Method for the production of aldehydes

1. A method for the production of aldehydes comprising reacting a member selected from the group consisting of mono-olefins, conjugated and nonconjugated polyolefins, cycloolefins and derivatives thereof, with carbon monoxide and hydrogen at a temperature of 20 to 150° C. and a pressure of 0.1 to 20 MPa in the presence of a nonaqueous ionic liquid of the formula (Q ⊕ ) a A a− and at least one rhodium compound and at least one sulfonated arylphosphine, wherein Q ⊕ is a singly charged ammonium cation, which may be substituted by organic groups, or the equivalent of a multiply charged ammonium cation, which may be substituted by organic groups, and A a− is an organic sulfonate or organic sulfate of the formula

R 1 SO 3 − ) a or R 2 OSO 3 − ) a   (1)

wherein R 1 and R 2 are independently selected from the group consisting of alkyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, an aryl of 6 to 14 carbon atoms, cycloalkyl of 3 to 7 carbon atoms and aralkyl of 7 to 20 carbon atoms; or R 1 has the formula

R 3 — O(CH 2n O m   (1a)

wherein R 3 is selected from the group consisting of alkyl of 1 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, aryl of 6 to 14 carbon atoms, cycloalkyl of 3 to 7 carbon atoms and aralkyl of 7 to 20 carbon atoms, n is an integer from 2–12 and m is an integer 1–100; and a is an integer and represents the number of the sulfones or sulfates bound to the organic radical and is at least equal to 1.

2. The method of claim 1 , wherein R 1 and R 2 are independently selected from the group consisting of alkyl of 1 to 12 carbon atoms, alkylaryl of 7 to 12 carbon atoms, aryl of 6–10 carbon atoms, cycloalkyl of 5 to 7 carbon atoms and aralkyl of 7 to 12 carbon atoms, R 3 is selected from the group consisting of alkyl of 1 to 12 carbon atoms, alkylaryl with of 7 to 12 carbon atoms, aryl of 6 to 10 carbon atoms, cycloalkyl of 5 to 7 carbon atoms and aralkyl of 7 to 12 carbon atoms, n is 2, 3 or 4, m is an integer between 1 to 50 and a is 1 or 2.

3. The method of claim 1 wherein the organic sulfonate is tosylate and the organic sulfate is octylsulfate.

4. The method of claim 1 wherein Q ⊕ are ammonium ions of the formulas

wherein R 4 , R 5 m R 6 and R 7 are individually selected from the group consisting of hydrogen aliphatic hydrocarbon of 1 to 20 carbon atoms, cycloaliphatic and aromatic hydrocarbon of 6 to 20 carbon atoms and alkoxy of 1 to 10 carbon atoms with the provision that at least one R 4 , R 5 , R 6 , R 7 is not hydrogen.

5. The method of claim 1 wherein Q ⊕ is selected from the group consisting of saturated or unsaturated cyclic and aromatic each with a tridentate nitrogen atom in a 4 to 10-membered heterocyclic ring having the formulas

where R 4 and R 5 are individually selected from the group consisting of hydrogen aliphatic hydrocarbon of 1 to 20 carbon atoms, cycloaliphatic and aromatic hydrocarbon of 6 to 20 carbon atoms and alkoxy of 1 to 10 carbon atoms.

6. The method of claim 1 wherein Q ⊕ is quaternary ammonium ions of the formulas

R 4 R 5 R 6 N ⊕ -G-N ⊕ R 7 R 8 R 9   (6)

R 4 R 5 N ⊕ ═CR 6 -G-R 6 C═N ⊕ R 4 R 5   (7)

wherein R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are individually selected from the group consisting of hydrogen, aliphatic hydrocarbon of 1 to 20 carbon atoms, cycloaliphatic and aromatic hydrocarbon of 6 to 30 carbon atoms, alkylaryl and aralkyl of 7 to 40 carbon atoms and alkoxy of 1 to 10 carbon atoms; G is (—CH 10− ) d , where R 10 is hydrogen or hydrocarbon of 1 to 5 carbon atoms and d is an integer from 1 to 8, or arylene of 6 to 30 carbon atoms or alkylenearyl of 7 to 40 carbon atoms.

7. The method of claim 1 wherein Q ⊕ is imidazolium ions of the formula

wherein R 13 ,R 14 , R 15 , R 16 and R 17 are individually selected from the group consisting of hydrogen, of 1 to 30 carbon atoms, aryl of 6 to 40 carbon atoms, alkylaryl of 7 to 40 carbon atoms and —SiR 3 18 wherein R 18 is alkyl of 1 to 30 carbon atoms or aryl of 6 to 40 carbon atoms.

8. The method of claim 7 , wherein Q ⊕ is selected from the group consisting of

ethyl-3-methyl-2,4,5-H-imidazolium, 1-propyl-3-methyl-2,4,5-H-imidazolium, 1-butyl-3-methyl-2,4,5-H-imidazolium, 1-butyl-3-ethyl-2,4,5-H-imidazolium, 1,3,4,5-tetramethyl-2-H-imidazolium, 2,4,5-trimethyl-1,3-H-imidazolium, 1,2,3,4,5-pentamethylimidazolium, 1,2,3,5-tetramethyl-4-H-imidazolium, 1,2,3,4-tetramethyl-5-H-imidazolium, 1,3,4,5,-tetraphenyl-2-H-imidazolium, 1,3-dimethyl-4,5-diphenyl-2-H-imidazolium, 1-ethyl-3-isopropyl-2,4,5-H-imidazolium, 1-butyl-3-octanyl-2,4,5-H-imidazolium, 1-propyl-3-octanyl-2,4,5-H-imidazolium, 1-ethyl-3-octanyl-2,4,5-H-imidazolium, 1-methyl-3-octanyl-2,4,5-H-imidazolium, 1,3-diisopropyl-4,5-dimethyl-2-H-imidazolium, 1,4,5-trimethyl-3-trimethylsilyl-2-H-imidazolium, 2-ethyl-4-methyl-1,3,5-H-imidazolium, 1,3-adamantyl-4,5-dimethyl-1-H-imidazolium, 1,2,4,5-tetramethyl-3-H-imidazolium, 1-methyl-2,3,4,5-H-imidazolium, 1,3-dimethyl-2,4,5-H-imidazolium, 2-methyl-4,5,-ethyl-1,3-H-imidazolium, 2,4,5-trimethyl-1,3-H-imidazolium, 1-ethyl-2,3,4,5-H-imidazolium, 1,3-diethyl-4,5-dimethyl-2-H-imidazolium, 1,3-diphenyl-4,5-dimethyl-2-H-imidazolium, 1,3-diphenyl-2,4,5-H-imidazolium, 1,3-dimethoxy-4,5-dimethyl-2-H-imidazolium, 1-trimethylsilyl-2,3,5-trimethyl-4-H-imidazolium.

9. The method of claim 1 wherein the sulfonated arylphosphine is a sulfonated triarylphosphine of the formula

wherein Ar 1 , Ar 2 and Ar 3 are individually aryl of 6 to 14 carbon atoms, Y 1 , Y 2 and Y 3 are individually selected from the group consisting of alkyl and alkoxy of 1 to 4 carbon atoms, chlorine, bromine, hydroxyl, cyanide, nitro and NR 18 R 19 , R 18 and R 19 are individually hydrogen, or alkyl of 1 to 4 carbon atoms, M is selected from the group consisting of lithium, sodium, potassium, magnesium, calcium and barium, m 1 , m 2 and m 3 are individually integers from 0 to 5, n 1 , n 2 and n 3 are individually integers from 0 to 3, and at least one of n 1 , n 2 and n 3 is equal to or greater than 1.

10. The method of claim 1 wherein the sulfonated arylphosphine is a sulfonated diarylphosphine of the formula

wherein m 1 and m 2 , are independently 0 or 1, the compound of formula (11) contains up to six —SO 3 M groups and M is selected from the group consisting of ammonium, a monovalent metal and the equivalent of a multivalent metal.

11. The method of claim 1 wherein the sulfonated arylphosphine is a sulfonated diarylphosphine of formula

wherein m 3 , m 4 , m 5 and m 6 are independently 0 or 1, the compound of formula (12) contains four to eight —SO 3 M groups, and M is selected from the group consisting of ammonium, a monovalent metal and the equivalent of a multivalent metal.

12. The method of claim 1 wherein the sulfonated arylphosphine is a sulfonated diarylphosphine of the formula

wherein R 20 and R 21 are individually alkyl of 1 to 6 carbon atoms or aralkyl of 7 to 14 carbon atoms, a and b are individually 1, 2 or 3, M is selected from the group consisting of ammonium, a monovalent metal and the equivalent of a multivalent metal, and Ar 4 and Ar 5 are individually aryl of 6 to 14 carbon atoms.

13. The method of claim 1 wherein for each mole of rhodium 2 to 1000 moles of phosphorus(III) are used.

14. The method of claim 1 wherein the rhodium concentration is 10 to 1000 ppm by weight, with respect to the ionic liquid.

15. The method of claim 1 wherein the reaction is carried out at 80 to 140° C.

16. The method of claim 1 wherein the reaction is carried out at pressures of 0.5 to 12 Mpa.

17. The method of claim 1 wherein olefins or olefin derivatives of 2 to 20 carbon atoms are used.

18. The method of claim 1 wherein the organic aldehyde-containing phase and the rhodium-containing ionic liquid are separated from one another by phase separation and the separated rhodium-containing ionic liquid is recycled completely or partially to the hydroformylation reaction vessel.

19. The method of claim 18 , wherein, during the phase separations a nonpolar organic solvent is added.