Process for hydroformylation of olefins using Pt and iodine or bromine

Abstract

Process for hydroformylation of olefins using Pt and iodine or bromine.

Claims

1. Process comprising the process steps of: a) initially charging an olefin; b) adding a compound of formula (I): ##STR00005## where R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are selected from: —H, —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl, and R.sup.9, R.sup.10 are selected from: —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl, and, if R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 are —(C.sub.6-C.sub.20)-aryl, the aryl ring may have substituents selected from: —(C.sub.1-C.sub.12)-alkyl, —O—(C.sub.1-C.sub.12)-alkyl; c) adding a Pt compound capable of forming a complex; d) adding an iodine compound or bromine compound; e) feeding in CO and H.sub.2; f) heating the reaction mixture from steps a) to e), to convert the olefin to an aldehyde.

2. Process according to claim 1, where R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are selected from: —(C.sub.1-C.sub.12)-alkyl, —(C.sub.6-C.sub.20)-aryl.

3. Process according to claim 1, where R.sup.5, R.sup.6, R.sup.7, R.sup.8 are —(C.sub.6-C.sub.20)-aryl.

4. Process according to claim 1, where R.sup.2 and R.sup.3 are —(C.sub.1-C.sub.12)-alkyl.

5. Process according to claim 1, where R.sup.1 and R.sup.4 are each —H.

6. Process according to claim 1, where R.sup.9 and R.sup.10 are —(C.sub.1-C.sub.12)-alkyl.

7. Process according to claim 1, wherein the compound (I) has the structure (1): ##STR00006##

8. Process according to claim 1, wherein the Pt compound is selected from: Pt(II)I.sub.2, Pt(II)Br.sub.2, Pt(IV)I.sub.4, Pt(IV)Br.sub.4, diphenyl(1,5-COD)Pt(II), Pt(II)(acac).sub.2, Pt(O)(PPh.sub.3).sub.4, Pt(O)(DVTS) solution (CAS:68478-92-2), Pt(0)(ethylene)(PPh.sub.3).sub.2, Pt(II)Br.sub.2(COD), tris(benzylideneacetone)Pt(0), Pt(II)(OAC).sub.2 solution, Pt(0)(t-Bu).sub.2, Pt(II)(COD)Me.sub.2, Pt(II)(COD)I.sub.2, Pt(IV)IMe.sub.3, Pt(II)(hexafluoroacetylacetonate).sub.2.

9. Process according to claim 1, wherein an iodine compound is added in process step d).

10. Process according to claim 9, wherein the iodine compound is added in an amount in the range of 0.1 to 10, measured in equivalents based on Pt.

11. Process according to claim 1, wherein a bromine compound is added in process step d).

12. Process according to claim 11, wherein the bromine compound is added in an amount in the range of 0.1 to 10, measured in equivalents based on Pt.

13. Process according to claim 1, comprising the additional process step e′): e′) adding a solvent.

14. Process according to claim 1, wherein CO and H.sub.2 is fed in at a pressure in a range from 1 MPa (10 bar) to 6 MPa (60 bar).

15. Process according to claim 1, wherein the reaction mixture is heated to a temperature in the range from 25° C. to 150° C.

Description

EXPERIMENTAL DESCRIPTION

[0047] A vial was charged with PtX.sub.2 (X=halogen), ligand, and an oven-dried stirrer bar. The vial is then sealed with a septum (PTFE-coated styrene-butadiene rubber) and phenolic resin cap. The vial is evacuated and refilled with argon three times. Toluene and 1-octene were added to the vial using a syringe. The vial was placed in an alloy plate, which was transferred to an autoclave of the 4560 series from Parr Instruments under an argon atmosphere. After purging the autoclave three times with CO/H.sub.2, the synthesis gas pressure was increased to 40 bar at room temperature. The reaction was conducted at 80° C. for 18 h. On termination of the reaction, the autoclave was cooled to room temperature and cautiously decompressed. Yield and selectivity were determined by GC analysis.

[0048] Variation of the Halogen

##STR00003##

[0049] Reaction Conditions:

[0050] 1.0 mmol of 1-octene, 0.5 mol % of PtX.sub.2, 2.0 equivalents of ligand (1), solvent: toluene, p(CO/H.sub.2): 40 bar, T: 80° C., t: 18 h.

[0051] Yields:

TABLE-US-00001 Ligand Halogen Yield [%] [00004] I/Br/Cl 96/24/0

[0052] As the experimental results show, the object is achieved by the process according to the invention.