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A kind of preparation method of 1-naphthol-based phosphine oxygen ligand

A naphthol-based phosphine and ligand technology is applied in the field of preparation of 1-naphthol-based phosphine oxygen ligands, and can solve the problems affecting the development and application of ligands, harsh conditions, difficult handling, etc., and achieves high yield and reaction Mild conditions and good substrate adaptability

Active Publication Date: 2021-11-09
FOSHAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the traditional methods for synthesizing 1-naphthylphosphine oxygen ligands have problems such as harsh conditions, difficult handling, and single structure, which greatly affect the development and application of such ligands.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0011] Preparation (2-phenyl-4-hydroxyaphthyl) diphenyl phosphate, structural formula:

[0012] In a 25 ml Schlenk tube equipped with a magnetized 25 ml Schlenk tube, phenylthynthyldin-based phenyl phosphate (0.1 mmol), benzoyl sulfur, 6.66 mg (0.008 mmol, 8%) [RHCP * (CH 3 CN) 3 ] (SBF 6 ) 2 5.5 mg (0.03 mmol, 30%) zinc acetate, then add 4.0 ml of dried DCE, placed in a preheated 80 ° C oil bath, reacted in a nitrogen atmosphere for 16 h, and the reaction is removed from the heat source, then Dichloromethane was added to the round bottom flask, and the solvent was removed with a rotary evaporator, ethyl acetate / dichloromethane = 1: 3 over silica gel columns to obtain 38.6 mg of the target product, and the yield was 92%.

[0013] The characterization of the compound is as follows:

[0014] 1 H NMR (400MHz, DMSO): δ 10.48 (S, 1H), 8.24 (D, J = 8.2 Hz, 1H), 7.60-7.54 (m, 1H), 7.54-7.37 (M, 11H), 7.20-7.12 (m, 2H), 7.04 (t, j = 7.6 Hz, 2H), 6.99-6.89 (m, 3H);

[0015] 13 C NMR (10...

Embodiment 2

[0019] Preparation (7-methyl-2-phenyl-4-hydroxyapanedaphthyl) diphenyrophosphate, structural formula:

[0020] In a 25 ml Schlenlenk tube with a magnetized, phenylethynthyne phenyl phosphate (0.1 mmol), 4-methylbenzoyl sulfur, and 6.66 mg (0.008 mmol, 8) were added. %) [RHCP * (CH 3 CN) 3 ] (SBF 6 ) 2 5.5 mg (0.03 mmol, 30%) zinc acetate, then add 4.0 ml of dried DCE, placed in a preheated 80 ° C oil bath, reacted in a nitrogen atmosphere for 16 h, and the reaction is removed from the heat source, then Dichloromethane was added to the round bottom flask, and the solvent was removed with a rotary evaporator, ethyl acetate / dichloromethane = 1: 3 over silica gel columns were 32.0 mg of the target product, and the yield was 74%.

[0021] The characterization of the compound is as follows:

[0022] 1 H NMR (400MHz, DMSO): Δ10.42 (S, 1H), 8.14 (D, J = 8.5 Hz, 1H), 7.53-7.46 (m, 6H), 7.39 (TD, J = 8.1, 2.1 Hz, 5H ), 7.15 (DD, J = 10.5, 4.03 (T, J = 7.6 Hz, 2H), 6.94 (S, 1H), 6.89 (DD,...

Embodiment 3

[0027] Preparation of (2-phenyl-4-hydroxy-7-methoxynylmethyl) diphenyl oxygen, structural formula:

[0028] Aphenyl Schlenlenk tube equipped with a magnetized 25 ml Schlenk tube was added to add phenylacetyl diphenyl phosphate (0.1 mmol), 4-methoxybenzyl sulfur, 6.66 mg (0.008 mmol, 8%) [RHCP * (CH 3 CN) 3 ] (SBF 6 ) 2 5.5 mg (0.03 mmol, 30%) zinc acetate, then add 4.0 ml of dried DCE, placed in a preheated 80 ° C oil bath, reacted in a nitrogen atmosphere for 16 h, and the reaction is removed from the heat source, then Dichloromethane was added to the round bottom flask, and the solvent was removed with a rotary evaporator, ethyl acetate / dichloromethane = 1: 3 paste the silica gel column to obtain 35.3 mg of the target product, and the yield was 78%.

[0029] The characterization of the compound is as follows:

[0030] 1 H NMR (400MHz, DMSO): Δ10.39 (S, 1H), 8.16 (D, J = 9.2 Hz, 1H), 7.50 (DD, J = 10.7, 7.8 Hz, 6H), 7.43-7.37 (M, 4H ), 7.25 (DD, J = 9.2, 2.5 Hz, 1H), 7.15 (T, ...

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PUM

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Abstract

The invention discloses a preparation method of 1-naphthyl phosphine oxygen ligand, which comprises uniformly mixing a sulfur ylide compound, a phenylethynyl phosphine oxide derivative, a catalyst, a Lewis acid and an organic solvent; React at a temperature of 100°C for 6-16 hours to obtain the finished product of 1-naphthylphosphine oxide ligand with the structural formula. The present invention can obtain the 1-naphthylphosphine oxygen ligand which is difficult to obtain in the existing synthetic method, and the steps are simple, only one step is required to construct the 1-naphthylphosphine oxygen ligand, and the reaction conditions are mild and the substrate It has good adaptability and high yield, and can synthesize a variety of 1-naphthylphosphine oxygen ligands with different substituents.

Description

Technical field [0001] The present invention relates to the field of organic synthesis, and more particularly to a method of preparing a 1-naphthol phosphine ligand. Background technique [0002] Organic phosphine oxide, due to its phosphorchalastogen atoms having alone toward electrons, there is a strong coordination ability, and a complex can be formed from a plurality of metal ions. The phosphine oxide can also be used as a ligand in a multi-metal catalytic homogeneous catalytic reaction. It is widely used in chemical industrial production. For example, the transition metal ions can be extracted from the aqueous solution, and the excitation wavelength of the metal ion can be adjusted in the organic light-emitting material, and the chiral phosphine ligand can be used as a chiral Lewis acid-type catalyst to an asymmetric synthesis. However, the method of traditional synthetic 1-naphthalein phosphine ligands has problems such as demanding, not easy to handle, structural single, e...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/53
CPCC07F9/5325
Inventor 谢吴成张滢简心仪林钦洪林佳豪
Owner FOSHAN UNIVERSITY