PT-PHENOXAZINE-IOD COMPLEX AND PT-PHENOXAZINE-BROMI COMPLEX

Description

[0001] The present invention relates to a Pt-phenoxazine iodine complex and Pt-phenoxazine bromine complex, as well as their use for catalyzing a hydroformylation reaction.

[0002] In P. Meessen et al., Journal of Organometallic Chemistry, 551, (1998), 165-170, the use of DPEphos (3) for the hydroformylation of methyl 3-pentenoate is described.

[0003] The present invention was based on the object of providing a novel complex. This complex should provide an increased yield in the catalysis of hydroformylation reactions compared to the complex described in the prior art.

[0004] This object is achieved by a complex according to claim 1.

[0005] Complex include: a) Pt; b) a ligand according to formula (I): where R 1< , R 2< , R 3< , R 4< , R 5< , R 6< , R 7< , R 8< are selected from: -H, -(C 1 -C 12 )-alkyl, -(C 6 -C 20 )-aryl, -(C 5 -C 20 )-heteroaryl, and in the event that R 1< , R 2< , R 3< , R 4< , R 5< , R 6< , R 7< , R 8< are -(C 6 -C 20 )-aryl or -(C 5 -C 20 )-heteroaryl, the ring systems can have (C 1 -C 12 )-alkyl substituents; c) an iodine ligand or bromine ligand.

[0006] The term (C 1 -C 12 )-alkyl encompasses straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C 1 -C 8 )-alkyl groups, particularly preferably (C 1 -C 6 )-alkyl, most preferably (C 1 -C 4 )-alkyl.

[0007] Suitable (C 1 -C 12 )alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-Ethylpropyl, n-Hexyl, 2-Hexyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 2,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-Ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.

[0008] The term (C 6 -C 20 )-aryl encompasses mono- or polycyclic aromatic hydrocarbon radicals having 6 to 20 carbon atoms. These are preferably (C 6 -C 14 )-aryl, particularly preferably (C 6 -C 10 )-aryl.

[0009] Suitable (C 6 -C 20 )-aryl groups are, in particular, phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, and coronenyl. Preferred (C 6 -C 20 )-aryl groups are phenyl, naphthyl, and anthracenyl.

[0010] For the purposes of the present invention, the term -(C 5 -C 20 )-heteroaryl encompasses mono- or polycyclic aromatic hydrocarbon radicals in which one or more C atoms are replaced by heteroatoms, preferably N, O or S. Examples of these include pyridyl, pyrimidyl, imidazolyl, thiophenyl, furanyl, pyrrolyl, pyrazolyl, thiazolyl or isoxazolyl. The mono- or polycyclic aromatic hydrocarbon radicals have 5 to 20 ring atoms, particularly preferably 6 to 14 ring atoms. Aryl is in particular phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl. In particular, aryl is phenyl, naphthyl and antracenyl.

[0011] Substituted -(C 5 -C 20 )-heteroaryl groups may, depending on the ring size, have one or more substituents. These substituents are preferably independently selected from -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl.

[0012] In one embodiment, R 5< , R 6< , R 7< , R 8< are selected from: -(C 6 -C 20 )-aryl, -(C 5 -C 20 )-heteroaryl.

[0013] In one embodiment, R 5< and R 6< form a fused ring system and R 7< and R 8< form a fused ring system.

[0014] In one embodiment, R 5< , R 6< , R 7< , R 8< are -Ph.

[0015] In one embodiment, R 1< and R 4< are -H.

[0016] In one embodiment, R 2< and R 3< are -H.

[0017] In one embodiment, R 1< , R 2< , R 3< , R 4< are -H.

[0018] In one embodiment, the compound according to formula (I) has the structure (1) or (2):

[0019] In one embodiment, the compound according to formula (I) has the structure (1):

[0020] In one embodiment, the compound according to formula (I) has the structure (2):

[0021] In one embodiment, the complex has exactly one ligand according to formula (I).

[0022] In one embodiment, the complex has at least two iodine ligands.

[0023] In one embodiment, the complex has exactly two iodo ligands.

[0024] In one embodiment, the complex has at least two bromine ligands.

[0025] In one embodiment, the complex has exactly two bromine ligands.

[0026] In addition to the complex itself, its use for catalyzing a hydroformylation reaction is also claimed.

[0027] Use of a previously described complex to catalyze a hydroformylation reaction.

[0028] In the following, the invention will be explained in more detail using exemplary embodiments. Experiment description

[0029] A vial was filled with PtX 2 (X = halogen), ligand, and an oven-dried stir bar. The vial was then sealed with a septum (PTFE-coated styrene-butadiene rubber) and a phenolic resin cap. The vial was evacuated three times and refilled with argon. Toluene and 1-octene were added to the vial using a syringe. The vial was placed in an alloy plate, which was transferred to a Parr Instruments 4560 series autoclave under an argon atmosphere. After purging the autoclave three times with CO / H 2, the synthesis gas pressure was increased to 40 bar at room temperature. The reaction was carried out for 20 h / 18 h at 120 °C / 80 °C. After the reaction was complete, the autoclave was cooled to room temperature and carefully depressurized. The yield and selectivity were determined by GC analysis. Variation of the halogen

[0030] Reaction conditions:

[0031] 10.0 mmol 1-octene, 0.1 mol% PtX 2 , 2.2 equivalents ligand, solvent: toluene, p(CO / H 2 ): 40 bar, T: 120 °C, t: 20 h. Exploit:

[0032] ligand halogen Yield [%] I / Br / Cl 99 / 33 / 8 Reaction conditions:

[0033] 1.0 mmol 1-octene, 0.5 mol% PtX 2 , 2.0 equivalent ligand, solvent: toluene, p(CO / H 2 ): 40 bar, T: 80 °C, t: 18 h. Exploit:

[0034] ligand halogen Yield [%] I / Cl 98 / 0

[0035] As the test results show, the problem is solved by the complex according to the invention.

Claims

1. Complex comprising: a) Pt; b) a ligand corresponding to formula (I): where R1, R2, R3, R4, R5, R6, R7, R8 are selected from: -H, -(C1-C12)-alkyl, -(C6-C20)-aryl, -(C5-C20)-heteroaryl, and, if R1, R2, R3, R4, R5, R6, R7, R8 are - (C6-C20)-aryl or - (C5-C20)-heteroaryl, the ring systems may have (C1-C12)-alkyl substituents; c) an iodine ligand or bromine ligand.

2. Complex according to Claim 1, wherein R5, R6, R7, R8 are selected from: -(C6-C20)-aryl, - (C5-C20)-heteroaryl.

3. Complex according to either of Claims 1 and 2, wherein R5 and R6 form a fused ring system and R7 and R8 form a fused ring system.

4. Complex according to either of Claims 1 and 2, wherein R5, R6, R7, R8 are -Ph.

5. Complex according to any of Claims 1 to 4, wherein R1, R2, R3, R4 are -H.

6. Complex according to any of Claims 1 to 5, wherein the compound of formula (I) has the structure (1) or (2):

7. Complex according to Claim 6, wherein the compound of formula (I) has the structure (1):

8. Complex according to Claim 6, wherein the compound of formula (I) has the structure (2):

9. Complex according to any of Claims 1 to 8, wherein the complex has exactly one ligand corresponding to formula (I).

10. Complex according to any of Claims 1 to 9, wherein the complex has at least two iodine ligands.

11. Complex according to Claim 10, wherein the complex has exactly two iodine ligands.

12. Complex according to any of Claims 1 to 9, wherein the complex has at least two bromine ligands.

13. Complex according to Claim 12, wherein the complex has exactly two bromine ligands.

14. Use of a complex according to any of Claims 1 to 13 for catalysis of a hydroformylation reaction.