Bisphosphites with 3, 4-dialkylphenol external units

Abstract

To provide a phosphorus-containing compound capable of achieving a good yield in hydroformylation of an olefin.SOLUTION: A compound represented by formula (I) is provided.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to bisphosphites having 3,4-dialkylphenol outer units and their use in hydroformylation. [Background technology]

[0002] Phosphorus-containing compounds play an important role as ligands in many reactions, such as hydrogenation, hydrocyanation, and also hydroformylation.

[0003] WO 02 / 00670 describes bisphosphite compounds, their metal complexes, and the use of these compounds and complexes in the hydroformylation of olefins. This document discloses, inter alia, compound (IIa):

[0004] [ka] [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 02 / 00670 Brochure Summary of the Invention [Problem to be solved by the invention]

[0006] The technical problem of the present invention is to provide compounds which allow good yields to be achieved in the hydroformylation of olefins. [Means for solving the problem]

[0007] This object is achieved by the compounds according to claim 1. Formula (I):

[0008] [ka]

[0009] (In the formula, R 1 , R 2 is -(C1-C4)-alkyl. Compound.

[0010] In one example, R 1 , R 2 is -CH3 or - t It's Bu.

[0011] In one example, R 1 , R 2 is -CH3

[0012] In one example, the compound has the structure (1): [ka]

[0013] It has.

[0014] In addition to the compounds themselves, methods of using the above compounds are also claimed. a) initially charging an olefin; b) adding the compound; c) adding a Rh-containing substance; d) providing H2 and CO; e) a step of heating the reaction mixture obtained from steps a) to d) to convert the olefin into an aldehyde. A method having the following.

[0015] In one variation of the method, the Rh-containing material is Rh(acac)(CO), Rh(acac)(cod) (Umicore, acac = acetylacetonate anion, cod = 1,5-cyclooctadiene), RhCO 12 is selected from.

[0016] In one variation of this method, the Rh-containing material is Rh(acac)(CO)2.

[0017] The invention will now be explained in more detail with reference to exemplary embodiments. [Example]

[0018] [ka]

[0019] 0.076 mol of naphthalene-1,8-diol was dried overnight at 50 °C under oil pump vacuum. The next day, a Schlenk flask was filled with argon and naphthalene-1,8-diol was dissolved in 350 mL of dry toluene. In a Schlenk flask that had been repeatedly evacuated and filled with inert gas, 0.114 mol of phosphorus trichloride was dissolved in 120 mL of dry toluene. Subsequently, the naphthalene-1,8-diol solution was added slowly and steadily to the PCl3 solution at -20 °C. Then, 0.165 mol of triethylamine was added slowly and steadily to the solution with rapid stirring at -20 °C. The solution was allowed to warm to room temperature and continued stirring overnight. The next day, the reaction mixture was filtered using a frit, the filter cake was washed twice with 25 mL of toluene each time, and the filtrate was concentrated under oil pump vacuum at 40 °C. Yield: 86%

[0020] [ka]

[0021] 0.064 moles of biphenol was dried overnight under oil pump vacuum. The next morning, a Schlenk flask was filled with argon and biphenol was dissolved in 200 mL of dry THF. The solution was then cooled to -20°C, and a 1.6M n-butyllithium solution (0.064 mol) in hexane was added dropwise. After the addition was complete, the reaction solution was stirred at -20°C for an additional 30 minutes and then slowly heated to room temperature. Under an inert gas atmosphere, 0.065 mol of chlorophosphite was dissolved in 100 mL of dry THF. The butyllithium-THF solution was then added slowly and steadily to the biphenol-THF solution at room temperature. The reaction solution was stirred overnight at room temperature and the next morning concentrated to dryness at 40°C under oil pump vacuum.

[0022] For purification, the resulting solid was added to 700 mL of degassed n-heptane, heated to 70 °C, and stirred for 2 h. The hot solution was filtered through Celite using a frit to separate the precipitated salt. The solution was then cooled to 0 °C and stirred for 4 h. The resulting solid was filtered through a frit, washed twice with 50 mL of cold n-heptane each time, and then dried under oil pump vacuum. Yield: 66%

[0023] [ka]

[0024] Under an inert gas atmosphere, 0.038 mol of organic phosphite was dissolved in 200 mL of dry toluene and 13.5 mL of triethylamine (0.095 mol, 2.5 equivalents). In a Schlenk flask that had been repeatedly evacuated and filled with inert gas, 0.046 mol of phosphorus trichloride was dissolved in 100 mL of dry toluene and cooled to 0 °C. The organic phosphite-Et3N solution was then added dropwise to PCl3 at 0 °C. The reaction solution was stirred overnight at room temperature. The ammonium chloride formed was filtered using a frit and washed twice with 50 mL of dry toluene. The filtrate was concentrated to dryness at 40 °C using an oil pump vacuum. Yield: 91%

[0025] [ka]

[0026] Under an inert gas atmosphere, 2.6 mmol of organodichlorophosphite was weighed and suspended in 30 mL of dry toluene. 6.6 mmol of the phenol derivative was weighed into a Schlenk flask, which was then briefly evacuated and backfilled with inert gas under oil pump vacuum. The Schlenk flask was then filled with argon, the phenol derivative was dissolved in 20 mL of dry toluene, and 13.1 mmol of degassed triethylamine was added. The phenol solution was then added slowly and steadily to the chlorophosphite suspension at room temperature. The reaction solution was stirred overnight at room temperature. The ammonium chloride formed was filtered through a frit and washed twice with 10 mL of dry toluene each time. The resulting filtrate was concentrated to dryness at 40 °C under oil pump vacuum. The dried filtrate was purified by column chromatography. Yield: 68%

[0027] Compound (2) and compound (IIa) were also prepared in the same manner as compound (1). Compound (2) and compound (IIa) are comparative compounds not belonging to the present invention.

[0028] [ka]

[0029] Catalyst Experiments An argon atmosphere was used. The reaction vessel was pre-dried at elevated temperature (80 °C) and under oil pump vacuum. The liquid material was degassed by bubbling argon for at least 15 minutes. The hydroformylation reaction was carried out in a 0.5 L autoclave from Berghof Products + Instruments GmbH equipped with a constant pressure device. The reactor was heated with an IKA oil bath. The reactor served as a gas exchange and temperature control device. Five glass vials (20 mL volume) containing the catalyst solution and a magnetic stir bar, crimped under argon, were placed in the reactor, allowing gas exchange between the vials and the reactor space. The temperature of the glass vials was controlled by the thermal oil present in the reactor. The designated reaction temperature was measured in the glass vials. The substrate used was n-octene (Oxeno GmbH, an octene isomer mixture consisting of 1-octene: 3%, cis + trans -2-octene: 49%, cis + trans -3-octene: 29%, cis + trans -4-octene: 16%, and structural isomer octene: 3%).

[0030] For the experiment, a stock solution was prepared in advance under an argon atmosphere. For this purpose, 0.0127 g of Rh(acac)(CO)2 and the corresponding amount of phosphite compound (MV Lig:Rh = 5:1) were weighed and mixed with 48.0 mL of toluene. Approximately 8 mL of this solution was dispensed into each vial, and the exact amount was weighed out. The vials were placed in the reactor and closed with the lid. The reactor was purged three times with argon and three times with synthesis gas (Linde; H2 (99.999%):CO (99.997%) = 1:1). After the pressure test was completed, the autoclave was heated to the specified temperature of 120 °C at a total pressure of 10 bar while stirring (900 rpm). After reaching the reaction temperature, the synthesis gas pressure was increased to 20 bar, and the reaction was initiated by metering in 2 mL of substrate each time using an HPLC pump. This resulted in an Rh concentration of 100 ppm. One hour after starting the reaction at constant pressure, a sample was taken from each vial and analyzed undiluted by gas chromatography (HP 6890, Petrocol® DH 150, 150 m × 0.25 mm × 1 μm). Residual olefins and aldehydes were quantitatively measured against the solvent toluene as an internal standard. The results shown in the table below are the average values ​​from one experiment.

[0031] Catalyst experiment results [Rh]: 100 ppm, pressure: 20 bar, temperature: 120°C, time: 1 hour An n-octene mixture composed of C8 isomers (1-octene, cis-2-octene, trans-2-octene, cis-3-octene, trans-3-octene, cis-4-octene, and trans-4-octene) was used.

[0032] [Table 1]

[0033] Experimental studies have demonstrated that the above objectives are achieved by the compounds of the present invention.

Claims

1. Formula (I): 【Chemistry 1】 (In the formula, R １ , R ２ is -(C １ -C ４ )-alkyl. Compound.

2. R １ , R ２ is -CH ３ or- ｔ The compound of claim 1 , wherein the compound is Bu.

3. R １ , R ２ is -CH ３ 3. The compound according to claim 1 or claim 2, wherein:

4. Structure (1): 【Chemistry 2】 The compound according to any one of claims 1 to 3, having the formula:

5. a) initially charging an olefin; b) adding a compound according to any one of claims 1 to 4; c) adding a Rh-containing material; d) H ２ and providing CO; e) heating the reaction mixture obtained from steps a) to d) to convert the olefin to an aldehyde. A method having the following.

6. The Rh-containing material is Rh(acac)(CO) ２ , Rh(acac)(cod) (Umicore, acac = acetylacetonate anion, cod = 1,5-cyclooctadiene), Rh ４ CO １２ The method of claim 5, wherein the compound is selected from the group consisting of:

7. The Rh-containing material is Rh(acac)(CO) ２ The method according to claim 5 or claim 6, wherein

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