Copper chloride-bipyridine

Bipyridine has been prepared by the action of ferric chloride,8,9 iodine,10 or a nickel-alumina catalyst10 on pyridine at temperatures ranging from 300° to 400°. It has also been obtained from the reaction of 2-bromopyridine and copper.11 The present procedure is a modification of a previously published, general method.3 The W7-J nickel catalyst was developed from the description of the W7 Raney nickel catalyst of Billica and Adkins.12... 

The reaction of 3-(chloromethyl)-A3-cephem 62 with organotins in the presence of copper(l) chloride, and the related copper(0)-promoted coupling reaction of 62 with allyl and benzyl bromides have been investigated <1997JOC3782>. It was found that both reactions could be achieved only in the presence of terpyridine (tpy) or bipyridine (bpy) as a ligand, to afford 3-alkyl-A3-cephems 63 and 3-(arylalkyl)-A3-cephems 64, respectively (Scheme 12). 

The ligands 6,6 -bis(2-hydroxyphenyl)-bpy, (44), and 6,6 -bis(2"-thienyl)-bpy, (45), each have two additional groups that may chelate. Ligand (44) has been shown to be tetradentate in some copper complexes, and was prepared from 6,6 -diacetyl bipyridine in 90% yield.237 The mono-substituted phenolic bipyridine is also known.238 The dithienyl substituted bipyridine was synthesized via Negishi coupling of 6,6 -dibromo bipyridine and 2-thienylzinc chloride.235... 

The use of reverse ATRP enlarges the scope of substrate polymers for controlled polymerizations even further because the required radical initiators can in many cases be provided more easily than ATRP initiators on surfaces of inert polymers. For example, poly(vinylidene fluoride) microfiltration membranes were irradiated with UV light and then exposed to air to create hydro(peroxide) species [11]. These were then used to initiate the reverse ATRP of methyl methacrylate in the presence of copper(I) chloride, 2,2 -bipyridine, and benzoylperoxide (Figure 3.5). Similar reaction schemes are applicable to (hydro)perox-ide patterns created directly on polymer surfaces using the lithographic methods discussed in Chapter 2. 

Cross-coupling reactions were carried out in direct aqueous miniemulsions with 1,2,4-tribromobenzene as crosslinker, and Pd as catalyst [147], in order to obtain aqueous latexes of crosslinked poly(p-phenylene ethynylene) with good optoelectronic properties. The Glaser couphng reaction was also used to synthesize fluorescent conjugated particles of poly(arylene diethynylenes) in direct miniemulsions [148]. For this, 4,4 -dinonyl-2,2 -bipyridine was found to be a suitable ligand for solubilizing the copper (I) chloride catalyst in the toluene droplets. In this case, a solution of the monomers in toluene was first mixed with the solution of the catalyst, and the resultant mixture then miniemulsified in an aqueous solution of cationic surfactant. 

A few reactions of aryl chlorides catalyzed by ligated copper complexes have been reported. The reaction of phenyl chloride with diphenylamine to form triarylamines catalyzed by the complexes of CuL(PPh3)Br in which L is 1,10-phenanthroline, neocuproine, or 2,2 -bipyridine occurred in about 50% yield. The favorable effect of potentially coordinating ortho substituents on the rates of Ullmann reactions has been exploited to couple o-chlorobenzoic acids with anilines to form N-arylanthranilic acids in aqueous or DMF solutions in the presence of pyridine. ... 

Benzylic and allylic alcohols are oxidised to the corresponding aldehydes or ketones in the presence of copper(n) chloride/cesium carbonate as a catalyst under oxygen (Scheme 15.44). A catalytically active p-hydrojyl-bridged trinuclear copper species was isolated and its X-ray crystal structure was determined. A highly efficient oxidation of propargylic alcohols to ynones under air has been carried out in the presence of copper nanoparticles (Cu Nps) with bipyridine as a ligand (Scheme 15.45). ... 

C1gH2 6Cl2Nfl02Pt, (1,3-Diaminocyclohexane)(2,2 -bipyridine)platinum-(II) chloride dihydrate, 43B, 1309 Cl6H2 eCuNgOg, Bis(3-aminopropyl)amine(di-2-pyridylamine)copper(II) nitrate, 44B, 931... 

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