Benzonitrile reduction

Ruhland reported a novel solid-phase C2-lithiation of the indole ring [279] using a linker that resembled the MOM-protecting group (Scheme 16). Lithiation of resin-bound indole 73 was accomplished by treatment with tert-butyllithium in toluene followed by quenching with benzonitrile. Reductive cleavage of 74 then gave amine 75 in an overall yield of 2%, proof of principle that this type of transformation is possible. 

The photochemical cyclization of anthranilonitriles (190 Section 4.04.2.1.2) yields indazoles (72CC126). Reduction of o-benzonitrile with lithium aluminum hydride yields indazole (75ACS(B)1089). 2-Aminoindazole (576) has been prepared in 94% yield from (574) via the o-phthaloyl derivative (575 = o-phthaloyl) (72JOC2351). Similarly, treatment... 

Fukuzumi S, Okamoto K, Gros CP, Guilard R. 2004. Mechanism of four-electron reduction of dioxygen to water by ferrocene derivatives in the presence of perchloric acid in benzonitrile, catalyzed by cofacial dicobalt porphyrins. J Am Chem Soc 126 10441. 

As discussed in Section IV, many studies of ET kinetics with SECM have been under conditions where constant composition in phase 2 can be assumed, but this severely restricts the range of kinetics that can be studied. With the availability of a full model for diffusion, outlined in Section IV, that lifts this restriction, Barker et al. [49] studied the reaction between ZnPor in benzene or benzonitrile and aqueous reductants, using CIO4 or tetrafluoroborate as potential-determining ions. 

Similar experiments were performed to measure the ET rate constants for the reaction between ZnPor in benzonitrile and aqueous reductants, Ru(CN)g, Mo(CN)g and FeEDTA (where EDTA denotes ethylenediaminetetra-acetic acid). Although the... 

The ITIES with an adsorbed monolayer of surfactant has been studied as a model system of the interface between microphases in a bicontinuous microemulsion [39]. This latter system has important applications in electrochemical synthesis and catalysis [88-92]. Quantitative measurements of the kinetics of electrochemical processes in microemulsions are difficult to perform directly, due to uncertainties in the area over which the organic and aqueous reactants contact. The SECM feedback mode allowed the rate of catalytic reduction of tra 5-l,2-dibromocyclohexane in benzonitrile by the Co(I) form of vitamin B12, generated electrochemically in an aqueous phase to be measured as a function of interfacial potential drop and adsorbed surfactants [39]. It was found that the reaction at the ITIES could not be interpreted as a simple second-order process. In the absence of surfactant at the ITIES the overall rate of the interfacial reaction was virtually independent of the potential drop across the interface and a similar rate constant was obtained when a cationic surfactant (didodecyldimethylammonium bromide) was adsorbed at the ITIES. In contrast a threefold decrease in the rate constant was observed when an anionic surfactant (dihexadecyl phosphate) was used. 

The most interesting aminomethyl derivative of condensation polymers that we have prepared to date Is derived from direct reduction of poly(2-cyano-l,3-phenylene arylene ether), 20. Enchainment of benzonitrile repeat units Is accomplished by coupling 2,6-dichlorobenzonitrile with the potassium salt of bisphenol-A copolymers with lower nitrile contents can be produced by copolycondensation of bisphenol-A, 2,6-dichlorobenzonitrile and 4,4 -dichlorodiphenyl sulfone.21 The pendent nitrile function provides an active site for further elaboration. 

Feldman and Eastman have suggested that the kinamycins may by reductively activated to form reactive vinyl radical (25) and orf/to-quinone methide (26) intermediates (Scheme 3.2c) [16]. The authors provided convincing evidence that the alkenyl radical 25 is generated when the model substrate dimethyl prekinamycin (24) is exposed to reducing conditions (tri-n-butyltin hydride, AIBN). Products that may arise from addition of this radical (25) to aromatic solvents (benzene, anisole, and benzonitrile) were isolated. The ort/io-quinone methide 26 was also formed,... 

Diiron enneacarbonyl, 50, 2J Diketones, from diazoketones and organoboranes, 53/ 82 3-DIKETONES FROM METHYL ALKYL KETONES 3-n-BUTYL-2,4-PENTANEDIONE, 51, 90 2,6-Dimethoxybenzaldehyde, by reduction of 2,6-dime thoxy-benzonitrile with Raney nickel alloy in formic acid,... 

The substituent effects on the photochemistry between benzene and secondary aliphatic amines53 were studied. Irradiation of toluene or chlorobenzene with diethylamine results in the formation of mixtures of addition and substitution products (equations 34 and 35). Irradiation of anisole or benzonitrile with diethylamine gives the substitution product 7V,7V-diethylaniline (equations 36 and 37). Irradiation of benzylfluoride with diethylamine results in a side-chain substitution (equation 38). The photoreaction of p-fluorotoluene with diethylamine gives both substitution and reduction products (equation 39). 

For example, reductive elimination of benzonitrile from (Et3P)2Pd(CN)Ph is promoted by the addition of triethyl phosphite [4], addition of benzoquinone promotes reductive eliminations in palladium chemistry (Chapter 12), etc., but in all cases different roles can be envisaged, such as simple ligand exchange. 

Fig. 3 Electrochemical and homogeneous standard free energies of activation for self-exchange in the reduction of aromatic hydrocarbons in iV.A -dimethylformamide as a function of their equivalent hard sphere radius, a. 1, Benzonitrile 2, 4-cyanopyridine 3, o-toluonitrile 4, w-toluonitrile 5, p-toluonitrile 6, phthalonitrile 7, terephthalonitrile 8, nitrobenzene 9, w-dinitrobenzene 10, p-dinitrobenzene 11, w-nitrobenzonitrile 12, dibenzofuran 13, dibenzothiophene 14, p-naphthoquinone 15, anthracene 16, perylene 17, naphthalene 18, tra 5-stilbene. Solid lines denote theoretical predictions. (Adapted from Kojima and Bard, 1975.)...

The drying and weighing of triethylamine hydrochloride should be carried out only after N-sulfinylaniline has been added to the solution of benzonitrile oxide, as otherwise the latter, not I)eing very stable in the free state, would dimerize resulting in the reduction in yield of the carbodiimide. 

Benzaldehyde, by condensation of phenyllithium with 1,1,3,3-tetra-methylbutyl isonitrile, 51,38 by reduction of benzonitrile with Raney nickel alloy, 51,22 BENZALDEHYDE, 3,4,5-TRIMETH-OXY-, 51,8... 

All the reductions are one-electron transfer processes. This has been demonstrated, for example, for the first four reductions of Cjq by bulk electrolysis in benzonitrile [11]. The anions up to a charge of4 are comparatively stable in solution for up to several days, especially at low temperatures. Despite their stability under CV-conditions, the penta- and hexaanions are not stable under these conditions [8]. 

Other methods that use 55 anions as precursor for the synthesis of fullerene-derivatives usually involve chemical formation of the anion. Alkylation of 55 has been accomplished, e.g. by reduction with propanethiol and potassium carbonate in DMF [91,92], sodium methanethiolate in acetonitrile [93], the naphthalene radical anion in benzonitrile[94], potassium naphthalide [95] or simply with zinc [96]. 

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