Nickel catalysts containing sulfonated

To the 8 L of 1 1 methanol/water mixture containing the (Z)-2-carbomethoxy-3-phenyl-2-propene-l-sulfonic acid sodium salt was added 60.0 g of W-24 raney nickel. The resulting suspension was pressurized under 50 psi of hydrogen and was allowed to shake on a Parr shaker for 24 h, at which time an additional 20.0 g of raney nickel catalyst was added. After 6 h under 50 psi of hydrogen, the catalyst was removed by filtration and the solution was concentrated to dryness. To the dry white solid was added ethyl acetate (6 L) and heptane (4 L) and the solution was vigorously stirred with a mechanical stirrer overnight. The white suspension was removed by filtration yielding 530.0 g (88%) of the desired 2-carbomethoxy-3-phenylpropane-l-sulfonic acid sodium salt as an amorphous powder. 

Huser and Perron have extended this work to the isomerization of 2-methyl-3-butenenitrile (2M3 BN) to 3-PN (isomerization step Eq. (6) 92% yield) [17]. This patent mentions the use of iron and palladium catalysts but does not provide examples beyond nickel. In other work these same inventors discuss the use of other water-soluble ligands such as those containing carboxylate, phosphate, and alkyl-sulfonate substituents [18], while also exploring a wide range of Lewis acid co-catalysts for the addition of HCN to 3-pentenenitrile (Eq. 7) [19]. In general, the addi-... 

Direct transfer from [Ru(bipy)3] via the nickel complex is also possible if SDS is added to the aqueous solution containing [Ru(bipy)3]. The more efficient electron transfer quenching by nickel in this case is believed to arise because the SDS molecules take [Ru(bipy)3] to the H20/Ph20 interface. The electron is carried across the membrane by the [Ni(S2C2Ph2)2] couple. Other neutral electron transfer catalysts include zwitterionic sulfonated viologens (see Section 61.5.4.2.3). 

This use of a relatively high hydrogenation temperature with nickel raises the important question of the stability at high temi ratures of the various shielded derivatives, principally sulfonic acids or sulfones, into which sulfur-containing catalyst poisons are converted by detoxication processes. It should however be pointed out that this question of stability will not in any case affect the use of detoxication methods for... 

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