Method for hydroformylating olefins in the presence of organophosphoric compounds

1. A process for hydroformylating olefins, comprising:

reacting a monoolefin or a monoolefin mixture having from 2 to 25 carbon atoms with a mixture of carbon monoxide and hydrogen in the presence of a heteroacylphosphite of general formula (1) or a corresponding complex with one or more metals of groups 4 to 10 of the Periodic Table of the Elements

wherein R 1 , R 2 , R 3 , R 4 and q are the same or different and are each a substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radical having from 1 to 70 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 wherein j=0-9, —OR 5 , —COR 5 , —CO 2 R 5 , —CO 2 M, —SiR 5 3 , —SR 5 , —SO 2 R 5 , —SOR 5 , —SO 3 R 5 , —SO 3 M, —SO 2 NR 5 R 6 , —NR 5 R 6 , —N═CR 5 R 6 ,

wherein R 5 and R 6 are the same or different and are each as defined for R 1 , and

M is an alkali metal, an alkaline earth metal ion which is present in the formula as one half, an ammonium or phosphonium ion, x, y, z are each independently O, NR 7 , S, where R 7 is as defined for q, and x, y, z are not simultaneously O, with the proviso that when q is a radical which has a structural formula (6c)

wherein the R 1 to R 4 radicals are each as defined for formula (1), x 1 , y 1 , z 1 are each independently O, NR 7 , S, where R 7 is as defined for q, T is an oxygen or an NR 30 radical, wherein R 30 is as defined for q, and the a position serves as the attachment point,

x and x 1 must not simultaneously be N, and

x must not be N when T is NR 30 .

2. The process as claimed in claim 1 , wherein the R 1 and R 2 , R 2 and R 3 and/or R 3 and R 4 radicals form a fused substituted or unsubstituted aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system.

3. The process as claimed in claim 1 , wherein the q radical consists of the W-R radicals wherein W is a divalent substituted or unsubstituted aliphatic, alicyclic, mixed aliphatic-alicyclic, heterocyclic, mixed aliphatic-heterocyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, hydrocarbon radical having from 1 to 50 carbon atoms, and the R radical is —OR 5 , —NR 5 R 6 , phosphite, phosphonite, phosphinite, phosphine or heteroacylphosphite of formula (6c), wherein R 5 and R 6 are the same or different and are as defined for R 1 .

4. The process as claimed in claim 3 , wherein

W is a radical of general formula (2)

where R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and are each as defined for R 1 ,

t is a divalent CR 16 R 17 , SiR 16 R 17 , NR 16 , O or S radical, and R 16 and R 17 are each as defined for R 5 and R 6 , n=0 or 1 and the a and b positions serve as attachment points.

5. The process as claimed in claim 4 , wherein in each case two adjacent R 9 to R 15 radicals together or a fused substituted or unsubstituted, aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system.

6. The process as claimed in claim 4 , wherein W is a radical of general formula (3):

wherein

R 18 , R 19 , R 20 , R 21 , R 22 and R 23 are the same or different and are each as defined for R 1 ,

t is a divalent CR 16 R 17 , SiR 16 R 17 , NR 16 , O or S radical, and R 16 and R 17 are each as defined for R 5 and R 6 , n=0 or 1 and the a and b positions serve as attachment points.

7. The process as claimed in claim 6 , wherein in each case two adjacent R 18 to R23 radicals together form a fused substituted or unsubstituted, aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system.

8. The process as claimed in claim 3 , wherein

W is a radical of general formula (4):

wherein u is adivalent group selected from radicals of formulae (5a), (5b) and (5c)

in which R 24 , R 25 , R 26 and R 27 are the same or different are each as defined for R 1 , and the a and b positions serve as attachment points.

9. The process as claimed in claim 8 , wherein two adjacent R 24 to R 27 radicals together form a fused substituted or unsubstituted, aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system.

10. The process as claimed in claim 3 , wherein

R represents radicals of general formulae (6a), (6b) and (6c):

wherein R 28 and R 29 are the same or different and are each as defined for R 1 ,

x, y, z and W are each defined as specified and

m=0 or 1, n=0 or 1, k=0 or 1, l=0 or 1,

and the position a serves as the attachment point.

11. The process as claimed in claim 1 , wherein the metal of groups 4 to 10 of the Periodic Table is selected from the group consisting of rhodium, platinum, palladium, cobalt and ruthenium.

12. The process as claimed in claim 1 , wherein further phosphorus ligands are present.

13. A process for making a compound, wherein said process comprises:

hydrocyanation, isomerization of an olefin or amidocarbonylation and wherein said process is conducted in the presence of heteroacylphosphines of formula (1)

or metal complexes thereof,

wherein R 1 , R 2 , R 3 , R 4 and q are the same or different and are each a substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radical having from 1 to 70 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 wherein j=0-9, —OR 5 , —COR 5 , —CO 2 R 5 , —CO 2 M, —SiR 5 3 , —SR 5 , —SO 2 R 5 , —SOR 5 , —SO 3 R 5 , —SO 3 M, —SO 2 NR 5 R 6 , —NR 5 R 6 , —N═CR 5 R 6 , wherein R 5 and R 6 are the same or different and are each as defined for R 1 , and M is an alkali metal ion, an alkaline earth metal ion, which is present in the formula as one half, an ammonium or phosphonium ion, x, y, z are each independently O, NR 7 , S, wherein R 7 is as defined for R 1 .

14. A process for carbonylation wherein the carbonylation is carried out in the presence of a heteroacylphosphite of formula (1)

or metal complexes thereof,

where R 1 , R 2 , R 3 , R 4 and q are the same or different and are each a substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radical having from 1 to 70 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0-9, —OR 5 , —COR 5 , —CO 2 R 5 , —CO 2 M, —SiR 5 3 , —SR 5 , —SO 2 R 5 , —SOR 5 , —SO 3 R 5 , —SO 3 M, —SO 2 NR 5 R 6 , —NR 5 R 6 , —N═CR 5 R 6 , wherein R 5 and R 6 are the same or different and are each as defined for R 1 , and M is an alkali metal ion, an alkaline earth metal ion which is present in the formula as one half, an ammonium or phosphonium ion, x, y, z are each independently 0, NR 7 , S, where R 7 is as defined for q, and x, y, z are not simultaneously 0, with the proviso that when q has a radical which has a structural formula (6c)

wherein the R 1 to R 4 radicals are each as defined for formula (1), x 1 , y 1 , z 1 are each independently O, NR 7 , S, where R 7 is as defined for q, T is an oxygen or an NR 30 radical, wherein R 30 is as defined for q, and the a position series as the attachment point, x and x 1 must not simultaneously be N and

x must not be N when T is NR 30 .