149222-24-2

Upstream product

• 95-49-8 2-methylchlorobenzene 
• 1101-41-3 Tetraphenyldiphosphin 
• 36042-94-1 bis(o-tolyl)chlorophosphine 
• 30309-80-9 di-o-tolylphosphine oxide 
• 29949-64-2 di(o-tolyl)phosphine 
• 6163-58-2 tris-(o-tolyl)phosphine 
• 75-05-8 acetonitrile 
• 73930-97-9 3-acetoxy-1,3-diphenylpropene 
• 1079-66-9 chloro-diphenylphosphine 

Relevant academic research and scientific papers

Radical-initiated P,P-metathesis reactions of diphosphanes: Evidence from experimental and computational studies

By combining the diphosphanes Ar2P-PAr2, where Ar = C6H5, 4-C6H4Me, 4-C6H4OMe, 3,5-C6H3(CF3)2, it has been shown that P,P-metathesis generally occurs rapidly under ambient conditions. DFT calculations have shown that the stability of unsymmetrical diphosphanes Z2P-PZ′2 is a function of the difference between the Z and Z′ substituents in terms of size and electronegativity. Of the mechanisms that were calculated for the P,P-metathesis, the most likely was considered to be one involving Ar2P radicals. The observations that photolysis increases the rate of the P,P-metatheses and TEMPO inhibits it, are consistent with a radical chain process. The P,P-metathesis reactions that involve (o-Tol)2P-P(o-Tol)2 are anomalously slow and, in the absence of photolysis, were only observed to take place in CHCl3 and CH2Cl2. The role of the chlorinated solvent is ascribed to the formation of Ar2PCl which catalyses the P,P-metathesis. The slow kinetics observed with (o-Tol)2P-P(o-Tol)2 is tentatively attributed to the o-CH3 groups quenching the (o-Tol)2P radicals or inhibiting the metathesis reaction sterically.

A new method to prepare functional phosphines through steady-state photolysis of triarylphosphines

The steady-state photolysis of triarylphosphine, Ar3P, was carried out using a xenon lamp or a high-pressure mercury lamp under an argon atmosphere in a solvent containing a functional group, CH3X. Gas chromatograph-mass spectroscopic analysis on the photolysis showed that a phosphine to which the functional group from the solvent is incorporated, Ar2PCH2X, was formed in a moderate yield, along with tetraaryldiphosphine, Ar2PPAr2. The product, Ar2PCH2CN, from the photolysis in acetonitrile (X=CN) was isolated by column chromatography. In the photolysis in other solvents tried here (ethyl acetate, acetone, 2-butanone, and 3,3-dimethyl-2-butanone), Ar2PCH2X formed in the reaction mixture was so labile on a silica-gel column that it was treated with S8 powder to convert to the corresponding phosphine sulfide, Ar2P(=S)CH2X. The resulting phosphine sulfide was isolated by column chromatography. The isolated products in these reactions, Ar2PCH2CN and Ar2P(=S)CH2X, were characterized by 1H, 13C, and 31P NMR spectroscopy, IR spectroscopy, and elemental analysis or high-resolution mass spectroscopy. The formation of Ar2PCH2X as well as Ar2PPAr2 is explained by homolytic cleavage of a P-C bond of Ar3P in the photoexcited state. This reactivity of Ar3P in the photoexcited state is in sharp contrast to that exerted under aerobic conditions, where Ar3P in the photoexcited state donates readily an electron to oxygen producing the radical cation, Ar3P·+. This photoreaction, which affords a functional phosphine, Ar2PCH2X, in one-pot with generating very small amounts of unidentified side products, has potential for use in preparing functional phosphines.

Synthesis and solid-state structures of gold(i) complexes of diphosphines

A series of functionalized diphosphine bisgold(i) complexes have been prepared from the corresponding diphosphine ligands Ar4P2 (Ar = MeC6H4, MeOC6H4, Me2NC6H4) and characterized by NMR spectroscopy and APCI mass spectrometry. Single-crystal X-ray diffraction analyses were performed to study the presence and importance of unsupported aurophilic interactions for the structure formation of these compounds. In general, the complexes featured monomeric structures with an antiperiplanar arrangement of the two AuCl units. The crystal packing greatly depended on the position of the substitution pattern (ortho vs. para). While for the ortho-substituted systems (OMe and NMe2) no ordered 3-dimensional networks were observed, the para-functionalized compounds formed regular layer structures. Here, aurophilic Au?Au interactions only played a minor role compared to intermolecular π?π interactions and hydrogen bonds.

Facile, Catalytic Dehydrocoupling of Phosphines Using β-Diketiminate Iron(II) Complexes

Catalytic dehydrocoupling of primary and secondary phosphines has been achieved for the first time using an iron pre-catalyst. The reaction proceeds under mild reaction conditions and is successful with a range of diarylphosphines. A proton acceptor is not needed for the transformation to take place, but addition of 1-hexene does allow for turnover at 50°C. The catalytic system developed also facilitates the dehydrocoupling of phenylphosphane and dicyclohexylphosphane. A change in solvent switches off dehydrocoupling to allow hydrophosphination of alkenes.

Selective dehydrocoupling of phosphines by lithium chloride carbenoids

The development of a simple, transition-metal-free approach for the formation of phosphorus-phosphorus bonds through dehydrocoupling of phosphines is presented. The reaction is mediated by electronically stabilized lithium chloride carbenoids and affords a variety of different diphosphines under mild reaction conditions. The developed protocol is simple and highly efficient and allows the isolation of novel functionalized diphosphines in high yields.

PalladIum-catalyzed enantioselective allylic phosphination

(Chemical Equation Presented) A new cat. for chiral phosphines: A highly enantioselective allylic phosphination reaction is realized using the Pd-Josiphos(L) catalyst system. This C-P bond forming reaction provides a new access to chiral phosphines (see scheme) that may be further functionalized. Cy=cyclohexyl, dba=trans,trans-dibenzylideneacetone.