Antimony reagents

In contrast, when l-bromo-2-butyne is employed in this sequence, allenylcarbi-nols are the major adducts (Table 9.63). In the former case, the allenyl antimony reagent is presumed to prevail whereas in the latter sequence, the terminal Me substituent causes the equilibrium to shift toward the sterically favored propargylic isomer. 

Table 9.63 Synthesis of allenylcarbinols from a propargylic antimony reagent.

Molybdate-Antimony Reagent dissolve lOg of ammonium molybdate m 40ml of 2M sulphuric acid, dissolve 0 1 g of sodium antimony tartrate m 50 ml of 2M sulphuric acid Mix die two solutions and dilute to 500 m 1 with 2M sulphuric acid... 

In this instance, the first-formed alkyl bis(phenylthio)antimony derivative is very air sensitive, and undergoes oxygen insertion into the carbon-antimony bond. The resultant peroxy intermediate then rearranges rapidly to the pentavalent derivative, from which the alcohol can be released on hydrolysis. The specific example shown below in Scheme 17 is indicative of the power of this transformation, although it must be admitted that the method requires very pure, thiophenol-free antimony reagent. 

Antimony tnfluoride is a mild fluorinating reagent. However, it is much mote effective ia the Swarts reactions where its effectiveness as a fluorinating reagent is dramatically iacteased by addition of CI2, Bt2, or SbCl to the reaction mixture (2). Antimony tnfluotide can be used for the replacement of chlorine or bromine ia halocatbons, hydtohalocatbons, and nonmetal and metal haUdes. Typical reactions can be summarized as follows ... 

The pyrometaHurgical processes, ie, furnace-kettle refining, are based on (/) the higher oxidation potentials of the impurities such as antimony, arsenic, and tin, ia comparison to that of lead and (2) the formation of iasoluble iatermetaUic compounds by reaction of metallic reagents such as 2iac with the impurities, gold, silver and copper, and calcium and magnesium with bismuth (Fig. 12). 

Silver diethyldithiocarbamate [1470-61-7] is a reagent commonly used for the spectrophotometric measurement of arsenic in aqueous samples (51) and for the analysis of antimony (52). Silver iodate is used in the determination of chloride in biological samples such as blood (53). 

Antimony trichloride is used as a catalyst or as a component of catalysts to effect polymerisation of hydrocarbons and to chlorinate olefins. It is also used in hydrocracking of coal (qv) and heavy hydrocarbons (qv), as an analytic reagent for chloral, aromatic hydrocarbons, and vitamin A, and in the microscopic identification of dmgs. Liquid SbCl is used as a nonaqueous solvent. 

Halostibines, Dihalostibines, and Related Compounds. Alkyl dichi oro- and alkyldibromostibines are readily prepared by the alkylation of the corresponding antimony trihaUde with an organolead reagent (67,104) ... 

A simple, rapid and seleetive eleetroehemieal method is proposed as a novel and powerful analytieal teehnique for the solid phase determination of less than 4% antimony in lead-antimony alloys without any separation and ehemieal pretreatment. The proposed method is based on the surfaee antimony oxidation of Pb/Sb alloy to Sb(III) at the thin oxide layer of PbSOyPbO that is formed by oxidation of Pb and using linear sweep voltammetrie (LSV) teehnique. Determination was earried out in eoneentrate H SO solution. The influenee of reagent eoneentration and variable parameters was studied. The method has deteetion limit of 0.056% and maximum relative standard deviation of 4.26%. This method was applied for the determination of Sb in lead/aeid battery grids satisfaetory. 

Dipping solution Mix 2 ml antimony(V) chloride with 8 ml carbon tetrachloride. Storage The reagent solution should always be freshly prepared. 

Alkyl silyl ethers are cleaved by a variety of reagents Whether the silicon-oxygen or the carbon-oxygen bond is cleaved depends on the nature of the reagent used Treatment of alkoxysilanes with electrophilic reagents like antimony tri-fluonde, 40% hydrofluonc acid, or a boron tnfluonde-ether complex results in the cleavage of the silicon-oxygen bond to form mono-, di-, and tnfluorosiloxanes or silanes [19, 20, 21) (equations 18-20)... 

Covalent fluondes of group 3 and group 5 elements (boron, tin, phosphorus, antimony, etc ) are widely used m organic synthesis as strong Lewis acids Boron trifluoride etherate is one of the most common reagents used to catalyze many organic reactions. A representative example is its recent application as a catalyst in the cycloadditions of 2-aza-l,3-dienes with different dienophiles [14] Boron trifluoride etherate and other fluonnated Lewis acids are effective activators of the... 

Procedure. Use a solution containing 0.15-1.8 mg antimony per 100 mL it should be slightly acidic with sulphuric acid (1.2-1.5M). Transfer a 10 mL aliquot to a 50 mL graduated flask, add 25 mL of the potassium iodide-ascorbic acid reagent, and dilute to the mark with 25 per cent v/v sulphuric acid. Mix thoroughly and measure the absorbance at 425 nm or at 330 nm using a reagent blank as reference solution. 

---