Ru-catalyzed cascade hydroformylation / hydrogenation / esterification using phosphine ligands

Abstract

Ru-catalyzed cascade hydroformylation / hydrogenation / esterification using phosphine ligands.

Description

Technical Field

[0001] This invention relates to Ru-catalyzed chain (Domino) hydroformylation / hydrogenation / esterification using phosphine ligands. Background Technology

[0002] EP 0 329 252 B1 describes a method for preparing carboxylic acids or esters. The method herein is catalyzed by using a combination of a ruthenium compound and an acidic compound. The acidic compound herein contains one of the following elements: phosphorus, antimony, arsenic, molybdenum, or tungsten.

[0003] A method for performing hydroformylation and subsequent reduction is described in I. Fleischer, KM Dyballa, R. Jennerjahn, R. Jackstell, R. Franke, A. Spannenberg, M. Beller, “From Olefins to Alcohols: Efficient and Regioselective Ruthenium-Catalyzed Domino Hydroformylation / Reduction Sequence”, Angew. Chem. Int. Ed. 2013, 52, 2949–2953. The olefin used is converted to an aldehyde and ultimately reduced to an alcohol. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method that directly leads to the formation of an ester from an olefin without separating intermediates. Here, the original olefin is to form the alcohol moiety of the ester, i.e., via oxygen bonding to a carbon atom of a C=O group. Furthermore, the alcohol moiety of the ester must have one more carbon atom than the olefin used.

[0005] This problem is solved by the method according to the present invention.

[0006] The method includes the following steps:

[0007] a) Initial feeding of an olefinic unsaturated compound;

[0008] b) Additive (I) ligands and Ru-containing compounds:

[0009] (I)

[0010] in

[0011] R 1 R2 R 3 Selected from: -(C1-C 12 -alkyl, -(C6-C 12 )-cycloalkyl, -(C6-C 20 )-Aryl,

[0012] The -(C6-C) 12 )-cycloalkyl groups and the -(C6-C 20 The aryl group may have substituents selected from: -(C1-C1) 12 -alkyl, -O-(C1-C 12 -alkyl, -SO3Na;

[0013] c) Adding an acid (II) having formula (IIa) or (IIb):

[0014] (IIa)

[0015] Where R 4 Yes - (C1-C 18 )-alkyl;

[0016] (IIb)

[0017] Where R 5 Yes - (C1-C 18 )-alkyl;

[0018] d1) Input CO;

[0019] e) Heating the reaction mixture obtained from a) to d) directly converts the olefinic unsaturated compound into an ester or diester of acid (II) without separating the intermediate.

[0020] Here, step d) includes method step d1) and optional additional method steps d2), d3) and d4).

[0021] Here, steps a), b), c), and d) can be performed in any desired order. However, typically, the addition of CO is performed after the co-reactants have been initially added to steps a) through c). Steps d) and e) can be performed simultaneously or sequentially. Alternatively, CO can be introduced in two or more steps, such that, for example, a portion of the CO is first introduced, the mixture is then heated, and then another portion of CO is introduced.

[0022] The expression "(C1-C 12 "-alkyl" includes straight-chain and branched alkyl groups having 1 to 12 carbon atoms. Suitable (C1-C2) 12)-alkyl groups, especially methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 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.

[0023] Statement (C6-C) 12 )-Cycloalkyl groups include monocyclic, bicyclic, or tricyclic hydrocarbon groups.

[0024] Statement (C6-C) 20 )-aryl groups comprise monocyclic or polycyclic aromatic hydrocarbon groups having 6 to 20 carbon atoms. These are preferably (C6-C 14 )-aryl, more preferably (C6-C 10 )-Aryl.

[0025] Suitable (C6-C) 20 )-Aromatic groups, especially phenyl, naphthyl, indene, fluorenyl, anthracene, phenanthrene, and tetraphenyl, Benzyl, pyrene, and phenyl groups. Preferred (C6-C) 20 The aryl group is phenyl, naphthyl, or anthracene.

[0026] 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. The olefinic unsaturated compounds preferably have one carbon-carbon double bond.

[0027] Preferably, the compounds are olefinic unsaturated compounds having 2 to 30 carbon atoms, more preferably 2 to 22 carbon atoms, and even more preferably 2 to 12 carbon atoms.

[0028] In one embodiment, 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.

[0029] In one implementation, R 1 Selected from: -(C1-C 12 -alkyl, -(C6-C 20 -Aryl, -(C5-C 20 )-Hybrid aromatics.

[0030] In one implementation, R 1 R 2 R 3 Selected from: -(C6-C 12 )-cycloalkyl, -(C6-C 20 )-Aryl.

[0031] In one implementation, R 1 R 2 R 3 Yes - (C6-C 12 )-cycloalkyl.

[0032] In one implementation, R 1 R 2 R 3 It is -Cy.

[0033] In one implementation, R 1 R 2 R 3 Yes - (C6-C 20 )-Aryl.

[0034] In one implementation, R 1 R 2 R 3 Yes - Ph.

[0035] In one implementation, R 1 R 2 R 3 They are the same group.

[0036] In one embodiment, the Ru-containing compound is selected from Ru3(CO). 12 , RuCl3·H2O, Ru(Cl)2(DMSO)4, Ru(acac)3.

[0037] In one embodiment, the Ru-containing compound is Ru3(CO). 12 .

[0038] In one implementation, R 4 Yes - (C1-C 12 )-alkyl.

[0039] In one implementation, R 4It is -(C1-C8)-alkyl.

[0040] In one implementation, R 5 Yes - (C1-C 12 )-alkyl.

[0041] In one implementation, R 5 It is -(C1-C8)-alkyl.

[0042] In one implementation, the method includes an additional method step d2):

[0043] d2) Input H2.

[0044] In one embodiment, the pressure of the H2 is in the range of 1 MPa (10 bar) to 6 MPa (60 bar).

[0045] In one implementation, the method includes an additional method step d3):

[0046] d3) Add H2O.

[0047] In one embodiment, the amount of H2O added is such that the molar ratio of H2O to the olefinic unsaturated compound is in the range of 1:1 to 10:1.

[0048] In one implementation, the method includes an additional method step d4):

[0049] d4) Add p-toluenesulfonic acid.

[0050] In one embodiment, the amount of acid (II) added in step c) is such that the molar ratio of the acid to the olefinic unsaturated compound is in the range of 2:1 to 10:1.

[0051] In one embodiment, the acid (II) has the formula (IIa).

[0052] In one embodiment, the acid (II) has the formula (IIb).

[0053] In one implementation, the ligand in method step b) is selected from:

[0054] (1)

[0055] (2)

[0056] (3).

[0057] In one embodiment, in step e), the reaction mixture is heated to a temperature between 50°C and 180°C, preferably between 80°C and 160°C, more preferably between 100°C and 150°C, to convert the olefinic unsaturated compound into an ester. Detailed Implementation

[0058] The present invention will be described in detail below through examples.

[0059] General Operating Procedures

[0060] All operations involving substances sensitive to air and moisture were performed in an argon atmosphere using dried glassware and the Schlenk technique. Chemicals were obtained from commercial manufacturers and, if of at least 98% purity, were used as supplied. Oxygen-free and dry solvents were prepared in advance by distillation under argon. Syngas (CO: 99.997%, H2 / CO: 1:1 + / - 1%) was obtained from Linde.

[0061] pass 1 H-NMR and 13 The product was analyzed by C-NMR spectroscopy. The NMR spectra were recorded on a Bruker AV 400 (400 MHz), Bruker AV 300 (300 MHz), or Fourier 300 (MHz) instrument. The chemical shift δ (ppm) relative to the solvent used was reported: the reference for CDCl3 was 7.26 ppm. 1 H-NMR) and 77.16 ( 13 C-NMR). Recorded using a broadband decoupling method. 13 C-NMR spectroscopy.

[0062] GC analysis was performed using a 30 m HP-5 column on an Agilent Technologies 7890A GC system. Argon was used as the carrier gas. Products were analyzed by GC or GC-MS, or separated by column chromatography (silica, ethyl acetate (EtOAc) / heptane). GC yields were calculated using an internal calibration method. Hexadecane was used as an internal standard.

[0063] Implementation of catalytic experiments

[0064]

[0065] Catalytic experiments were conducted in 4 mL glass vials with screw caps and PTFE spacers. The vials were equipped with oven-dried magnetic stir bar and connected to a gas atmosphere using a needle. The reaction batch size was 2 mL. The vials were placed in a 300 mL Parr 4560 autoclave and stirred using a magnetic stirrer. In the first step, Ru3(CO) was... 12 Acetic acid (5 mol%), ligand (5.5 mol%), and PTSA·H₂O (20.6 mol%) were weighed into the vial. The vial was sealed with a screw cap equipped with a septum and connected to an argon atmosphere via a sleeve. The vial was purged and purged three times with argon. Acetic acid (1.17 mL), H₂O (0.35 mL), and 1-octene (3 mmol) were injected using a Hamilton syringe. The vial was transferred to the autoclave under an argon atmosphere. The autoclave was tightly sealed and first purged three times with 10 bar CO at room temperature. Subsequently, 40 bar CO was applied, and the autoclave was placed on an aluminum block on a magnetic stirrer and heated to 140 °C and held for 20 hours. After 20 hours, the autoclave was cooled to room temperature and carefully depressurized. 100 µL of hexadecane was introduced into the reaction solution as an internal standard. The yield was determined by GC analysis.

[0066] The reactions were carried out under similar conditions for ligands (1) through (3) and for the contrast ligand (4). Since the contrast ligand (4) is a bidentate ligand, only 2.75 mol% was used instead of 5.5 mol%. In order to obtain a constant molar ratio of PTSA·H2O:L (3.75:1), the amount was reduced to 10.3 mol%.

[0067] (4)

[0068] Reaction conditions

[0069] 1-Octenene: 3 mmol

[0070] Ru3(CO) 12 5 mol% Ru

[0071] Ligands (1) to (3): 5.5 mol% based on 1-octene

[0072] Ligand (4): 2.75 mol% based on 1-octene

[0073] PTSA·H2O, using (1) to (3): 20.6 mol%

[0074] PTSA·H2O, when using (4): 10.3 mol%

[0075] H2O:1-octene = 6.5:1 (molar ratio)

[0076] HOAc:1-Octenene = 6.75:1 (molar ratio)

[0077] CO pressure: 40 bar

[0078] Temperature: 140℃

[0079] Reaction time: 20 hours

[0080] Experimental results

[0081]

[0082] The method of the present invention

Claims

1. A method that includes the following steps: a) Initial feeding of an olefinic unsaturated compound having 2 to 12 carbon atoms; b) Additive (I) ligands and Ru-containing compounds: （I） in R 1 R 2 R 3 Selected from: -(C6-C 12 )-cycloalkyl, -(C6-C 20 )-Aryl, The -(C6-C) 12 )-cycloalkyl groups and the (C6-C 20 The aryl group may have substituents selected from: -(C1-C1) 12 -alkyl, -O-(C1-C 12 -alkyl, -SO3Na; The Ru-containing compound is selected from: Ru3(CO) 12 , RuCl3·H2O, Ru(Cl)2(DMSO)4, Ru(acac)3; c) Add an acid (II) having formula (IIa) or (IIb): (IIa) Where R 4 Yes - (C1-C 18 )-alkyl; (IIb) Where R 5 Yes - (C1-C 18 )-alkyl; d1) Input CO; e) Heating the reaction mixture obtained from a) to d) directly converts the olefinic unsaturated compound into an ester or diester of acid (II) without separating the intermediate; This method includes additional method step d2). d2) Input H2; Additional method step d3): d3) Add H2O; and Additional method step d4): d4) Add p-toluenesulfonic acid.

2. The method of claim 1, wherein 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.

3. The method according to claim 1 or 2, wherein R 1 R 2 R 3 They are the same group.

4. The method according to claim 1 or 2, wherein R 4 Yes - (C1-C 12 )-alkyl.

5. The method according to claim 1 or 2, wherein R 5 Yes - (C1-C 12 )-alkyl.

6. The method according to claim 1 or 2, wherein the pressure of the H2 is in the range of 1 MPa (10 bar) to 6 MPa (60 bar).

7. The method according to claim 1 or 2, wherein the amount of H2O added is such that the molar ratio of H2O to the olefinic unsaturated compound is in the range of 1:1 to 10:

1.

8. The method according to claim 1 or 2, wherein the amount of acid (II) added in step c) of the method is such that the molar ratio of the acid to the olefinic unsaturated compound is in the range of 2:1 to 10:

1.

9. The method according to claim 1 or 2, wherein the acid (II) has the formula (IIa).

10. The method according to claim 1 or 2, wherein the ligand in step b) of the method is selected from: （1） （2） （3）。

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