Phosphite compounds and the metal complexes thereof

1. A phosphite of the formula I,

where R 1 , R 2 , R 3 and R 4 are each independently a monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radical having from 1 to 50 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0–9, —OR 9 , —COR 9 , —CO 2 R 9 , —CO 2 M, —SR 9 , —SO 2 R 9 , —SO 3 R 9 , —SO 3 M, —SO 2 NR 9 R 10 , —NR 9 R 10 , or —N═CR 9 R 10 , where R 9 and R 10 are independently a H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radical having from 1 to 25 carbon atoms and M is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a phosphonium ion,

or adjacent radicals R 1 to R 4 together form a fused substituted or unsubstituted aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system;

Q is a k-valent substituted or unsubstituted aliphatic, alicyclic, mixed aliphatic-alicyclic, aromatic, heteroaromatic, or mixed aliphatic-aromatic hydrocarbon radical having from 1 to 50 carbon atoms, where aliphatic parts of Q may contain one or more of oxygen, sulfur or nitrogen,

k is at least 2 and R 1 , R 2 , R 3 and R 4 in the individual structural elements bound to Q can be different from one another.

2. The phosphite as claimed in claim 1 , wherein at least two adjacent radicals R 1 to R 4 together form a fused aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system which is unsubstituted or is substituted by at least one radical selected from among aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphaticheterocyclic hydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0–9, —OR 9 , —COR 9 , —CO 2 R 9 , —CO 2 M, —SR 9 , —SO 2 R 9 , —SOR 9 , —SO 3 R 9 , —SO 3 M, —SO 2 NR 9 R 10 , —NR 9 R 10 or —N═CR 9 R 10 .

3. The phosphite as claimed in claim 1 , wherein Q is a divalent hydrocarbon radical of the formula III

and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently a monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroatomic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radical having from 1 to 50 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0–9, —OR 9 , —COR 9 , —CO 2 R 9 , —CO 2 M, —SR 9 , —SO 2 R 9 , —SO 3 R 9 , —SO 3 M, —SO 2 NR 9 R 10 , —NR 9 R 10 , or —N═CR 9 R 10 where R 9 and R 10 are independently a H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radical having from 1 to 25 carbon atoms and M is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a phosphonium ion,

W is the divalent radical CR 19 R 20 , where R 19 and R 20 are as defined for R 9 and R 10 ,

m=0–1 and

the positions a and b represent the linkage points.

4. The phosphite as claimed in claim 1 , wherein Q is a calix[n]arene radical of the formula IV

where R 21 , R 22 and R 23 are independently a substituted or unsubstituted aliphatic and aromatic hydrocarbon radical having from 1 to 25 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0–9, —OR 24 , —COR 24 , —CO 2 R 24 , —CO 2 M, —SR 24 , —SO 2 R 24 , —SOR 24 , —SO 3 R 24 , —SO 3 M, —SO 2 NR 24 R 25 , —NR 24 R 25 , —N═CR 24 R 25 , where R 24 and R 25 are independently a H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radical having from 1 to 25 carbon atoms and M is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a phosphonium ion,

or adjacent radicals R 21 to R 23 together form a fused substituted or unsubstituted aromatic, heteroaromatic, aliphatic, mixed aromaticaliphatic or mixed heteroaromatic-aliphatic ring system;

Y is the divalent radical CR 24 R 25 or CR 24 R 25 —O—CR 24 R 25 ,

n=3–6 and

the positions a represent the linkage points or are occupied by OR 24 , where R 24 and R 25 are as defined above.

5. A phosphite-metal complex comprising a metal of group 4, 5, 6, 7, 8, 9 or 10 of the Periodic Table of the Elements and one or more phosphites as claimed in claim 1 .

6. The phosphite-metal complex as claimed in claim 5 , wherein the metal is rhodium, platinum, palladium, cobalt or ruthenium.

7. A process for the hydroformylation of olefins, which comprises

reacting a monoolefin or monoolefin mixture with a mixture of carbon monoxide and hydrogen in the presence of a phosphite-metal complex as claimed in claim 5 .

8. A process for preparing a phosphite as claimed in claim 1 , which comprises

(a) reacting an α-hydroxyarylcarboxylic acid of the formula (1)

with PCl 3 , PBr 3 or PI 3 in the presence of a base to form a halodioxaphosphorinone of the formula (2),

where Hal=Cl, Br or I, and

(b) reacting the halodioxaphosphorinone (2) in the presence of a base with

(i) a diol HO-Q-OH to give a phosphite of the formula (I), or

(ii) a dicarboxylic acid HOOC-Q-COOH to give a phosphite of the formula (II).

9. The process for preparing a phosphite as claimed in claim 8 , wherein two differently substituted halodioxaphosphorinones (2a) and (2b) are synthesized in (a) and are then reacted in succession with a diol in (b) (i) or reacted in succession with a dicarboxylic acid in (b) (ii) to give an unsymmetrical phosphite.

10. A process for preparing a phosphite-metal complex as claimed in claim 5 , which comprises reacting a metal of group 4, 5, 6, 7, 8, 9 or 10 of the Periodic Table in elemental form or in the form of a chemical compound with the phosphite of formula (I).

11. A catalyst comprising the phosphite as claimed in claim 1 .

12. A homogeneous catalyst comprising the phosphite as claimed in claim 1 .

13. A hydroformylation catalyst comprising the phosphite as claimed in claim 1 .

14. A hydroformylation catalyst comprising the phosphite metal complex as claimed in claim 5 .

15. The process as claimed in claim 7 wherein the reacting is carried out in the presence of one or more additional phosphorous-containing ligands.

16. A phosphite of the formula II,

where R 1 , R 2 , R 3 and R 4 are each independently a monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroatomic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radical having from 1 to 50 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0–9, —OR 9 , —COR 9 , —CO 2 R 9 , —CO 2 M, —SR 9 , —SO 2 R 9 , —SO 3 R 9 , —SO 3 M, —SO 2 NR 9 R 10 , —NR 9 R 10 , or —N═CR 9 R 10 , where R 9 and R 10 are independently a H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radical having from 1 to 25 carbon atoms and M is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a phosphonium ion,

or adjacent radicals R 1 to R 4 together form a fused substituted or unsubstituted aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system;

Q is a k-valent substituted or unsubstituted aliphatic, alicyclic, mixed aliphatic-alicyclic, heterocyclic, aromatic, heteroaromatic, or mixed aliphatic-aromatic hydrocarbon radical having from 1 to 50 carbon atoms, where aliphatic parts of Q may contain one or more of oxygen, sulfur or nitrogen,

k is at least 2 and R 1 , R 2 , R 3 and R 4 in the individual structural elements bound to Q can be different from one another.

17. The phosphite as claimed in claim 16 , wherein at least two adjacent radicals R 1 to R 4 together form a fused aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system which is unsubstituted or is substituted by at least one radical selected from among aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic heterocyclic hydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0–9, —OR 9 , —COR 9 , —CO 2 R 9 , —CO 2 M, —SR 9 , —SO 2 R 9 , —SOR 9 , —SO 3 R 9 , —SO 3 M, —SO 2 NR 9 R 10 , —NR 9 R 10 or —N═CR 9 R 10 .

18. The phosphite as claimed in claim 16 , wherein Q is a divalent hydrocarbon radical of the formula III

and R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently a monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroatomic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radical having from 1 to 50 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0–9, —OR 9 , —COR 9 , —CO 2 R 9 , —CO 2 M, —SR 9 , —SO 2 R 9 , —SO 3 R 9 , —SO 3 M, —SO 2 NR 9 R 10 , —NR 9 R 10 , or —N═CR 9 R 10 where R 9 and R 10 are independently a H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radical having from 1 to 25 carbon atoms and M is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a phosphonium ion,

W is the divalent radical CR 19 R 20 , where R 19 and R 20 are as defined for R 9 and R 10 ,

m=0–1 and

the positions a and b represent the linkage points.

19. The phosphite as claimed in claim 16 , wherein Q is a calix[n]arene radical of the formula IV

where R 21 , R 22 and R 23 are independently a substituted or unsubstituted aliphatic and aromatic hydrocarbon radical having from 1 to 25 carbon atoms, H, F, Cl, Br, I, —CF 3 , —CH 2 (CF 2 ) j CF 3 where j=0–9, —OR 24 , —COR 24 , —CO 2 R 24 , —CO 2 M, —SR 24 , —SO 2 R 24 , —SOR 24 , —SO 3 R 24 , —SO 3 M, —SO 2 NR 24 R 25 , —NR 24 R 25 , —N═CR 24 R 25 , where R 24 and R 25 are R 9 and R 10 are independently a H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radical having from 1 to 25 carbon atoms an alkaline and M is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a phosphonium ion,

or adjacent radicals R 21 to R 23 together form a fused substituted or unsubstituted aromatic, heteroaromatic, aliphatic, mixed aromatic aliphatic or mixed heteroaromatic-aliphatic ring system;

Y is the divalent radical CR 24 R 25 or CR 24 R 25 —O—CR 24 R 25 ,

n=3–6 and

the positions a represent the linkage points or are occupied by OR 24 , where R 24 and R 25 are as defined above.

20. A phosphite-metal complex comprising a metal of group 4, 5, 6, 7, 8, 9 or 10 of the Periodic Table of the Elements and one or more phosphites as claimed in claim 16 .

21. The phosphite-metal complex as claimed in claim 5 , wherein the metal is rhodium, platinum, palladium, cobalt or ruthenium.

22. The phosphite-metal complex as claimed in claim 20 , wherein the metal is rhodium, platinum, palladium, cobalt or ruthenium.

23. A process for the hydroformylation of olefins, which comprises

reacting a monoolefin or monoolefin mixture with a mixture of carbon monoxide and hydrogen in the presence of a phosphite-metal complex as claimed in claim 20 .

24. A process for preparing a phosphite as claimed in claim 16 , which comprises

(a) reacting an α-hydroxyarylcarboxylic acid of the formula (1)

with PCl 3 , PBr 3 or PI 3 in the presence of a base to form a halodioxaphosphorinone of the formula (2),

where Hal=Cl, Br or I, and

(b) reacting the halodioxaphosphorinone (2) in the presence of a base with

(i) a diol HO-Q-OH to give a phosphite of the formula (I), or

(ii) a dicarboxylic acid HOOC-Q-COOH to give a phosphite of the formula (II).

25. The process for preparing a phosphite as claimed in claim 24 , wherein two differently substituted halodioxaphosphorinones (2a) and (2b) are synthesized in (a) and are then reacted in succession with a diol in (b) (i) or reacted in succession with a dicarboxylic acid in (b) (ii) to give an unsymmetrical phosphite.

26. A process for preparing a phosphite-metal complex as claimed in claim 20 , which comprises reacting a metal of group 4, 5, 6, 7, 8, 9 or 10 of the Periodic Table in elemental form or in the form of a chemical compound with the phosphite of formula (I).

27. A catalyst comprising the phosphite as claimed in claim 16 .

28. A homogeneous catalyst comprising the phosphite as claimed in claim 20 .

29. A hydroformylation catalyst comprises the phosphite as claimed in claim 16 .

30. A hydroformylation catalyst comprising the phosphite metal complex as claimed in claim 20 .