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Novel tridentate phosphine ligand and application of same to linear hydroformylation and similar reactions

A tridentate phosphine ligand, chemical reaction technology, applied in the preparation of carbon monoxide reaction, organic compound/hydride/coordination complex catalyst, organic chemistry, etc., can solve the problems that have not been reported in the literature of tridentate phosphine ligand

Active Publication Date: 2013-01-16
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At the same time, there is no literature report on any tridentate phosphine ligand

Method used

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  • Novel tridentate phosphine ligand and application of same to linear hydroformylation and similar reactions
  • Novel tridentate phosphine ligand and application of same to linear hydroformylation and similar reactions
  • Novel tridentate phosphine ligand and application of same to linear hydroformylation and similar reactions

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0112] Preparation of 2,2′,6-trimethoxybiphenyl (the preparation method of 2,2′,6-trimethoxybiphenyl can be found in literature: Chem.Eur.J.2003,9,3209-3215), synthesis The reaction formula is as follows:

[0113]

[0114] Add 29.9 g of m-diphenylmethyl ether into a dry 500 ml Schlenk bottle filled with nitrogen, and then add 170 mL of anhydrous tetrahydrofuran (THF) under the protection of nitrogen to obtain a mixed solution. 136 mL of 1.6 mol / L n-hexane solution of n-butyllithium was added dropwise to obtain a reaction system. After reacting for 1 h, 69 mL of a THF solution of o-bromoanisole was added dropwise to the reaction system, wherein the mass of o-bromoanisole was 18.7 g. After stirring at room temperature for 1 h, the temperature was raised to 60° C. for 12 h. After the reaction, the reaction system was cooled to room temperature, quenched by adding 200mL of water, the organic phase was separated, the aqueous phase was extracted twice with ether, the organic pha...

Embodiment 2

[0116] The preparation of 2,2′,6-trimethoxybiphenyl, the synthesis reaction formula is as follows:

[0117]

[0118] Add 182 mg of 2,6-dimethoxyphenylboronic acid to a dry Schlenk tube, and then add 2.2 mg of Pd(OAc) to the glove phase 2 , 14.3mg of Xphos, 318.5mg of anhydrous K 3 PO 4 . After replacing the Schlenk tube with a nitrogen atmosphere, 0.5 mmol of o-bromoanisole and 3 ml of anhydrous THF were added to obtain a reaction system, and the reaction system was reacted at 60° C. for 24 h. After the reaction was finished, add 3ml of water to quench, extract 3 times with dichloromethane, combine the obtained organic phases with anhydrous sodium sulfate, dry and spin dry, use petroleum ether and ethyl acetate as eluents and go through silica gel column chromatography The product obtained was a white solid with a yield of 82%. Rf=0.2(hexane / AcOEt=10:1); 1 H NMR (300MHz, CDCl 3 ):δ=3.63(s,6H;2OCH 3 ),3.66(s,3H;OCH 3 ),6.55-6.58(d, 3 J(H,H)=8.3Hz,2H;3,5-H),6.89-7.12...

Embodiment 3

[0120] The preparation of 2,2′,6-trihydroxybiphenyl, the synthesis reaction formula is as follows:

[0121]

[0122] 2.44 g of 2,2',6-trimethoxybiphenyl was added to a dry 250 mL Schlenk bottle, and after replacing the Schlenk bottle with a nitrogen atmosphere, 100 mL of anhydrous dichloromethane was added to obtain a mixed solution. Add 4.4 mL of boron tribromide dropwise to the mixed solution at -78 °C to obtain a reaction system. The reaction system was raised to room temperature and reacted for 5 h. After the reaction was finished, the reaction system was cooled to 0°C, quenched by adding 50ml of water dropwise, the organic phase was separated and collected, the aqueous phase was extracted three times with ethyl acetate, each extraction was performed with 25mL ethyl acetate, the organic phases were combined and washed with anhydrous After drying over sodium sulfate, it was filtered and spin-dried, and the residue was separated by silica gel column chromatography with p...

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Abstract

The invention discloses a novel tridentate phosphine ligand and application of the same to linear hydroformylation and similar reactions. The tridentate phosphine ligand is applied to efficient high-selectivity hydroformylation for the first time at present and applicable to efficient high-selectivity isomerized hydroformylation, hydrocarboxylation, hydrocyanation, isomerized formylation, hydroaminomethylation and the similar reactions. During the linear hydroformylation, selectivity of the tridentate phosphine ligand is obviously higher than that of a corresponding bidentate phosphine ligand. Besides, compared with a corresponding quadridentate phosphine ligand, the tridentate phosphine ligand is approximate in selectivity, easier to synthesize and higher in yield and displays higher TON (turnover number). The novel tridentate phosphine ligand selectively converts 1-hexylene and 1-octylene into n-heptaldehyde (used for synthesis of orange essence and rose essence) and n-nonaldehyde (flavoring matter) and is of great significance to hydroformylation-based industrial production.

Description

technical field [0001] The present invention relates to a series of novel tridentate phosphine ligands and their use in linear hydroformylation and similar reactions. Background technique [0002] The hydroformylation reaction was discovered by Professor Otto Roelen in 1938 [1] , and then widely used in industry, and now hydroformylation has become the largest homogeneous catalytic reaction in industrial production. The annual production of aldehydes and alcohols through Fe, Zn, Mn, Co, Cu, Ag, Ni, Pt, Pd, Rh, Ru, Ir and other metal-catalyzed hydroformylation reactions has reached 10 million tons [2] . [0003] In industry, the important intermediate butyraldehyde is obtained through the linear hydroformylation reaction catalyzed by Rh with propylene as the starting material, and the annual production of the plasticizer dioctyl phthalate (DEHP) through subsequent reactions reaches 3 million t, the reaction process see figure 1 . At the same time, in order to increase th...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/572C07F9/6584C07F9/46C07F9/145C07F9/6571C07F9/6568C07F9/6574C07F9/50C07F9/48B01J31/24C07C45/50C07C47/02C07C47/228
Inventor 张绪穆陈才友
Owner WUHAN UNIV
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