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US 2004/0110960 A1Published application
Ligands for pnicogen chelate complexes with a metal of subgroup VIII and use of the complexes as catalysts for hydroformylation, carbonylation, hydrocyanation or hydrogenation
AssigneeBASF SE
InventorsWolfgang Ahlers, Rocco Paciello, Dieter Vogt, Peter Hofmann
Life of this patent
Estimating the term…
Abstract
Pnicogen chelate compounds which have two pnicogen-containing groups joined to one another via a xanthene-like or triptycene-like molecular skeleton and in which at least one pyrrole group is covalently bound via its nitrogen atom to each pnicogen atom form complexes with metals of transition group VIII which are useful as catalysts for the hydroformylation of olefins.
Claims18
A pnicogen chelate compound of the formula I
- 30
- where
- Q is a bridging group of the formula
- 31
- where
- A1 and A2 are each, independently of one another, O, S, SiRaRb, NRc or CRdRe, where
- Ra, Rb and Rc are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- Rd and Re are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group Rd together with a further group Rd or the group Re together with a further group Re form an intramolecular bridging group D,
- D is a divalent bridging group selected from among the groups
- 32
- where
- R9 and R10 are each, independently of one another, hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are joined to one another to form a C3-C4-alkylene bridge,
- R11, R12, R13 and R14 are each, independently of one another, hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO3H, sulfonate, NE1E2, alkylene-NE1E2E3+X−, acyl or nitro,
- c is 0 or 1,
- Y is a chemical bond,
- R5, R6, R7 and R8 are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COORf, COO−M+, SO3Rf, SO−3M+, NE1E2, NE1E2E3+X−, alkylene-NE1E2E3+X−, ORf, SRf, (CHRgCH2O)xRf, (CH2N(E1))xRf, (CH2CH2N(E1))xRf, halogen, trifluoromethyl, nitro, acyl or cyano,
- where
- Rf, E1, E2 and E3 are identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl,
- Rg is hydrogen, methyl or ethyl,
- M+ is a cation,
- X− is an anion and
- x is an integer from 1 to 120,
- or
- R5 and/or R7 together with two adjacent carbon atoms of the benzene ring to which they are bound form a fused ring system having 1, 2 or 3 further rings,
- a and b are each, independently of one another, 0 or 1,
- Pn is a pnicogen atom selected from among the elements phosphorus, arsenic or antimony,
- and
- R1, R2, R3, R4 are each, independently of one another, hetaryl, hetaryloxy, alkyl, alkoxy, aryl, aryloxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy or an NE1E2 group, with the proviso that R1 and R3 are pyrrole groups bound via the nitrogen atom to the pnicogen atom Pn, or R1 together with R2 and/or R3 together with R4 form a divalent group E of the formula
- Py—I—W
- containing at least one pyrrole group bound via the pyrrole nitrogen to the pnicogen atom Pn,
- where
- Py is a pyrrole group,
- I is a chemical bond or O, S, SiRaRb, NRc or CRhRi,
- W is cycloalkyl, cycloalkoxy, aryl, aryloxy, hetaryl or hetaryloxy,
- and
- Rh and Ri are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- or form a bispyrrole group of the formula
- Py—I—Py
- bound via the nitrogen atoms to the pnicogen atom Pn.
36 more elements
A pnicogen chelate compound of the formula II
- 38
- where
- R15, R16, R17 and R18 are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, W′COORk, W′COO−M+, W′(SO3)Rk, W′(SO3)−M+, W′PO3(Rk) (R1), W′(PO3)2−(M+)2, W′NE4E5, W′(NE4E5E6)+X−, W′ORk, W′SRk, (CHR1CH2O)yRk, (CH2NE4)yRk, (CH2CH2NE4)yRk, halogen, trifluoromethyl, nitro, acyl or cyano,
- where
- W′ is a single bond, a heteroatom or a divalent bridging group having from 1 to 20 bridge atoms,
- Rk, E4, E5, E6 are identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl,
- R1 is hydrogen, methyl or ethyl,
- M+ is a cation equivalent,
- X− is an anion equivalent and
- y is an integer from 1 to 240,
- where two adjacent radicals R15, R16, R17 and R18 together with the carbon atom of the pyrrole ring to which they are bound may also form a fused ring system having 1, 2 or 3 further rings,
- with the proviso that at least one of the radicals R15, R16, R17 and R18 is not hydrogen and that R19 and R20 are not joined to one another,
- R19 and R20 are each, independently of one another cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- a and b are each, independently of one another 0 or 1,
- Pn is a pnicogen atom selected from among the elements phosphorus, arsenic or antimony, preferably phosphorus,
- Q is a bridging group of the formula
- 39
- where
- A1 and A2 are each, independently of one another, O, S, SiRaRb, NRc or CRdRe, where
- Ra, Rb and Rc are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl,
- Rd and Re are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or the group Rd together with a further group Rd or the group Re together with a further group Re form an intramolecular bridging group D,
- D is a divalent bridging group selected from among the groups
- 40
- where
- R9 and R10 are each, independently of one another, hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, carboxyl, carboxylate or cyano or are joined to one another to form a C3-C4-alkylene bridge,
- R11, R12, R13 and R14 are each, independently of one another, hydrogen, alkyl, cycloalkyl, aryl, halogen, trifluoromethyl, COOH, carboxylate, cyano, alkoxy, SO3H, sulfonate, NE1E2, alkylene-NE1E2E3+X−, acyl or nitro,
- c is 0 or 1,
- R5, R6, R7 and R8 are each, independently of one another, hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, COORf, COO−M+, SO3Rf, SO−3M+, NE1E2, NE1E2E3+X−, alkylene-NE1E2E3+X−, ORf, SRf, (CHRgCH2O)xRf, (CH2N(E1))xRf, (CH2CH2N(E1))xRf, halogen, trifluoromethyl, nitro, acyl or cyano,
- where
- Rf, E1, E2 and E3 are identical or different radicals selected from among hydrogen, alkyl, cycloalkyl and aryl,
- Rg is hydrogen, methyl or ethyl,
- M+ is a cation,
- X− is an anion and
- x is an integer from 1 to 120,
- or
- R5 and/or R7 together with two adjacent carbon atoms of the benzene ring to which they are bound form a fused ring system having 1, 2 or 3 further rings.
33 more elements
The use of a catalyst comprising at least one compound of the formula I or II for hydroformylation, carbonylation, hydrocyanation or hydrogenation.
Dependencies are inferred from the claim text.