DIPHOSPHITES WITH TRANS-CONSTANT SUBSTITUTES

Description

[0001] The invention relates to diphosphites with trans-positioned substituents and their use in hydroformylation.

[0002] Phosphorus-containing compounds play a crucial role as ligands in a variety of reactions, e.g. in hydrogenation, hydrocyanation and also in hydroformylation.

[0003] The reaction between olefin compounds, carbon monoxide, and hydrogen in the presence of a catalyst to form aldehydes richer by one carbon atom is known as hydroformylation or oxation. Compounds of transition metals from Group VIII of the Periodic Table of the Elements are often used as catalysts in these reactions. Known ligands include compounds from the classes of phosphines, phosphites, and phosphonites, each containing trivalent phosphorus P III< . A good overview of the current state of the art in the hydroformylation of olefins can be found in R. Franke, D. Selent, A. Börner, "Applied Hydroformylation," Chem. Rev., 2012 (112), 11, 5675-5732, DOI:10.1021 / cr3001803. WO 2008 / 071508 A1 discloses compounds used in catalysis.

[0004] The technical object of the invention is to provide a compound with which an increased yield of aldehyde can be achieved in the hydroformylation of olefins.

[0005] The object is achieved by a connection according to claim 1.

[0006] Compound according to formula (I): where R 1< , R 2< , R 3< , R 4< are selected from: -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl and R 5< is selected from: -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, -Ph.

[0007] In one embodiment, R 1< is selected from: -CH 3 , -OCH 3 , - tert< Bu.

[0008] In one embodiment, R 1< is - tert< Bu.

[0009] In one embodiment, R 2< is selected from: -CH 3 , -OCH 3 , - tert< Bu.

[0010] In one embodiment, R 2< is - tert< Bu.

[0011] In one embodiment, R 3< is selected from: -CH 3 , -OCH 3 , - tert< Bu.

[0012] In one embodiment, R 3< is - tert< Bu.

[0013] In one embodiment, R 4< is selected from: -CH 3 , -OCH 3 , - tert< Bu.

[0014] In one embodiment, R 4< is - tert< Bu.

[0015] In one embodiment, R 5< is selected from: -CH 3 , -OCH 3 , - tert< Bu, -Ph.

[0016] In one embodiment, R 5< is -Ph.

[0017] In one embodiment, the compound has the structure (1):

[0018] In addition to the compound itself, a method is also claimed in which the previously described compounds are used.

[0019] Procedure comprising the following steps: a) Initially charging an olefin; b) adding a previously described compound; c) adding a Rh compound; d) supplying H 2 and CO; e) heating the reaction mixture from a) to d), whereby the olefin is converted to an aldehyde.

[0020] In a variant of the process, the Rh compound is selected from: Rh(acac)(CO) 2 , [(acac)Rh(COD)] (Umicore, acac = acetylacetonate anion; COD = 1,5-cyclooctadiene), Rh 4 CO 12 .

[0021] In a variant of the process, the Rh compound is Rh(acac)(COD).

[0022] In a variant of the process, H 2 and CO are added in process step d) at a pressure in the range of 1 to 6 MPa (10 to 60 bar).

[0023] In a variant of the process, H 2 and CO are added in process step d) at a pressure in the range of 1.5 to 4.5 MPa (15 to 45 bar).

[0024] In a variant of the process, the reaction mixture is heated in process step e) to a temperature in the range of 80 °C to 160 °C.

[0025] In a variant of the process, the reaction mixture is heated in process step e) to a temperature in the range from 100 °C to 140 °C.

[0026] In the following, the invention will be explained in more detail using an exemplary embodiment. Synthese ( 1 ): 2,4,8,10-Tetra-tert.-butyl-6-((3,3',5,5'-tetra-tert.-butyl-2'-(((4R,5R)-4,5-diphenyl-1,3,2-dioxaphospholan-2-yl)oxy)-[1,1'-biphenyl]-2-yl)oxy)dibenzo[d,f][1,3,2]dioxaphosphepin

[0027]

[0028] To a solution of 3,3',5,5'-tetra- tert .-butyl-2'-((2,4,8,10-tetra- tert A solution of n-BuLi (0.533 M solution in hexane, 1.10 ml, 0.587 mmol) was added dropwise to .-butyldibenzo [d,f][1,3,2]dioxaphosphepin-6-yl)oxy)-[1,1'-biphenyl]-2-ol (0.474 g, 0.558 mmol) in THF (3 ml) at -20 °C. After 20 min, the reaction solution was allowed to warm to 0 °C and then added dropwise to a solution of (4 R ,5 R)-2-chloro-4,5-diphenyl-1,3,2-dioxaphospholane (0.163 g, 0.587 mmol) in THF (3 ml). After stirring overnight at room temperature, the solvent was removed under vacuum, and the white residue was treated with toluene (7 ml), and the undissolved components were filtered off. The filtrate was again concentrated under vacuum, and the crude product was dried at 60 °C. For purification, the crude product was dissolved in acetonitrile at boiling temperature. After cooling, the precipitate was filtered off, and the product was isolated as a white solid (0.39 g, 0.357 mmol, 64% yield).

[0029] Elemental analysis (calculated for C 70 H 92 O 6 P 2 = 1091.448 g / mol): C = 77.22 % (77.03 %); H = 8.57 % (8.50 %); P = 5.50 % (5.68 %). ESI-TOF HRMS: m / z = 1090.6369 [M +< +H], calculated m / z = 1091.6448 (found 1091.6449) [M +< +Na], calculated m / z = 1113.6262 (found 1113.6276) Synthese ( 2 ): 2,4,8,10-Tetra-tert.-butyl-6-((3,3',5,5'-tetra-tert.-butyl-2'-(((4S.5R)-4,5-diphenyl-1,3,2-dioxaphospholan-2-yl)oxy)-[1,1'-biphenyl]-2-yl)oxy)dibenzo[d,f][1,3,2]dioxaphosphepin

[0030]

[0031] To a solution of 3,3',5,5'-tetra- tert .-butyl-2'-((2,4,8,10-tetra- tert .-butyldibenzo [ d,f A solution of n-BuLi (0.532 M solution in hexane, 1.00 ml, 0.532 mmol) was added dropwise to [1,3,2]dioxaphosphepin-6-yl)oxy)-[1,1'-biphenyl]-2-ol (0.430 g, 0.506 mmol) in THF (3 ml) at -20 °C. After 20 min, the reaction solution was allowed to warm to 0 °C and then added dropwise to a solution of (4 R ,5 S)-2-chloro-4,5-diphenyl-1,3,2-dioxaphospholane (0.148 g, 0.532 mmol) in THF (2 ml). After stirring overnight at room temperature, the solvent was removed under vacuum, and the white residue was treated with toluene (6 ml), and the undissolved components were filtered off. The filtrate was again concentrated under vacuum, and the crude product was dried at 60 °C. For purification, the crude product was dissolved in acetonitrile (5 ml) at boiling temperature. After cooling, the precipitate was filtered off, and the product was isolated as a white solid (0.22 g, 0.202 mmol, 40% yield).

[0032] Elemental analysis (calculated for C 70 H 92 O 6 P 2 = 1091.448 g / mol): C = 77.22 % (77.03 %); H = 8.45 % (8.50 %); P = 5.68 % (5.68 %). ESI-TOF HRMS: m / z = 1090.6369 [M +< +H], calculated m / z = 1091.6448 (found 1091.6442) [M +< +Na], calculated m / z = 1113.6262 (found 1113.6256) Catalysis experiments

[0033] The hydroformylation was carried out in a 200 ml autoclave from Premex Reactor AG, Lengau, Switzerland, equipped with pressure control, gas flow measurement, a gassing stirrer, and a pressure pipette. To minimize the influence of moisture and oxygen, the toluene used as solvent was purified in a Pure Solv. MD-7 system and stored under argon. The olefin cis / trans-2-pentene (Aldrich) used as substrate was heated to reflux over sodium and distilled under argon. Solutions of the catalyst precursor and the ligand, each in toluene, were mixed in the autoclave under an argon atmosphere. Rh(acac)(COD) (Umicore, acac = acetylacetonate anion; COD = 1,5-cyclooctadiene) was used as the catalyst precursor. The autoclave was heated to 12 bar to a final pressure of 20 bar while stirring (1500 rpm). After reaching the reaction temperature, the olefin was forced into the autoclave at an overpressure set in the pressure pipette.The reaction was conducted at constant pressure (20 bar) (pressure regulator from Bronkhorst, NL) for 4 hours. After the reaction time, the autoclave was cooled to room temperature, depressurized while stirring, and purged with argon. 1 ml of the reaction mixture was removed immediately after the stirrer was switched off, diluted with 10 ml of pentane, and analyzed by gas chromatography: HP 5890 Series II plus, PONA, 50 mL x 0.2 mm x 0.5 µm.

[0034] The experiment was carried out with the compounds ( 1 ) and ( 2 ) carried out.

[0035] The connection ( 2 ) serves as a reference ligand. Results of the catalysis experiments

[0036] [Rh]: 100 ppm, p: 20 bar, T: 120 °C; t: 4 h; Rh:L = 1:2 Table: Hydroformylation of cis / trans-2-pentene ligand Aldehyde yield [%] ( 1 )* 100 ( 2 ) 97 * compound according to the invention

[0037] The tests carried out prove that the task is solved by a compound according to the invention.

Claims

1. Compound of formula (I): wherein R1, R2, R3, R4 are selected from: -(C1-C12)-alkyl, -O-(C1-C12)-alkyl, and R5 is selected from: -(C1-C12)-alkyl, -O-(C1-C12)-alkyl, - Ph.

2. Compound according to Claim 1, wherein R1 is selected from: -CH3, -OCH3, -tertBu.

3. Compound according to either of Claims 1 and 2, wherein R1 is -tertBu.

4. Compound according to any of Claims 1 to 3, wherein R2 is selected from: -CH3, -OCH3, -tertBu.

5. Compound according to any of Claims 1 to 4, wherein R2 is -tertBu.

6. Compound according to any of Claims 1 to 5, wherein R3 is selected from: -CH3, -OCH3, -tertBu.

7. Compound according to any of Claims 1 to 6, wherein R3 is -tertBu.

8. Compound according to any of Claims 1 to 7, wherein R4 is selected from: -CH3, -OCH3, -tertBu.

9. Compound according to any of Claims 1 to 8, wherein R4 is -tertBu.

10. Compound according to any of Claims 1 to 9, wherein R5 is selected from: -CH3, -OCH3, -tertBu, -Ph.

11. Compound according to any of Claims 1 to 10, wherein R5 is -Ph.

12. Compound according to any of Claims 1 to 11, wherein the compound has the structure (1):

13. Process comprising the process steps of: a) initially charging an olefin; b) adding a compound according to any of Claims 1 to 12; c) adding a Rh compound; d) feeding in H2 and CO; e) heating the reaction mixture from a) to d), to convert the olefin to an aldehyde.

14. Method according to Claim 13, wherein the Rh compound is selected from: Rh(acac) (CO)2, [(acac)Rh(COD)] (Umicore, acac = acetylacetonate anion; COD = 1,5-cyclooctadiene), Rh4CO12.

15. Process according to either of Claims 13 and 14, wherein the Rh compound is Rh(acac) (COD).