Acetylene using Raney nickel

Nickel catalysts have been employed successfully for the semihydrogenation of various acetylenic compounds.1 Dupont was the first to study the hydrogenation of acetylenes using Raney Ni. Little or no change in the rate of hydrogenation on the uptake of 1 equiv of hydrogen was observed with the monosubstituted acetylenes, 1-heptyne... 

Raney nickel deactivated with piperidine and zinc acetate has been used for semihydrogenation of acetylenic compounds. 

Triple bonds in side chains of aromatics can be reduced to double bonds or completely saturated. The outcome of such reductions depends on the structure of the acetylene and on the method of reduction. If the triple bond is not conjugated with the benzene ring it can be handled in the same way as in aliphatic acetylenes. In addition, electrochemical reduction in a solution of lithium chloride in methylamine has been used for partial reduction to alkenes trans isomers, where applicable) in 40-51% yields (with 2,5-dihydroaromatic alkenes as by-products) [379]. Aromatic acetylenes with triple bonds conjugated with benzene rings can be hydrogenated over Raney nickel to cis olefins [356], or to alkyl aromatics over rhenium sulfide catalyst [54]. Electroreduction in methylamine containing lithium chloride gives 80% yields of alkyl aromatics [379]. 

CH2 CH.OOC.CH(C2H5).C4H9 mw 170.25 liq, sp gr 0.8751 at 20/20° fr p -90°, bp 185.2°, fl p 165°F insol in w. It can be prepd from acetylene, 2-ethylhexanoic acid, zinc oxide and Raney nickel heated under pressure. Used in polymers and emulsi-fying paints... 

The Reppe process is used to make 1,4-1 butanediol from acetylene. In this process, acetylene and formaldehyde are reacted in the presence of a copper-bismuth catalyst. The resulting intermediate, 2-butyne-l,4-diol is hydrogenated over a Raney nickel catalyst ... 

Raney nickel A porous solid catalyst made from an activated alloy of nickel and aluminium. The nickel is the catalytic metal with the aluminium as the structural support It was developed by American mechanical engineer Murray Raney (1885-1966) in 1926 for the hydrogenation of vegetable oil and is now used in hydrogenation reactions in various forms of organic synthesis. It is widely used as an industrial catalyst for the conversion of olefins and acetylenes to paraffins, nitriles, and nifro compounds to amines, and benzene to cyclohexane amongst others. 

Equimolar quantities of acetylenedicarboxylic acid esters (166) and 2-N-substituted l,3-dithiolan-2-imines (169) undergo a 1,3-dipolar cycloaddition, with elimination of ethylene, to yield A -thiazoline-2-thiones (168). The same products result from 2-alkylthio-l,3,4-thiadiazoline-5-thiones (167), with loss of alkyl thiocyanate as shown. They are desulphurized to the corresponding thiazolinones (172) by the action of mercuric acetate in acetone-acetic acid. They react with two further moles of the acetylenic reagent (166) to produce the spiranes (170 e.g. = R = COzMe), which are in turn desulphurized and cleaved by Raney nickel to the AMhiazoline derivatives (171). An analogous series of reactions was carried out using propiolic acid esters. ... 

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