Compound 4-cyanobenzene

Reductive elimination on transition metal complexes seems to be enhanced by coordination of electron-withdrawing 71-acids such as cyanobenzene and cyanoethylene. For example, the reductive elimination reaction of NiR2(bpy) (R=alkyl or aryl group bpy =2,2 -bipyridyl) is enhanced by electron-withdrawing olefinic and aromatic compounds [12-16] (Scheme 1). 

Reaction of 4-t-butoxycarbonylbenzene oxide (111, R = t-Bu) with lithium hydroxide in aqueous dioxane yielded (-butyl (rans-2,3-dihydroxy-2,3-dihydrobenzoate (255).152 In an aqueous solution, the compound undergoes both H30+- and water-catalyzed aromatization as well as a HO -catalyzed reaction at higher pH ranges. With a more electron-deficient 4-cyanobenzene oxide (256) the kinetics of the base-catalyzed hydrolysis show a first-order dependence on [HO ] above pH 9.2... 

Yasuda, Pac, and Shima reported the photoamination of aromatic compounds by use of ammonia and primary amines as nucleophiles in the presence of m-di-cyanobenzene as an electron acceptor [30,32], Irradiation of an acetonitrile-water (9 1) solution containing phenanthrene and m-dicyanobenzene in the presence of ammonia or primary amines gives 9-amino-9,10-dihydrophenanthrene deriva-... 

Synthesis of 4,4 -(5-cyanobenzene)-l,3-bis[l,2,3,5-diselenadiazolyl] 28 was reported (Scheme 53) <1993CM820>. The starting material, 5-cyanobenzene-l,3-bis[iV,iV,iV1-tris(trimethylsilyl)carboxamidine] 329, was prepared by treatment of 1,3,5-tricyanobenzene 328 with 2equiv of lithium bis(trimethylsilyl)amide, followed by transmetalation with trimethylsilyl chloride. Reaction of the bis(amidine) 329 with 4 molar equiv of SeCh affords the bis(l,2,3,5-diselenadiazolium) dication as its dichloride salt [28][Cl2]. Reduction of the dication with triphenyl-antimony affords compound 28 in 26% from the bis(amidine) 329. 

Palmisano et al. [41] in a study on the selectivity of hydroxyl radical in the partial oxidation of different benzene derivatives have investigated how the substituent group affect the distribution of the hydroxylated compounds. The reported results show that the primary photocatalytic oxidation of compounds containing an electron donor group (phenol, phenylamine, etc.) leads to a selective substitution in ortho and para positions of aromatic molecules while in the presence of an electron-withdrawing group (nitrobenzene, benzoic acid, cyanobenzene, etc.) the attack of the OH radicals is nonselective, and a mixture of all the three possible isomers is obtained. 

An example is found in the compound [3,3 5, 3" 5",3" -quaterpyridine(Cu2l2)] 2G, where G is the guest molecule, either nitrobenzene or cyanobenzene, see Figure 6.22. Apparently the 3D net is templated by these inclusion molecules as a guest free preparation results in a 2D-net [30]. 

Aldehydes and ketones are useM building blocks in organic synthesis. The direct a-C-H substitutions of carbonyl compounds are well known. However, selective P-C(sp )-H functionalization remains rare. The MacMillan group introduced Site activation model by dual aminocatalysis and photocatalysis, opening up a practical synthetic route to P-substituted aldehydes and ketones (Scheme 3.25). With this novel strategy, radical-radical coupling of enaminyl radical with electron-poor cyanobenzene radical anion can elegantly produce P-aiylated aldehydes and ketones [74]. A recombination of enaminyl radical with imine anion radical was also developed [75]. In the presence of Michael acceptors, radical addition of enaminyl radical to electron-deficient alkenes affords P-alkylated aldehydes [76]. 

Depending upon the bridging ligands, e.g. pyrazine or diiso-cyanobenzene whole the variety of bridged macrocyclic metal complexes e.g. [PcFe(pyz)] and [PcFe(dib)] [1>2] have been synthesized and characterized. The e compounds show a semi-conducting behavior to an Upper limit of 10 S/cm without oxidative doping. 

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