| 摘要 |
The invention relates to the preparation of multidentate phosphine compounds (1), having a bridging group with substituents A and B from the group of alkyl (C1 to C12), alkoxy, ester, amide or (hetero)aryl (C4 to C14) groups, and 9-phosphabicyclononane groups, wherein a 9-phosphabicyclononane is reacted, in the presence of an acidic catalyst, with a 9-phospha-bicyclononane alkenylmonophosphine (2) with R1, R2 and R3 representing hydrogen, alkyl (C1 to C12), alkoxy, ester, amide or (hetero)aryl (C4 to C14) groups. The invention also relates to the use of alkenylmonophosphine compounds for the preparation of multidentate phosphine compounds. The invention further relates to novel 9-phospha-bicyclononane alkenylmonophosphines (2), especially P-{2-(2-butenyl)}-9-phospha-bicyclononane, and preparation thereof by transition metal catalysed cross-coupling reaction of 9-phosphabicyclononanes with halogen or sulphonate substituted alkenes. The invention further more generally relates to the preparation of multidentate phosphines (3), having a bridging group substituted by hydrogen and substituents A and B which may be linked together so as to form a ring with the bridging carbon atoms and which can be alkyl (C1 to C12), alkoxy, ester, amide or (hetero)aryl (C4 to C14) groups, wherein an Rc, Rd disubstituted phosphine is reacted, in the presence of an acidic catalyst, with an alkenylmonophosphine compound (4) comprising an Ra, Rb disubstituted phosphine group, Ra to Rd representing alkyl or optionally substituted phenyl groups, of which Ra and Rb, and/or Rc and Rd may be linked together, and which Ra to Rd groups optionally may be substituted by lower alkyl (C1 to C6), or alkoxy groups The invention finally relates to the use of multidentate phosphine compounds as represented by formula (1), or compounds as represented in formula (3), as ligands for transition metal catalysts to be used in hydrogenation reactions, cross-coupling reactions and carbonylations of alkenes or conjugated diene compounds.
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