Trans-3-pentenenitrile

In the course of a continuous search for new strategies to produce Nylon monomers, the DSM company has described an attractive approach for the synthesis of adipic acid or 6-aminocaproic acid precursors. Indeed, in a recent patent, this company has claimed the hydroformylation of 3-pentenoic acid into 5-formylvaleric acid in biphasic medium (Eq. 3). With a water-soluble platinum complex of tetra-sulfonated trans-1,2-bis(diphenylphosphinomethylene)cyclobutane as catalyst, the selectivity for 5-formylvaleric acids reached 62% [15]. The same catalytic system allows also the hydroformylation of trans-3-pentenenitrile with 91.4% selectivity. 

With a water-soluble platinum complex of tetrasulfonated trans-l,2-bis(diphenyl-phosphinomethylene)cyclobutane as catalyst, the 5-formylvaleric acid selectivity reached 62% [9], The same catalytic system allows also the hydroformylation of trans-3-pentenenitrile with 91.4% selectivity. 

After the first Ni-catalyzed addition step of HCN to 1,3-butadiene leading to a 30 70 nonequilibrium mixture of the 1,2- and the 1,4-monoadducts 2M3BN and t3PN (trans-3-pentenenitrile), isomerization to the 7 93 equilibrium mixture of these two unsaturated mononitriles, again Ni-catalyzed, is necessary before in a final step the second addition of HCN, after Ni-catalyzed, Lewis acid-promoted isomerization of t3PN to 4PN, results in adiponitrile. 

Internal olefins (2-butene, 2-hexene) were also successfully hydroformylated in water with complexes prepared in situ from [PtCl2(COD)] and the tetrasulfonated diphosphines 37 at 100 °C and 80 bar syngas [148,149]. The same catalysts were suitable for the hydroformylation of 2- and 3-pentenoic acids and trans-2-pentenenitrile, too [150], The co-... 

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