Trimethyltin chloride

Under nitrogen, 115( 1 eq.) was reacted with BuLi (2 eq.) at 0°C for 1 h followed by treatment with trimethyltin chloride (2.5 eq.) in THF at room temperature for 30 min. Then a solution of 116 (1 eq.) and PdCl2(Ph3As)2 (0.02 eq.) in THF was combined and the mixture was stirred at reflux overnight. The polymer was precipitated with MeOH followed by filtration and dried under vacuum. GPC (polystyrene standards) Mn = 2000. 

Trimethyltin chloride reacts with carboxylic acids at 100° to give the corresponding chloride carboxylates Me2Sn(Cl)OCOR (187, 188), and diethyltin dihydride, triethyltin hydride, hexaethylditin, and bis(triethyltin) oxide have been shown to react with lead tetraacetate to give diethyltin diacetate or triethyltin acetate, as appropriate (189). 

Dimethyltin dichloride (hRf 15-20), trimethyltin chloride (h/ f 55-60), dibutyltin dichloride (h/ f 70-75) and tributyltin methoxide (h/ f 80-85) appeared in long-wavelength UV light (X = 365 nm) as yellow fluorescent chromatogram zones on a dark background. The detection limits (calculated as Sn) lay between 5 and 10 ng (dimethyltin dichloride, dibutyltin dichloride, tributyltin methoxide) and 50 ng (trimethyltin chloride) substance per chromatogram zone. 

Fig. 1 Fluorescence scan of a chromatogram track with 100 ng substance (calculated as Sn) each per chromatogram zone 1 = dimethyltin dichloride, 2 = trimethyltin chloride, 3 = dibutyltin dichloride, 4 = tributyltin methoxide.

The direct and indirect assessment of the aneuploidy-inducing potency of a number of organotin compounds was reported by Jensen et al. (1991a). The effects of dimethyltin dichloride, diphenyltin dichloride, trimethyltin chloride, tributyltin chloride, and triphenyl-tin chloride at 10 -10 mol/1 on chromosomal contractions in cultures of human peripheral lymphocytes were investigated. Diphenyltin dichloride, trimethyltin chloride, tributyltin chloride, and triphenyl-tin chloride appeared to be very strong inducers of chromosomal supercontraction, indicating that these compounds induce aneuploidy, probably by affecting... 

Trimethylaniline lb 268 Trimethyltin chloride lb 319 Trimipramine lb 352,354,355 Trinitrobenzenesulfonic acid, reagent... 

Phosphine and lithium aluminium hydride form lithium tetra-phosphinoaluminate (15) which reacts with trimethyltin chloride to give the phosphine (16). 

Dimethylaminodimethylarsine, Trimethyltin chloride Krommes, P. et al., J. Organomet. Chem., 1976,110, 195-200 Interaction in ether to produce diazomethy ldimethylarsine is accompanied by violent foaming, and eye protection is essential. 

The diester 110 (E = CC Et) reacts with a mixture of trimethyltin chloride and sodium cyanoborohydride under AIBN catalysis to give the cyclopentane 111 as a 4 1 mixture of cis- and fraws-isomers. The products are destannylated to the acetals 112 by treatment with methanolic ceric ammonium nitrate (CAN). The 1,7-octadienyl derivative 113 was similarly converted into the cyclohexanes 114 (cis/trans = 1 1) (equation 60)67. 

The methyl-[14C]-dimethyltin chloride was used to compare the performance of packed and megabore capillary columns in a gas chromatographic analysis for separating mixtures of a carbon-14 labelled trimethyllead chloride, tetramethyltin, dimethyltin dichloride and methyltin trichloride. The megabore column was able to separate all four methyltin compounds quickly, i.e., before the tetramethyltin decomposed into trimethyltin chloride and dimethyltin dichloride (equation 47), a reaction which did occur on the packed columns. Thus, the megabore column enabled the determination of the precise distribution of the various methyltin compounds in an environmental sample. The packed columns, on the other hand, could not separate dimethyltin dichloride and the methyltin trichloride and allowed significant decomposition of the tetramethyltin during the 15 minutes the analysis required. 

The various tetraalkyltin compounds were then identified and quantitated by GC MS and gas chromatography-atomic absorption analyses. The results indicated that tin(II) chloride in the simulated sea water was converted into methyltin trichloride and dimethyltin dichloride. The tin(IV) chloride, on the other hand, only formed methyltin trichloride. No trace of trimethyltin chloride was found from either tin(II) or tin(IV). The maximum amount of methyltin trichloride was formed near pH = 6 and at a salinity of 28%. The rate expression for the reaction is... 

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. 

Ducklings fed diets containing 50 mg trimethyltin chloride/kg died within 60 days (Fleming etal. 1991)... 

Brown, A.W., R.D. Verschoyle, B W. Street, and W.N. Aldridge. 1984. The neurotoxicity of trimethyltin chloride in hamsters, gerbils and marmosets. Jour. Appl. Toxicol. 4 12-21. 

The third methodology in pyridylstannane synthesis is unique to 2,6-dihalopyridines whose synthesis using the conventional lithiation method is low-yielding (17% yield) [57]. Schubert et al. prepared 2,6-bis(trimethyltin)pyridine (70) via an SnAt displacement of 2,6-dichloropyridine with sodium trimethylstannane, derived in situ from trimethyltin chloride [58-60]. 

Other tin reagents have found use in Pd-catalyzed cross-couplings with halopyridines as well. The Stille coupling of 3-iodopyridine with ethoxy(tributylstannyl)acetylene gave rise to 3-ethoxyethynylpyridine (100), which was then hydrolyzed to the corresponding ethyl 3-pyridylacetate (101) [88], Carbamoylstannane 102 was prepared by sequential treatment of lithiated piperidine with carbon monoxide and trimethyltin chloride. Stille coupling of carbamoylstannane 102 and 3-bromopyridine provided a unique entry to amide 103 [89],... 

Two frequently used methods for preparing stannylthiazoles involve either direct metalation or halogen-metal exchange followed by treatment with alkyltin chloride. Dondoni et al. described a preparation of 2-, 4- and 5-trimethylstannylthiazoles in 1986 [28], For instance, 2-trimethylstannylthiazole was readily obtained by quenching 2-lithiothiazole, derived from direct metalation of thiazole, with trimethyltin chloride. 

By lithiation of 4-methyloxazole with n-BuLi and subsequent quenching with trimethyltin chloride, Dondoni et al. prepared 2-trimethylstannyl-4-methyloxazole [18], which was then coupled with 3-bromofuran to provide the expected furylthiazole. 

Trimethylstibine, 3 58, 69 Trimethylstibine oxide, 3 73 Trimethylstibine sulfide, 3 74 Trimethylsylil groups, 13 537 Trimethyltin chloride, 24 823 Trimethylvinylammonium chloride. See Neurine... 

The triorganotin oxides and hydroxides are relatively straightforward. The complete structure of trimethyltin hydroxide has not yet been determined, but exposure of a solution of trimethyltin chloride to moisture gives the half-hydrolysis product Me3SnCbMe3Sn0H H20, in which trigonal-planar Me3Sn units are alternately bridged by Cl and OH, with rSnO = 212.5(2) and 212.1(2) pm, and rSnCl = 290.7(3) and 289.2(3) pm (Equation (132)).353... 

The recovery of methyltins from sediments was tested by using anoxic, sulphitic clay sediments from a mid-salinity region of Chesapeake Bay. Monomethyltin (11.2ng) and dimethyltin (11.5ng) were completely recovered from sediment. However, recovery of lOng of trimethyltin chloride from sediment was only about 70%. 

The /3-trimethyltin-substituted alkenylborane 36 was prepared in situ by treatment of triethylborane with 1-lithio-l-hexyne to form the lithium 1-alkynyltriethyl-borate 35 followed by trimethyltin chloride (Scheme 20.9) [37]. The trimethyltin chloride-induced migration of an ethyl group from boron to the adjacent acetylenic carbon is stereoselective with the boron and the tin substituents in 36 cis to each... 

A third method of estimating solvent basicity is provided by the donor number concept 14 ). The donor number of a solvent is the enthalpy of reaction, measured in kcal per mole, between the solvent and a Lewis add such as antimony (V) chloride. (Other Lewis acids, such as iodine or trimethyltin chloride, may be used, but the scale most often reported is that for SbCl5.) Available values for the SbCls donor number have been included in Table 1. Plots of the Walden product versus solvent basicity (A//SbC1 ) for several solvents are shown for lithium, sodium, and potassium ions in Fig. 10 and for the tetraalkylammon-... 

We note that while tin reagents have often been employed for the organoboron halides/ the use of organostannanes as starting materials can also be applied to the synthesis of heavier group 13 derivatives. In the context of polyfunc-tional Lewis acid chemistry, this type of reaction has been employed for the preparation of ort/ o-phenylene aluminum derivatives. Thus, the reaction of 1,2-bis(trimethylstannyl)benzene 7 with dimethylaluminum chloride, methylaluminum dichloride or aluminum trichloride affords l,2-bis(dimethylaluminum)phenylene 37, l,2-bis(chloro(methyl)aluminum)phenylene 38 and 1,2-bis(dichloroalumi-num)phenylene 39, respectively (Scheme 16). Unfortunately, these compounds could not be crystallized and their identities have been inferred from NMR data only. In the case of 39, the aluminum derivative could not be separated from trimethyltin chloride with which it reportedly forms a polymeric ion pair consisting of trimethylstannyl cations and bis(trichloroaluminate) anions 40. 

The enantioselective addition of the amino organolithium reagents consists of two stereo-controlled reactions, the asymmetric deprotonation (equation 14) and the following addition to electrophiles. The stereochemical course of the addition depends on the electrophile E. In the cases where heterocyclic enone or a,-unsaturated lactones are the electrophiles (entries 5-7), the addition proceeds with retention of configuration. In contrast, with the other electrophiles in Table 10 and trimethyltin chloride in equation 15, the addition proceeds with inversion of configuration. In the addition which proceeds with retention of configuration, a pre-complexation between the electrophiles and lithium may be involved (equation 16). 

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