Triarylbismuth dichlorides,

Various 3-(3 - and 4 -substituted phenyl)-4-hydroxycoumarins were easily accessible by reaction of 4-hydroxycoumarins with triarylbismuth dichloride and triarylbismuth dinitrate under basic conditions or with triphenylbismuth diacetate (47) under neutral conditions. In the latter reaction, the best yields were obtained when the reaction was performed in methylene dichloride in the dark.40... 

The carboxyl ligands introduced are derived from the solvent employed. When this reaction is performed in dichloromethane, triarylbismuth dichloride is isolated in good yield. 

Metathesis of triarylbismuth dichloride with a variety of metal salts such as fluoride, azide, cyanide, carboxylates and sulfonates has been used frequently for the synthesis of triarylbismuth(V) compounds of the type Ar Bi Y 2, where Y is the corresponding anionic group (Section 3.1.1). The reaction of triphenyl-bismuth dichloride with mercuric chloride in an alkaline medium leads to triphenylbismuthine, while treatment of triphenylbismuth dicyanide with mercuric oxide results in the formation of triphenylbismuthine oxide (Section... 

The most convenient method for the preparation of pentaarylbismuth is the reaction between triarylbismuth dichloride and 2 equiv. of aryllithium [90B-S]. 

Crystalline bismuthine imides bearing an A-sulfonyl group have been prepared by the condensation of triphenylbismuth difluoride with A,A-bis(tri-methylsilyl)sulfonamides or of triarylbismuth dichloride with sulfonamides [93JFC(63)179]. The latter combination is also applicable to the synthesis of trianylbismuthine A -acylimides [99OM2580]. 

Triphenylbismuth oxide [7173-99-1/, C gH BiO, has been prepared from triphenylbismuth dicyanide [41083-16-3], C2QH25B1N2, and mercuric oxide (151), and from triphenylbismuth dichloride and moist silver oxide (152). The ir and Raman spectra of this compound suggest that it is polymeric and has Bi—O—Bi bonds (153). Triphenylbismuth dihydroxide, and triarylbismuth hydroxide haUdes, eg, triphenylbismuth hydroxide chloride... 

Staphylococcus aureus infections (159). Triphenylbismuth dichloride [594-30-9], C2gH25BiCl2, is active agaiast bean mst (160). Triarylbismuth dihaUdes have been used as catalysts for the carbonation of epoxides to form cycHc carbonates (161). 

Organobismuth(III) halides may be prepared by elimination of aryl halide from triarylbismuth(V) dichlorides or dibromides upon heating (equation 4). Presumably, a bis-muth(V) compound is the intermediate when triarylbismuth compounds are treated with iodine or when trialkylbis-muth complexes are treated with chlorine, bromine, or iodine, but the intermediates have not been isolated and organobismuth halides are obtained directly (equation 5). The tris(trifluoromethyl)bismuth behaves like the trialkyl compounds without the observation of a bismuth(V) intermediate. ... 

Triphenylbismuth carbonate generally does not react with amines, although phenyl transfer to the amino functionality was first observed during an attempt of oxidation of the hydroxyl function of an aminoalcohol by triphenylbismuth carbonate in chloroform. It also reacted with iV-phenylhydro-xylamine under neutral or basic conditions to give diphenylnitroxyl and iV,iV-diphenylacetamide after reductive acetylation (29-33%). No reaction was noted between triphenylbismuth carbonate and nitrosobenzene. High-yielding -arylation was found in the reaction of amino-alcohols with triarylbismuth diacetate in methylene dichloride under reflux. 5... 

Typical reaction modes of triarylbismuth dihalides and derivatives are shown in Scheme 3.4. Representative reactions of triphenylbismuth dichloride are listed in Table 3.5. 

Aryliodoninm salts, Aral X [50], and some other hypervalent aryliodonium compounds take a part in further important alternative cross-coupling reactions with arylboronic acids [51], aryltrifluoroborates [52], triarylbismuth(V) compounds [53], and diaryltellurium dichlorides [54] to afford biaryls in good to excellent yields. For example, hypervalent iodine compoimd 466, readily produced from 2-iodobenzoic acid, reacts with arylboronic acids in palladium-catalysed process in Suzuki-Miyaura-fashion to give the 2-arylbenzoic acids in high yields [51], Table 12. 

Unfortunately, the method works well only with para- and /neto-substituted triarylbismuth compounds, while the /jara-substituted ones failed to give the reaction or resulted in very low yields [73]. Arylation of phenols and other electron-rich aromatics, e.g. indole, with triarylbismuth(V) dichlorides, carbonates and related compounds is readily affected under neutral conditions, by simple stirring in... 

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