Phenyltins

Phenyl isocyanate, conversion to di-phenylcarbodiimide, 43,31 Phenyl isocyanide, 41,103 Phenyllithium, reaction with allyltri-phenyltin, 41, 30 standardization of, 41, 32 Phenylmagnesium bromide, 41, 91 reaction with ( r(-butyl perbenzoate, 41,91... 

Butyl- and phenyltin compounds, particularly the trialkylated forms are very toxic to marine life. The antifouling paints, mainly tributyltin (TBT) but also triphenyltin (TPhT) caused and continue to cause substantial damage because of their slow biodegradation and their accumulation in the biota, notwithstanding a substantial reduction in application through multi-national regulation). 

In 1973, Taddei succeeded in preparing optically active (+)-benzyl-z-propylmethyl-phenyltin, (+)-(62), by a reaction of the optically unstable z -propylmethylphenyltin menthoxide with benzylmagnesium bromide U) (see Table 4). This asymmetric induction very probably does not yield an optically pure compound but is a very rapid and facile route to optically active organotin compounds of unknown optical purity. 

Equation 11.31 Stille reaction with the F-21-tagged phenyltin reagent. 

The analytical response of inorganic and organic tin compounds of formula R SnX 4 was studied for direct hydride generation and measurement with a non-dispersive AFD (atomic fluorescense detector). Tributyltin and phenyltin compounds gave unsatisfactory results. This was corrected by warming the sample with a dilute Br2-HN03 solution37. 

Butyltin and phenyltin compounds in samples of environmental, industrial and biological origin can be determined by the following general scheme42-48 ... 

A considerable number of organometallic species of germanium, tin and lead have been detected in the natural environment. A number of these are nonmethyl compounds which have entered the environment after manufacture and use (e.g. butyltin and phenyltin compounds by diffusion from antifouling paints on boats, and ethylleads from leaded gasoline). Only a few methyl compounds are now manufactured and used (e.g. some methyltin compounds are used as oxide film precursors on glass)1. 

Hamasaki and coworkers87 investigated the genotoxicity of 14 organic tin compounds (methyl-, butyl- and phenyltins) and inorganic tin (SnCU) on Escherichia coli and on Bacillus subtilis. Dibutyltin dichloride, tributyltin chloride, tributyltin chloride, bis(tributyl-tin)oxide, dimethyltin dichloride and trimethyltin chloride were all found to be genotoxic. 

Phenyltin compounds significantly inhibit natural killer cell function and possible natural killer cell-mediated immunotoxic potential of these compounds in humans (Whalen et al. 1999). The toxic potential followed the order of triphenyltin > diphenyltin > monophenyltin however, phe-nyltins were less toxic than butyltins to human natural killer cells (Whalen et al. 1999). 

Whalen, M.M., S. Hariharan, and B.G. Loganathan. 1999. Inhibition of human natural killer (NK) cell function in vitro by phenyltin compounds. Book of Abstracts, Part 1, ENVR 113. 218th American Chemical Society National Meeting, New Orleans, August 22-26, 1999. 

Recently, Li and co-workers also reported the Rh-catalyzed arylstannane addition to enones in water under reflux.139 The addition of KOH helps the reaction to proceed smoothly (Scheme 50). A tentative mechanism was proposed for the Rh-catalyzed conjugated addition of phenyltin trichloride under basic conditions (Scheme 51). Later, this kind of reaction was found to work even in water at 50 °C. 

Langner, M., Gabrielska, J., Kleszcynska, H. and Pruchnik, H. (1998). Effect of phenyltin compounds on lipid bilayer organization, Appl. Organomet. Chem., 12, 99-107. 

Rozycka-Roszak, B., Pruchnik, H. and Kaminski, E. (2000). The effect of some phenyltin compounds on the thermotropic phase behaviour and the structure of model membranes, Appl. Organomet. Chem., 14, 465 -72. 

Lithium anilide reacts with phenyl- or methyltin trichloride to give polynuclear Sn-N compounds, in which the phenyltin derivatives are four-coordinate and bicyclic (Equation (168)), and the methyltin derivatives are five-coordinate and tetracyclic.504... 

Phenyltin sesquisulfide, (Pf S Sg), with an adamantine-like structure, reacts with Na2S to give the sodium thiolate, PhSnS33-Na+3, with near-tetrahedral tin.512... 

Radical anions have also been obtained recently from the tin equivalents of the alkynes, the distannynes (see Section 3.14.24.6). Reduction of 2,6-di(2,4,6-triisopropylphenyl)phenyltin(ll) chloride (ArSnCl) with potassium in THF gave [ArSnSnAr] K+, which showed g= 2.0069, (117Sn) = 0.83 mT, (119Sn) = 0.85 mT, and in the crystal, the radical anion adopts a tram-bent structure. The 2,6-di(2,6-diisopropylphenyl)phenyltin analog behaves similarly.533 534... 

In recent years, the first distannynes have been obtained. Reduction of 2,6-di(2,6-diisopropylphenyl)phenyltin(ll) chloride (Ar SnCl) or 2,6-di(2,4,6-triisopropylphenyl)phenyltin(n) chloride (ArSnCl) with sodium or potassium has given not only the stannynes Ar Sn=SnAr and ArSn=SnAr, but also the radical anion [ArSn=SnAr, and the dianions [ ArSn=SnAr] and [Ar Sn=SnAr ]=.534 The properties of the Ar compounds are as shown in Table 11. 

In situ derivativization and supercritical fluid extraction has been used for the simultaneous extraction and determination of butyl tin and phenyltin compounds in soils and sediments [73]. 

Cal et al. [85] carried in situ derivativisation and supercritical fluid extraction for the simultaneous determination of butyltin and phenyltin compounds in sediments. 

In basic aqueous solutions with a [Rh(COD)2]BF4 catalyst, phenyltin trichloride was found to react with aromatic aldehydes or unsaturated ketones. In the presence of a strong aqueous alkali (KOH) PhSnCU is readily hydrolysed and the products of this reaction, such as e.g. PhSn(OH)3 add to the carbonyl function of aldehydes or undergo conjugate addition to unsaturated ketones (Scheme 6.35). In the absence of KOH no reaction takes place at all. Yields are generally high [73]. 

Phenyltin chloride Aldrich Phenyltin trichloride Stannane, trichlorophenyl- (8,9) (1124-19-2)... 

C. Brornotris[2-(perfluorohexyl)ethyl]tin. The fluorous phenyltin product (17.2 g, 13.9 mmol) and dry ether (80 mL) are transferred to a 250-mL, three-necked flask that had been dried in an oven and cooled to 0°C under argon. Bromine (0.71 mL, 14 mmol) is added dropwise over 30 min to the mixture. The addition rate is adjusted to keep the temperature between 0° and 1°C. The mixture is warmed to 25°C and stirred for 7 hr. The reaction mixture is transferred to a 250-mL, round-bottomed flask. The ether and excess bromine are removed under reduced pressure to leave a yellow oil. The oil is dissolved in FC-72 (75 mL) and transferred to a 250-mL separatory funnel. The bromine and bromobenzene by-products are removed by washing three times with methylene chloride (3 x 75 mL) leaving the fluorous layer colorless. The FC-72 is removed under reduced pressure to provide 15.8 g (12.7 mmol, 92%) of a colorless oil (Note 6). 

For the determination of organotin compounds (tributyltin, triphenyltin, triethyltin, and tetra-ethyltin) a MAE is proposed before the normal phase (NP) HPLC/UV analysis [35], In organotin and arsenic speciation studies, hydride generation is the most popular derivatization method, combined with atomic absorption and fluorescence spectroscopy or ICP techniques [25,36], Both atmospheric pressure chemical ionization (APCI)-MS and electrospray ionization ESI-MS are employed in the determination of butyltin, phenyltin, triphenyltin, and tributyltin in waters and sediments [37], A micro LC/ESI-ion trap MS method has been recently chosen as the official EPA (Environmental Protection Agency) method (8323) [38] it permits the determination of mono-, di-, and tri- butyltin, and mono-, di-, and tri-phenyltin at concentration levels of a subnanogram per liter and has been successfully applied in the analysis of freshwaters and fish [39], Tributyltin in waters has been also quantified through an automated sensitive SPME LC/ESI-MS method [40],... 

Electrophilic addition to 9-vinylcarbazole occurs in the Markovnikov sense, thus hydrogen chloride,hydrogen bromide,chlorine, and bromine in carbon tetrachloride, and iodine chloride in pyridine are recorded as adding with initial electrophilic attack at the methylene. Mercuric acetate in methanol gave 9-(2-acetoxymercuri-l-methoxyethyl)carbazole. Although 9-vinylcarbazole gave an iodohydrin, comparable reaction with methanolic sodium hypochlorite led to 9-(2-chlorovinyl)carbazole. Catalytic reduction of the latter produced 9-(2-chloroethyl)carbazole. Tri-phenyltin hydride gave 96. ... 

---