Bismuth reaction with

Other methods for safely cleaning apparatus containing sodium residues or disposing of waste sodium are based on treatment with bismuth or lead (103), inert organic Hquids (104—106), or by reaction with water vapor carried in an inert gas stream (107). 

Bismuth trichloride shows considerable tendency to form addition compounds. Reaction with ammonia yields the colodess, easily volatili2ed bismuth trichloride triammine [66172-89-2] BiCl ANH, as well as the red, thermally unstable bismuth trichloride hemiammine [66172-90-5] 2BiCl2 NH. Compounds of formula BiCl NO, BiCl 2N02, and BiCl NOCl may be isolated these are stable in dry air but are decomposed by moisture. Bismuth... 

Chlorination of bismuth or mercuric oxides results in precipitation of relatively insoluble basic chlorides, ie, BiOCl and HgO HgCl2. However, the reaction with is slow and does not produce high concentrations of HOCl (121). With HgO, the HOCl solutions may contain significant amounts of... 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

Bismuth Nitride. BiN, mw 223.01, N 6.28%, blk cryst, d 7.8g/cc. Prepd from Bi tribromide or trioxide by reaction with potassamide in liq ammonia. The dry nitride explds when treated with w or dil acids si decompn with w vapor. 

Bismuth(III) triflate is also a powerful acylation catalyst that catalyzes reactions with acetic anhydride and other less reactive anhydrides such as benzoic and pivalic anhydrides.113 Good results are achieved with tertiary and hindered secondary alcohols, as well as with alcohols containing acid- and base-sensitive functional groups. 

Allylation of acyloyl-imidazoles and pyrazoles61 with allyl halide mediated by indium in aqueous media provides a facile regioselective synthesis of P, y-unsaturated ketones (Scheme 11.1), which has been applied to the synthesis of the monoterpene artemesia ketone. The same product can be obtained by indium-mediated allylation of acyl cyanide (Eq. 11.35).62 Samarium, gallium, and bismuth can be used as a mediator for the allylation of nitrones and hydrazones to give homoallylic hydroxylamine and hydrazides in aqueous media in the presence of Bu4NBr (Scheme 11.2).63 The reaction with gallium and bismuth can be increased dramatically under microwave activation. 

The most effective synthetic control of the thiolation of bismuth has been achieved using reactions of bismuth chloride with aminothiolate salts (potassium) prepared in situ. Although the reactions are not quantitative, the molecular stoichiometry can be reliably selected and a systematic series of mono-, bis-, and tris-thiolates have been isolated and comprehensively characterized. (189). 

Polonium is found only in trace amounts in the Earths crust. In nature it is found in pitchblende (uranium ore) as a decay product of uranium. Because it is so scarce, it is usually artificially produced by bombarding bismuth-209 with neutrons in a nuclear (atomic) reactor, resulting in bismuth-210, which has a half-hfe of five days. Bi-210 subsequently decays into Po-210 through beta decay The reaction for this process is Bi( ) Bi — °Po + (3-. Only small commercial milligram amounts are produced by this procedure. 

Unnilseptium, or bohrium, is artificially produced one atom at a time in particle accelerators. In 1976 Russian scientists at the nuclear research laboratories at Dubna synthesized element 107, which was named unnilseptium by lUPAC. Only a few atoms of element 107 were produced by what is called the cold fusion process wherein atoms of one element are slammed into atoms of a different element and their masses combine to form atoms of a new heavier element. Researchers did this by bombarding bismuth-204 with heavy ions of chromium-54 in a cyclotron. The reaction follows Bi-209 + Cr-54 + neutrons = (fuse to form) Uns-262 + an alpha decay chain. 

To elucidate the reaction pathway, deuterium-labeled allenyl pinacol boronate 10 was prepared, and the addition reaction with hydrazonoester 6 was conducted in the presence of Bi(OH)3 and Cu(OH)2 (Scheme 4). In both Bi- and Cu-catalyzed cases, the reactions proceeded smoothly (in quantitative yields in both cases). In the Bi(OH)3-catalyzed reaction, a major product was allenyl compound 11, in which the internal position was deuterized. It was assumed that a propargyl bismuth was formed via transmetalation from boron to bismuth, followed by addition to hydrazonoester via y-addition to afford allenyl compound 11. Thus, two y-additions could selectively provide a-addition products [75, 76, 105, 106]. It was confirmed that isomerization of 10 did not occur. Recently, we reported Ag20-catalyzed anti-selective a-addition of a-substituted allyltributyltin with aldehydes in aqueous media [107], On the other hand, in the Cu(OH)2-catalyzed reaction, a major product was propargyl compound 12, in which the terminal position was deuterized. A possible mechanism is that Cu(OH)2 worked as a Lewis acid catalyst to activate hydrazonoester 6 and that allenyl boronate 10 [83-85] reacted with activated 6 via y-addition to afford 12. 

C-C Bond Forming Reactions with Bismuth Ylides... 

Scheme 9 Reaction of bismuth ylides with aldehydes [45, 46]...

Scheme 11 Reactions of bismuth ylides with a-dicarbonyl compounds [46, 67-70]...

---