Open external unit-based benzopinacol-based bisphosphite ligand

Abstract

To provide novel compounds which deliver an increased yield in hydroformylation of olefins.SOLUTION: The invention provides compounds of formula (I) in the figure. (In the formula, R1 to R14 are each independently -H, -(C1-C12)-alkyl, or the like.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a bisphosphite ligand based on benzopinacol having an open external unit and its use in hydroformylation.

Background Art

[0002] Patent Document 1 describes a hydroformylation method using a bisphosphite ligand. In particular, the use of ligand (D-1) is described.

[0003]

Chemical Formula

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The technical problem to be solved by the present invention is to provide a novel compound that brings about an improvement in the yield in the hydroformylation of olefins as compared with compounds known from the prior art.

Means for Solving the Problems

[0006] This problem is solved by the compound according to claim 1. Compound of formula (I):

[0007]

Chemical Formula

[0008] (wherein R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 are each independently selected from -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C4-C 12 )-aryl, and radical R 1 , R 2 , R 3 , R 4 , R 5 and radical R 6 , R 7 , R 8 , R 9 , R 10 may form a fused system with each other.)

[0009] Thus, radical R 1 , R 2 , R 3 , R 4 , R 5 may be connected to each other via one or more rings, and as a result, a new aromatic system may be formed. The same applies correspondingly to radical R 6 , R 7 , R 8 , R 9 , R 10 . In contrast, for example, no fused system is formed between radical R 5 and R 6 . Radicals R 5 and R 6 are not on the same phenyl radical.)

[0010] The expressions "-(C1-C 12 )-alkyl" and "-O-(C1-C 12)-Alkyl" includes linear and branched alkyl groups having 1 to 12 carbon atoms. These are preferably -(C1-C8)-alkyl groups or -O-(C1-C8)-alkyl groups, particularly preferably -(C1-C4)-alkyl groups or -O-(C1-C4)-alkyl groups.

[0011] In one embodiment, R 11 and R 14 are -(C1-C 12 )-alkyl.

[0012] In one embodiment, R 11 and R 14 are - tert Bu.

[0013] In one embodiment, R 12 , R 13 are selected from -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl.

[0014] In one embodiment, R 12 and R 13 are -OCH3 or - tert Bu.

[0015] In one embodiment, R 12 and R 13 are -OCH3. In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are selected from -H, -(C1-C 12 )-alkyl, -(C4-C 12 )-aryl.

[0016] In one embodiment, R 1 , R 2 , R 3, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is selected from -H, - tert Bu, -(C4-C6)-aryl.

[0017] In one embodiment, the compound has one of structures (1) to (3).

[0018]

Chemical formula

[0019] In addition to the compound itself, the method of using the compound is also claimed. a) First, an ethylenically unsaturated compound is introduced, b) The above compound and a substance containing Rh are added, c) H2 and CO are introduced, d) Heating the reaction mixture of steps a) to c) to convert the ethylenically unsaturated compound into an aldehyde A method having.

[0020] In this method, steps a), b) and c) can be carried out in any order. However, usually, CO is added after the co-reactants are first introduced in steps a) and b). Furthermore, CO can also be introduced in two or more steps, for example, by first introducing a part of CO, then heating the mixture, and then introducing the remaining CO.

[0021] The ethylenically unsaturated compound used as a reactant in the method according to the present invention has one or more carbon-carbon double bonds. For the sake of simplicity, these compounds are hereinafter also referred to as olefins. The double bond may be terminal or internal.

[0022] In a variant of the method, the ethylenically unsaturated compound does not contain any additional functional groups in addition to the carbon-carbon double bond.

[0023] In a variant of the method, the ethylenically unsaturated compound is selected from ethene, propene, 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.

[0024] In a variant of the method, the Rh-containing substance is Rh(acac)(CO)2, [(acac)Rh(COD)] (Umicore, acac = acetylacetonate anion, COD = 1,5-cyclooctadiene), Rh4CO 12 selected from.

[0025] In a variant of the method, CO is introduced in step c) at a pressure in the range of 1 to 6 MPa (10 to 60 bar).

[0026] In a variant of the method, the reaction mixture is heated in step d) to a temperature in the range of 80 °C to 160 °C. The present invention will be described in more detail below using examples.

Examples

[0027] Synthesis of bis(4-(tert-butyl)phenyl)(3,3'-di-tert-butyl-5,5'-dimethoxy-2'-((4,4,5,5-tetraphenyl-1,3,2-dioxaphospholan-2-yl)oxy)-[1,1'-biphenyl]-2-yl)phosphite (1)

[0028]

Chemical formula

[0029] A solution of 2-((3,3'-di-tert-butyl-2'-((dichlorophosphanyl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy)-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane (0.7254 g, 0.8496 mmol) in 10 mL of toluene is added dropwise with a mixture of 4-tert-butylphenol (0.2808 g, 1.8691 mmol) and triethylamine (2.39 mL) in 8 mL of toluene at room temperature. The mixture is stirred overnight, filtered, and the filtrate is concentrated to dryness under reduced pressure. The resulting solid is dried at 60 °C / 0.1 mbar for 2 hours. Yield: 0.869 g (0.8036 mmol, 94%). Elemental analysis (C 68 H 74 O8P2, calculated = 1081.273 g / mol), C = 75.43 (75.53), H = 7.06 (6.90), P = 5.79 (5.73). ESI-TOF HRMS: m / z = 1103.4775; [M + +Na], calculated m / z = 1103.4756. 31 P NMR (CD2Cl2): δ 132.2 (d, J PP = 49 Hz); 145.3 (d, J PP = 49 Hz). 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.

[0030] Synthesis of 3,3'-di-tert-butyl-5,5'-dimethoxy-2'-((4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane-2-yl)oxy)-[1,1'-biphenyl]-2-yl-di(naphthalen-1-yl)phosphite (2)

[0031]

Chemical Structure

[0032] To 2-((3,3’-Di-tert-butyl-2’-((dichlorophosphanyl)oxy)-5,5’-dimethoxy-[1,1’-biphenyl]-2-yl)oxy)-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane (0.5622 g, 0.6585 mmol) in 8 mL of toluene, a mixture of 1-naphthol (0.2088 g, 1.4487 mmol) and triethylamine (1.85 mL) in 6 mL of toluene is added dropwise at room temperature. The mixture is stirred overnight, filtered, and the filtrate is concentrated to dryness under reduced pressure. The obtained solid is dried at 60 °C / 0.1 mbar for 2 hours, and then put into 6 mL of hot acetonitrile. The solid obtained after storing this solution at -29 °C is separated, washed with a small amount of cold acetonitrile, and dried. Yield: 0.480 g (0.449 mmol, 68%). Elemental analysis (C 68 H 62 Calculated for C ESI-TOF HRMS: m / z = 1091.3801; [M + +Na], calculated m / z = 1091.3817. 31 P NMR (CD2Cl2): δ 135.5 (d, J PP = 30 Hz); 146.2 (d, J PP = 30 Hz) ppm. 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.

[0033] Synthesis of [1,1'-Biphenyl]-2-ylbis(naphthalen-2-yl)phosphite (3) of 3,3'-Di-tert-butyl-5,5'-dimethoxy-2'-((4,4,5,5-tetraphenyl-1,3,2-dioxaphospholan-2-yl)oxy)-

[0034] [Chemical formula]

[0035] To 2-((3,3'-Di-tert-butyl-2'-((dichlorophosphanyl)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)oxy-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane (0.5971 g, 0.6993 mmol) in 8 mL of toluene, a mixture of 2-naphthol (0.2218 g, 1.5386 mmol) and triethylamine (1.96 mL) in 6 mL of toluene is added dropwise at room temperature. The mixture is stirred overnight, filtered, and the filtrate is concentrated to dryness under reduced pressure. The obtained solid is dried at 60 °C / 0.1 mbar for 2 hours, and then put into 6.5 mL of hot acetonitrile. The solid obtained after storing this solution at -29 °C is separated, washed with a small amount of cold acetonitrile, and dried. Yield: 0.470 g (0.439 mmol, 63%). Elemental analysis (C 68 H 62 Calculated value for C8H8O8P2 = 1069.178 g / mol): C = 76.18 (76.39), H = 5.88 (5.85), P = 5.74 (5.79). ESI-TOF HRMS: m / z = 1091.3811; [M + +Na], calculated value of m / z = 1091.3817. 31 31P NMR (CD2Cl2): δ 131.8 (d, J PP = 56 Hz); 145.0 (d, J PP = 56 Hz) ppm. 11H 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.

[0036] Catalyst experiment Hydroformylation was carried out in a 200 mL autoclave manufactured by Premex Reactor AG (Renggau, Switzerland) equipped with a pressure holding valve, a gas flow meter, a sparging stirrer, and a pressure pipette. To minimize the influence of moisture and oxygen, toluene used as a solvent was purified by a Pure Solv.MD-7 system and stored under argon. The olefin cis / trans-2-pentene (Aldrich) used as a substrate was refluxed and heated using sodium and distilled under argon. A toluene solution of the catalyst precursor and the ligand was mixed in the 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 with stirring (1,500 rpm) to a pressure of 12 bar and finally 20 bar. After reaching the reaction temperature, the olefin was injected into the autoclave by the positive pressure maintained in the pressure pipette. The reaction was carried out at a constant pressure (a closed-loop pressure control device from Bronkhorst (Netherlands)) for 4 hours. At the end of the reaction time, the autoclave was cooled to room temperature, depressurized with stirring, and purged with argon. Immediately after turning off the stirrer switch, 1 mL of each reaction mixture was taken out, diluted with 10 mL of pentane, and analyzed by gas chromatography. HP5890 series II plus, PONA, 50 m × 0.2 mm × 0.5 μm.

[0037] The compounds (1) to (3) according to the present invention were reacted using the comparative ligand (D-1).

[0038] [Chemical formula]

[0039] Reaction conditions Olefin: 2-pentene, Solvent: Toluene, Mass ratio of rhodium: 100 ppm, Pressure (p): 20 bar, Temperature (T): 120 °C, Time (t): 4 hours, Rh:Ligand ratio = 1:2. The results are summarized in the following table.

[0040] [Table 1] * Compound according to the present invention

[0041] As shown by the experimental results, the problem is solved by the compound according to the present invention.

Claims

1. Compound of formula (I): 【Chemical 1】 (wherein, 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 are each independently selected from -H, -(C １ -C １２ )-alkyl, -O-(C １ -C １２ )-alkyl, -(C ４ -C １２ )-aryl, Radical R １ , R ２ , R ３ , R ４ , R ５ and radical R ６ , R ７ , R ８ , R ９ , R １０ may form a condensed ring system with each other.)

2.

3. R １１ and R １４ is -(C １ -C １２ )-alkyl, the compound according to claim 1.

4. R １１ and R １４ is - ｔｅｒｔ Bu, the compound according to claim 1.

5. R １２ 、 R １３ is -(C １ -C １２ )-alkyl, -O-(C １ -C １２ )-alkyl selected from the group consisting of, the compound according to claim 1.

6. R １２ and R １３ is -OCH ３ or - ｔｅｒｔ is Bu, the compound according to claim 1.

7. R １ 、R ２ 、R ３ 、R ４ 、R ５ 、R ６ 、R ７ 、R ８ 、R ９ 、R １０ is -H, -(C １ -C １２ ), -alkyl, -(C ４ -C １２ ), -aryl, and is selected from the group consisting of the compounds according to claim 1.

8. R １ 、 R ２ 、 R ３ 、 R ４ 、 R ５ 、 R ６ 、 R ７ 、 R ８ 、 R ９ 、 R １０ is -H, - ｔｅｒｔ Bu, -(C ４ -C ６ )-aryl, and the compound according to claim 1 Structures (1) - (3): The compound according to claim 1, having one of 【Chemical 2】

9. a) First, an ethylenically unsaturated compound is introduced, b) The compound according to claim 1 and a substance containing Rh are added, d) The reaction mixture of the above steps a) - c) is heated to convert the olefin to an aldehyde c) H ２ and CO are introduced, A method having

10. The ethylenically unsaturated compound in step a) is selected from ethene, propene, 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 a mixture thereof. The method according to claim 9.

11.

12. The substance containing Rh is Rh(acac)(CO) ２ , [(acac)Rh(COD)] (Umicore, acac = acetylacetonate anion, COD = 1,5-cyclooctadiene), Rh ４ CO １２ The method according to claim 9, selected from In step c), CO is introduced at a pressure in the range of 1 - 6 MPa (10 - 60 bar). The method according to claim 9.

13. In step d), the reaction mixture is heated to a temperature in the range of 80°C - 160°C. The method according to claim 9. ​

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