5142-75-6

Usage

Uses

Used in Organic Synthesis:
TRI-P-TOLYLBISMUTHINE is used as a reagent for creating carbon-bismuth bonds, which is crucial in the synthesis of various organic bismuth compounds. Its ability to form stable bonds with carbon atoms makes it a valuable component in the development of new organic compounds with potential applications in various fields.
Used in Catalytic Processes:
In the realm of catalysis, TRI-P-TOLYLBISMUTHINE serves as a catalyst or a precursor to catalysts that facilitate chemical reactions. Its involvement in these processes can enhance reaction rates and selectivity, contributing to more efficient and sustainable chemical production methods.
Used as a Precursor in the Production of Bismuth-Containing Compounds:
TRI-P-TOLYLBISMUTHINE is utilized as a starting material for the synthesis of other bismuth-containing compounds. Its unique properties allow for the creation of a diverse range of bismuth compounds with specific applications in various industries.
Used in Medicinal Chemistry:
TRI-P-TOLYLBISMUTHINE is employed as a precursor for bismuth-based pharmaceuticals. Its low toxicity compared to other heavy metals makes it an attractive candidate for the development of new drugs and therapeutic agents, potentially leading to advancements in medicine and healthcare.

InChI:InChI=1/3C7H7.Bi/c3*1-7-5-3-2-4-6-7;/h3*3-6H,1H3;/rC21H21Bi/c1-16-4-10-19(11-5-16)22(20-12-6-17(2)7-13-20)21-14-8-18(3)9-15-21/h4-15H,1-3H3

Upstream product

• 106-38-7 para-bromotoluene 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 60-29-7 diethyl ether 
• 51752-29-5 bis(4-methylphenyl)bismuth chloride 
• 703-55-9 1-naphthylmagnesiumbromide 
• 64-17-5 ethanol 
• 6729-64-2 tri(p-tolyl)bismuth dichloride 
• 67-64-1 acetone 
• 594-19-4 tert.-butyl lithium 
• 7787-58-8 bismuth(III) bromide 
• 15738-23-5 sodium tetrakis(4-tolyl)borate 
• 7440-69-9 bismuth 
• 7787-60-2 bismuth(III) chloride 
• 19028-28-5 di p-tolyl iodonium chloride 

Downstream Products

• 2417-95-0 p-tolyllithium 
• 51752-29-5 bis(4-methylphenyl)bismuth chloride 
• 537-64-4 bis(p-tolyl)mercury 
• 603-33-8 triphenylbismuthane 
• 613-33-2 (4,4'-dimethyl-1,1'-biphenyl) 
• 104-93-8 p-methylanizole 
• 64-19-7 acetic acid 
• 108-88-3 toluene 
• 10519-06-9 1-butoxy-4-methylbenzene 
• 155905-62-7 3,4-dimethyl-N-(p-tolyl)aniline 
• 312934-66-0 1,2-Bis(t-butyloxycarbonyl)-2-(4-methylphenyl)-1-phenylhydrazine 
• 27331-34-6 1-(4-methylphenyl)naphthalene 

Relevant academic research and scientific papers

Synthesis of highly functionalized triarylbismuthines by functional group manipulation and use in palladium- and copper-catalyzed arylation reactions

Organobismuthines are an attractive class of organometallic reagents that can be accessed from inexpensive and nontoxic bismuth salts. Triarylbismuthines are particularly interesting due to their air and moisture stability and high functional group tolerance. We report herein a detailed study on the preparation of highly functionalized triarylbismuth reagents by triple functional group manipulation and their use in palladium- and copper-catalyzed C-, N-, and O-arylation reactions.

Palladium-Catalyzed Synthesis of α-Diimines from Triarylbismuthines and Isocyanides

In this study, we report a highly selective coupling reaction between triarylbismuthines and isocyanides using palladium diacetate as the catalyst, affording α-diimines, with the formation of three C-C bonds. Among several aryl sources (Ar-YLn: Y = B, Sn, Pb, Sb, Bi, I), only triarylbismuthines successfully undergo coupling with isocyanides to selectively afford α-diimines. The coupling reaction exhibits the advantages of high atom economy and convenient operation, with no need for any additive.

Stability and toxicity of tris-tolyl bismuth(v) dicarboxylates and their biological activity towards Leishmania major

A series of 29 tris-tolyl bismuth(v) di-carboxylato complexes of composition [Bi(Tol)3(O2CR)2] involving either ortho, meta or para substituted tolyl ligands have been synthesized and characterised. Of these 15 were assessed for their toxicity towards Leishmania promastigotes and human fibroblast cells, with ten then being subsequently assessed against parasite amastigotes. The carboxylate ligands are drawn from a series of substituted and biologically relevant benzoic acids which allow a comparison with earlier studies on [BiPh3(O2CR)2] and analogous Sb(v) [SbAr3(O2CR)2] (Ar = Ph and Tol) complexes. Twelve complexes have been structurally characterized by single crystal X-ray diffraction and shown to adopt a typical trigonal bipyramidal geometry in which the three tolyl ligands occupy the equatorial plane. NMR studies on two illustrative examples indicate that the complexes are stable in D2O and DMSO but only have a half-life of 1.2 hours in culture medium, with glucose being a contributing factor in decomposition and reduction to Bi(Tol)3. Despite their short lifetime many complexes show significant toxicity towards promastigotes at low concentration (3(O2CC6H3(2-OH,5-C6H3(2,4-F2)))2] and 838 for [Bi(m-Tol)3(O2CC6H4(2-OAc))2]. Best activity and selectivity is observed with complexes containing o- and m-tolyl ligands, and it appears the primary influence on fibroblast toxicity is the Ar ligand while the carboxylate influences promastigote toxicity. The complexes are less effective in vitro against the parasite amastigotes, where longer incubation times and harsher chemical and biological environments are encountered in the assay. Nevertheless, there were some statistically relevant differences at 1 μM against the positive controls with the best performing complexes being [Bi(o-Tol)3(O2CC6H4(2-EtO))2] and [Bi(m-Tol)3(O2CC6H4(2-OAc))2].

Synthesis of highly functionalized diaryl ethers by copper-mediated O-arylation of phenols using trivalent arylbismuth reagents

Highly functionalized diaryl ethers were prepared by copper(II) acetate mediated O-arylation reaction of phenols using trivalent organobismuthanes. The reaction is performed under simple conditions and tolerates a wide diversity of functional groups on the phenol and on the organobismuth reagent. Substoichiometric amounts of catalyst can be used by performing the reaction under an oxygen atmosphere. The N-arylation of pyridones is also reported. Highly functionalized diaryl ethers were prepared by a copper(II) acetate mediated O-arylation reaction of phenols using trivalent organobismuthanes (see scheme). The reaction is performed under simple conditions and tolerates a wide diversity of functional groups on the phenol and on the organobismuth reagent. Substoichiometric amounts of catalyst can be used by performing the reaction under an oxygen atmosphere. The N-arylation of pyridones is also reported. FG=functional group.

Palladium-catalyzed cross-coupling reaction of functionalized aryl- and heteroarylbismuthanes with 2-halo(or 2-Triflyl)azines and -diazines

The palladium-catalyzed cross-coupling of highly functionalized organobismuthanes with 2-halo(or 2-triflyl)pyridines, -pyrimidines, -pyrazines, and -pyridazines is reported. The reaction tolerates numerous functional groups, including aldehydes. The synthesis of a shelf-stable (formylphenyl)bismuth reagent and its use in a cross-coupling reaction is also described. The palladium-catalyzed cross-coupling of highly functionalized organobismuthanes with 2-halo(or 2-triflyl)pyridines, -pyrimidines, -pyrazines, and -pyridazines is reported. The reaction tolerates numerous functional groups, including aldehydes. The synthesis of a shelf-stable (formylphenyl)bismuth reagent and its use in cross-coupling reactions is also described. Copyright

Insertion of benzyne into a Bi-S bond: A new synthetic route to ortho -functionalized bismuthanes and its application to the synthesis of dibenzothiophene

ortho-Arylthio triarylbismuthanes [2-(Ar′S)C6H 4]nBiAr3-n have been conveniently synthesized by insertion of benzyne into the bismuth-sulfur bond of (Ar′S) nBiAr3-n (n = 1, 2). A similar insertion takes place when a homologous antimony congener is used, but no reaction is observed with its phosphorus analogue. This suggests a clear difference in the bond strength between pnictogen-sulfur bonds. The carbon-bismuth bond of [2-(2-BrC 6H4S)C6H4]nBiAr 3-n undergoes Pd-catalyzed intramolecular cross-coupling to produce dibenzothiophene in good yield. An X-ray crystallographic study of 2-(2-BrC 6H4S)C6H4BiTol2 (Tol = 4-MeC6H4) reveals that this molecule is present in a dimeric structure, where the six heteroatoms including bismuth, sulfur, and bromine are linked through the nonbonded intramolecular bismuth-sulfur and intermolecular sulfur-bromine and bromine-bromine interactions.

Remarkable substituent effects on the oxidizing ability of tetraarylbismuthonium tetrafluoroborates in alcohol oxidation

Substituent effects on the oxidizing ability of tetraarylbismuthonium tetrafluoroborates in alcohol oxidation are reported. Intermolecular and intramolecular competition experiments on geraniol oxidation by the combined use of tetraarylbismuthonium tetrafluoroborates and N,N,N′,N′- tetramethylguanidine (TMG) have revealed that the oxidizing ability of the bismuthonium salt increases by the introduction of methyl groups at the ortho position and an electron-withdrawing group at the para position of the aryl ligands. The intermolecular and intramolecular H/D kinetic isotope effects observed for the competitive oxidation of p-bromobenzyl alcohols have shown that the present oxidation reaction consists of fast pre-equilibrium leading to alkoxytetraarylbismuth(V) intermediates (first step) and α-hydrogen abstraction by the aryl ligand attached to the bismuth (second step). The experimental results demonstrate that the electron-deficient aryl ligands enhance the electrophilicity at the bismuth center to put forward the first step and that the bulky ligands destabilize the alkoxybismuth(V) intermediates to accelerate the second step. The newly explored mesityl- and 2,6- xylyltriarylbismuthonium salts have proven to convert primary and secondary alcohols to the corresponding carbonyl compounds with high efficiency under mild conditions. A remarkable steric effect of these oxidants has also been exhibited in the chemoselective oxidation between primary and secondary benzylic alcohols.

A new methodology for synthesis of aryl bismuth compounds: Arylation of bismuth(III) carboxylates by sodium tetraarylborate salts

Sodium tetraarylborate salts Na[BAr4] (Ar = C6H 3 (Ph), C6H4-MeA (tolyl), C6H 4-F-4) are found to be efficient arylating species for a range of bismuth(III) aromatic and aliphatic carboxylates including Bi(Hsal*) 3 (Hsal* = 2-HO-C6H4CO2 - (Hsal); 4-Me-2-HO-C6H3CO2 - (Hsal4Me); or 3-MeO-2-HO-C6H 3CO2- (Hsal3OMe)) and Bi(O 2CR)3 (R = Me, CMe3, and CF3) to produce triaryl bismuth compounds. The reactions may be carried out in ethanol, tetrahydrofuran, or acetone. The arylbismuth bis(salicylates) BiPh(Hsal) 2 and Bi(tolyl)(Hsal)2 exhibit similar reactivity in refluxing THF and may be used to produce mixed arylbismuthines BiPh x(tolyl)3-x. Formation of the known arylbismuth compounds was confirmed by IR spectroscopy, X-ray crystallography, NMR spectroscopy ( 1H, 11B, 13C, and 19F), and mass spectrometry. This is a facile synthesis of both symmetrical and unsymmetrical triarylbismuthines involving the aryl group transfer from the tetraarylborate ions to bismuth(III) under mild conditions.

Synthesis, structures, and some reactions of [(Thioacyl)thio]- and (Acylseleno)antimony and -bismuth derivatives ((RCSS)xMR 3-x1 and (RCOSe)xMR3-x1 with M=Sb, Bi and x=1-3)

A series of [(thioacyl)thio]- and (acylseleno)antimony and [(thioacyl)thio]- and (acylseleno)bismuth, i.e., (RCSS)xMR 3-x1 and (RCOSe)xMR3-x1 (M = Sb, Bi, R1 = aryl, x = 1 - 3), were synthesized in moderate to good yields by treating piperidinium or sodium carbodithioates and -selenoates with antimony and bismuth halides. Crystal structures of (4-MeC 6H4CSS)2Sb(4-MeC6H4) (9b′), (4-MeOC6H4COSe)2Sb(4-MeC 6H4) (12c′), (4-MeOC6H 4COS)2Bi(4-MeC6H4) (15c′), and (4-MeOC6H4CSS)2BiPh (18c) along with (4-MeC6H4COS)2SbPh (6b) and (4-MeC 6H4COS)3Sb (7b) were determined (Figs. 1 and 2). These compounds have a distorted square pyramidal structure, where the aryl or carbothioato (=acylthio) ligand at the central Sb- or Bi-atom is perpendicular to the plane that includes the two carbodithioato (=(thioacyl)thio), carboselenato (=acylseleno), or carbothioato ligand and exist as an enantiomorph pair. Despite the large atomic radii, the C=S...Sb distances in (RCSS)2MR1 (M = As, Sb, Bi; R1 = aryl) and the C=O...Sb distances in (RCOS)xMR3-x 1 (M = As, Sb, Bi; x = 2, 3) are comparable to or shorter than those of the corresponding arsenic derivatives (Tables 2 and 3). A molecular-orbital calculation performed on the model compounds (MeC(E)E1) 3-xMMex (M = As, Sb, Bi; E = O, S; E1 = S, Se; x = 1, 2) at the RHF/LANL2DZ level supported this shortening of C=E...Sb distances (Table 4). Natural-bond-orbital (NBO) analyses of the model compounds also revealed that two types of orbital interactions nS → σ*MC and nS → σ* MS(1) play a role in the (thioacyl)thio derivatives (MeCSS) 3-xMMex (x = 1, 2) (Table 5). In the acylthio- MeCOSMMe2 (M = As, Sb, Bi), nO → σ* MC contributes predominantly to the orbital interactions, but in MeCOSeSbMe2, none of nO → σ*MC and nO → σ*MSe contributes to the orbital interactions. The nS → σ*MC and nS → σ*MS(1) orbital interactions in the (thioacyl)thio derivatives are greater than those of nO → σ*MC and nO → σ*ME in the acylthio and acylseleno derivatives (MeCOE)3-xMMex (E = S, Se; M = As, Sb, Bi; x = 1, 2). The reactions of RCOSeSbPh2 (R = 4-MeC6H4) with piperidine led to the formation of piperidinium diphenylselenoxoantimonate(1-) (=piperidinium diphenylstibinoselenoite) (H2NC5H10) +Ph2SbSe-, along with the corresponding N-acylpiperidine (Table 6). Similar reactions of the bis-derivatives (RCOSe)2SbR1 (R, R1 = 4-MeC6H 4) with piperidine gave the novel di(piperidinium) phenyldiselenoxoantimonate(2-) (=di(piperidinium) phenylstibonodiselenoite), [(H2NC5H10)+] 2(PhSbSe2)2-, in which the negative charges are delocalized on the SbSe2 moiety (Table 6). Treatment of RCOSeSbR21 (R, R1=4-MeC6H 4) with N-halosuccinimides indicated the formation of Se-(halocyclohexyl) arenecarboselenoates (Table 8). Pyrolysis of bis(acylseleno)arylbismuth at 150° gave Se-aryl carboselenoates in moderate to good yields (Table 9).

Synthesis, structure and reactions of μ- oxobis(arenesulfonatotriarylbismuth)

Hydrolysis of triarylbismuth bis(arenesulfonates) in acetone gives bismuth derivatives of the general formula [Ar3Bi(OSO2Ar')] 2O (Ar = Ph, p-Tol; Ar' = Ph, C6H4Me-4, C 6H3Me2-2,4, C6H3Me 2-3,4). The structure of μ-oxobis[(3,4-dimethylbenzenesulfonato) triphenylbismuth] was established by means of X-ray diffraction. The molecule has a linear centrosymmetric structure with the bridging oxygen atom in the inversion center. The bismuth atom has a distorted trigonal bipyramidal coordination with the bridging oxygen atom and the arenesulfonate group in axial positions. The Bi-C and Bi-Oterm distances are 2.200(2), 2.204(3), and 2.442(2) A, and the Bi-Obr distances are 2.067(1) A. 2004 MAIK "Nauka/Interperiodica".