170285-00-4Relevant academic research and scientific papers
Efficient potassium hydroxide promoted P-arylation of aryl halides with diphenylphosphine
Chen, Jin,Dai, Bencai,Liu, Changchun,Shen, Zhihao,Zhou, Yang
, (2021/06/26)
A simple synthetic method of triarylphosphine compounds by KOH-promoted P-Arylation reaction of aryl halides with diphenylphosphine is presented. Notably, this transformation could smoothly proceed with high yields under transition-metal-free and mild reaction conditions. In addition, this protocol is valuable for industrial application due to the convenient operation and readily accessible aromatic halides. A possible explanation of the reaction mechanism was proposed based on the experimental data.
General and selective copper-catalyzed reduction of tertiary and secondary phosphine oxides: Convenient synthesis of phosphines
Li, Yuehui,Das, Shoubhik,Zhou, Shaolin,Junge, Kathrin,Beller, Matthias
supporting information; experimental part, p. 9727 - 9732 (2012/07/14)
Novel catalytic reductions of tertiary and secondary phosphine oxides to phosphines have been developed. Using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes, PO bonds are selectively reduced in the presence of other reducible functional groups (FGs) such as ketones, esters, and olefins. Based on this transformation, an efficient one pot reduction/phosphination domino sequence allows for the synthesis of a variety of functionalized aromatic and aliphatic phosphines in good yields.
Aromatic Radical Nucleophilic Substitution Reactions Initiated by Sodium Amalgam in Liquid Ammonia
Austin, Eduardo,Alonso, Ruben A.,Rossi, Roberto A.
, p. 4486 - 4489 (2007/10/02)
Neither 1-chloronaphthalene nor 2-chloroquinoline reacted with Ph2P- ions in liquid ammonia.However, in the presence of sodium amalgam , reaction did occur, and the substitution products 1-naphthyldiphenylphosphine and 2-quinolinyldiphenylphosphine (isolated as the P-oxides), respectively, were obtained in good yield. p-Bromoanisole reacted with Na(Hg) amalgam in the presence of Ph2C- ions in liquid ammonia to give anisole as the only product, but when benzonitrile was used as a redox catalyst, a good yield of the substitution product p-anisyldiphenylphosphine (isolated as the P-oxide) was obtained.It is believed that Na(Hg) amalgam initiated these SRN1 reactions.Preparative-scale reactions gave good yields of the substitution products.
Relative Reactivities of Amide, Diphenylphosphide, and Diphenylarsenide Ions toward Aryl Radicals
Alonso, Ruben A.,Bardon, Alicia,Rossi, Roberto A.
, p. 3584 - 3587 (2007/10/02)
Competition experiments have been carried out in liquid ammonia at reflux temperature to determine the relative rate constants for the coupling reactions of amide (NH2-), diphenylphosphide (Ph2P-), and diphenylarsenide (Ph2As-) toward aryl radicals.It is proposed that these nucleophiles react under photostimulation with halo aromatic substrates through an SRN1 mechanism of aromatic substitution.Relative rate constants of NH2- vs.Ph2P- ions toward 2,4,6-trimethylphenyl radicals and Ph2P- vs.Ph2As- ios toward 2-quinolyl radicals have been determined.The results here reported indicate that NH2- (1.00) - (6.4) = Ph2As- (6.4).The fact that there is not a difference in the rate constants of Ph2P- vs.Ph2As- suggests that both nucleophiles react at diffusion-controlled rate.In competition experiments of Ph2P- vs.Ph2As- ions toward phenyl radicals, it was found that Ph2P- (1.00) > Ph2As- (0.44).The decrease of the Ph2As- ion reactivity is attributed to the reversible coupling of this nucleophile with phenyl radicals.
