Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 4(1), 75-77, January (2014) Res. J. Chem. Sci. International Science Congress Association 75 Characterization and Pesticidal Studies of Dibutyltin (IV) Derivatives of diphenylamine-2-hydroxy-2’-carboxylic acidPachouri Manoj Kumar and Mittal PankajDepartment of Applied Sciences (Chemistry), Hindustan Institute of Technology and Management, Keetham, Agra, 282 007, INDIAAvailable online at: www.isca.in, www.isca.me Received 26th December 2013, revised 13th January 2014, accepted 16th January 2014Abstract Organotin (IV) compounds of diphenylamine derivatives have synthesized by the reaction of dibutyltin diisopropoxide with diphenylamine-2-hydroxy-2’-carboxylic acid in 1:1, 1:2 and 2:1 molar ratios. These compounds have been characterized by elemental analyses, IR spectral analyses, H NMR spectral analyses and molar conductance measurements. The products are screened for pesticidal activities against the pest ‘Red Flour Beetle’ (Tribolium castaneum). The compounds exhibited enhanced pesticidal effects as compared to the ligand. Keywords: Dibutyltin, Diphenylamine, IR, H NMR, Pesticidal. IntroductionThe organotin comounds are of paramount importance from academic point of view as well as tin may form coordination complexes with suitable ligands displaying enhanced its coordination number. The organotin compounds have been used as biocidals1-3 as well as pesticidals4-8. The present work deals with the synthesis, characterization and pesticidal studies of dibutyltin (IV) compounds of diphenylamine-2-hydroxy-2’-carboxylic acid. Material and Methods Experimental: Synthesis of dibutyltin diisopropoxide(DBTDIP): Isopropanol (3.1 ml, 0.04 M) in 10 ml dry benzene was mixed and stirred with sodium metal (0.92 g, 0.04 M) under anhydrous condition till the complete dissolution of sodium metal. 6.1 g of dibutyltin dichloride (0.02 M) in 15 ml dry benzene was mixed drop-wise in the reaction mixture with continuous shaking by using dropping funnel. The reaction mixture was refluxed for about 2.5 hours. The product so obtained was filtered and the filtrate was distilled under reduced pressure on a wax bath. On distillation, a colourless liquid was obtained which changed to light brown upon standing. Synthesis of Diphenylamine-2-hydroxy-2’-carboxylic acid (dphc): 1.56 gm (0.01 M) o-chlorobenzoic acid and 1.09 gm (0.01 M) o-amino phenol were taken in 100 ml of distilled water in a flask. This mixture was made slightly alkaline with KCOsolution and a little copper oxide was mixed in the reaction mixture. The reaction mixture was refluxed on an oil bath for about 4 hours and cooled. One gram activated charcoal was added and boiled for about one hour to decolourise the product. It was filtered, concentrated and cooled. The obtained solution was acidified with dil. HCl in excess till the precipitation of the resultant product was complete. The obtained crude product was dissolved in ethyl alcohol for recrystallization and the recrystallized compound was dried over anhydrous calcium chloride in a desiccator to get brown powder. Synthesis of Dibutyltin (IV) derivatives of Diphenylamine-2-hydroxy-2’-carboxylic acid: Dibutyltin (IV) derivatives of Diphenylamine-2-hydroxy-2’-carboxylic acidwere synthesized by refluxing DBTDIP with dphc in dry toluene in 1:1, 1:2 and 2:1 molar ratios. A mixture of DBTDIP {1.4 ml (0.004 M)/ 1.4 ml (0.004 M)/ 1.4 ml (0.004 M)} and dphc {0.92 g (0.004 M)/ 1.84 g (0.008 M)/ 0.46 g (0.002 M)} was suspended in 30 ml dry toluene in a round bottom flask fitted with water condenser and a guard tube containing anhydrous CaCl. The solution was condensed for about 12-16 hrs on a wax bath. On cooling in a desiccator for over night, the coloured solid was separated out which was filtered and washed with dry ether. The obtained product was recrystallized from DMSO and dried under reduced pressure over anhydrous CaCl to get coloured crystalline solid. Physical and Analytical Measurements: The purity of derivatives was determined by running their TLC for single spot on silica gel-G plate and by the repeated melting point determination of recrystallized samples taken in open capillary tube and thus uncorrected. These compounds were analyzed for elemental analysis on Carlo Erba Micro Analyser-1108 at the RSIC, CDRI, Lucknow. Tin (IV) metal was estimated by decomposing the compound with conc. HNO followed by Conc. HSO and then neutralized and precipitated by liq. NHas tin oxide10. Infra-red spectrum of compounds was recorded by Perkin Elmer RX-1 spectrometer and H NMR spectrum was recorded by PMR Brucker AC 300 MHz spectrometer at RSIC, CDRI, Lucknow. The molar conductance was determined by using Systronics conductivity meter 306. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(1), 75-77, January (2014) Res. J. Chem. Sci. International Science Congress Association 76 Results and Discussion The physical and analytical data of dibutyltindiisopropoxide and its derivatives are given in table-1. All the synthesized derivatives were found stable and hygroscopic at room temperature. They are soluble in DMF and DMSO and insoluble in water. The low values of molar conductance of these derivatives (3.8 – 4.9 ohm-1cmmol-1) indicate their behaviour as non-electrolytes11. Infra-red spectral analysis: In the IR spectrum of DBTDIP, the weak peaks around 2910 cm-1 and 2865 cm-1 indicate C-H of –CH- and –CH of the butyl group12,13. The strong peak at 1370 cm-1 occurs due to C-H bending vibration of geminal dimethyl structure of the isopropoxy group14. A weak peak at 1145 cm-1 occurs due to C-O present in isopropoxy group.14The medium peak around 645 cm-1 and a weak peak around 620 cm-1 may be due to Sn-C.15 The weak peak around 535 cm-1and a strong peak around 460 cm-1 may be due to Sn-O16. In the IR spectrum of dphc, a medium peak around 3440 cm-1 may be due to O-H stretching vibration and 2640 cm-1 due to O-H stretching of –COOH group. The sharp peak at 1685 cm-1 takes place for –CO stretching vibration of –COOH group. In the IR spectra of dibutyltin(IV) derivatives of dphc, a medium band at 3040 cm-1 may be due to C-H of the aromatic ring12,14. The weak peaks at 2940 cm-1 and 2850 cm-1 indicate C-H of –CH- and –CH of the butyl group12,13. The weak peak in the region 1145 cm-1 corresponds for C-O of the isopropoxy group in 2:1 derivative14. A strong peak around 1435 cm-1 corresponds to COO stretching vibrations while a strong peak around 1630 cm-1 may be due to asCOO stretching vibrations17. The separation value, COO of about 195 cm-1suggested the presence of bridged carboxylate group18A strong peak around 1375 cm-1 occurs due to C-H bending of the geminal dimethyl structure of the isopropoxy group14 in 2:1 derivative. The medium peak around 640 cm-1 and weak peak around 610 cm-1 occur due to Sn-C15, while weak peak around 540 cm-1 and strong peak around 460 cm-1 occurs due to Sn-16The absence of free hydroxyl (-OH) band in the region 3500-3200 cm-1 in 1:1 and 2:1 derivatives suggests possible bonding of hydroxyl oxygen to tin, while this band is appeared in 1:2 derivative at 3460 cm-1. H NMR spectral analysis: In the nmr spectrum of DBTDIP, a multiplet between 1.20 – 1.60 ppm may be due to protons of butyl group19 attached with tin. A multiplet between 0.70 – 1.20 ppm may be due to protons of isopropoxy group. In the nmr spectrum of dphc, a multiplet is shown between 7.20 – 8.10 ppm, which corresponds for aromatic protons. A singlet at 10.50 ppm, 11.30 ppm and 3.45 ppm corresponds to –OH, -COOH and –NH- protons respectively. In the nmr spectra of synthesized dibutyltin (IV) derivatives of dphc, a multiplet is shown between 7.10 – 8.20 ppm, which corresponds to aromatic protons. The multiplet between 1.00 – 1.40 ppm in 1:1 and 1:2 derivatives and 0.50 – 1.30 ppm in 2:1 derivative may be due to protons of butyl group19 attached with tin. A hump around 10.70 ppm is obtained in 1:2 derivative which corresponds to –OH group proton which is absent in 1:1 and 2:1 derivatives. A singlet is obtained in the region 3.50 – 3.65 ppm corresponds to –NH- proton. Table-1 Physical, Analytical and Pesticidal Data of DBTDIP and its derivatives with dphcS. No. Compound (Molecular Formula) Ratio Colour m.p./ b.p. (±2C) % Analysis Found/ (Calcd.) % mortality data at different concentrations C H N Sn 0.08%(w/v) 0.06%(w/v) 0.03% (w/v) 1 DBTDIP (C 14 H 32 O 2 Sn) Light brown liquid 130.5 at 10 mm 48.40 (47.90) 9.80 (9.12) -- 32.95 (33.84) 40 33 18 2 dphc (C 13 H 11 O 3 N) Brown solid 144 68.75 (68.12) 5.24 (4.80) 6.85 (6.11) -- 17 10 8 3 BuSn(L) (C2127NSn) 1:1 Dark brown solid 140 55.21 (54.78) 6.14 (5.80) 3.84 (3.04) 26.12 (25.87) 48 43 37 4 BuSn(LH)(C3438Sn) 1:2 Black solid 95 59.88 (59.22) 5.64 (5.52) 4.76 (4.06) 17.25 (17.27) 47 37 30 5 (BuSn)L(OPr i (C3555NSn) 2:1 Brownish black solid 108 52.74 (52.05) 7.43 (6.82) 1.98 (1.73) 29.62 (29.49) 53 47 38 Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(1), 75-77, January (2014) Res. J. Chem. Sci. International Science Congress Association 77 Pesticidal activity: All the synthesized derivatives were screened for their pesticidal activities on a Red Flour Beetle Tribolium castaneum), a storage food grain pest adopting bio-assay technique20. A comparative study of % pest mortality (table-1) indicates the enhancement of pesticidal activity of derivatives as compared to ligand. ConclusionFrom the above analysis, it has been found that all the synthesized derivatives are stable at room temperature. The pesticidal activity of dibutyltin (IV) derivatives of diphenylamine 2-hydroxy-2’-carboxylic acid is higher as compared to ligand fragments. References 1.Arakawa Y., Main Group Metal Chem., 12, 1 (1989)2.Saxena A.K., Appl. Organometal. Chem., , 39 (1987)3.Dey K. and Mukhopadhyay S., J. Indian Chem. Soc., 78, 73 (2001)4.Gupta P.R., Mishra R.C. and Dogra G.S., Indian J. Agric. Sci., 51, 514 (1981) 5.Studies on monobutyltin (IV) derivatives of 3-hydroxy-2-naphthoic acid, Mittal P., Pachouri M.K. and Sharma R.C., Asian J. of Chemistry, 18(1), 737 (2006)6.Pesticidal behavior of monobutyltin (IV) derivatives of salicylic acid against Red Flour Beetle, Mittal P., Pachouri M.K. and Sharma R.C., J. Ind. Council Chem.,23(2), 23 (2006)7.Characterization and pesticidal studies of some new Dibutyltin (IV) derivatives of 1-hydroxy-2-naphthoic acid, Mittal Pankaj and Pachouri Manoj Kumar, Res. J. chem. Sci., 2(4), 61-63 (2012) 8.Synthetic, characterization and pesticidal studies of Dibutyltin (IV) derivatives of salicylic acid, Mittal Pankaj, Pachouri Manoj Kumar and Singh Narendra Pal, Res. J. chem. Sci., 3(3), 79-81 (2013)9.Gaur D.P., Srivastava G. and Mehrotra R.C., J. Organometal. Chem., 63, 221 (1973)10.Vogel A.I., Quantitative Inorganic Analysis, Longmans, London, (1975) 11.Kettle S.F.A., Coordination Compounds, Thomas Nelson and Sons, 168 (1975)12.Bellamy L.J., The Infra-red Spectra of Complex Molecules, Methuen, London, (1962)13.Nakanishi K. and Soloman P.H., Infra-red Absorption Spectroscopy 2nd Ed., Holden-Day, London, (1962) 14.Silverstein R.M., Bassler G.C. and Morrill T.C., Spectrometric Identification of Organic Compounds, John Wiley, New York, (1981)15.Brown M.P., Okawara R. and Rochow E.G., Spectrochim. Acta, 16, 595 (1960)16.Pardhy S.A., Gopinathan S. and Gopinathan C., Synth. React. Inorg. Met. Org. Chem., 13, 305 (1983) 17.Peruzzo V., Plazzogna G. and Tagliavini G., Organometal. Chem., 24, 347 (1970)18.Srivastava, T.N. and Singh, J.D., Indian J. Chem., 24A, 489 (1985) 19.Asahi Research Centre Co. Ltd. Tokyo, Hand Book of Proton NMR Spectra and Data, Vol. 2nd & 4th, Academic Press, Japan, (1985)20.U.S. Environmental Protection Agency, Report of DDT Advisory Committee(1975)