Organotin esterification of (E)-3-(3-fluoro-phenyl)-2-(4-chlorophenyl)-2-propenoic acid: synthesis, spectroscopic characterization and in vitro biological activities. Crystal structure of [Ph3Sn(OC(O)C(4-ClC6H4) = CH(3-FC6H4))]

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Abstract

Nine organotin esters, Me2SnL2 1, Me3SnL 2, n-Bu2SnL2 3, n-Bu3SnL 4, Ph3SnL 5, (PhCH2)2SnL2 6, [(Me2SnL)2O]2 7, Et2SnL2 8 and n-Oct2SnL2 9, of (E)-3-(3-fluorophenyl)-2-(4-chlorophenyl)-2-propenoic acid, HL have been synthesized and characterized by elemental analysis, IR, Multinuclear NMR (1H, 13C and 119Sn) and mass spectrometry. The geometry around the tin atom has been deduced and compared both in solution and solid states. The crystal structure of compound 5 has been determined by X-ray single crystal analysis, which shows a tetrahedral geometry around the tin atom with space group P1¯. These compounds have also been screened for bactericidal, fungicidal activities and cytotoxicity data.

Graphical abstract

Nine organotin(IV) compounds containing (E)-3-(3-fluorophenyl)-2-(4-chlorophenyl)-2-propenoate ligand were synthesized, screened for biological activity and characterized by spectroscopic and single crystal X-ray analysis.

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Introduction

Organometallic compounds comprise an important class of antitumor agents [1]. Among the organometallic compounds organotin carboxylates have been shown increasing interest due to their activity against various types of cancer. In fact many of the di-n-butyltin(IV), tri-n-butyltin(IV) and triphenyltin (IV) complexes display interesting antitumor activities. Recent work also reveals higher antitumor activities for various di- and tri-organotin fluoro-substituted carboxylates than their non-fluorinated analogues [2]. Another aspect of major interest in organotin carboxylates is of their structural diversity. Beside diorganotin dicarboxylates, triorganotin esters also show rich and diverse structural chemistry. For example the structures of triorganotin carboxylates range from a discrete form to polymer chain as shown in Scheme 1 [3], [4], [5]. Keeping in view the structural and biological diversity of organotin(IV) carboxylates and in connection with our interest in coordination chemistry of organotin compounds with different carboxylic acids [6], [7], [8], [9], [10], here we present the synthesis, characterization and in vitro biological activity of a carboxylic acid, (E)-3-(3-fluorophenyl)-2-(4-chlorophenyl)-2-propenoic acid (Fig. 1) and its organotin compounds.

Section snippets

Results and discussion

Reaction of R2SnCl2 and R3SnCl with the silver salt of (E)-3-(3-fluorophenyl)-2-(4-chlorophenyl)-2-propenoic acid in 1:2 and 1:1 molar ratio, respectively, led to the formation of complexes according to Eqs. (1), (2). Reactions of n-Bu2SnO, (n-Bu3Sn)2O and n-Oct2SnO with ligand acid (1:2 molar ratio) in boiling toluene afforded the compounds 3, 4 and 9, respectively, with azeotropic removal of water (Eqs. (3), (4)). The compound 7 was synthesized according to the reported method by refluxing

Antibacterial activity

Almost all of the synthesized compounds were subjected to screening test for their antibacterial activity, using the agar well diffusion method [29] and data are listed in Table 8. It is concluded that organotin(IV) derivatives of ligand acid show marginally high activity than the acid itself but considerably lower than the reference drug.

The results further demonstrated that diorganotin(IV) compounds show better activity against various bacteria than triorganotin(IV) derivatives.

Antifungal activity

The selected

Conclusions

Organotin esters of (E)-3-(3-fluorophenyl)-2-(4-chlorophenyl)-2-propenoic acid are prepared successfully and characterized by the spectroscopic techniques. The ligand acts as bidentate as suggested by the IR analysis except for compound 5, which in both solid and solution state shows the tetrahedral geometry around tin atom. The exhibition of characteristic IR bands and two signals of same intensity in 119Sn NMR confirms compound 7 as dimeric dicarboxylatotetraorganodistannoxane. Multinuclear

Experimental

All the di- and tri-organotin chlorides were procured from Aldrich or Fluka while dibenzyltin dichloride was prepared by the reported method [33]. The ligand (E)-3-(3-fluorophenyl)-2-(4-chlorophenyl)-2-propenoic acid was synthesized by the Perkin condensation method in the laboratory [34]. All the solvents were dried before use by the literature methods [35].

Instrumentation

Melting points were determined in capillary tubes using a MPD Mitamura Riken Kogyo (Japan) Electro thermal melting point apparatus and are uncorrected. Infrared absorption spectra were recorded as KBr pellets or neat liquid on a Bio-Rad Excaliber FT-IR, model FTS 3000 MX spectrometer (USA). 1H, 13C and 119Sn NMR spectra were recorded on a Bruker AM 250 spectrometer (Germany), using CDCl3 as an internal reference [δ 1H(CDCl3) = 7.25 and δ 13C(CDCl3) = 77.0]. 119Sn NMR spectra were obtained with Me4

Acknowledgments

S.A. is thankful to the Quaid-i-Azam University, Islamabad, Pakistan, for financial support. S.R. is grateful to the University of Azad Jammu & Kashmir, Muzaffarabad for the grant of a study leave.

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