EP-4741370-A1 - BISPHOSPHITE WITH TERT-BUTYL RESIDUES ON THE CENTRAL COMPONENT

Abstract

Bisphosphite with tert -butyl residues on the central building block and an open and a closed wing building block.

Inventors

• BÜKER, Julia
• Wessner, Maximilian
• SALE, Anna Chiara
• FRANKE, ROBERT
• FRIDAG, DIRK
• BILKE, Marius
• BRUNS, Bastian
• Bürk, Vincent
• KUCMIERCZYK, PETER
• Markovic, Ana
• PESCHKE, Roland

Assignees

• Evonik Oxeno GmbH & Co. KG

Dates

Publication Date

20260513

Application Date

20241112

Claims (4)

1. Compound having the structure (1):
2. The procedure encompasses the following procedural steps: a) Submission of an olefin; b) Addition of a compound according to claim 1; c) Addition of a substance comprising Rh; d) Supply of H2 and CO; e) Heating the reaction mixture from a) to d), whereby the olefin is converted to an aldehyde.
3. Method according to claim 2, wherein the substance comprising Rh is selected from: Rh(acac)(CO) 2 , Rh(acac)(cod) (Umicore, acac = acetylacetonate anion; cod = 1,5-cyclooctadiene), Rh 4 CO 12 .
4. Method according to one of claims 2 or 3, where the substance comprising Rh is Rh(acac)(CO) 2 .

Description

The invention relates to a bisphosphite with tert-butyl residues on the central building block and an open and a closed wing building block. Furthermore, the invention relates to the use of the bisphosphite in hydroformylation. Phosphorus-containing compounds play a crucial role as ligands in a variety of reactions, e.g. in hydrogenation, hydrocyanation and also in hydroformylation. The technical objective of the invention is to provide a compound with which a good yield can be achieved in the hydroformylation of olefins. The problem is solved by a connection according to claim 1. Compound having the structure (1): In addition to the compounds themselves, a method is also claimed in which the previously described compounds are used. The procedure encompasses the following procedural steps: a) Submission of an olefin; b) Addition of the previously described compound; c) Addition of a substance comprising Rh; d) Supply of H2 and CO; e) Heating the reaction mixture from a) to d), whereby the olefin is converted to an aldehyde. In one variant of the procedure, the substance comprising Rh is selected from: Rh(acac)(CO) 2 , Rh(acac)(cod) (Umicore, acac = acetylacetonate anion; cod = 1,5-cyclooctadiene), Rh 4 CO 12 . In one variant of the procedure, the substance comprising Rh is Rh(acac)(CO) 2 . The invention will now be explained in more detail using exemplary embodiments. synthesis 0.076 mol of naphthalene-1,8-diol were dried overnight at 50 °C using an oil pump vacuum. The following day, the Schlenk condenser was flooded with argon, and the naphthalene-1,8-diol was dissolved in 350 mL of dried toluene. In a segregated Schlenk condenser, 0.114 mol of phosphorus trichloride were dissolved in 120 mL of dried toluene. The naphthalene-1,8-diol solution was then added dropwise at -20 °C to the PCI 3 solution. Subsequently, 0.165 mol of triethylamine were added dropwise to the solution at -20 °C with high-speed stirring. The solution was brought to room temperature and stirred overnight. The next day, the reaction mixture was filtered, the filter cake was washed twice with 25 mL each time with toluene, and the filtrate was concentrated using an oil pump vacuum at 40 °C. Yield: 86% 0.016 mol of biphenol was weighed out, dried overnight using an oil pump vacuum, and flooded with argon the following morning. The biphenol was dissolved in 40 mL of toluene. Under an inert gas atmosphere, 0.016 mol of chlorophosphite was weighed out, dissolved in 40 mL of toluene, and mixed with 0.016 mol of degassed triethylamine. The chlorophosphite-toluene solution was added dropwise to the biphenol solution at room temperature over 1 h and stirred at 40 °C for 24 h. The reaction mixture was The filter cake was filtered and washed twice with 20 ml of toluene each time. The resulting filtrate was concentrated and dried under oil pump vacuum at 40 °C. Yield: 75% Under an inert gas atmosphere, 11.9 mmol of monophosphite was weighed out and dissolved in 150 ml of dried toluene and 29.8 mmol of degassed triethylamine. In a sequestered Schlenk flask, 14.9 mmol of phosphorus trichloride was dissolved in 100 ml of dried toluene and cooled to 0 °C. The organochlorophosphite-triethylamine solution was then added to the phosphorus trichloride solution at 0 °C. The reaction mixture was stirred at room temperature for 24 h. The resulting ammonium hydrochloride was filtered and washed twice with 50 ml of dried toluene each time. The filtrate was then concentrated to dryness under oil pump vacuum at 45 °C. Yield: 87% Synthesis (1) Under an inert gas atmosphere, 2.9 mmol of organodichlorophosphite were weighed out and suspended in 30 mL of dried toluene. 6.7 mmol of phenol were weighed out in a Schlenk flask and briefly separated by oil pump vacuum. The flask was then flooded with argon, and the phenol was dissolved in 20 mL of dried toluene. 14.3 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 resulting ammonium hydrochloride was filtered off by frit and washed twice with 10 mL of dried toluene each time. The filtrate was then concentrated to dryness by oil pump vacuum at 40 °C. The dried filtrate was purified by column chromatography. Yield: 53% Connection (2) (comparison connection): Synthesis (2) Compound (2) was prepared analogously to compound (1). For this purpose, 2.9 mmol of organodichlorophosphite were weighed out under an inert gas atmosphere and suspended in 30 ml of dried toluene. 3.5 mmol of 1,8-naphthalenediol were weighed out in a Schlenk flask and briefly separated by oil pump vacuum. The Schlenk flask was then flooded with argon, and the biphenol was dissolved in 20 ml of dried toluene. 14.3 mmol of degassed triethylamine was then added. The biphenol solution was then added slowly and steadily to the chlorophosphite suspension at room temperature. The reaction s