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Preparation method of biphenyl triphosphane ligand and application thereof in gradually substituting PPh3 (Triphenylphosphine) in hydroformylation

A technology of biphenyl triphosphine and phosphine ligands is applied in chemical instruments and methods, carbon monoxide reaction preparation, organic compound/hydride/coordination complex catalysts, etc., and can solve the problems of low reaction rate, poor selectivity and high cost , to achieve the effect of high reaction rate, high selectivity and low cost

Active Publication Date: 2014-05-21
WUHAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] Aiming at the problems of poor selectivity, low reaction rate and difficult separation in the linear hydroformylation reaction using triphenylphosphine, and the high cost of the linear hydroformylation reaction using tridentate phosphine ligands, the present invention provides A series of biphenyl triphosphine ligands, preparation methods and their application in linear hydroformylation reactions, in PPh 3 In the linear hydroformylation reaction system as a ligand, gradually adding the biphenyl triphosphine ligand can greatly improve the selectivity of the linear hydroformylation reaction, and the cost is low. In addition, the preparation method of the present invention also has the advantages of easy synthesis , high product yield, scalable synthesis and other advantages,

Method used

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  • Preparation method of biphenyl triphosphane ligand and application thereof in gradually substituting PPh3 (Triphenylphosphine) in hydroformylation
  • Preparation method of biphenyl triphosphane ligand and application thereof in gradually substituting PPh3 (Triphenylphosphine) in hydroformylation
  • Preparation method of biphenyl triphosphane ligand and application thereof in gradually substituting PPh3 (Triphenylphosphine) in hydroformylation

Examples

Experimental program
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Effect test

Embodiment 1

[0028] Preparation of 2,2′,6-trimethylbiphenyl:

[0029]

[0030] Add 2.06g of Pd to the 2L Schlunk bottle successively 2 (dba) 3 (tris(dibenzylideneacetone) dipalladium), 1.56 g of HPtBu 3 BF 4 (tri-tert-butylphosphine tetrafluoroborate), 66.76 g of 2-methylphenylboronic acid, 139.75 g of potassium fluoride dihydrate. After the addition was complete, the reaction bottle was replaced with a nitrogen atmosphere. Under nitrogen protection, 76.95 g of 2,6-dimethylbromobenzene and 1 L of anhydrous THF (tetrahydrofuran) were added to obtain a reaction system. The reaction system was reacted at room temperature for 5 hours, THF was spin-dried under reduced pressure, 400 mL of water was added, and extracted three times with ethyl acetate (500 mL of ethyl acetate each time), the obtained organic phase was dried over anhydrous sodium sulfate and then spin-dried under reduced pressure , and the residue was subjected to flash column chromatography to obtain 80.35 g of the target ...

Embodiment 2

[0033] Preparation of 2,2′,6-tricarboxybiphenyl:

[0034]

[0035] Into a 2L four-neck round bottom flask, 26.7g of 2,2',6-trimethylbiphenyl, 2.44g of cetyltrimethylammonium bromide and 1.2L of water were added in sequence to obtain a reaction system. Raise the reaction system to 80°C and add 193.4g of potassium permanganate to react for 12 hours until the red color of potassium permanganate in the system to be reacted fades. The reaction system was filtered to obtain a colorless water phase. After extracting with toluene to remove cetyl ammonium bromide in the colorless water phase, the obtained water phase was rotary evaporated under reduced pressure to about 150 mL, and 50 mL of concentrated hydrochloric acid was added. At this time, a white solid was precipitated, and the white solid was filtered and dried in a vacuum oven to obtain 95.75 g of the target compound (4), with a yield of 82%. 1 H NMR (400MHz, CD 3 OD):δ=8.02-8.06(m,3H),7.47-7.53(m,2H),7.38-7.42(m,1H),7.05...

Embodiment 3

[0038] Preparation of 2,2′,6-tris(methylcarboxylate)-biphenyl:

[0039]

[0040] Add 95.0g of 2,2′,6-tricarboxylic acid biphenyl to a dry 1L Schlenk bottle, replace the Schlenk bottle with a nitrogen atmosphere, add 400mL thionyl chloride at 0°C, and reflux for 24 hours , After removing excess thionyl chloride by rotary evaporation under reduced pressure, a light yellow solid was obtained. Subsequently, under the protection of nitrogen, 250mL of anhydrous methanol and 150mL of anhydrous triethylamine were added, and heated to reflux for 5 hours. After the reaction solvent was removed by rotary evaporation under reduced pressure, 300mL of water was added and extracted three times with ethyl acetate (each time using acetic acid ethyl ester 400mL). The obtained organic phase was dried over anhydrous sodium sulfate and then spin-dried under reduced pressure to obtain a light yellow solid, which was recrystallized in petroleum ether and ethyl acetate to obtain 98.07 g of the wh...

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Abstract

The invention discloses a preparation method of a biphenyl triphosphane ligand and an application thereof in hydroformylation reaction. The prepared biphenyl triphosphane ligand has the structure shown as a formula (I) or formula (II) described in the specification. In the formula (I), aryl substituent Ar is benzene, p-methyl benzene, m-benzenyl trifluoride, p-benzenyl trifluoride, 3, 5-dibenzenyl trifluoride, 3, 5-difluorobenzene, 3, 5-dimethyl benzene, 3, 5-di-tert-butyl benzene, 3, 5-di-tert-butyl-4-metoxybenzene, p-metoxybenzene, p-dimethylamino benzene, 2-pyridine, p-fluorobenzene or 2, 3, 4, 5, 6-pentafluoro benzene; in the formula (II), R is in a cyclic phosphonate structure. The biphenyl triphosphane ligand disclosed by the invention can be used as a linear hydroformylation reaction catalyst, so that the selectivity and reaction rate of hydroformylation reaction can be remarkably improved. The biphenyl triphosphane ligand is low in cost and has a huge practical value.

Description

technical field [0001] The invention relates to a series of preparation methods of biphenyl triphosphine ligands and stepwise replacement of PPh in hydroformylation 3 Applications. Background technique [0002] Since the hydroformylation reaction was discovered by Professor Otto Roelen in 1938 (Chem Abstr, 1994, 38-550.), it has been widely used in industry. Since aldehydes can be easily converted into corresponding alcohols, carboxylic acids, esters, imines and other compounds with important uses in organic synthesis, aldehydes synthesized by hydroformylation have been widely used in industrial production. synthesis. The annual industrial production of aldehydes produced by hydroformylation has reached 10 million tons (Adv. Synth. Catal. 2009, 351, 537–540). [0003] In the hydroformylation reaction, although bidentate phosphine ligands and tetradentate phosphine ligands have been widely reported and patented by large foreign chemical companies such as BASF, Dow, Shell a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50C07F9/58C07F9/6568C07F9/6571C07F9/6574B01J31/24C07C47/02C07C45/50
Inventor 张绪穆陈才友
Owner WUHAN UNIV
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