Triphenylbismuth dichloride

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) ... 

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... 

Triphenylbismuth dichloride (3) reacts with sodium azide and sodium cyanide to afford triphenylbismuth diazide and triphenylbismuth dicyanide. Thermolysis of these compounds leads to phenyl azide or to benzonitrile, respectively. ... 

Reaction of sodium thiocyanate with triphenylbismuth dichloride (3) leads directly to phenyl thiocyanate. Although no intermediate was detected, the reaction is likely to proceed by ligand coupling of a pentavalent thiocyanate derivative. ... 

The nature of the substituents on the phenolic substrate appeared to govern more or less efficiently the regioselectivity of the arylation reactions. This was clearly demonstrated by a study of the phenylation reaction of a variety of substituted phenols by triphenylbismuth dichloride under basic conditions. ... 

The behaviour of the most sterically hindered 2,6-di-rerr-butylphenol (25) and its derivatives was very dependent upon the reaction conditions. In the presence of a base favouring electron-transfer (such as BTMG), oxidation reactions took place with triphenylbismuth dichloride or triphenylbismuth carbonate leading to the diphenoquinone (26). Para-phenylation with formation of (27) was observed for the first time in the reaction of the potassium phenolate of 2,6-di-re rr-butylphenol with triphenylbismuth dichloride and in the reaction of the phenol (25) with tetraphenylbismuthonium tosylate in the presence of BTMG. Even ortho- and para-phenylation with concomitant de-rerr-butylation occurred in the reaction of the potassium salt of 2,4,6-tri-re r/-butylphenol with triphenylbismuth dichloride. 2... 

By contrast, the sodium salt of acetylacetone (31) was reported to react with triphenylbismuth dichloride in THE to lead to an unstable bismuthonium ylide (37). It was formed nearly quantitatively after 1 hour at 0-5°C, but was not isolated. Addition of triethylamine and methanesulfonyl chloride led to the isolation of a l,3-oxathiole-3,3-dioxide derivative (38) in 65% yield. On the other hand, this bismuthonium ylide (37) afforded the mono-C-phenylated product, 3-phenylacetylacetone (35), on standing at room temperature. However, the precise experimental conditions and the yields of the latter reaction were not reported. " ... 

The reaction of dimedone (39) with tetraphenylbismuthonium derivatives and BTMG gave the a,a-diphenyl derivative (40). But when dimedone (39) was treated with triphenylbismuth carbonate, an ylide (41) was obtainedP This ylide was later isolated as a stable crystalline compound. This ylide (41) can also be prepared by reaction of the sodium salt of dimedone either with triphenylbismuth dichloride or with triphenylbismuth oxide. Similarly, Meldrum s acid gave the corresponding bismuthonium ylide with triphenylbismuth carbonate and with triphenylbismuth dichloride.3 36 uch ylides can also be made by decomposition of the appropriate dicarbonyl diazonium derivative in the presence of triphenylbismuthane catalysed by bis(hexafluoroacetylacetonato)copper (II) 37 These ylides react with aldehydes to give cyclopropanes, dihydrofurans and a,p-unsaturated carbonyl... 

With caprolactam-type malonic derivatives, completely different results were observed depending on the structure of the lactams. Thus, 3-cyano-e-caprolactam (42) reacted with pentaphenylbismuth to give 74% of the expected 3-cyano-3-phenyl-e-caprolactam (43). But 3-methoxycarbonyl-e-caprolactams (44) and (45) did not react with pentaphenylbismuth. The -phenylcaprolactam derivative (46) was obtained through reaction of (44) with triphenylbismuth dichloride and base. 39... 

Other stabilized anions that were successfully C-arylated include the anions of nitroalkanes, a-methyl-a-nitrocarboxylic acid derivatives, esters, triphenylmethane, indole and scatole. Nitroalkanes gave high yields of the a-C-aryl derivatives. Ita the presence of BTMG, 2-nitropropane reacts with triphenylbismuth dichloride or tetraphenylbismuthonium p-toluenesulfonate to lead to a-nitrocumene (86 or 77% respectively). The reaction using triphenylbismuth dichloride and TMG was applied to the synthesis of a-methyl-a-phenylglycine via arylation of a-nitropropionic acid esters. ... 

O-Phenylation of tertiary alcohols can be realized through reaction with pentaphenylbismuth (4), a benzyne intermediate being involved. r rf-Butyl phenyl ether (80) was also obtained in rather low yields in the reaction of triphenylbismuth diacetate with rerr-butyl alcohol used as solvent in the presence of potassium carbonate or by reaction of triphenylbismuth dichloride with lithium ten-... 

Arylthiols were converted to mixed arylphenylsulfides by reaction with pentaphenylbismuth (4) or with tetraphenylbismuthonium trifluoroacetate (6). Oxidation products were also formed in minor amounts (<15%). On the other hand, thiols were readily converted to the corresponding disulfides by treatment either with triphenylbismuth dichloride (3) or with triphenylbismuth carbonate (5) in the presence of sodium hydride.2533... 

Amides are generally not phenylated by triphenylbismuth caibonate and only in poor yields with tetraphenylbismuthonium derivatives under neutral conditions. However, amides can be 7V-phenylated by triphenylbismuth dichloride in the presence of BTMG, although only one example was reported (see also section 6.2.2. l). ... 

Oximes were cleaved by tetraphenylbismuthonium trifluoroacetate under basic conditions to regenerate the ketone, but stable O-triphenylbismuth bisoximates were obtained from the reaction of an oxime with triphenylbismuth dichloride under basic conditions.59 Imides were phenylated in moderate yields by tetraphenylbismuthonium trifluoroacetate. In the reaction of indole with tetraphenylbismuthonium trifluoroacetate under neutral conditions, 3,A diphenylindole was isolated as a very minor side product (2%).33... 

Moreover, the synthesis and good stability of the covalent carbon-bismuth compound in the case of acetone, 2-oxopropyltriphenylbismuthonium perchlorate, excluded this type of intermediate as a common pathway, although this view was questioned by Suzuki et The reaction of the sodium salt of acetylacetone with triphenylbismuth dichloride led to a bismuthonium salt (37) decomposing slowly at room temperature to give eventually 3-phenylpentane-2,4-dione (35). ... 

To a stirred suspension of triphenylbismuth dichloride (2.56 g, 5 mmol) in 95% ethanol (60 ml) was added hydrazine hydrate (2.0 g). Reduction occurred immediately. The solution was decolorized and triphenylbismuthine precipitated out of solution. Stirring was continued for 1 h and then the mixture was poured into water (300 ml). The aqueous suspension was extracted with ether, the organic layer was separated and dried, and the solvent was removed to give the product (2.1 g, 95.4%), m.p. 75-76°C [40JA665]. 

Triphenylbismuth dichloride (5.1 g) and lead thiocyanate (6 g) were boiled in ethanol (200 ml)... 

A benzene solution of triphenylbismuth dichloride and an aqueous solution of silver acetate were mixed with vigorous stirring. The benzene layer was then separated and concentrated under reduced pressure. Dilution with light petroleum caused triphenylbismuth diacetate to precipitate. This was recrystallized from a mixture of benzene and light petroleum, m.p. 173°C [70CJC2488]. 

Triphenylbismuth dichloride and bis(trifluoroacetate) react with one equiv. of sodium salt of p-nitrophenol to give the corresponding triphenylbismuth(V) compounds of the type Ph3BiX(OAr) [85JCS(P1)2657]. Sodium or guanidium salts of 3,5-di-ferf-butylphenol and 8-hydroxyquinoline are also transferrable by this method. 

Treatment of triphenylbismuth carbonate with sulfonic acids aifords triphenylbismuth disulfonates, which are converted to triphenylbismuth dichloride by metathesis [86ZAAC(539)110]. 

Triphenylbismuth difluoride has been synthesized by thermal decomposition of a cationic triphenylbismuth(V) complex [Ph3Bi(OAsPh3)2][Bp4]2 in dichloromethane [731C944]. Tetraphenylbismuth tribromide is transformed thermally to triphenylbismuth dibromide [52LA(578)136], while tetraphenylbismuth triphenylsiloxide is readily cleaved by HCl to give triphenylbismuth dichloride [75DOK(225)581]. 

Most triorganylbismuth dihalides and related compounds have a non-ionic, five-coordinate structure, in which the bismuth atom possesses a trigonal bipyramidal geometry (Fig. 3.1). The X-ray analyses of trimethylbismuth dichloride (mean Bi-C and Bi-Cl bond lengths, 2.20 and 2.61 A mean C-Bi-C and Cl-Bi-Cl bond angles, 120 and 178°, respectively) and triphenylbismuth dichloride (mean Bi-C and Bi-Cl bond lengths, 2.12 and 2.57 A mean C-Bi-C and Cl-Bi-Cl bond angles, 120 and 176°, respectively) have clearly shown that three carbon atoms adjacent to the bismuth occupy the... 

Pentacoordinate cationic complexes of the type (Ph3BiL2)Y2 can be prepared by the reaction of triphenylbismuth dichloride with a silver salt AgY in the presence of a ligand molecule L [73IC944]. These complexes are stable in the solid state, but decompose in solution. Triphenylbismuth difluoride is formed from the thermal decomposition of [Ph3Bi(OAsPh3)2][BF4]2. 

The reaction of triphenylbismuth carbonate with cyclic 1,3-dicarbonyl compounds, such as dimedone and Meldrum s acid, gives highly stabilized triphenylbismuthonium ylides (Section 3.5.1). Moderately stabilized acyclic bismuthonium ylides can be prepared from triphenylbismuth dichloride and a 1,3-diketone or a 1,3-disulfone in the presence of a suitable base. A similar base-promoted reaction of triphenylbismuth dihalides with Al-sulfonylamines or amides has been used for the preparation of stabilized bismuthine imides bearing the Af-sulfonyl or Af-acyl moiety (Section 3.6.1). 

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