CN-122011034-A - Bisphosphites having tertiary butyl groups in the central unit

Abstract

The present invention relates to bisphosphites having a tertiary butyl group in the central unit and having open and closed external units.

Inventors

• BUCK JAN
• Wiessner M.
• A. C. Salle
• R. FRANK
• D. Friedag
• M. bilk
• B. bloomer
• V. Burk
• P. Cook Milchik
• A. Markovich
• R. Pesk

Assignees

• 赢创奥克森诺有限责任两合公司

Dates

Publication Date

20260512

Application Date

20251111

Priority Date

20241112

Claims (4)

1. 1. A compound having structure (1): 。
2. 2. A method comprising the following method steps: a) Preloading an olefin; b) Adding a compound according to claim 1; c) Adding a substance containing Rh; d) H 2 and CO are introduced; e) Heating the reaction mixture from a) to d), thereby converting the olefin into an aldehyde.
3. 3. The method according to claim 2, Wherein the Rh-containing material is selected from Rh (acac) (CO) 2 , rh (acac) (cod) (Umicore, acac=acetylacetonate anion; cod=1, 5-cyclooctadiene), rh 4 CO 12 .
4. 4. The method according to claim 2 or 3, Wherein the Rh-containing substance is Rh (acac) (CO) 2 .

Description

Bisphosphites having tertiary butyl groups in the central unit Technical Field The present invention relates to bisphosphites having a tertiary butyl group in the central unit and having open and closed external units. Furthermore, the invention relates to the use of the bisphosphites in hydroformylation. Background Phosphorus-containing compounds play a vital role as ligands in a variety of reactions, for example in hydrogenation, hydrocyanation and hydroformylation. Disclosure of Invention The technical object of the present invention is to provide compounds which are capable of obtaining good yields in the hydroformylation of olefins. This object is achieved by a compound according to claim 1. A compound having structure (1): 。 in addition to the compounds themselves, methods in which the above-described compounds are used are also claimed. The method comprises the following method steps: a) Preloading an olefin; b) Adding the aforementioned compound; c) Adding a substance containing Rh; d) H 2 and CO are introduced; e) Heating the reaction mixture from a) to d), thereby converting the olefin into an aldehyde. In a variant of this method, the Rh-containing substance is selected from Rh (acac) (CO) 2, rh (acac) (cod) (Umicore, acac=acetylacetonate anion; cod=1, 5-cyclooctadiene), rh 4CO12. In one variation of this method, the Rh-containing material is Rh (acac) (CO) 2. Detailed Description The present invention will be described in more detail with reference to examples. Synthesis First stage 0.076 Mol naphthalene-1, 8-diol was dried overnight at 50℃under vacuum with an oil pump. The next day, the schlenk flask was filled with argon and naphthalene-1, 8-diol was dissolved in 350 ml dry toluene. In a schlenk flask, which was repeatedly evacuated and filled with an inert gas, 0.114 mol phosphorus trichloride was dissolved in 120 ml dry toluene. Subsequently, naphthalene-1, 8-diol solution was slowly and continuously added dropwise to PCl 3 solution at-20 ℃. Thereafter, 0.165 mol triethylamine was slowly added dropwise to the solution under high speed stirring at-20 ℃. The solution was allowed to return to room temperature and stirring continued overnight. The next day the reaction mixture was filtered using a frit, the filter cake was washed twice with toluene (25 ml each) and the filtrate was concentrated by oil pump vacuum at 40 ℃. The yield thereof was found to be 86%. Second stage 0.016 Mol bisphenol was weighed, dried overnight with an oil pump under vacuum, and the next morning was filled with argon. Bisphenol was dissolved in 40 ml toluene. Under an inert gas atmosphere, 0.016 mol g of chlorophosphite was weighed, dissolved in 40 ml g of toluene, and 0.016 g mol g of degassed triethylamine was added. The chlorophosphite-toluene solution was added dropwise to the bisphenol solution at room temperature over 1 hour and stirred at 40 ℃ for 24 hours. The reaction mixture was filtered through a frit and the filter cake was washed twice with toluene (20 ml each). The resulting filtrate was concentrated and dried by oil pump vacuum at 40 ℃. The yield thereof was found to be 75%. Third stage 11.9 Mmol of monophosphite was weighed out under an inert gas atmosphere and dissolved in 150. 150 ml of dry toluene and 29.8 mmol of degassed triethylamine. In a schlenk flask, which was repeatedly evacuated and filled with an inert gas, 14.9 mmol phosphorus trichloride was dissolved in 100 ml dry toluene and cooled to 0 ℃. The organophosphite-triethylamine solution was then added to the phosphorus trichloride solution at 0 ℃. The reaction mixture was stirred at room temperature for 24 hours. The ammonium hydrochloride formed was filtered off with a frit and washed twice with dry toluene (50 ml each time). The resulting filtrate was then concentrated to dryness in vacuo by an oil pump at 45 ℃. The yield thereof was found to be 87%. Synthesis (1) 2.9 Mmol of the organic dichlorophosphite was weighed under an inert gas atmosphere and suspended in 30. 30 ml of dry toluene. 6.7 mmol phenol was weighed into a schlenk flask, briefly evacuated repeatedly by oil pump vacuum and filled with inert gas. Subsequently, the schlenk flask was filled with argon, phenol was dissolved in 20 ml dry toluene, and 14.3 mmol degassed triethylamine was added. Subsequently, the phenol solution was slowly and continuously added to the chlorophosphite suspension at room temperature. The reaction solution was stirred at room temperature overnight. The ammonium hydrochloride formed was filtered off with a frit and washed twice (10 ml each time) with dry toluene. The resulting filtrate was then concentrated to dryness in vacuo by an oil pump at 40 ℃. The dried filtrate was purified by column chromatography. The yield thereof was found to be 53%. Compound (2) (comparative compound): Synthesis (2) The preparation method of the compound (2) is similar to that of the compound (1). For this purpose, 2.9 mmol of the organic dichlorophosphite was weighed un