Diphosphites with a dicyclohexylphosphino radical

Abstract

Diphosphite having a dicyclohexylphosphino radical and its use in hydroformylation.

Description

Technology Field

[0001] The present invention relates to a diphosphite having a dicyclohexylphosphino radical and its use in hydroformylation. Background Technology

[0002] Phosphorus-containing compounds play an important role as ligands in various reactions, for example, hydrogenation, hydrocyanation, and hydroformylation.

[0003] The reaction of reacting an olefin compound, carbon monoxide, and hydrogen in the presence of a catalyst to produce an aldehyde containing one or more carbon atoms is known as hydroformylation or the oxo process. In such reactions, transition metal compounds of Group VIII of the periodic table are often used as catalysts. Known ligands include, for example, P, each having a trivalent value. III These are compounds of the phosphine, phosphite, and phosphonite class containing [...]. A good overview of the current status of olefin hydroformylation is found in the literature (R. Franke, D. Selent, A. Boerner, "Applied Hydroformylation", Chem. Rev., 2012 (112), 11, 5675-5732 It can be found at , DOI:10.1021 / cr3001803). The problem to be solved

[0004] The technical objective of the present invention is to provide a compound that enables the achievement of an increased aldehyde yield in the hydroformylation of olefins. means of solving the problem

[0005] The above objective is achieved by the compound according to claim 1.

[0006] Compound of chemical formula (I):

[0007]

[0008] Here, R 1 , R 2 , R 3 , R4 -(C1-C 12 )-alkyl, -O-(C1-C 12 )-Selected from alkyl.

[0009] In one embodiment, R 1 -OCH3, - tert Selected from Bu.

[0010] In one embodiment, R 1 silver - tert It is Bu.

[0011] In one embodiment, R 2 is -OCH3, - tert Selected from Bu.

[0012] In one embodiment, R 2 Is - tert It is Bu.

[0013] In one embodiment, R 2 is -OCH3.

[0014] In one embodiment, R 3 -OCH3, - tert Selected from Bu.

[0015] In one embodiment, R 3 silver - tert It is Bu.

[0016] In one embodiment, R 4 is -OCH3, - tert Selected from Bu.

[0017] In one embodiment, R 4 Is - tert It is Bu.

[0018] In one embodiment, R 4 is -OCH3.

[0019] In one embodiment, the compound has a structure (1) or (2):

[0020]

[0021] In one embodiment, the compound has a structure (1):

[0022]

[0023] In one embodiment, the compound has a structure (2):

[0024]

[0025] In addition to the compound itself, a method of using the compound described above is also claimed.

[0026] Method including the following steps:

[0027] a) A step of initially charging olefins;

[0028] b) a step of adding the compound described above;

[0029] c) Step of adding Rh compound;

[0030] d) Step of supplying H2 and CO;

[0031] e) a step of heating the reaction mixture from a) to d) to convert the olefin into an aldehyde.

[0032] In one variation of the method, the Rh compound is Rh(acac)(CO)2, [(acac)Rh(COD)] (Umicore, acac = acetylacetonate anion; COD = 1,5-cyclooctadiene), Rh4CO 12 Selected from.

[0033] In one variation of the method, the Rh compound is Rh(acac)(COD).

[0034] In one variation of the method, in method step d), H2 and CO are supplied at a pressure in the range of 1 to 6 MPa (10 to 60 bar).

[0035] In one variation of the method, in method step d), H2 and CO are supplied at a pressure in the range of 1.5 to 4.5 MPa (15 to 45 bar).

[0036] In one variation of the method, in step e) of the method, the reaction mixture is heated to a temperature within the range of 80°C to 160°C.

[0037] In one variation of the method, in step e) of the method, the reaction mixture is heated to a temperature within the range of 100°C to 140°C. Specific details for implementing the invention

[0038] The present invention will be described in more detail below with reference to the embodiments.

[0039] Synthesis (1): 4,8-di-tert-butyl-6-((3,3'-di-tert-butyl-2'-((dicyclohexylphosphanyl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphene

[0040]

[0041] At -20°C, a 0.533 M solution of n-butyllithium (1.7 ml; 0.906 mmol) in hexane is added dropwise to a solution of 3,3'-di-tert-butyl-2'-((4,8-di-tert-butyl-2,10-dimethoxydibenzo[d,f][1,3,2]dioxaphosphen-6-yl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-ol (0.6749 g; 0.906 mmol) in THF (9 ml). The mixture is stirred at this temperature for 20 minutes, heated to 0°C, and a solution of chlorodicyclohexylphosphine (0.2214 g; 0.9513 mmol) in THF (4 ml) is added. The mixture is heated to room temperature, stirred overnight, and the solvent is removed under vacuum. The residue is dissolved in toluene (9 ml), the resulting mixture is filtered, the filtrate is concentrated under vacuum, and dried at 50°C / 0.1 mbar for 2 hours. The obtained residue is crystallized from hot acetonitrile (8 ml). Filtered and vacuum dried to obtain 0.630 g (0.670 mmol, 74%).

[0042] Elemental analysis (C 56 H 78 Calculated for O8P2 = 941.18 g / mol): C = 71.35 (71.47); H = 8.40 (8.35); P = 6.42 (6.58)%.

[0043] ESI-TOF HRMS: m / z= 941.5244; [M++H], calculated m / z= 941.5250.

[0044] Synthesis (2): 2,4,8,10-tetra-tert-butyl-6-((3,3',5,5'-tetra-tert-butyl-2'-((dicyclohexylphosphanyl)oxy)-[1,1'-biphenyl]-2-yl)oxy)dibenzo[d,f][1,3,2]dioxaphosphene

[0045]

[0046] At -20°C, a 0.533 M solution of n-butyllithium (1.14 ml; 0.6054 mmol) in hexane is added dropwise to a solution of 3,3',5,5'-tetra-tert-butyl-2'-((2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphen-6-yl)oxy)-[1,1'-biphenyl]-2-ol (0.4897 g; 0.5766 mmol) in THF (5 ml). The mixture is stirred at this temperature for 20 minutes, heated to 0°C, and a solution of chlorodicyclohexylphosphine (0.1436 g; 0.6170 mmol) in THF (3 ml) is added. The mixture is heated to room temperature, stirred overnight, and the solvent is removed under vacuum. The residue is dissolved in toluene (9 ml), the resulting mixture is filtered, the filtrate is concentrated under vacuum, and dried at 50°C / 0.1 mbar for 2 hours. The residue is dissolved in THF (3.5 ml). After the addition of acetonitrile (approx. 5 ml), the precipitated solid is filtered, washed with a small amount of acetonitrile, and dried. Yield: 0.272 g (0.260 mmol, 45%).

[0047] Elemental analysis (C 68 H 102Calculated for O4P2 = 1045.50 g / mol): C = 78.23 (78.12); H = 9.74 (9.83); P = 5.71 (5.93)%.

[0048] ESI-TOF HRMS: m / z=1045.7322; [M++H], calculated m / z=1045.7332.

[0049] Synthesis (3): ((3,3',5,5'-tetra-tert-butyl-[1,1'-biphenyl]-2,2'-diyl)bis(oxy))bis(dicyclohexylphosphane)

[0050]

[0051] At -20°C, a 0.533 M solution of n-butyllithium (6.56 ml; 3.494 mmol) in hexane is added dropwise to a solution of 3,3',5,5'-tetra-tert-butyl-[1,1'-biphenyl]-2,2'-diol (0.6832 g; 1.6638 mmol) in THF (12 ml). The mixture is stirred at this temperature for 20 minutes, heated to 0°C, and a solution of chlorodicyclohexylphosphine (0.8287 g; 3.5606 mmol) in THF (6 ml) is added. The mixture is heated to room temperature, stirred overnight, and the solvent is removed under vacuum. The residue is dissolved in toluene (20 ml), the resulting mixture is filtered, the filtrate is concentrated under vacuum, and dried at 50°C / 0.1 mbar for 2 hours. The residue is dissolved in THF (6 ml). After adding acetonitrile (4 ml), the precipitated solid is filtered and dried. Yield: 0.469 g (0.582 mmol, 35%).

[0052] ESI-TOF HRMS: m / z=803.6021; [M++H]; calculated m / z=803.6025.

[0053] Catalytic experiment

[0054] Hydroformylation was performed in a 200 ml autoclave from Premex Reactor AG, Lengau, Switzerland, equipped with a pressure-maintaining valve, gas flow meter, sparging stirrer, and pressure pipette. To minimize the effects of moisture and oxygen, toluene used as a solvent was purified in a Pure Solv. MD-7 system and stored under argon. The olefin cis / trans-2-pentene (Aldrich) used as a substrate was refluxed over sodium and distilled under argon. The toluene solution of the catalyst precursor and the toluene solution of the ligand were mixed in an autoclave under an argon atmosphere. [(acac)Rh(COD)] (Umicore, acac = acetylacetonate anion; COD = 1,5-cyclooctadiene) was used as the catalyst precursor. The autoclave was heated at 12 bar with stirring (1500 rpm) to a final pressure of 20 bar. After reaching the reaction temperature, the olefin was injected into the autoclave through a positive pressure set in a pressure pipette. The reaction was carried out for 4 hours at a constant pressure of 20 bar (closed-loop pressure regulator from Bronkhorst, Netherlands). When the reaction time was finished, the autoclave was cooled to room temperature, depressurized with stirring, and purged with argon. Immediately after turning off the stirrer, 1 ml of the reaction mixture was recovered, diluted with 10 ml of pentane, and analyzed by gas chromatography (HP 5890 Series II Plus, PONA, 50 m x 0.2 mm x 0.5 μm).

[0055] Experiments were performed using compounds (1), (2) and (3).

[0056] Here, compound (3) acts as a reference ligand.

[0057] Results of the catalytic experiment

[0058] [Rh]: 100 ppm, p: 20 bar, T: 120°C; t: 4 h; Rh:L = 1:2

[0059] Table

[0060] Hydroformylation of cis / trans-2-pentene

[0061]

[0062] * Compound according to the present invention

[0063] The experiments performed demonstrate that the stated purpose is achieved by the compound according to the present invention.

Claims

Claim 1 Compound of chemical formula (I): Here, R 1 , R 2 , R 3 , R 4 -(C1-C 12 )-alkyl, -O-(C1-C 12 )-Selected from alkyl. Claim 2 In paragraph 1, R 1 This -OCH3, - tert A compound selected from Bu. Claim 3 In paragraph 1 or 2, R 1 this - tert Bu compound. Claim 4 In paragraph 1 or 2, R 2 -OCH3, - tert A compound selected from Bu. Claim 5 In paragraph 1 or 2, R 2 go - tert Bu compound. Claim 6 In paragraph 1 or 2, R 2 A compound that is -OCH3. Claim 7 In paragraph 1 or 2, R 3 This -OCH3, - tert A compound selected from Bu. Claim 8 In paragraph 1 or 2, R 3 this - tert Bu compound. Claim 9 In paragraph 1 or 2, R 4 -OCH3, - tert A compound selected from Bu. Claim 10 In paragraph 1 or 2, R 4 go - tert Bu compound. Claim 11 In paragraph 1 or 2, R 4 A compound that is -OCH3. Claim 12 A compound having structure (1) or (2) in claim 1 or 2. Claim 13 A method for hydroformylating an olefin comprising the following steps: a) initially filling the olefin; b) adding a compound according to claim 1 or 2; c) adding a Rh compound; d) supplying H2 and CO; e) heating the reaction mixture from a) to d) to convert the olefin into an aldehyde. Claim 14 In paragraph 13, the Rh compound is Rh(acac)(CO)2, [(acac)Rh(COD)] (acac = acetylacetonate anion; COD = 1,5-cyclooctadiene), Rh4CO 12 A method selected from. Claim 15 In paragraph 13, the method in which the Rh compound is Rh(acac)(COD).

Images