Bisphosphite ligands with open lateral building blocks based on benzene pinacol

Abstract

The present invention relates to bisphosphite ligands with open lateral building blocks based on benzopinacol and their use in hydroformylation.

Description

[0001] This invention relates to bisphosphite ligands with open side units based on benzinolide, and their use in hydroformylation.

[0002] WO 2008 / 071508 A1 describes a hydroformylation method using bisphosphite ligands. In particular, the use of ligand (D-1) is described.

[0003] (D-1)

[0004] The technical problem solved by this invention is to provide novel compounds that provide increased yields in the hydroformylation of olefins compared to compounds known in the prior art.

[0005] This problem is solved by compounds as defined below.

[0006] Compounds of formula (I):

[0007] (I)

[0008] in

[0009] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 Each is independently selected from -H, -(C1-C 12 -alkyl, -O-(C1-C 12 -alkyl, -(C4-C 12 )-Aryl and group R 1 R 2 R 3 R 4 R 5 and group R 6 R 7 R 8 R 9 R 10 They can form fused systems.

[0010] Therefore, group R 1 R 2 R 3 R 4 R 5New aromatic systems can be formed by connecting one or more rings together. Correspondingly, the same applies to the group R. 6 R 7 R 8 R 9 R 10 Conversely, for example, in group R 5 and R 6 They cannot form a fused system. Group R 5 and R 6 They are not located on the same phenyl group.

[0011] Terminology - (C1-C) 12 -alkyl and -O-(C1-C 12 -alkyl includes straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably -(C1-C8)-alkyl or -O-(C1-C8)-alkyl, and particularly preferably -(C1-C4)-alkyl or -O-(C1-C4)-alkyl.

[0012] In one implementation, R 11 and R 14 -(C1-C 12 )-alkyl.

[0013] In one implementation, R 11 and R 14 for- tert Bu.

[0014] In one implementation, R 12 R 13 Selected from -(C1-C 12 -alkyl, -O-(C1-C 12 )-alkyl.

[0015] In one implementation, R 12 and R 13 -OCH3 or - tert Bu.

[0016] In one implementation, R 12 and R 13 It is -OCH3.

[0017] In one implementation, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10Selected from -H, -(C1-C 12 -alkyl, -(C4-C 12 )-Aryl.

[0018] In one implementation, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Selected from -H, - tert Bu、-(C4-C6)-aryl.

[0019] In one embodiment, the compound has one of structures (1) to (3):

[0020]

[0021] In addition to the compound itself, protection is also required for the methods of using the compound.

[0022] The method includes the following steps:

[0023] a) Pre-insertion of olefinic unsaturated compounds;

[0024] b) Add the compounds described above and substances containing Rh;

[0025] c) Supply H2 and CO,

[0026] d) Heat the reaction mixture of a)-c) to convert the olefinic unsaturated compound into an aldehyde.

[0027] In this method, steps a), b), and c) can be performed in any desired order. However, CO is typically added after the reaction participants have been pre-placed in steps a) and b). Furthermore, CO can also be supplied in multiple steps, such that, for example, a portion of CO is supplied first, the mixture is heated, and then another portion of CO is supplied.

[0028] The olefinic unsaturated compounds used as reactants in the method according to the invention contain one or more carbon-carbon double bonds. For simplicity, these compounds are also referred to olefins below. The double bonds can be terminal or internal.

[0029] In a variant of this method, the olefinic unsaturated compound does not contain any functional groups other than carbon-carbon double bonds.

[0030] In a variant of this method, the olefinic unsaturated compound is selected from: ethylene, propylene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.

[0031] In a variant of this method, the Rh-containing substance is selected from Rh(acac)(CO)2, [(acac)Rh(COD)] (Umicore, acac = acetylacetonate anion; COD = 1,5-cyclooctadiene), Rh4CO 12 .

[0032] In a variant of this method, CO is supplied at a pressure of 1-6 MPa (10-60 bar) in step c).

[0033] In a variant of this method, the reaction mixture is heated to a temperature of 80°C to 160°C in step d).

[0034] The present invention will now be described in more detail with reference to embodiments.

[0035] bis(4-(tert-butyl)phenyl)(3,3'-di-tert-butyl-5,5'-dimethoxy-2'-((4,4,5,5-tetraphenyl- Synthesis of 1,3,2-dioxophosphazenecyclopentan-2-yl)oxy)-[1,1'-biphenyl]-2-yl)phosphite (1):

[0036]

[0037] At room temperature, a mixture of 4-tert-butylphenol (0.2808 g; 1.8691 mmol) and triethylamine (2.39 ml) in 8 ml of toluene was added dropwise to a solution of 2-((3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-4,4,5,5-tetraphenyl-1,3,2-dioxophosphazenecyclopentane (0.7254 g; 0.8496 mmol) in 10 ml of toluene. The mixture was stirred overnight and filtered, and the filtrate was concentrated to dryness under reduced pressure. The resulting solid was dried at 60 °C / 0.1 mbar for 2 h. Yield: 0.869 g (0.8036 mmol, 94%).

[0038] Elemental analysis (C 68 H 74 The calculated value of O8P2 is 1081.273 g / mol: C = 75.43 (75.53); H = 7.06 (6.90); P = 5.79 (5.73).

[0039] ESI-TOF HRMS: m / z = 1103.4775; [M + +Na], Calculated m / z = 1103.4756.

[0040] 31 P NMR (CD2Cl2): δ 132.2 (d, J PP = 49 Hz); 145.3 (d, J PP = 49 Hz).

[0041] 1 H NMR (CD2Cl2): δ 1.15 (s, 9H); 1.33 (s, 9H); 1.35 (s, 9H); 1.53 (s,9H); 3.55 (s, 3H); 3.76 (s, 3H); 6.71-7.43 (m, 32H) ppm.

[0042] 3,3'-Di-tert-butyl-5,5'-dimethoxy-2'-((4,4,5,5-tetraphenyl-1,3,2-dioxophosphazenecyclopentane) Synthesis of alkyl-2-yl)oxy)-[1,1'-biphenyl]-2-yl di(naphthyl-1-yl)phosphite (2):

[0043]

[0044] At room temperature, a mixture of 1-naphthol (0.2088 g; 1.4487 mmol) and triethylamine (1.85 ml) in 6 ml of toluene was added dropwise to a solution of 2-((3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-4,4,5,5-tetraphenyl-1,3,2-dioxophosphazenecyclopentane (0.5622 g; 0.6585 mmol) in 8 ml of toluene. The mixture was stirred overnight and filtered, and the filtrate was concentrated to dryness under reduced pressure. The resulting solid was dried at 60 °C / 0.1 mbar for 2 h and then contained in 6 ml of hot acetonitrile. After storing the solution at -29 °C, the resulting solid was separated, washed with a small amount of cold acetonitrile, and dried. Yield: 0.480 g (0.449 mmol, 68%).

[0045] Elemental analysis (C 68 H 62 Calculated value of O8P2 = 1069.178 g / mol): C = 76.36 (76.39); H = 5.95 (5.85); P = 5.67 (5.79).

[0046] ESI-TOF HRMS: m / z = 1091.3801; [M + +Na], calculation m / z = 1091.3817.

[0047] 31 P NMR (CD2Cl2): δ 135.5 (d, J PP = 30 Hz); 146.2 (d, J PP = 30 Hz) ppm.

[0048] 1 H NMR (CD2Cl2): δ 1.14 (s, 9H); 1.63 (s, 9H); 2.94 (s, 3H); 3.87 (s, 3H); 6.33 (d, 4 J HH = 3.1 Hz; 1H); 6.74 (d, 4 J HH = 3.1 Hz; 1H); 6.89-7.84 (m,35H); 8.12 (m, 1H) ppm.

[0049] 3,3'-Di-tert-butyl-5,5'-dimethoxy-2'-((4,4,5,5-tetraphenyl-1,3,2-dioxophosphazenecyclopentane) Synthesis of alkyl-2-yl)oxy)-[1,1'-biphenyl]-2-yl di(naphthyl-2-yl)phosphite (3):

[0050]

[0051] At room temperature, a mixture of 2-naphthol (0.2218 g; 1.5386 mmol) and triethylamine (1.96 ml) in 6 ml of toluene was added dropwise to a solution of 2-((3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-4,4,5,5-tetraphenyl-1,3,2-dioxophosphazenecyclopentane (0.5971 g; 0.6993 mmol) in 8 ml of toluene. The mixture was stirred overnight and filtered, and the filtrate was concentrated to dryness under reduced pressure. The resulting solid was dried at 60 °C / 0.1 mbar for 2 h and then contained in 6.5 ml of hot acetonitrile. After storing the solution at -29 °C, the resulting solid was separated, washed with a small amount of cold acetonitrile, and dried. Yield: 0.470 g (0.439 mmol, 63%).

[0052] Elemental analysis (C 68 H62 The calculated value of O8P2 is 1069.178 g / mol: C = 76.18 (76.39); H = 5.88 (5.85); P = 5.74 (5.79).

[0053] ESI-TOF HRMS: m / z = 1091.3811; [M + +Na], calculation m / z = 1091.3817.

[0054] 31 P NMR (CD2Cl2): δ 131.8 (d, J PP = 56 Hz); 145.0 (d, J PP = 56 Hz) ppm.

[0055] 1 H NMR (CD2Cl2): δ 1.15 (s, 9H); 1.58 (s, 9H); 3.48 (s, 3H); 3.77 (s, 3H); 6.78 (m, 1H); 6.83 (m, 1H); 6.86 (m, 1H); 6.93-7.03 (m, 8H); 7.07-7.23(m, 11); 7.35-7.52 (m, 10H); 7.66 (m, 1H); 7.72-7.85 (m, 5H) ppm.

[0056] Catalysis experiment

[0057] Hydroformylation was carried out in a 200 ml autoclave equipped with a pressure holding valve, gas flow meter, jet stirrer, and pressure pipette from Premex Reactor AG, Lengau (Switzerland). To minimize the effects of moisture and oxygen, toluene was purified in a Pure Solv. MD-7 system and stored under argon atmosphere using toluene as a solvent. The olefin cis / trans-2-pentene (Aldrich), used as the substrate, was heated under reflux on sodium and distilled under argon atmosphere. Separate toluene solutions of the catalyst precursor and ligand were mixed in the autoclave under 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) until a final pressure of 20 bar was reached. After reaching the reaction temperature, the olefin was injected into the autoclave under positive pressure regulated by the pressure pipette. The reaction was carried out at constant pressure (using a closed-loop pressure regulator (Nachdruckregler) from Bronkhorst (Netherlands)) for 4 hours. At the end of the reaction time, the autoclave was cooled to room temperature, depressurized, and purged with argon while stirring. In each case, 1 ml of the reaction mixture was immediately removed after the stirrer was turned off, diluted with 10 ml of pentane, and analyzed by gas chromatography: HP5890 Series II plus, PONA, 50 m x 0.2 mm x 0.5 µm.

[0058] The reaction was carried out using compounds (1) to (3) according to the invention and using a contrasting ligand (D-1).

[0059] (D-1)

[0060] Reaction conditions:

[0061] Olefin: 2-pentene, Solvent: toluene, Rhodium mass ratio: 100 ppm, pH: 20 bar, T: 120°C, t: 4 h, Rh:ligand ratio = 1:2.

[0062] The results are compiled in the table below:

[0063]

[0064] Compounds according to the present invention

[0065] As the experimental results show, the compounds of the present invention solve this problem.

Claims

1. Compounds of formula (I): (I) in R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 Each is independently selected from -H, -(C1-C 12 -alkyl or -O-(C1-C 12 )-alkyl; or Compounds having the following structure (2) or (3): ， 。 2. The compound according to claim 1, Where R 11 and R 14 -(C1-C 12 )-alkyl.

3. The compound according to claim 1, Where R 11 and R 14 for- tert Bu.

4. The compound according to any one of claims 1-3, Where R 12 R 13 Selected from -(C1-C 12 -alkyl, -O-(C1-C 12 )-alkyl.

5. The compound according to any one of claims 1-3, Where R 12 and R 13 -OCH3 or - tert Bu.

6. The compound according to any one of claims 1-3, Where R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Selected from -H or -(C1-C) 12 )-alkyl.

7. The compound according to any one of claims 1-3, Where R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Selected from -H or - tert Bu.

8. The compound according to any one of claims 1-3, The compound has one of the structures (1) to (3): 。 9. A method that includes the following steps: a) Pre-insertion of olefinic unsaturated compounds; b) Add the compound according to any one of claims 1-8 and the substance containing Rh; c) Supply H2 and CO, d) Heat the reaction mixture from a) to c) to convert the olefin into an aldehyde.

10. The method according to claim 9, The olefinic unsaturated compound in step a) is selected from: ethylene, propylene, 1-butene, cis- and / or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and / or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, or mixtures thereof.

11. The method according to claim 9, Substances containing Rh are selected from: Rh(acac)(CO)2, [(acac)Rh(COD)] (Umicore, acac = acetylacetone anion; COD = 1,5-cyclooctadiene), Rh4CO 12 .

12. The method according to any one of claims 9-11, In step c), CO is supplied at a pressure ranging from 1 to 6 MPa (10 to 60 bar).

13. The method according to any one of claims 9-11, In step d), the reaction mixture is heated to a temperature of 80°C to 160°C.

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