Sains Malaysiana 32: 79-86 (2003)                                                                                Sains Fizis dan Gunaan /

Physical & Applied Science

Synthesis and Characterisation of some Diorganotin

Bis(N- methyl 0- nitrobenzohydroxamate)

Elhadi Elba Saad, Y. Farina, Ibrahim Baba & Abdul Hamid Othman

School of Chemical Sciences and Food Technology

Faculty of Science and Technology

Universiti Kebangsaan Malaysia

43600 UKM Bangi, Selangor D.E., Malaysia

ABSTRACT

Diorganotin(IV) complexes of N-methyl o-nitrobenzohydroxamic acid were synthesised by refluxing diorganotin(IV) oxide and the free ligand using a Dean and Stark water separator. The N-methyl o-nitrobenzohydroxamic acid was derived from the corresponding o-nitrobenzoyl chloride and N­methylhydroxylamine in the presence of sodium hydrogen carbonate. The isolated complexes were characterized by elemental analysis and spectroscopic methods such as infrared, ^lH and ¹³C nuclear magnetic resonance. Results of analysis carried out on the diorganotin(IV) complexes of N-methyl o­nitrobenzohydroxamic acid showed a 1:2 stoichiometry with general formula R₂Sn[O-NO₂C₆P₄CONCH₃O]₂ (R= methyl, n-butyl and phenyl). The coordina­tion mode occurs by deprotonation of the hydroxy group and subsequent (0,0) coordination of the carbonyl oxygen. Attempted recrystallization of n­dibutyltin(IV) bis(N-methyl o-nitrobenzohydroxamate) from a mixture oftolu­ene and methanol yielded amorphous solids.

ABSTRAK

Kompleks diorganotin(IV) N-metit o-nitrobenzohidroksamat disintesiskan melalui teknik refluks di antara diorganostanum(IV) oksida dan ligan bebas menggunakan alat radas Dean dan Stark. Asid N-metil 0­nitrobenzohidroksamik diterbitkan daripada o-nitrobenzohidklorida dan N-­metithidroksitamina dengan kehadiran natrium hidrogen karbonat. Kompleks telah dicirikan melalui analisis unsur dan kaedah spektroskopi seperti inframerah dan resonans magnet nukleus RMN (^IH & ¹³C). Keputusan analisis menunjukkan kompleks diorganostanum(IV) terbitan asid N-metit 0­nitrobenzohidroksamik adalah dalam kadar 1:2 denganformula umum R₂Sn[O­N0₂C₆H₄CONCH₃O₂ (R=metil, n-butil dan fenil). Pengkoordinatan didapati berlaku melalui penyahproton kumpulan hidroksi. Dua atom oksigen terlibat dalam pengkoordinatan melalui oksigen hidroksi dan karbonil. Penghabluran semula kompleks n-dibutilstanum(IV) bis(N-metil o-nitrobenzohidrosamat) dalam campuran pelarut toluena-metanol menghasitkan pepejal amorfus.

REFERENCES/RUJUKAN

Agrawal, Y. K. 1980. Hydroxamic acids and their analytical applications. Rev. Anal. Chem. 5: 3-28.

Choudhuri, S. K., Das Dutta S., Chatterjee R. & Roy Chowdhury J. 1991. Antitumor activity of some organotin complexes of hydroxamic acids derived from dibasic carboxylic acids. Chemotherapy 37:122-127.

Das, M. K., Nath, M. & Zuckermann, J. I. 1983. Di- and Triorganotin(IV) Derivatives of N,N substituted hydroxylamines. Inorg. Chim. Acta 71: 49-59.

Drovetskaia, T. Y., Yashina, N. S.,Leonova, T. Y., Jorg Lorberth Sigrid Wocadlo Werner Massa & Jurgen Pebler. 1996. Synthesis and structure of some Diethyl­and Diphenyltin Bishydroxamates. J. Organomet. Chem. 507: 201-205.

Evans, C. J. & Smith, P. J. 1998. Chemistry of tin, 2^nd ed, London: Blackie. Evans, C. J. & Karpel, S. 1985. Organotin compounds in modern technology. J. Organomet. Chem. Libr. 16: 83.

Gielen, M.1996. Tin-based antitumour drugs new developments. Coord. Chem. Rev. 151: 41-5l.

Gielen, M. 1989. Tin based antitumour drug. In Gielen M. (ed.), NATO ASI Series, Ser. H: Cell Biology. vol. 37.

Gixasolo, M. A., Guli, G., Rel1erito, 1. & Stocco, G. C. 1995. Complexes of Tryptophan Dipeptides with the R2Sn(IV) 2+ Ion (R= Me, Ph): spectroscopic studies, solution properties and structural implications. Appl. Organomet. Chem. 9: 241-250.

Harrison, P. G., King, T. J. & Richards, J. A. 1975. Structural studies in main group chemistry. Part VIII. The crystal and molecular structure of Bis(N-methyl N­acetylhydroxylamino)dimetyltin(IV). J. Chem. Soc., Dalton Trans. 9: 826-830.

Harrison, P. G. & Richards, J. A. 1980. Structural studies in main group chemistry; xxv*. Tin Derivatives of N-acylhydroxylamines: Further studies. J. Organomet. Chem. 185: 9-5l.

Jousseaume, B., Pereyre, M., & Smith, P. J. 1998. Chemistry of tin, 2^nd ed. London: Blackie.

Karger, H. K. 1982. Chemistry and Biology of Hydroxamic Acids. New York.

Maehr, H. 1971. Antibiotic and Other Naturally Occurring Hydroxamic Acids and Hydroxamates. Pure Appl. Chem. 28: 603-636.

Majumdar, A.K. 1972.  N-Benzoylphenylhydroxylamine and its Analogues.  Oxford: Pergamon Press.

Neilands, J.B. 1967. Hydroxamic acids in nature. Science. 156: 1443-1447.

Pereyre, M., Quintard, J.P. & Raham, A. 1987.  Tin in organic synthesis. London: Butterworths.

Plunden, S.J., Cusack, P.A., & Hill, R. 1985. The industrial uses of tin chemical, The Royal Society of Chemistry. London.

Petrosyan, V.S., Yashina, N.S. Sizova, T. V., Leonova, T.V., Aslanov, L.A., Yatsenko, A.V. & Pellerito, L. 1994.  Synthesis and structures of some diorganotin bis(hydroxamates).  Appl. Organomet. Chem. 8: 11-17.

Taylor, R.J., May, I., Wallwork, A.L., Denniss, I. S., Hill, N.J., Galkin, B. Ya., Zilberman, B. Ya. & Frdorov, Yu. S.J. 1998. The application of formo- and aceto-hydroxamic acids in nuclear fuel reprocessing. Alloys and comp. 271-534.

Ulrich, H. & Sayigh, A.A.R. 1963. Hydroxyamino-derivatives from formaldehyde. Their reaction with acylhalides. J. Chem. Soc. 1098-1101.