Butyronitrile reduction

Catalysts show remarkable product variation in hydrogenation of simple nitriles. Propionitrile, in neutral, nonreactive media, gives on hydrogenation over rhodium-on-carbon high yields of dipropylamine, whereas high yields of tripropylamine arise from palladium or platinum-catalyzed reductions (71). Parallel results were later found for butyronitrile (2S) and valeronitrile (74) but not for long-chain nitriles. Good yields of primary aliphatic amines can be obtained by use of cobalt, nickel, nickel boride, rhodium, or ruthenium in the presence of ammonia (4J 1,67,68,69). 

Zinc sulfide, with its wide band gap of 3.66 eV, has been considered as an excellent electroluminescent (EL) material. The electroluminescence of ZnS has been used as a probe for unraveling the energetics at the ZnS/electrolyte interface and for possible application to display devices. Fan and Bard [127] examined the effect of temperature on EL of Al-doped self-activated ZnS single crystals in a persulfate-butyronitrile solution, as well as the time-resolved photoluminescence (PL) of the compound. Further [128], they investigated the PL and EL from single-crystal Mn-doped ZnS (ZnS Mn) centered at 580 nm. The PL was quenched by surface modification with U-treated poly(vinylferrocene). The effect of pH and temperature on the EL of ZnS Mn in aqueous and butyronitrile solutions upon reduction of per-oxydisulfate ion was also studied. EL of polycrystalline chemical vapor deposited (CVD) ZnS doped with Al, Cu-Al, and Mn was also observed with peaks at 430, 475, and 565 nm, respectively. High EL efficiency, comparable to that of singlecrystal ZnS, was found for the doped CVD polycrystalline ZnS. In all cases, the EL efficiency was about 0.2-0.3%. 

Redox potentials for i-2 were determined in butyronitrile containing O.IM tetra-n-butylammonium perchlorate using a Pt disc electrode at 21. These potentials were measured relative to a saturated calomel electrode using ac voltammetry.(lQ) Both the one electron oxidations and reductions of i-2 exhibited good reversibility. The half-wave potentials for the one-electron oxidation and reduction of i-2, ZnTPP, and two model quinones are given in Table I. 

Synthesis (Cavalla and White (Wyeth), 1969 1969 Bradley 1980 Kleemann et al. 1999) By condensation of 2-(m-methoxyphenyl)butyronitrile with ethyl 4-iodobutyrate by means of NaNH2 in liquid NH3 to give ethyl 5-cyano-5-(m-methoxyphenyl)heptanoate, which is cyclized by hydrogenation with H2 over Raney Ni in cyclohexane to yield 6-ethyl-6-(m-methoxyphenyl)hexahydro-2H-azepin-2-one this ketone is reduced with LiAIH4 in THF to 3-ethyl-3-(m-methoxyphenyl)hexahydro-IH-azepine, which in turn, is reductively methylated with HCHO, H2 and Pd/C in ethanol to give 1-methyl-3-ethyl-3-(m-methoxyphenyl)-hexahydro-1H-azepine, and finally demethylated by refluxing with 80% HBr to yield a racemic mixture of the final product. 

Fig. 12 Plot of emission energy (from 77 K butyronitrile spectra) against the difference between the ground state oxidation and reduction potentials for 16-29, and the linear least-squares fit. Reprinted with permission from [43]. (1996) American Chemical Society...

Oxidation potential in CH2CI2 and reduction potential in dimethylformamide or butyronitrile, spectroscopic data in CH2CI2, benzene, or toluene, according to Ref (10) Ref. (11) gives the same oxidation potential for H2TPB and reports 1/2° = 0.40 V versus SCE for MgBChl. 

The stereospecific conversion of cyclohexene into the corresponding amido selenide 54 is illustrated in Scheme 8. These amidoselenenylation reactions are commonly employed for the preparation of allylic and saturated amides by oxidative or reductive deselenenylation. Propionitrile, butyronitrile, benzonitrile and ethyl cyanoacetate may be used in place of acetonitrile. Styrene gave poor results and other electron-rich olefins such as 1-methylcyclohexene or 2,3-di-methylbut-2-ene did not give the amidoselenenylation products. The reaction can also be effected starting from the hydroxy- or methoxyselenenylation products of alkenes, in the presence of water and trifluoromethanesulfonic acid in this case the nitriles are used in stoichiometric amounts [48c]. This methodology was employed to prepare the amidoselenenylation products of styrene, 55, and of electron-rich olefins. It was necessary, however, to replace the phenyl-... 

Reduction of a-ketocyclopropanes. Cyclopropyl methyl ketone (1) is reduced by the reagent in methanol under the influence of radical initiators [hi/, azobisiso-butyronitrile, 1,45] to propyl methyl ketone as the only product of reduction (51 % yield). In the absence of an initiator the reaction is slow and results in reduction of the carbonyl group. ... 

Hydrogenation of butyronitrile derivative 6 over platinum oxide in acidic medium yields quinolizidine 7, by reduction of the pyridine ring first and piperidone derivative 8 by reduction of the cyano group ... 

Vs SCE at 25 °C with 0.1 M TBAP b Two electron process c EPiC (irreversible) d Reductions in butyronitrile... 

Exclusive substitution at C2 occurs under photostimulation, by reaction of CHPhCN ion with 2,4-dichloropyrimidine (58% yield). On the other hand, a mixture of monosubstitution, disubstitution, and monosubstitution with reductive dehalogenation occurs in the reaction of this anion and the anion derived from 2-phenyl butyronitrile with 2,6-dibromopyridine. Both anions react with 3-bromoquin-ohne-1-oxide to afford the corresponding 3-substituted quinoline-1-oxides (82 to 91%) by a thermal-initiated S jl mechanism. ... 

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