62238-34-0Relevant articles and documents
Comparison of “on water” and solventless procedures in the rhodium-catalyzed hydroformylation of diolefins, alkynes, and unsaturated alcohols
Alsalahi,Trzeciak
, p. 41 - 48 (2016/07/06)
Catalytic systems containing Rh(acac)(CO)2 or Rh/PAA (PAA?=?polyacrylic acid) and hydrophobic phosphine (PPh3) were used in the hydroformylation of diolefins, alkynes, and unsaturated alcohols under solventless and “on water” conditions. The total yield of dialdehydes obtained from 1,5-hexadiene and 1,7-octadiene reached 99%, and regioselectivity towards linear dialdehydes was higher in the “on water” system. The tandem hydroformylation-hydrogenation of phenylacetylene led to the formation of saturated aldehydes (3-phenylpropanal and 2-phenylpropanal) at 98% conversion with a good regioselectivity towards the linear aldehyde in the “on water” reaction. In contrast, solventless conditions appeared better in the hydroformylation of 1-propen-3-ol. 4-Hydroxybutanal, formed in this reaction with an excellent selectivity, was next transformed to tetrahydrofuran-2-ol via a ring-closure process. Cyclic products were also obtained in hydroformylation of 1-buten-3-ol. In reaction of undec-1-ol and 2-allylphenol linear aldehydes were formed with the yield 69–87%. The hydroformylation of 3-buten-1-ol performed under “on water” conditions showed very good regioselectivity towards a linear aldehyde, 5-hydroxypentanal. Further cyclization of the aldehyde to tetrahydropyran-2-ol was observed.
1,5-Hexadiene selective hydroformylation reaction catalyzed with Rh(acac)2/P(OPh)3 and Rh(acac)(CO)(PPh3)/PPh3 complexes
Trzeciak, A.M.,Ziolkowski, J.J.
, p. 107 - 112 (2007/10/02)
Hydroformylation of 1,5-hexadiene, catalyzed by the system Rh(acac)2/P(OPh)3 (I), leads to the formation of mono- and dialdehydes, 4-heptenal, 2-Me-3-hexenal and octane-1,8-dial, 2,5-Me2-hexanedial respectively.The yield of dialdehydes increases with temperature and pressure and reaches 100percent at 80 deg C and 10 atm of CO/H2 = 1.The reaction catalyzed by Rh(acac)(CO)(PPh3)/PPh3 (II) system produces, besides dialdehydes, monoaldehydes with a terminal double bond, namely 6-heptenal and 2-Me-5-hexenal.The migration of the double bonds in monoaldehydes dependsmainly on the donor properties of modifying ligands.Phosphine when used as a modifying ligand (II), because of its strong donor properties, restricts isomerization (double bond migration) and diminishes yield of 4-heptenal.In contrast, when less strongly donating ligands such as phosphite are used as modifying ligands (I), independently of its steric properties, 4-heptenal is the main reaction product.Key words: Hydroformylation; Rhodium; Hexadiene; Catalysis