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Use of bisphosphine ligand in hydroformylation of olefin

A bisphosphine ligand and hydroformyl technology, which is applied in the preparation of carbon monoxide reaction, organic compound/hydride/coordination complex catalyst, organic chemistry, etc., can solve the problems of less research and achieve high reaction conversion rate and selectivity sex excellent effect

Active Publication Date: 2010-07-07
SHANGHAI GREENCARBON HI TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Different from the first two types of ligands, the research on this type of ligands, especially the pyrrole-substituted bidentate phosphoramidite ligands, in the Rh(I)-catalyzed hydroformylation of alkenes is still relatively small.

Method used

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  • Use of bisphosphine ligand in hydroformylation of olefin
  • Use of bisphosphine ligand in hydroformylation of olefin
  • Use of bisphosphine ligand in hydroformylation of olefin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1: Synthesis of the following bidentate phosphoramidite ligands

[0032]

[0033] Dipyrrole phosphorus chloride Synthesis from phosphorus trichloride and pyrrole: add anhydrous tetrahydrofuran (200mL) and phosphorus trichloride (8.7mL, 0.1mol) to a 500mL three-neck flask under argon atmosphere, add pyrrole (13.9mL, 0.2 mol) and triethylamine (28mL, 0.2mol) in anhydrous tetrahydrofuran (50mL) solution, after 2 hours of dropwise addition, slowly warm up to room temperature and stir overnight, remove triethylamine hydrochloride by filtration under argon atmosphere, reduce pressure Most of the solvent was evaporated, and the residue was purified by distillation under reduced pressure. Fractions at 80° C. (1 mmHg) were collected to obtain 16.0 g of a colorless oil, with a yield of 81%. 1 H NMR (300MHz, CDCl 3 )δ7.07-7.10 (m, 4H), 6.39 (t, J = 2.1Hz, 4H); 31 P NMR (121.46MHz, CDCl 3 )δ104.35(s).

[0034] Under argon atmosphere, add dipyrrole phosphorus chlori...

Embodiment 2

[0036] Example 2: Synthesis of the following bidentate phosphoramidite ligands

[0037]

[0038] Under argon atmosphere, add dipyrrole phosphorus chloride (600mg, 3.0mmol) and anhydrous tetrahydrofuran (5mL) into a 50mL Schlenk tube respectively, cool to 0°C, drop (0.26g, 1.2mmol) and anhydrous triethylamine (0.46mL, 3.3mmol) in anhydrous tetrahydrofuran (5mL) solution, slowly warming up to room temperature and stirring overnight, stop the reaction, spin off the solvent under reduced pressure, column chromatography ( Eluent: petroleum ether: CHCl 3 =1 / 1) 239 mg of a colorless oily substance was isolated, with a yield of 37%.

[0039] 1 H NMR (400MHz, CDCl 3 )δ=7.61(d, J=7.2Hz, 2H), 7.37(t, J=7.5Hz, 2H), 7.17(t, J=7.2Hz, 2H), 6.91(s, 8H), 6.77(d, J=7.8Hz, 2H), 6.34(d, J=1.5Hz, 8H); 31 P NMR (121.46MHz, CDCl 3 ,) δ=107.14(s); 13 C NMR (75MHz, CDCl 3 )δ=151.37, 151.22, 133.33, 131.47, 131.05, 124.26, 121.47, 121.36, 121.24, 119.14, 118.95, 112.78, 112.43, 112.36; , 1...

Embodiment 3

[0040] Example 3: Synthesis of the following bidentate phosphoramidite ligands

[0041]

[0042] Under argon atmosphere, add dipyrrole phosphorus chloride (600mg, 3.0mmol) and anhydrous tetrahydrofuran (5mL) into a 50mL Schlenk tube respectively, cool to 0°C, drop (0.656g, 1.2mmol) and anhydrous triethylamine (0.46mL, 3.3mmol) in anhydrous tetrahydrofuran (5mL) solution, slowly warming up to room temperature and stirring overnight, stop the reaction, spin off the solvent under reduced pressure, column chromatography ( Eluent: petroleum ether: CHCl 3 =1 / 1) isolated to obtain 826mg of yellow solid with a yield of 79%.

[0043] m.p.60-61℃; 1 H NMR (400MHz, CDCl 3 )δ=7.27-7.17(m, 14H), 7.03-7.00(m, 10H), 6.82-6.79(m, 8H), 6.55(dd, J=1.6, 6.8Hz, 2H), 6.24(dd, J= 2.0, 2.4Hz, 8H), 5.41(s, 2H); 31 P NMR (121.46MHz, CDCl 3 ,) δ=106.26(s); 13 C NMR (75MHz, CDCl 3 )δ=192.99,149.87,149.77,142.97,140.01,134.16,132.05,131.02,130.98,129.26,128.43,128.34,126.57,126.42,121.56,121.3...

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Abstract

The invention relates to a substitutive bidentate phosphoramidite ligand of a diphenyl ketone framework in the catalysis of hydroformylation and Isomerization-hydroformylation of isomerised olefins. In an atmosphere of an inert gas or N2, the ligand is reacted with an Rh salt in an organic solvent to obtain a ligand / Rh catalyst. In the atmosphere of the inert gas or N2, an olefin substrate is added into solution of the ligand / Rh salt catalyst, CO and H2 are charged into the solution respectively to undergo a raction to form the a hydroformylated product, namely a compound having formyls, wherein the conversion rate of the reaction is high; and the selectivity of the n-alkanal product is high. The substitutive bidentate phosphoramidite ligand of the diphenyl ketone framework has a structural formula below.

Description

technical field [0001] The invention relates to a catalyst for preparing olefin hydroformylation or olefin isomerization-hydroformylation reaction by substituting bidentate phosphoramidite ligand of diphenyl ketone skeleton. The catalyst can be used to catalyze the hydroformylation reaction of olefinic compounds to synthesize compounds containing aldehyde groups. Background technique [0002] Since the discovery of olefin hydroformylation by Roelen in 1938, since this process can conveniently and effectively convert the cheap and easy-to-obtain basic chemical raw material olefins into a variety of important fine chemicals, so far, it has become the largest homogeneous One of the catalytic processes. [Yin Yuanqi, "Oxylation Chemistry", Chemical Industry Press, Beijing, 1995], [Frohning, C.D.; Kohlpaintner, C.W. in Applied Homogeneous Catalysis with Organometallic Compounds, ed.By Cornils, B.; Herrmann, W.A.VCH, Weinheim, New York, 1996, Vol 1, pp29-104.], [Bhaduri, S.; Muke...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/49B01J31/22C07C47/02
Inventor 丁奎岭彭新高王正吴江
Owner SHANGHAI GREENCARBON HI TECH CO LTD
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