino)phenyl)-3,5-bis(2,4,6-trioxotetra hydro pyrimidine- 5(2H)-ylidene) hepta-1,6-dien-4-yl) diazenyl)-3-hydroxy benzene sulfonamide (M₅)

yield 79.98 %, m. p >283°C decomp; IR:(N-H) 3285.49cm−1, (O-H) 3435.22cm−1, (C-H, aliphatic) 2928.01cm−1, (C-H, alkene) 3081.03 cm−1, (N=N) 1554.83, (C=O amide) 1683.86 cm−1, (C=C alkene) 1639.49cm−1, (C=C aromatic)1516.05cm-1

4-((3,5-bis(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-ylidene)-1,7-bis(4-dimethyl amino) phenyl )hepta-1,6-dien-4-yl) diazenyl)-3-hydroxy benzene sulfonamide (M₆)

yield 85.22 %, m. p 169-171°C; 1H-NMR (DMSO): δ 1.17-1.19 (d, 6H, CH3), δ 6.61-7.61 (m,12H) for aromatic ring, δ 10.61 (s, 1H, NH), δ 3.33 (s, 1H) for (HC-C=O); 13C-NMR (DMSO): 117.11,123.15,127.26, 129.41,130.71-136.58(C) Phenyl ring, 146.62,175.73-180.30 C(C=O),58.17 C(CH-),15.73(C,CH₃); IR: (NH₂) 3228.34-3334.92 cm−1, (O-H) 3374.92 cm−1, (C-H, aliphatic) 2958.87cm−1, (C-H, alkene) 3100.02 cm−1, (N=N) 1560.41, (C=O ketone) 1647.21 cm−1, (C=C alkene) 1593.20 cm-1

Preparation of Compounds (M₇andM₈):

Chalcone (M₁) (0.001 mole), hydroxylamine hydrochloride, 2,4-dinitrophenyl hydrazine, (0.002 mole) and sodium acetate (0.001 mole) in ethanol (25 mL) has been refluxed for eight hours. The mixture has been concentrated by purifying the solvent under lessened pressure and poured into icy water. The gotten precipitate has been filtered, washed and recrystallized by means of ethanol.

Fig 8: FT-IR Spectrum of Comp. M7

Fig 9: FT-IR Spectrum of Comp. M8

(E)-4-((bis (5-(4-chlorophenyl) isoxazol-3-yl) methyl) diazenyl)-3-hydroxybezene sulfonamide (M₇):

yield 76.77 %, m. p (157-159)°C ; 1H-NMR (DMSO): δ 6.78-6.81 (d,2H,CH=C), δ 7.68-7.71 (d,2H,NH2),7.84-8.43 (m,11H) for aromatic ring, δ 9.68 (s, 1H, OH), δ 3.05 (s, 1H), δ; 13C-NMR(DMSO): : 111.33,113.07, 117.24,118.76,124.97,126.48,128.20,132.03 (C )Phenyl ring , 25.79 C,CH,154.68 C,C=N , 144.61 C=C; IR: (NH₂) 3244.27-3417.86 cm−1, ,(O-H ) 3300.00 cm−1,(C-H, aliphatic) 2940.09cm−1 ,(C-H, alkene) 3059.10 cm−1 ,(N=N ) 1597.06, (C=N) 1680.23 cm−1, (C=C alkene) 1618.26 cm-1

(E)-4-((bis(5-(4-chlorophenyl)-1-(2,4-dinitrophenyl)-1H-pyrazol-3-yl)methyl)diazenyl)-3-hydroxybezene sulfonamide (M₈):

yield 80.91%, m. p (183-185)°C; IR: (NH₂) 3292.49-3402.43 cm−1, (O-H ) 3336.85 cm−1,(C-H, aliphatic) 2908.73cm−1, (C-H, alkene) 3100.01 cm−1, (N=N) 1548.84, (C=N) 1625.99 cm−1, (C=C alkene) 1593.20 cm-1.

Fig 10: H-NMR Spectrum of Comp. M

Fig 11: H-NMR Spectrum of Comp. M1

Fig 12: H-NMR Spectrum of Comp. M2

Fig 13: H-NMR Spectrum of Comp. M6

Fig 14: H-NMR Spectrum of Comp. M7

Fig 15: C13NMR Spectrum of Comp. M

Fig 16: C13NMR Spectrum of Comp. M1

Fig 17: C13NMR Spectrum of Comp. M2

Fig 18: C13NMR Spectrum of Comp. M6

Fig 19: C13NMR Spectrum of Comp. M7

RESULTS AND DISCUSSION:

In our work for synthesis of azo compound from reaction between 3-hydroxy-4-amino benzene sulfonamide and reaction with p-chloro benzaldehyde to produce chalcone derivative and preparation of six membered rings oxazine, thiazine, pyrimidine derivatives by reaction with urea, thiourea, quinidine hydrochloride and preparation chalcone derivative containing barbiturate and Meldrum moiety by reaction with barbituric, Meldrum acids and preparation five memdered rings oxazole, pyrazole derivatives by reaction with hydroxyl amine hydrochloride and 2,4dinitrophenyl hydrazine. involves the following steps: the first step involves the preparation of azo compound. The reaction sequence is outlined in Scheme 1.

CONCLUSION:

This paper considers a categorization of 3-hydroxy-4-aminobenzene sulfonamide derivatives. The investigated 3-hydroxy-4-aminobenzene sulfonamide has been taken as primary material with acetylacetone to formulate newfangled azo compound then azo compound reacts with p-chloro benzaldehyde in absolute ethanol to prepare chalcone derivatives then chalcone derivatives react with diverse compounds such as urea thiourea, quandin, Meldrum's acid, barbituric acid, hydroxyl amine hydrochloride, 2,4-dinitrophenyl hydrazine to organize novel heterocyclic compounds.

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Received on 16.02.2019 Modified on 02.03.2019

Research J. Pharm. and Tech. 2019; 12(7): 3282-3288.

DOI: 10.5958/0974-360X.2019.00555.9