127783-75-9Relevant articles and documents
Synthetic method of 4-hydroxy-4'-biphenyl nitrile
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Paragraph 0007; 0028, (2018/09/21)
The invention discloses a preparation method of 4-hydroxy-4'-biphenyl nitrile. The method comprises: reacting 4-hydroxybiphenyl (2) with acetyl chloride to generate 4-acetic acid biphenyl (3), reacting 4-acetic acid biphenyl (3) with oxalyl chloride under aluminium trichloride catalysis to generate 4-chlorocarbonyl-4'-acetic acid biphenyl (4), reacting 4-chlorocarbonyl-4'-acetic acid biphenyl (4)with ammonia water to generate 4-formamido-4'-acetic acid biphenyl (5), dehydrating 4-formamido-4'-acetic acid biphenyl (5) under phosphorus oxychloride catalysis to generate 4-cyano-4'-acetic acid biphenyl (6), and deacetylating 4-cyano-4'-acetic acid biphenyl (6) in the presence of sodium hydroxide to generate 4-hydroxy-4'-biphenyl nitrile (1). The method is simple in process, is economic and eco-friendly, and is suitable for industrial amplification requirement.
Cyanation of aryl bromides with K4[Fe(CN)6] catalyzed by dichloro[bis{1-(dicyclohexylphosphanyl)piperidine}]palladium, a molecular source of nanoparticles, and the reactions involved in the catalyst-deactivation processes
Gerber, Roman,Oberholzer, Miriam,Frech, Christian M.
supporting information; experimental part, p. 2978 - 2986 (2012/04/04)
Dichloro[bis{1-(dicyclohexylphosphanyl)piperidine}]palladium [(P{(NC 5H10)(C6H11)2}) 2PdCl2] (1) is a highly active and generally applicable C-C cross-coupling catalyst. Apart from its high catalytic activity in Suzuki, Heck, and Negishi reactions, compound 1 also efficiently converted various electronically activated, nonactivated, and deactivated aryl bromides, which may contain fluoride atoms, trifluoromethane groups, nitriles, acetals, ketones, aldehydes, ethers, esters, amides, as well as heterocyclic aryl bromides, such as pyridines and their derivatives, or thiophenes into their respective aromatic nitriles with K4[Fe(CN)6] as a cyanating agent within 24 h in NMP at 140 °C in the presence of only 0.05 mol % catalyst. Catalyst-deactivation processes showed that excess cyanide efficiently affected the molecular mechanisms as well as inhibited the catalysis when nanoparticles were involved, owing to the formation of inactive cyanide complexes, such as [Pd(CN)4]2-, [(CN)3Pd(H)]2-, and [(CN)3Pd(Ar)]2-. Thus, the choice of cyanating agent is crucial for the success of the reaction because there is a sharp balance between the rate of cyanide production, efficient product formation, and catalyst poisoning. For example, whereas no product formation was obtained when cyanation reactions were examined with Zn(CN)2 as the cyanating agent, aromatic nitriles were smoothly formed when hexacyanoferrate(II) was used instead. The reason for this striking difference in reactivity was due to the higher stability of hexacyanoferrate(II), which led to a lower rate of cyanide production, and hence, prevented catalyst-deactivation processes. This pathway was confirmed by the colorimetric detection of cyanides: whereas the conversion of β-solvato-α-cyanocobyrinic acid heptamethyl ester into dicyanocobyrinic acid heptamethyl ester indicated that the cyanide production of Zn(CN)2 proceeded at 25 °C in NMP, reaction temperatures of >100 °C were required for cyanide production with K4[Fe(CN) 6]. Mechanistic investigations demonstrate that palladium nanoparticles were the catalytically active form of compound 1. A balancing act: Compound 1 (see scheme) is a highly active cyanation catalyst. Furthermore, a sharp balance between the rates of cyanide generation, efficient product formation, and catalyst deactivation owing to excess cyanide was observed in deactivation processes. Copyright
Palladium catalyzed cross-couplings of organozincs in ionic liquids
Sirieix,Ossberger,Betzemeier,Knochel
, p. 1613 - 1615 (2007/10/03)
Negishi cross-coupling reactions between aryl- or benzylzinc halides and various aryl iodides smoothly occur in ionic liquids in the presence of the new ionic phosphine ligand 2. This solvent allows a facile work-up and rapid cross-coupling reactions at r
Preparation of polyfunctional aryl and alkenyl zinc halides from functionalized unsaturated organolithiums and their reactivity in cross-coupling and conjugated addition reactions
Klement, Ingo,Rottlaender, Mario,Tucker, Charles E.,Majid, Tahir N.,Knochel, Paul,Venegas, Patricia,Cahiez, Gerard
, p. 7201 - 7220 (2007/10/03)
Functionalized aryl and alkenyl iodides undergo an iodine-lithium exchange at -90 to -80°C providing polyfunctional organolithiums which are stable for a short time at these low temperatures and can be transmetalated to organozinc derivatives by the addition of zinc bromide. The resulting unsaturated organozinc halides can then be warmed up and are perfectly stable at 25°C. They react directly with tosyl cyanide. In the presence of CuCN·2LiCl, they add in a Michael-fashion to alkylidenemalonates. In the presence of catalytic amounts of Pd(dba)2 and TPP or TFP, they undergo readily a cross-coupling at 25°C with aryl and alkenyl iodides. The Pd-catalyzed coupling of arylzinc bromides with aryl triflates could also be achieved by using dppf as a ligand and 60°C as reaction temperature.
Process for the preparation of unsymmetric biaryl compounds
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, (2008/06/13)
Unsymmetric biaryl compounds are prepared by coupling two different halogenoaromatics by reaction with a metal and carrying out the reaction in the presence of catalytic amounts of a nickel compound, a promoter and a phosphorus-containing ligand.
SYNTHESIS OF 4-ALKOXY-4'-CYANOBIPHENYLS
Ruolene, Yu. I.,Adomenas, P. V.,Adomenene, O. K.,Denis, G. I.
, p. 1192 - 1195 (2007/10/02)
A preparative method was developed for the synthesis of liquid crystals of the 4-alkoxy-4'-cyanobiphenyl group.It involves the nitration of 4-cyanobiphenyl to 4-nitro-4'-cyanobiphenyl, reduction of the latter, diazotization of the obtained 4-amino-4'-cyanobiphenyl, and alkylation of the 4-hydroxy-4'-cyanobiphenyl formed during decomposition of the diazonium salt.
