Bis-phosphites having tert-butyl group in central unit

Abstract

The present invention relates to bisphosphites having a tert-butyl group in the central unit and having open and closed outer units.

Description

Technical Field

[0001] This invention relates to bisphosphites having a tert-butyl group in the central unit and having open and closed external units. Furthermore, this invention also relates to the use of this bisphosphite in hydroformylation. Background Technology

[0002] Phosphorus compounds play a crucial role as ligands in a variety of reactions, such as hydrogenation, hydrocyanation, and hydroformylation. Summary of the Invention

[0003] The technical objective of this invention is to provide compounds that can achieve good yields during the hydroformylation of olefins.

[0004] This objective is achieved by the compound according to claim 1.

[0005] Compounds having structure (1): .

[0006] In addition to the compound itself, protection is also required for the method of using the compound.

[0007] This method includes the following steps: a) Pre-loading olefins; b) Add the aforementioned compound; c) Add substances containing Rh; d) Introduce H2 and CO; e) Heat the reaction mixture from a) to d), thereby converting the olefin into an aldehyde.

[0008] In a variant of this method, the Rh-containing substance is selected from: Rh(acac)(CO)2, Rh(acac)(cod) (Umicore, acac = acetylacetone anion; cod = 1,5-cyclooctadiene), Rh4CO 12 .

[0009] In a variant of this method, the substance containing Rh is Rh(acac)(CO)2. Detailed Implementation

[0010] The present invention will now be described in more detail with reference to the embodiments.

[0011] synthesis Phase 1 0.076 mol naphthalene-1,8-diol was dried under vacuum overnight at 50 °C using an oil pump. 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 repeatedly evacuated and filled with inert gas, 0.114 mol phosphorus trichloride was dissolved in 120 mL of dry toluene. Subsequently, the naphthalene-1,8-diol solution was slowly and continuously added dropwise to a PCl3 solution at -20 °C. Then, 0.165 mol triethylamine was slowly 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 using glass frit, the filter cake was washed twice with toluene (25 mL each time), and the filtrate was concentrated under vacuum using an oil pump at 40 °C. Yield: 86%.

[0012] Phase Two Weigh 0.016 mol of bisphenol and dry it under vacuum overnight using an oil pump. The next morning, purge with argon. Dissolve the bisphenol in 40 ml of toluene. Under an inert atmosphere, weigh 0.016 mol of phosphite and dissolve it in 40 ml of toluene, then add 0.016 mol of degassed triethylamine. Add the phosphite-toluene solution dropwise to the bisphenol solution over 1 hour at room temperature, and stir at 40°C for 24 hours. Filter the reaction mixture through a glass filter, and wash the filter cake twice with toluene (20 ml each time). Concentrate the resulting filtrate under vacuum using an oil pump at 40°C and then dry. Yield: 75%.

[0013] Phase Three Weigh 11.9 mmol of organochlorine phosphite into 150 mL of dry toluene and 29.8 mmol of degassed triethylamine under an inert atmosphere. In a Schlenk flask repeatedly evacuated and filled with inert gas, dissolve 14.9 mmol of phosphorus trichloride in 100 mL of dry toluene and cool to 0 °C. Then, at 0 °C, add the organochlorine phosphite-triethylamine solution to the phosphorus trichloride solution. Stir the reaction mixture at room temperature for 24 hours. Filter the resulting ammonium hydrochloride through glass frit and wash twice with dry toluene (50 mL each time). The resulting filtrate is then concentrated to dryness under vacuum using an oil pump at 45 °C. Yield: 87%.

[0014] Synthesis (1) Weigh 2.9 mmol of organic dichlorophosphite under an inert atmosphere and suspend it in 30 mL of dry toluene. Weigh 6.7 mmol of phenol into a Schlenk flask, briefly evacuate the flask under vacuum using an oil pump, and then fill it with inert gas. Next, fill the Schlenk flask with argon gas, dissolve the phenol in 20 mL of dry toluene, and add 14.3 mmol of degassed triethylamine. Then, slowly and continuously add the phenol solution to the dichlorophosphite suspension at room temperature. Stir the reaction solution overnight at room temperature. Filter the generated ammonium hydrochloride through glass frit and wash twice more with dry toluene (10 mL each time). Concentrate the resulting filtrate to dryness under vacuum using an oil pump at 40 °C. Purify the dried filtrate by column chromatography. Yield: 53%.

[0015] Compound (2) (Comparative Compound): Synthesis (2) The preparation of compound (2) was similar to that of compound (1). For this purpose, 2.9 mmol of organic dichlorophosphite was weighed under an inert atmosphere and suspended in 30 ml of dry toluene. 3.5 mmol of 1,8-naphthalenediol was weighed into a Schlenk flask and briefly evacuated and filled with inert gas using an oil pump. Then, the Schlenk flask was filled with argon, and biphenyl was dissolved in 20 ml of dry toluene, followed by the addition of 14.3 mmol of degassed triethylamine. The biphenyl solution was then slowly and continuously added to the dichlorophosphite suspension at room temperature. The reaction solution was stirred overnight at room temperature. The resulting ammonium hydrochloride was filtered off with glass frit and subsequently washed twice with dry toluene (10 ml each time). The resulting filtrate was then concentrated to dryness under vacuum using an oil pump at 40°C. The dried filtrate was purified by column chromatography.

[0016] Catalysis experiment The operation was conducted under an argon atmosphere. The reaction vessel was pre-dried at 80°C and under vacuum by an oil pump. The liquid material was degassed by argon bubbling for at least 15 minutes. Hydroformylation was carried out in a 0.5 L high-pressure vessel from Berghof Products + Instruments GmbH equipped with a constant pressure device. The reactor was heated by an oil bath from IKA. The reactor served as a gas exchange and temperature control device. Five 20 mL glass vials containing catalyst solution and magnetic stir bar, pressed together under argon, were placed in the reactor to allow gas exchange between the vials and the reactor space. The vials were conditioned by the heat transfer oil contained in the reactor. The specified reaction temperature was measured inside the vials. The substrate used was n-octene (Oxeno GmbH, a mixture of octene isomers consisting of 1-octene: 3%; cis+trans-2-octene: 49%; cis+trans-3-octene: 29%; cis+trans-4-octene: 16%; main-chain isooctene: 3%).

[0017] For the experiment, a stock solution was prepared beforehand under an argon atmosphere. To this end, 0.0127 g of Rh(acac)(CO)₂ and the corresponding amount of the phosphite compound (MV Lig:Rh = 5:1) were weighed and filled into 48.0 mL of toluene. Approximately 8 mL of this solution was dispensed into vials, each accurately weighed. The vials were placed in the reactor and sealed. The reactor was purged three times with argon and three times with syngas (Linde; H₂ (99.999%): CO (99.997%) = 1:1). After pressure testing, the autoclave was heated to the desired temperature of 120 °C at a total pressure of 10 bar with stirring (900 rpm). Once the reaction temperature was reached, the syngas pressure was increased to 20 bar, and 2 mL of substrate was metered in using an HPLC pump to initiate the reaction. This yielded an Rh concentration of 100 ppm. One hour after the reaction began under constant pressure, samples were taken from each vial and analyzed by gas chromatography undiluted: HP 6890, Petrocol® DH 150, 150 m x 0.25 mm x 1 µm. Residual olefins and aldehydes were quantified using toluene as an internal standard. The results listed in the table below are averages from the experimental run.

[0018] Catalytic experimental results [Rh]: 100 ppm, p: 20 bar, T: 120℃; t: 1 hour The mixture of n-octene used consists of C8 isomers: 1-octene, cis-2-octene, trans-2-octene, cis-3-octene, trans-3-octene, cis-4-octene, and trans-4-octene.

[0019] Table 1: ligands Yield [%] (1)* 51 (2) 6 *According to an embodiment of the present invention.

[0020] The experiments conducted demonstrated that the compound of the present invention achieved the stated objective.

Claims

1. Compounds having structure (1): 。 2. A method, comprising the following method steps: a) Pre-loading olefins; b) Add the compound according to claim 1; c) Add substances containing Rh; d) Introduce H2 and CO; e) Heat the reaction mixture from a) to d), thereby converting the olefin into an aldehyde.

3. The method according to claim 2, The Rh-containing substances are selected from: Rh(acac)(CO)2, Rh(acac)(cod) (Umicore, acac = acetylacetone anion; cod = 1,5-cyclooctadiene), Rh4CO 12 .

4. The method according to any one of claims 2 or 3, The substance containing Rh is Rh(acac)(CO)2.

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