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CN-121991130-A - Bisphosphites having naphthalene diol central units

CN121991130ACN 121991130 ACN121991130 ACN 121991130ACN-121991130-A

Abstract

The invention relates to bisphosphites having a naphthalene diol central unit and to the use thereof in hydroformylation.

Inventors

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

Assignees

  • 赢创奥克森诺有限责任两合公司

Dates

Publication Date
20260508
Application Date
20251103
Priority Date
20241105

Claims (11)

  1. 1.A compound of formula (I) or (II): (I) (II) wherein R 1 、R 2 、R 3 、R 4 is selected from the group consisting of- (C 1 -C 4 ) -alkyl, -O- (C 1 -C 4 ) -alkyl.
  2. 2. A compound according to claim 1, Wherein R 1 、R 2 、R 3 、R 4 is selected from-CH 3 、- t Bu、-O-CH 3 .
  3. 3. The compound according to any one of claim 1 or 2, Wherein at least one of the radicals R 1 、R 2 、R 3 、R 4 is- t Bu.
  4. 4. A compound according to any one of claim 1 to 3, Wherein at least one of the radicals R 1 、R 2 is- t Bu.
  5. 5. The compound according to any one of claim 1 to 4, Wherein at least one of the radicals R 3 、R 4 is- t Bu.
  6. 6. The compound according to any one of claim 1 to 5, Wherein the compound has the structure (1) or (2): (1) (2)。
  7. 7. a compound according to any one of claim 1 to 6, Wherein the compound has the structure (1): (1)。
  8. 8. a compound according to any one of claim 1 to 6, Wherein the compound has structure (2): (2)。
  9. 9. A method comprising the following method steps: a) Preloading an olefin; b) Adding a compound according to any one of claims 1 to 8; 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.
  10. 10. The method according to claim 9, wherein the method comprises, 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 .
  11. 11. The method according to any one of claim 9 or 10, Wherein the Rh-containing substance is Rh (acac) (CO) 2 .

Description

Bisphosphites having naphthalene diol central units Technical Field The invention relates to bisphosphites having a naphthalene diol central unit and to the use thereof in hydroformylation. Background Phosphorus-containing compounds play a vital role as ligands in a variety of reactions, for example in hydrogenation, hydrocyanation and hydroformylation. WO 02/00670 A1 describes bisphosphite compounds and their use in the hydroformylation of olefins. Among them, compound I f is shown: (I f)。 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 of formula (I) or (II): (I) (II) wherein R 1、R2、R3、R4 is selected from the group consisting of- (C 1-C4) -alkyl, -O- (C 1-C4) -alkyl. In one embodiment, R 1、R2、R3、R4 is selected from-CH 3、-tBu、-O-CH3. In one embodiment, at least one of the groups R 1、R2、R3、R4 is- t Bu. In one embodiment, at least one of the groups R 1、R2 is- t Bu. In one embodiment, at least one of the groups R 3、R4 is- t Bu. In one embodiment, the compound has structure (1) or (2): (1) (2)。 in one embodiment, the compound has structure (1): (1)。 in one embodiment, the compound has structure (2): (2)。 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 The 3 mmol reaction was dissolved in 30 ml dry toluene and 6 mmol degassed triethylamine was added. 3.3 mmol chlorophosphite was suspended in 30 ml dry toluene and then added dropwise to the first solution with vigorous stirring. The ammonium hydrochloride formed was filtered off using a frit, the filter cake was washed twice with toluene (10 ml each time) and the resulting filtrate was concentrated to dryness by oil vacuum at 40 ℃. The resulting product was purified by column chromatography. The yield thereof was found to be 13%. The 3 mmol reaction was dissolved in 30 ml dry toluene and 6 mmol degassed triethylamine was added. 8 mmol of 2-phenylphenol are dissolved in 30 ml of dry toluene and then added dropwise to the first solution with vigorous stirring. The ammonium hydrochloride formed was filtered off using a frit, the filter cake was washed twice with toluene (10 ml each time) and the resulting filtrate was concentrated to dryness by oil vacuum at 40 ℃. The resulting product was purified by column chromatography. The yield thereof was found to be 19%. Catalytic experiments The operation was performed using an argon atmosphere. The reaction vessel was previously dried under the action of temperature (80 ℃) and oil pump vacuum. The liquid mass was degassed by argon bubbling for at least 15 minutes. The hydroformylation was carried out in a 0.5-liter autoclave from Berghof Products + Instruments GmbH, which was equipped with a constant pressure device. The reactor was heated by an oil bath from IKA company. The reactor is used for gas exchange and as a temperature regulating device. Five glass vials (20 ml) containing catalyst solution and magnetic stirrer and crimped under argon were placed into the reactor to allow gas exchange between the vials and the reactor space. The glass bottle was warmed by the conduction oil contained in the reactor. The indicated reaction temperature was measured in a glass bottle. The substrate used was n-octene (Oxeno GmbH, octene isomer mixture consisting of 1-octene: 3%, cis + trans-2-octene: 49%, cis + trans-3-octene: 29%, cis + trans-4-octene: 16%, backbone isomeric octenes: 3%). For the experiments, stock solutions were prepared in advance under an argon atmosphere. For this, 0.0127 g Rh (acac) (CO) 2 and the corresponding amount of phosphite compound (MV Lig: rh=5:1) were weighed out and filled with 48.0 ml of toluene. About 8 ml of each solution was dispensed into vials and the exact amount was weighed. The vials were placed into the reactor and closed. Three purges with argon and three purges with synthesis gas (Linde; H 2 (99.999%): CO (99.997%) =1:1). After the pressure test was completed, the autoclave was heated to the desired temperature of 120 ℃ with stirring (900 revolutions per minute) at a total pressure of 10 bar. After the reaction temperature had been reached, the synthesis gas pressure was increased to 20 bar