Microwave Induced Synthesis of Azo Compound: A Solvent Free Path For Some Dyes
Nirupma Jadon and Sadhana Singh*
Department of Chemistry, B.N.P.G. College, Udaipur (Raj.) India – 313001
ABSTRACT:
An efficient method for the exclusive one pot synthesis of sodium salt of Benzidine diazo-bis-1-naphthyl amine-4-sulphonic acid (An Azo compound) under conditions of microwave irradiation. The Reaction was found to follow diazotization and condensation mechanism with removal of water molecules. Formation of product was confirmed through TLC, M.P. and spectral analysis. The reaction was carried out in a single pot without using solvent in a domestic microwave oven and Sodium 4-[{4-[(2-nitrophenyl)amino]phenyl}diazenyl] benzene sulfonate.
KEYWORDS: Sodium salt of Benzidine diazo-bis-1-naphthyl amine-4-sulphonic acid (An Azo compound), microwave irradiations, one pot synthesis, dyes, solvent free path, IR and Mass Spectroscopy and Sodium 4-[{4-[(2-nitrophenyl)amino]phenyl}diazenyl] benzene sulfonate.
INTRODUCTION:
Microwave dielectric heating is rapidly becoming popular in organic synthesis, as a source of thermal energy for organic reactions in organic solvents or dry media1,2. Organic molecules absorb the microwave energy selectively enhancing the rate of reaction. The more chemistry was earlier restricted to the use of high boiling point polar solvent like DMSO, DMF etc. Later few low boiling point solvents like toluene3 were used but were found to generate serious hazards. To overcome the problem in microwave synthesis later on solvent free patah4-5 was developed. Verma6 has carried out solvent free synthesis of thio-acetones and thioamides. Rajanarendar et al.7 carried out synthesis of some new isoxazolyltriazinan-2-ones under microwave irradiation. Bhagat8 has carried out synthesis of 1-(3-Chlorophenyl)-3,5-diayl-pyrazoles under microwave irradiation.
A solvent free synthesis of 2,3-dihydropyrol [3,2-c] quinoline using microwave has been reported9. Microave assisted solid phase synthesis of derivatives of thioharbituric acid has been reported10. Microwave assisted solvent free synthesis of substituted cromenes was carried out by Meenakshi and Ravi Chandaran11.
Solvent free improved synthesis of some substituted 1-3-diaryl propones and 3,5-diaryl-6-carbethoxy cyclohexenione under microwave irradiation was carried out by Jhala et al.12. Solid state induced heterocyclization under microwave irradiation for synthesizing of 2-phenyl-3-hydroxyquinoline-4(H)-1 was reported by Heravi et al.13 solvent free synthesis of triphenyl methane dyes was carried out by Mehta14. The chemistry of dyes and their derivatives has been as interesting field of study.
The present work describes the synthesis of sodium salt of Benzidine diazo-bis-1-naphthyl amine-4-sulphonic acid.
Melting point were determined by melting point apparatus. Thin layer chromatography was performed on silica gel sheets. The IR spectra of samples were recorded on FT-IR spectrometer in the range 4000-400 cm-1 region using nujol technique.
General Procedure :
Synthesis of Sodium salt of Benzidinediazo-bis-1-naphthyl amine-4-sulphonic acid :
It is a simple benzidine bisazo-dye stuff. It was prepared by taking tetrazotised (bis-diazotised) benzidine coupled with 2 molecules of naphthionic acid solution in a vessel and the mixture heated for 8 min at P-2 in microwave after formation it was filter and wash. The dye was salted out by NaCl and recrystallized with alcohol. Where light red solid product was obtained.
M.P. = > 300, Yield = 65.6%, M.F. = C32H22N6Na2O6S2, M.W. = 696
Elemental Analysis (%) :
C = 55.12, H = 3.15, O = 13.75, N = 12.05, S = 9.18.
IR (Nujol, max, cm-1) : 1620 (Ar. System C=C), 3103 (ArCH=CH), 2270 (N2+), 800-600 (C-S), 1100-990 (S=O), 700-600 (S-O), 1340 (C-N), 3458 (N-H).
Mass spectrum : m/z M± = 696; M± (–N2, C12H8) = 488, M± (–NH2) = 456, M± (Na) = 442, M± (–N2, C20H14N2Na2O6S2) = 152.
Compound-1
Synthesis of Sodium 4-[{4-[(2-nitrophenyl)amino]phenyl}diazenyl] benzene sulfonate :
0.01 mol. of orange IV was stirred with water and slowly added in con. sulphuric acid with stirring. Now place the reaction mixture in a freezing mixture bath (ice + salt) and add fuming nitric acid and heated for 6 min. at P-2 in microwave. Cooled and poured into crushed ice. The solid product was separated out. Recrystallized the solid from ethanol. M.P. = 235°C, Yield = 65%, M.F. = C18H13N4NaO5S, M.W. = 420
Elemental analysis (%) :
C = 51.42, H = 3.09, O = 19.4, N = 13.33, S = 8.53.
IR (Nujol, nmax, cm-1) :
2265 (N2+), 3020 (ArCH=CH), 1133-990 (S=O), 1320 (C-N), 3400-3500 (N-H), 1567-1380 (NO2), 1625-1680 (N=O).
Mass spectrum : m/z
M± = 420, M± (–N2, C6H4SO3Na) = 190, M± (–NO2) = 144, M± (–H) = 143, M± = (–N2, C12H9N2O2) = 179.
Compound-2
ACKNOWLEDGEMENTS:
The authors are thankful to Prof. B.L. Verma for his kind support in the present work to CDRI, Lucknow for spectral analysis.
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Received on 21.05.2011 Modified on 28.05.2011
Accepted on 04.06.2011 © AJRC All right reserved
Asian J. Research Chem. 4(8): August, 2011; Page 1243-1244