Process for preparing tertiary phosphines

Process for preparing compounds of the formulae (Ia) and (Ib)

• PR1nAr(3-n) (Ia)
• R12P—B—PR12 (Ib)
• wherein
• R1 is in each case C1-C12-alkyl, SiR23, (C1-C8-alkylene)-SiR23, C1-C12-fluoroalkyl, or C5-C15-arylalkyl where the radicals
• R2 are in each case independently C1-C12-alkyl
• and wherein, in formula (Ia),
• n is one or two and
• Ar is a substituted or unsubstituted aryl radical
• and wherein, in formula (Ib),
• B is an unsubstituted or substituted radical from the group of C1-C12-alkylene, C2-C12-alkenylene, C4-C20-arylene, C8-C40-bisarylene, and C10-C30-ferrocenylene,
• comprising:
• reacting halophosphines of the formulae (IIa) or (IIb)
• PXnAr(3-n) (IIa)
• X2P—B—PX2 (IIb)
• wherein
• n is one or two and
• X is in each case independently chlorine, bromine or iodine and
• Ar in formula (IIa) has the same definition as specified under the formula (Ia) and B in formula (IIb) has the same definition as specified under the formula (Ib)
• with organomagnesium compounds of the formulae (IIIa)
• (R1)mMg(Y)(2-m) (IIIa)
• wherein
• R1 have the definitions specified under the formula (Ia) and
• m is one or two and
• Y is chlorine, bromine or iodine or
• reacting halophosphines of the formula (IIc)
• R12PX (IIc)
• wherein
• R1 has the definition given under the formulae (Ia) and (Ib)
• with organomagnesium compounds of the formula (IIIb)
• B—(MgY)2 (IIIb)
• wherein
• B has the definition specified under the formula (Ib)
• Y is chlorine, bromine or iodine
• and
• wherein the reaction is in each case carried out in the presence of one or more copper compounds, wherein the tertiary phosphines are precipitated in the form of the analogous phosphonium tetrafluoroborates, hexafluorophosphates, hydrogen hexafluorozirconates, hydrogen hexafluorotitanates or sulphonates by using tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorozirconic acid, hexa-fluorotitanic acid or sulphonic acids.