Bisphosphites with 2-phenylphenol external units

Abstract

To provide a phosphorus-containing coordination compound capable of exhibiting good n-selectivity in the hydroformylation of an olefin.SOLUTION: The compound is represented by formula (I). Wherein R1, R2 are selected from H, alkyl, O-alkyl.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to bisphosphites having 2-phenylphenol 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] A technical object of the present invention is to provide a compound that can exhibit good n-selectivity 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] Compounds of (In the formula, R 1 , R 2 is selected from -H, -(C1-C6)-alkyl, -O-(C1-C6)-alkyl).

[0010] In one example, R 1 , R 2 is selected from -(C1-C6)-alkyl, -O-(C1-C6)-alkyl.

[0011] In one example, R 1 is -(C1-C6)-alkyl.

[0012] In one example, R 1 teeth,- t It's Bu.

[0013] In one example, R 2 is selected from -(C1-C6)-alkyl, -O-(C1-C6)-alkyl.

[0014] In one example, R 2 teeth,- t Bu or -O-CH3.

[0015] In one example, R 2 teeth,- t It's Bu.

[0016] In one example, R 2 is -O-CH3.

[0017] In one example, the compound has the structure (1):

[0018] [ka]

[0019] Or structure (2): [ka]

[0020] It has.

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

[0022] [ka]

[0023] It has.

[0024] In one example, the compound has the structure (2):

[0025] [ka]

[0026] It has.

[0027] 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.

[0028] 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.

[0029] In one variation of this method, the Rh-containing material is Rh(acac)(CO)2.

[0030] The invention will now be explained in more detail with reference to exemplary embodiments. [Example]

[0031] synthesis

[0032] [ka]

[0033] 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%

[0034] [ka]

[0035] 0.064 moles of biphenol was dried overnight under oil pump vacuum. The next morning, a Schlenk flask was filled with argon and the 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.

[0036] For purification, 700 mL of degassed n-heptane was added to the solid obtained, and the mixture was heated to 70° C. and stirred for 2 h. To separate the precipitated salt, the hot solution obtained was filtered through Celite using a frit. The solution was then cooled to 0° C. and stirred for 4 h. The solid obtained was then filtered through a frit, washed twice with 50 mL of cold heptane each time, and dried under oil pump vacuum. Yield: 66%

[0037] [ka]

[0038] 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. Then, at 0 °C, the organic phosphite-Et3N solution was added dropwise to PCl3 slowly and steadily. 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 resulting filtrate was concentrated to dryness at 40 °C using an oil pump vacuum. Yield: 91%

[0039] [ka]

[0040] 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 using an 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 hydrochloride formed was filtered using a frit and washed twice with 10 mL of dry toluene each time. The resulting filtrate was concentrated to dryness at 40 °C using an oil pump vacuum. The dried filtrate was purified by column chromatography. Yield: 78%

[0041] Compounds (2) to (6), (IIa) and (7) were prepared in the same manner as compound (1).

[0042] Compounds (3) to (6), (IIa) and (7) are comparative compounds not belonging to the present invention.

[0043] [ka]

[0044] Catalyst Experiments An argon atmosphere was used. The reaction vessel was previously 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 was carried out in a 0.5 L autoclave from Berghof Products + Instruments GmbH equipped with a constant pressure device. An oil bath from IKA was used to heat the reactor. The reactor served as a gas exchange and temperature control unit. 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 hot 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 containing 1-octene: 3%, cis + trans -2-octene: 49%, cis + trans -3-octene: 29%, cis + trans -4-octene: 16%, and structural isomer octene: 3%).

[0045] 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 the lids were closed. The reactor was purged three times with argon and three times with synthesis gas (Linde, H2 (99.999%):CO (99.997%) = 1:1). After completing the pressure test, 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 (HP6890, Petrocol® DH150, 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.

[0046] 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.

[0047] [Table 1]

[0048] [Table 2]

[0049] Experiments carried out have demonstrated that the stated objects are achieved by the compounds according to the invention.

Claims

1. Formula (I): 【Chemistry 1】 is a compound of In the formula, R １ , R ２ is -H, -(C １ -C ６ )-alkyl, —O—(C １ -C ６ )-alkyl.

2. R １ , R ２ is -(C １ -C ６ )-alkyl, —O—(C １ -C ６ 2. The compound of claim 1, wherein the aryl group is selected from the group consisting of aryl, aryl, aryl- ...

3. R １ is -(C １ -C ６ 3. The compound according to claim 1 or 2, wherein the aryl group is aryl.

4. R １ teeth,- ｔ The compound according to any one of claims 1 to 3, wherein the compound is Bu.

5. R ２ is -(C １ -C ６ )-alkyl, —O—(C １ -C ６ 5. The compound of claim 1, wherein the aryl group is selected from the group consisting of aryl, aryl, aryl- ...

6. R ２ teeth,- ｔ Bu or —O—CH ３ The compound according to any one of claims 1 to 5,

7. R ２ teeth,- ｔ The compound according to any one of claims 1 to 6, wherein the compound is Bu.

8. R ２ is -O-CH ３ The compound according to any one of claims 1 to 6, wherein

9. Structure (1): 【Chemistry 2】 Or structure (2): 【Transformation 3】 The compound according to any one of claims 1 to 8, having the formula:

10. The structure (1): 【Chemistry 4】 The compound according to any one of claims 1 to 9, having the formula:

11. The structure (2): 【Transformation 5】 The compound according to any one of claims 1 to 9, having the formula:

12. a) initially charging an olefin; b) adding a compound according to any one of claims 1 to 11; 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.

13. 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 12, wherein the compound is selected from the group consisting of:

14. The Rh-containing material is Rh(acac)(CO) ２ The method according to claim 12 or claim 13, wherein

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