Triphenylbismuth

Biphenyl formation by the ligand coupling of triphenylbismuth is promoted by Pd(OAc) [418],... 

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). 

When triphenylbismuth dichloride, ia acetone, is treated with silver perchlorate, ia absolute ethanol, tetraphenylbismuthonium perchlorate [43047-28-5], C24H2QBiC104, is formed (165). If, however, the same reaction is carried out only ia acetone, the following reaction occurs (166) ... 

Stmcture (1) is an unstable blue soHd which caimot be obtained in a pure state (167) stmcture (2) [105071-90-7] however, is stable (168). Stmcture (2) was obtained from triphenylbismuth carbonate and dimedone. More recendy a number of bismuthonium yUdes, eg, (3) [119016-81 -8] (169), have been prepared and their reactions studied. 

It can also be prepared by the reaction of phenyUithium with tetraphenylbismuth chloride or the /V-triphenylbismuth derivative of 4-toluenesulfonamide... 

Triphenylbismuth (bismuth triphenyl) [603-33-8] M 440.3, m 75-76 , 77-78 , 78.5 , d 4 1.6427(melt). Dissolve in EtOH, ppte with H2O, extract with Et20, dry and evaporate when the residue crystallises. It has been recrystd from EtOH and Et20-Et0H and is a stable compound. [J Chem Soc suppl pl21 I949 Chem Ber 37 4620 1904 J Am Chem Soc 62 665 1940 UV J Chem Phys 22 1430 1954.]... 

The redCQon of l-nitrocyclohexene with triphenylbismuth thchloride in the presence of triethyldmine gives the deconjugated arylated product, as shovm in Eq 5 69 ... 

Aromatic compounds can also be arylated by aryllead tricarboxylates. Best yields ( 70-85%) are obtained when the substrate contains alkyl groups an electrophilic mechanism is likely. Phenols are phenylated ortho to the OH group (and enols are a phenylated) by triphenylbismuth dichloride or by certain other Bi(V) reagents. O-Phenylation is a possible side reaction. As with the aryllead tricarboxylate reactions, a free-radical mechanism is unlikely. ... 

Barton and coworkers have explored the arylation of various nucleophiles including nitroalkanes using bismuth reagents.105 Reaction of 2-nitropropane with triphenylbismuth carbonate gives 2-nitro-2-phenylpropane in 80% yield.106 Recently, this arylation has been used for the synthesis of unusual amino acids. Arylation of a-nitro esters with triphenylbismuth dichloride followed by reduction gives unique a-amino acids (Eq. 5.68).107... 

The reaction of 1-nitrocyclohexene with triphenylbismuth dichloride in the presence of triethylamine gives the deconjugated arylated product, as shown in Eq. 5.69.108... 

Triphenylbismuth dichloride, 4 33 Triphenylbismuth difluoride, 4 27 Triphenylbismuth dimethacrylate, 4 33 Triphenylbismuthine, 4 26 Triphenylbismuth iodide isocyanate, 4 32 Triphenylbismuth iodide azide, 4 32 Triphenylbismuth oxide, 4 32 Triphenylcarbamate... 

Alkenyltriphenylbismuthonium salts are formed by refluxing triphenylbismuth difluoride BF3 OEt2 and alkenyl-trimethylsilanes (Scheme 22).247... 

Aromatic amines RNH2 (R = Ph, 2-MeCgH4 or 4-MeOCgH4) are phenylated by triphenylbismuth in the presence of 0.5 equivalent of copper(II) acetate to yield diarylamines RNHPh. Butylamine yields a mixture of TV-butylaniline and N-butyldiphenylamine in this reaction and piperidine gives TV-phenylpiperidine36. A similar alkylation of the secondary amines pyrrolidine, piperidine and morpholine with trimethylbismuth or tris(2-phenylethyl)bismuth in the presence of copper(II) acetate affords tertiary amines, e.g. 14. The reaction proceeds by way of transient pentavalent bismuth compounds37. 

Recently, triphenylbismuth has been used for rhodium-catalyzed conjugate addition (Eq. 4) ]36]. The reaction carried out in the presence of [RhCl(COD)]2 or... 

Although it was first prepared by Verma et al. in 1983 starting from Bi(III) trifluoroacetate [58], our group developed another strategy for the preparation of Bi(OTf)3 [32]. The key point of our synthetic strategy is based on the acidic cleavage of the three carbon-bismuth bonds of triphenylbismuth by triflic acid in dichloromethane (Scheme 1). A study of the hydration of Bi(0Tf)3xH20 revealed that this compound can exist as three different hydrates, the nonahydrate, the tetrahydrate, and the dehydrate [35], The structures of the nona- and tetrahydrate forms have been determined by ab-initio calculations [35] and XRD [36]. 

When treated with iodine pentafluoride, triphenylbismuthane gives triphenylbismuth difluoride but no evidence for the formation of bismuth(V) derivatives was found in the reactions with tris(4-fluorophenyl)bismuthane and tris(trifluoromethyl)bismuthane. Fluorine-aryl (or alkyl) exchange takes place in these cases instead of oxidative fluorination.139140... 

Arylation. Although some oxidations with triphenylbismuth carbonate occur with quantitative conversion to (Cf,H,)jBi, some proceed with Bi-C cleavage. Although attempts to trap aryl radicals have failed, this cleavage can be used in a synthesis for transfer of an aryl group from Bi to N.1 Examples ... 

Triphenylbismuth difluoride [2023-48-5], C18H15BiF2, has been obtained in a similar manner (63). 

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