Tri-«-butyltin chloride

Reader, S., H.B. Steen, and F. Denizeau. 1994. Intracellular calcium and pH alterations induced by tri- -butyltin chloride in isolated rainbow trout hepatocytes a flow cytometric analysis. Arch. Biochem. Biophys. 312 407-113. 

Tsuda, T, S. Aoki, M. Kojima, and T. Fujita. 1992. Accumulation and excretion of tri- -butyltin chloride and triphenyltin chloride by willow shiner. Comp. Biochem. Physiol. 101C 67-70. 

Tsuda, T, S. Aoki, M. Kojima, and H. Harada. 1991. Accumulation of tri- -butyltin chloride and hiphenyltin chloride by oral and via gill intake of goldhsh Carassius auratus). Comp. Biochem. Physiol. 99C 69-72. Tsuda, T, H. Nakanishi, S. Aoki, and J. Takebayashi. 1986. Bioconcentration of butyltin compounds by round Crucian carp. Toxicol. Environ. Chem. 12 137-143. 

Palladium-catalyzed hydrostannylation is stereoselective, giving syn-adduct. Regioselectivity is not always perfect, however. Exclusive formation of (-B)-l-stannylalkene is obtained only when 1-alkyne with a bulky substituent is employed (Scheme 34) [147-150]. Nicolaou also reported a stereo- and regio-selective hydrostannylation (Scheme 35) [151]. Use of a combination of tri-butyltin chloride and poly(methylhydro)siloxane in the presence of TBAF is also an impressive method in this class [152]. 

A cyano group can be introduced using palladium and zinc cyanide, potassium cyanide or potassium ferrocyanide, the last having the significant advantage of low toxicity, and can be carried out with either a paUadium " or copper catalyst. Tri-n-butyltin cyanide can be used similarly, but a modification using catalytic tri- -butyltin chloride with potassium cyanide is much to be preferred. ... 

ALKENES Cuprous iodide. Diisobulylaluminum hydride. Dipropenylcopperlithium. Ethyl a-trifluoromethylsulfonyloxy acetate. Iodine. (l-LithiovinyI)tinnethylsilane. Lithium dialkyl cuprates. Lithium phenylethynolate. Methylcopper. Methylhthium. Sodium bislrimetliylsilylamide. Thioiiyl chloiide-Trietliylamine. Titanium(O). p-Toluenesulfonic acid. Tri./. butyltin chloride. Tricthyl orthoformatc. 

The reagent is prepared in 707o yield by reaction of tri- -butyltin chloride with Mg in THF.i... 

Geissler and Kriegsmann " reported on the gas chromatography of mixtures of the various butyltin chlorides. They showed that at a column temperature of 160 C to ISO C butyltin trichloride reacted with tetrabutyltin, but that mixture containing tetrabutyltin, tri-butyltin chloride and dibutyltin dichloride were unaltered. (Figure 121). The 2-metre column used was packed with 18% of silicone oil OE 4011 on Sterchamol, and the carrier gas was hydrogen (3.5 litres per hour). A thermal-conductivity detector was used. 

Azatriquinacene 39 has been successfully synthesized in three steps starting from azatriquinane 37. Azatriquinane 37 on treatment with sulfuryl chloride under photochemical irradiation gave nonachloride 89 which on reduction with tri- -butyltin hydride provided the 2,3,5,6,8,9-hexachloroazatriquinane 198 in 53% yield. This on treatment with lithium in tert-butyl alcohol gave completely dehalogenated azatriquinacene 38 in an acceptable 32% yield (Scheme 84) <2000JOC7253>. 

An estimate of the accuracy of both analytical methods was performed on bis(tri-n-butyltin) oxide and tri-n-butyltin chloride solutions (8.9-35.6 ig/l) prepared in filtered (0.45 im) near-shore seawater free of detectable organ-otins. Average mean recoveries of 92.8% by both methods were determined for tributyltin standard solutions. Low ng/1 levels of mono-, di-, and tributyltin were found in samples taken from San Diego Bay. 

The most widely used, and often most convenient reagents for such one-pot reactions are sodium hypochlorite (45) or hypobromite (16). These reactions are performed in the presence of an organic base (generally triethylamine) that normally enhances the yield of cycloaddition products (45). This method was employed for many intermolecular reactions (71) and also seems especially suited for intramolecular ones (72-77) as well as for the solid-phase synthesis (78) of 2-isoxazolines. Hypohalite can also be replaced by sodium broruite in combination with a catalytic amount of tri-u-butyltin chloride (79). In a related method, O-tributylstannyl oximes were treated with tert-butyl hypochlorite to produce nitrile oxides that were trapped with aUcenes or alkynes to afford the corresponding isoxazolines or isoxazoles in moderate to good yield (80). 

Another limitation is seen when extra strain is included in the compound to be reduced. Dehalogenation of 3,3-dichlorobicyclo[2.2.0]hexan-2-one with zinc/ammonium chloride in methanol gave, at best, a 25% yield of 3-chlorobicyclo[2.2.0]hexan-2-one (14) together with cyclohexenone and 6-chlorohex-5-enoic acid.128 The best results were achieved with the zinc/ acetic acid system, while addition of water, silver-promoted zinc reduction in methanol, tri-butyltin hydride reduction or hydrogenolysis with palladium in methanol did not result in formation of 14, but various other ring-opened products. 

Figure 6.12 The cellular toxicity of TBT caused by damage to the thiols of the Ca2+ pump. This leads to dramatic mobilization of calcium from the ER. The filled circles represent ATP-dependent Ca2+ transporters. Abbreviations TBT, tri-n-butyltin chloride ER, endoplasmic reticulum.

J. T. Groves, S. Kittisopikul, Dehalogenation reactions catalyzed by tri-n-butyltin chloride. Competition for carbon radicals by borohydride and tin hydride. Tetrahedron Lett. 49 429I (1977). 

In a fume hood, 19.2 g. (0.059 mole) of tri-n-butyltin chloride and then 140 ml. of ethylene glycol dimethyl ether (monoglyme) which has been purified by distillation from calcium hydride at atmospheric pressure on an efficient fractionating column (fraction used boils at 85 1°C.) are added to a pressure-equalized 250-ml. dropping funnel, and the funnel gently agitated to dissolve all the tributyltin chloride. 

In the initial studies about the reaction of /V.zV-disubstituted formamides with alkaline metals to give glyoxylic amides, the participation of carbamoyl metal derivatives as intermediates was postulated83. The first preparation of the carbamoyllithium 77 was described two years later by a mercury-lithium transmetallation from compound 76 at —75 °C (Scheme 20)84. The authors proposed also an aminocarbene structure 78 and studied its reactivity with methanol, methyl iodide, carbonyl compounds, esters, acyl chlorides, mercury(II) chloride and tri-n-butyltin chloride providing compounds 79. 

Prepared by reaction of tri-n-butyltin chloride with triflic acid. 

Fluorinated aUcyl vinyl and aryl cadmium reagents can be prepared in excellent yields just by stirring the fluorinated halides with activated cadmium metal. These reagents can then be used to prepare the corresponding fluorinated stan-nanes, which are versatile synthetic intermediate, by reacting them with tri-n-butyltin chloride at room temperature. Similar methods have been used to synthesize fluorinated copper reagents. ... 

SYNS CHLORID TRI-n-BUTYLCINICITY (CZECH) TRIBUTYLCHLOROSTANNANE TRI-n-BUTYLTIN CHLORIDE TRI-n-BUTYLZINN-CHLORID (GERMAN)... 

Preparation. The reagent is prepared in 81% yield by the reaction of tri-n-butyltin chloride (Metal and Thermit Corporation) with CH2=CHCH2CH2MgBr. 

J. T. Groves, S. Kittisopikul, Dehalogenation reactions catalyzed by tri-n-butyltin chloride. Competition for carbon radicals by borohydride and tin hydride, Tetrahedron Lett. 49 4291 (1977). N. M. Weinshenker, G. A. Crosby, and J. Y. Wong, Polymeric Reagents. IV. Synthesis and utilization of an insoluble polymeric organotin dihydride reagent, J. Org. Chem. 40 1966 (1975). 

The di-O-tosylates (prepared by action of tosyl chloride in pyridine) are reduced with zinc (Nal/Zn route e Tipson-Cohen reaction) [13]. Cyclic ortho-esters (prepared by reaction of the diol with ethyl orthoformate) are transformed into olefins by simple heating in the presence of acids (Eastwood reaction, route b) [14]. Cyclic thiocarbonates (obtained by reaction of a diol with thiophosgene or (V,(V -thiocarbonyl-di-imidazole) are reduced to olefin with trimethyl phosphite (Corey-Winter method, route c) [15]. Finally, reduction of vicinal di-xanthates with tri- -butyltin hydride according to the Barton procedure [16] affords olefins via a reductive elimination process route a). The Corey-Winter, Garegg, and Tipson-Cohen methods are most commonly applied for deoxygenation of sugar diols. 

Thallium(I) cyanide was introduced by Taylor and McKillop as a reagent. Aromatic and heteroaromatic acyl cyanides are produced in go yield, whereas aliphatic acid halides lead under these conditions mainly to dimerization products. 18-Crown-6 is a good catalyst for the preparation of cyanoformate in methylene chloride with potassium cyanide and chloroformates. Similarly, tetraethylammonium cyanide gives cyanoformates in high yield under very mild conditions. Aroyl cyanides are generated easily by phase transfer catalysis with tetra-n-butylammonium bromide. Tri- -butyltin cyanide proved successful only with aromatic acid halides, leading to dimerization products with aliphatic compounds. ... 

Table 4.5.1 Effects of tri-n-butyltin chloride on the lytic function, binding function, ATP levels, CD16 levels, CD56 levels, granzyme B levels, and perforin levels of human NK cells ...

Effects of n-butyltin Chlorides on Human NK Cell Function Tri-n-Butyltin Chloride (TBTC)... 

Exactly how organostannanes exert their toxicity is complex and not well understood. It has been known since 1958 that organostannanes disrupt oxidative phosphorylation in mitochondria and this action was subsequently demonstrated to arise from inhibition of ATP synthases. A tritium labelling study indicated that tri-n-butyltin chloride interacts with a specific ion channel sub-unit in ATP synthase. A second mitochondrial protein, stannin (Snn) has also been identified as a triorganotin receptor responsible for tissue-specific toxicity. ... 

---