Coupling Reactions Involving Reactions of Aryldiazonium Salt

JCBPS; Section A; August 2015 – October 2015, Vol. 5, No. 4; 3860-3867.

E- ISSN: 2249 –1929

Journal of Chemical, Biological and Physical Sciences An International Peer Review E-3 Journal of Sciences Available online atwww.jcbsc.org Section A: Chemical Sciences CODEN (USA): JCBPAT

Research Article

Coupling Reactions Involving Reactions of Aryldiazonium Salt: Part-III. Chemoselective Condensation with -Naphthol to Synthesize Sudan-I, its Nitro Derivatives and Antibacterial Potential C. J. Patil*1, Manisha C. Patil2, Vivek Rane1, Kunal Mahajan1 and C. A. Nehete1 1

Organic Research Laboratory, Department of Chemistry, Smt. G. G. Khadse, College, Muktainagar-425 306, (MS), India.

2

Deptartment of Zoology, A. G. D. Bendale Mahila College, Jalgaon-425 001, (MS), India. Received: 12 July 2015; Revised: 19 September 2015; Accepted: 26 September 2015

Abstract: Synthesis of azo dye viz. Sudan I, 1-(Phenylazo)-naphthalen-2-ol, I and its nitro derivatives, II-IV is reported. They are characterized by their colour, elemental analysis, physical constant such as melting point range, TLC and spectral characterization viz. UV-visible and IR-spectra were studied. The nitro substituted derivatives of Sudan I, I i.e the products, II-IV, by introducing nitro group the aniline part at different positions are synthesized. The synthesized azo compounds were screened for the antibacterial activity against Solmonella typhi and Bacillus cereus. Keywords: -Naphthol, Aryldiazonium Salts, Diazotization, Azo dyes(-N=N-), UV-Vis, FTIR, antibacterial activity. INTRODUCTION In chemistry azo dyes of phenolic compounds play a major role in synthesizing many of the commercial dyes and analytical reagent. The dyes are marketed mainly in the form of azo disperse, azo-vat, azo-acid dyes, etc. Most of these commercially available dyes have the naphthalene moiety bearing hydroxyl groups as an auxochrome group. Due to the simple process of the synthesis, usually an aqueous medium and the almost unlimited choice of starting products, an extremely wide variety of azo dyes skeleton is possible. The number of combinations is further increased by the fact that a dye molecule can also contain several groups. The practical uses of dyes in the various industrial field shows that azo compounds are the largest class of industrial synthesized organic dyes. The azo dyes 3860

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are a distinct and clearly defined class, characterized by the presence of one or more azo (-N=N-) groups. They have no analogues among the natural colouring matter. They are all prepared by a common process involving diazotizing an aromatic primary amine and the formed diazonium salt solution is coupled with a phenol or an aromatic amine with a free ortho or para-position or with certain other components having reactive positions such as aryl amide and certain ketonic acid, etc. Sudan I, is a powder with an orange-red appearance, a lysochrome, a carcinogen, a diazo-conjugate dye with the chemical formula of l-(phenylazo)-2-naphthol. Because of its attractive orange-red colour, Sudan I is also used for colouring various fast foodstuffs, including particular brands of curry powder and chili powder. Although the use of Sudan I in foods is now banned in many countries, because Sudan I, Sudan III and Sudan IV have been classified under category 3 carcinogens, they are not classifiable as to its carcinogenicity to humans1,2, by the international agency for research on cancer. Sudan I is still being used in some orange-coloured smoke formulations and as a colouring for cotton refuse used in chemistry experiments. Its few brand names are Atul Orange R. Benzene-l-azo2-naphthol, Brasilazina oil Orange, Brilliant oil Orange R, Calcogas M. Sudan I is a carcinogen as proved from the laboratory tests on rats showed growth of cancerous tumors in the liver and bladder part of body. These tests have led to the additive being banned from use in foods throughout the EU, as it may pose an increased risk of cancer. Azodyes are characterized by chromophoric azo group. Azo dyes are used as corrosion inhibitors for the dissolution of carbon steel in HCl acid solution3. Azo compounds have received much attention due to their versatile skeleton and uses in many practical applications such as colouring fiber, photoelectronic applications, printing systems, optical storage technology and in various analytical techniques4 and in industrial synthesis of organic dyes5. The azo compounds also find their wide applications as a polymer additive6, also the azo dye-additive is mainly used to colour waxes, oils, petrol, solvents and polishes and successful in textile processing, paper, food, cosmetic medicine, leather, plastics, varnish, automobile7-9. Generally, azo dyes are electrochemically active, both in reduction and oxidation potential region10-12. Analysis of Sudan I and its homologues, viz. Sudan II, Sudan III and Sudan IV in food by HPLC with ECD. Comparison of glassy carbon electrode with carbon nanotube ionic liquid gel modified electrode13. The theoretical results are qualitatively illustrated by SWV (voltammogram) of azo-dye Sudan III11. As seen from above discussion, azo dyes are easy to prepare and very important for technical purposes in many types of industries. Recently, we have reviewed14 azo derivatives of salicylic acids in pharma. Also, our previous reports15,16 deals with reactions involving aryldiazonium moiety. Herein we report Part-III of this series which deals with synthesis of Sudan I and its nitro derivatives in aniline part of molecule, antibacterial properties of these compounds are determined. Scheme of Synthesis: NH2

OH

N2 Cl NaNO2 in NaOH

2

Substituted aniline

R

N

HCl, 0-5 0C R

OH

N

R Substituted diazonium salt

1-Substituted phenylazo-naphthalen-2-ol R = -H(I); -2'-NO2(II); -3'-NO2(III) and -4'-NO2(IV).

EXPERIMENTAL General: All the chemicals and solvents were obtained from E-Merck, India and are of synthesis and the Spectroscopic grade respectively. They were used without further purification. Silica gel-G was 3861



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used to monitor the progress of reactions, by TLC and visualized by iodine vapour chamber. The colour observed was recorded by visual method and melting point range was taken in an one end open capillary tube. The purity of the compounds was ascertained by melting point range determination (in one end open capillary method), and by Silica gel-G TLC. The UV-Vis spectra were recorded on a Shimadzu-1800 instrument (wavelength,  in nm). Quartz cuvette of path length 1 cm was used for measurements in solution. The FTIR spectra were recorded on a Shimadzu FTIR 8400 spectrophotometer(Model-IR Affinity-1) using sample mixed in powder form with KBr powder, the frequency values, „‟, are in cm-1. The overall purity and structural assignment of the products was based respectively on the elemental (CHN) analyses, TLC and UV-Vis, FTIR spectral data. The bacterial strains, Solmonella typhi and Bacillus cereus, are purchased from National Centre for Cell Science(NCCS), Pune, India and maintained at Smt. G. G. Khadse College, to determine the antibacterial activity of synthesized compounds. General procedure for synthesis of azo dyes compound, I-IV: Aniline or its nitro derivatives (1 mol) was added in concentrated HCI (5 ml, 1:1 ratio) and boiled for 10 minutes. This solution was then cooled to 0-5C in ice water bath. Aqueous sodium nitrite (1 mol, 10 ml) solution in cold condition was then added to this solution dropwise with vigorous stirring. The temperature of the reaction mixture was kept to 0-5C for 1 hour to give diazonium chloride solution. The reaction mixture shows the positive test of nitrous acid on starch-iodide paper (blue colour is obtained on the potassium-iodide starch paper). Then the resulting diazonium solution was poured dropwise with vigorous stirring to a suspension of -Naphthol in water (10 ml, 1 mol) at 0-5C for the coupling reaction. The pH of the reaction mixture was maintained at 8 to 9 by simultaneous addition of 10 % aqueous sodium hydroxide solution. On complete addition, the orange to red coloured dyes were precipitated. The precipitated product separated upon dilution with water (100 ml) was filtered off, washed with water several times, dried and crystallized using absolute ethanol. It was then purified by column chromatography (eluent Dichloromethane/ n-Hexane) to give the purified material. The purity of the synthesized compounds, I–IV were ascertained by TLC method and were characterized by colour, physical constant (melting point range) and by UV-visible and IR-spectra. Synthesized azo compounds were screened for the antibacterial activity, against Solmonella typhi and Bacillus cereus bacterial strain by using the method reported in earlier16. RESULTS AND DISCUSSION The synthesized compounds, Sudan I, I and its nitro derivatives, II-IV in aniline part were characterized by analytical method such as colour(see Fig. 1) and elemental analysis which are in close agreement(by 5%) with the theoretically calculated values.

Fig. 1: Colour Characteristics of the synthesized Sudan I and its Nitro Derivatives, I - IV. 3862



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The TLC of the synthesized compounds I - IV is as shown (see Fig. 2) in the following photograph.

Fig. 2: TLC shows the prepared Sudan I, I and derivatives, II-IV The homogeneity of the synthesized compounds was carried out by the method of thin-layer chromatography using silica gel G as the stationary phase on glass plates of about 15 cm in height and dichloromethane as the mobile phase and allowing the solvent front to ascend 10 cm above the line of application. Apply to the plate 0.1% w/v solution of synthesized compounds I–IV separately in dichloromethane. Develop the plate in dichloromethane and remove it and mark immediately the solvent front level, allow plate to dry in air and put it in the iodine chamber. The thin layer chromatogram shows only one spot for each compound. The TLC of each azo compound showed single coloured spot indicated the homogencity of the synthesized, Sudan I and its nitro derivatives also. The Sudan I, I and its nitro derivatives II-IV(using o-/ m- and p-Nitro anilines) were also characterized by determining the physical constants and they are uncorrected. The results of analytical results and physical constants results are depicted in Table 1. Table 1: The Analytical and Physical data for Sudan I, (I) and its Nitro Derivatives, (II-IV). Compound ID.

Aniline derivative

Phenolic compound

Colour

Mol. for

*m.p. range °C

I

Aniline

2-Naphthol

Orange-red

C16H12N2O

130-131

II

o-Nitro-aniline

2-Naphthol

Orange

C16H11N3O3

185-190

III

m-Nitroaniline

2-Naphthol

Orange

C16H11N3O3

189-190

IV

p-Nitro-aniline

2-Naphthol

Brilliant red

C16H11N3O3

117-118

* Physical constants are uncorrected.

All the studied azo compounds showed four peaks in UV-Vis spectra in ethanol in the studied range 600 nm to 260 nm. In the UV-Vis spectral analysis of azo compound shows the three peaks in the 3863



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range 492-470 nm, 325-297 nm and 279-295 nm. These are attributed to n* and * transitions due to presence of nitro group (auxochrome) and azo group transitions and aromatic phenyl ring transition of moderate energy.

In addition to this the synthesized compounds, I-IV were also characterized by spectral analysis viz. UV-Vis, and FTIR and the obtained results are reported in the Table 2. The Table 2 also indicates the assigned structures from the spectral results.

FTIR spectra for the Sudan I and its nitro derivatives, I - IV are depicted in Fig. 3a to 3d.

Fig. 3a) FTIR Spectrum of 1-(Phenylazo)- Fig. 3b) FTIR Spectrum of 1-(2-Nitro-phenylazo)naphthalen-2-ol, Sudan I, I. naphthalen-2-ol, II.

Fig.

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3c) FTIR Spectrum of 1-(3-Nitro- Fig. 3d) FTIR Spectrum of 1-(4-Nitro-phenylazo)phenylazo)-naphthalen-2-ol, III. naphthalen-2-ol, IV.



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Table 2: The Spectral Data for Sudan I (I) and its Derivatives II-IV. Sr. No.

Comp. ID

IR (cm-1)

UV (nm)

Assigned Structure OH

1.

I*

478 421 309 279

1618 – 1580 for aromatic ring C=C-C str. (conjugated) 1364 for –N=N- and 3425 –O-H str.

492 390 300 282

1617–1575 for aromatic ring C=C-C str. (Conjugated). 1365 for –N=N- and 1389 for N-O str. 1560 for N-O str. 3431 –O-H str.

N N

OH

2.

II

N N O

N

O

3.

4.

III

IV

OH

470 425 w Sh 297 279

1620–1586 for aromatic ring C=C-C str. (conjugated) 1368 for –N=N- and 1389 for N-O str. 1562 for N-O str. 3427 –O-H str.

OH

484-325 295

1615–1579 for aromatic ring C=C-C str. (conjugated) 1361 for –N=N- and 1389 for N-O str. 1561 for N-O str. 3426 –O-H str.

N N

N

O

O

N

O N

N O

* It is present as an impurity in Sunset Yellow dye. It was used to colour many food stuff- curry and chilli powder.

Antibacterial Activity: The synthesized Sudan I, I and its nitro derivatives, II–IV were also screened for the biological activity viz. antibacterial activity against bacterial strains used Solmonella typhi and Bacillus cereus as per the method reported17. The results of the zone of inhibition (in mm) are depicted in Table 3. Table 3: Antibacterial Activity indicating Zone of Inhibition (mm) of the compounds, I-IV. Strain used

ID of Compound Std.

I

II

III

IV

Solmonella typhi

12

6

7

8

7

Bascillus cereus

18

9

9

7

8

Concentration of azo compound: 20 µg; Std.: Oflaxacin, 5 µg.

The results showed that the compounds are less active than the standard drug, Oflaxacin in case of the studied strains.

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CONCLUSION Three azo compounds have been prepared and characterized on the basis of analytical and spectral data. Aniline or substituted aniline, are used for the preparation of diazoninium salt (solution form), then they are reacted upon with -Naphthol to from Sudan I, I and its nitro derivatives, II-IV. These compounds will be useful as colour in food products and as a building block by organic researchers in the near future. Screening of these compounds against pathogenic microorganism reveals that these compounds have the capacity of inhibiting metabolic growth of some microorganisms to different extent. The antimicrobial activity of the compounds depends on the nature of substituent present on the aromatic ring. The studied compounds, shows less antibacterial activity when compared to standard drug Ofloxacin. ACKNOWLEDGEMENTS The authors are thankful to Chairman, The Muktainagar Taluka Education Society, Muktainagar for continuous encouragement and appreciation of our work and Principal, Smt. G. G. Khadse College, Muktainagar and Principal, Dr. A. G. D. Bendale Mahila College, Jalgaon for providing laboratories facilities. Also, greatful acknowledgement is made of the valuable assistance of Mr. Bhangale Gopal and Mr. Patil Sunil, non-teaching staff of Smt. G. G. Khadse College, Muktainagar. REFERENCES 1. a) http://monographs.iarc.fr/ENG/Classification/index.php (visited on 29-01-2015); b) V. J. Cogliano, R. Baan, K. Straif, Y. Grosse, B. Lauby-Secretan, F. El Ghissassi, V. Bouvard, L. Benbrahim-Tallaa, N. Guha, C. Freeman, L. Galichet and C. P. Wild, J. Natl. Cancer Inst., 2011, 103(24), 1827, DOI: 10.1093/jnci/djr483, Preventable Exposures Associated With Human Cancers. 2. N. A. Refat, Z. S. Ibrahim, G. G. Moustafa, K. Q. Sakamoto, M. Ishizuka and S. Fujita, The induction of Cytochrome P450 1A1 by Sudan dyes, J. Biochem. Mol. Toxicol., 2008, 22(2), 77, doi:10.1002/jbt.20220. PMID 18418879. 3. M. Abdullah, A. S. Fouda, S. A. Shama and E. A. Afifi, African J. Pure and Applied Chem., 2008, 2(9), 83. 4. M. R. Yazdanbakhsh and E. Moradi-E-Rufchahi, Synthesis, characterization and spectroscopic properties of some new azo dyes derived from 6-aminopyrimidine-2, 4(1H, 3H)-dione, Orient. J. Chem., 2009, 25, 41. 5. H. E. Fierz-David and L. Blangey, Fundamental Processes of Dye Chemistry, Translated from the Fifth Austrian Edition, By Paul W. Vittum, (Interscience Publishers), Inc., New York, 1949. 6. A. P. Naik, K. R. Desai and H. S. Patel, Synthesis of azo dyes based on alphaNaphtholformaldehyde oligomer and their application on textile, Iran. Poly. J., 2001, 10, 1. 7. N. Menek, G. Turgut and M. Odabasoglu, Turk. J. Chem., 1999, 23, 423. 8. https://www.sigmaaldrich.com/content/dam/sigmaaldrich/docs/Fluka/General_Information/1/analytix5_2011.pdf (visited on 1st Aug. 2014) 9. H. Zollinger, Colour Chemistry (VCH Weinhein, Germany), 1991. 10. A. Dyes, Ullman's Encyclopedia of Industrial Chemistry, 1985, A(3), 246. 11. V. Mireski and R. Gulaboski, The theoretical results are qualitatively illustrated by SWV (voltamograms) of the azo-dye Sudan-III, Croatica. Chem. Acta., 2003, 76(1), 37. 3866



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12. S. Zbaida and W. G. Levine, Chem. Res. Toxicol., 1991, 4(1), 82. 13. O. Chailpakul, W. Wonsawat, W. Siangparh, K. Grudpan, Y. Zhoo and Z. Zhu, Food Chemistry, 2008, 109(4), 876. 14. C. J. Patil and C. A. Nehete, Int. J. Pharm. Sci. Rev. Res., 2015, 33(2), 248. 15. C. J. Patil, Pooja A. Patil, P. B. Patil and M. C. Patil, Der. Chemica. Sinica., 2015, 6(5), 108. 16. C. J. Patil, M. C. Patil, N. R. Pachpole and V. S. Waykole, Der. Chemica. Sinica., 2015, 6(5), 115. 17. C. J. Patil, C. A. Nehete and H. A. Mahajan, Int. J. Green and Herbal Chem., 2013, 2(2), 241. 

This work is partly(oral) presented at Conference on “Recent Trends in Engineering Sciences-NCRTES-2012” at J. T. Mahajan College of Engineering, Faizpur on 4-5 Jan 2012. for Part-I and Part-II see reference 14 and 15. Corresponding author: C. J. Patil, [email protected] Organic Research Laboratory, Department of Chemistry, Smt. G. G. Khadse College, Muktainagar-425 306, (MS), India.

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