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Pincer-shaped skeleton ligand containing phosphine bond and preparation of ligand, and preparation method of Pincer-shaped organic compound

A pincer-shaped, skeleton-like technology, applied in the field of preparation of Pincer-type metal-organic compounds, to achieve the effects of high yield, low cost, and easy availability of raw materials

Inactive Publication Date: 2014-07-02
QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] It is difficult for existing phosphine-containing pincer skeleton ligands to carry out coordination reactions with anhydrous inorganic salts in organic solvents. It is necessary to improve the solubility of inorganic salts first, and then synthesize new metal inorganic salts for coordination synthesis reactions.

Method used

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  • Pincer-shaped skeleton ligand containing phosphine bond and preparation of ligand, and preparation method of Pincer-shaped organic compound
  • Pincer-shaped skeleton ligand containing phosphine bond and preparation of ligand, and preparation method of Pincer-shaped organic compound
  • Pincer-shaped skeleton ligand containing phosphine bond and preparation of ligand, and preparation method of Pincer-shaped organic compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] In the structural formula of the pincer skeleton ligand containing a phosphono bond, when R1, R2 and R4 are hydrogen, R3 is a methyl group.

[0023] The synthetic route of this phosphono bond-containing pincer skeleton ligand is as follows:

[0024]

[0025] The synthesis method is:

[0026] (1) Dissolve 8 mL of diphenylphosphine in 60 mL of tetrahydrofuran, cool down to -78°C, add 26 mL of cyclohexane containing 0.52 mol of lithium diisopropylamide into the above tetrahydrofuran containing diphenylphosphine, and stir for reaction 2 -3h. Then rise to room temperature and react for 30 min.

[0027] (2) Cool down the reaction solution obtained in step (1) to -78°C, and drop 100mL of tetrahydrofuran containing 0.018mol 3,5-dibromomethyltoluene into the reaction solution obtained in step (1) in the above step (1) when the temperature is lowered to -78°C , and dropwise addition was completed within 30 minutes. The reaction was then stirred overnight at room temperatur...

Embodiment 2

[0032] When R1, R2 and R4 are methyl groups in the structural formula of the pincer skeleton ligand containing phosphono bonds, R3 is hydrogen.

[0033] The synthetic route of this phosphono bond-containing pincer skeleton ligand is as follows:

[0034]

[0035] The synthesis method is:

[0036] (1) Mix m-trimethylbenzene and paraformaldehyde at a molar ratio of 1:2, dissolve in 40 mL of acetic acid solution containing 33% hydrobromic acid by mass ratio, and react at 80°C for 8 hours. Then add water, stir and analyze for 1-2h, filter and wash, and dry to obtain a white solid. The solid was recrystallized in chloroform to give 2,4-dibromomethyl-1,3,5-trimethylbenzene.

[0037] (2) Dissolve 12.5mL of diphenylphosphine in 125mL of tetrahydrofuran, lower to -78°C, then add 40mL of cyclohexane containing 0.2mol of lithium diisopropylamide into the tetrahydrofuran of diphenylphosphine, and stir Reaction 2-3h. Then rise to room temperature and react for 30min.

[0038] (3) Lo...

Embodiment 3

[0043] The difference from Example 1 is that the 1,3-dibromobenzyl derivative can be prepared from 1,5-dibromomethyl-2,4-dimethylbenzene, 1,5-dibromomethyl-2, 3,4-trimethylbenzene or 1,3-dibromomethyl-2,4,5,6-tetramethylbenzene for replacement; the specific preparation is to mix benzene derivatives and paraformaldehyde at a molar ratio of 1:2 Mix and add 40-50mL of hydrobromic acid in 33% acetic acid solution, react at 80°C for 6-12 hours; add water after reaction, stir for 1-2 hours, filter and wash, and dry to obtain a white solid in chloroform Recrystallized and set aside.

[0044] The benzene derivatives are toluene, m-trimethylbenzene, m-xylene, 1,2,3-trimethylbenzene or 3,4,5-trimethyltoluene.

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Abstract

The invention relates to preparation of a Pincer-shaped metallic organic compound, and particularly relates to a pincer-shaped skeleton ligand containing a phosphine bond and preparation of the ligand, and a preparation method of the Pincer-shaped organic compound. The structural formula of the ligand is shown in a formula 1 described in the specification, wherein R1, R2, R3 and R4 can be hydrogen or methyl. The ligand is simple in synthetic process, low in cost, high in yield, easily available in raw materials, and mild in reaction conditions. The chemical formula of the Pincer-shaped metallic organic compound formed by the pincer-shaped skeleton ligand containing the phosphine bond and cobalt atoms is C35H34Cl2CoO2P2, and the structural formula of the Pincer-shaped metallic organic compound can be abbreviated into (DPPM)CoCl2, wherein DPPM is 2,4-diphenyl dibenzyloxy phosphoiyl methylene mesitylene, the molecular weight is 678.43, the DPPM belongs to a triclinic system, the space group is P1, and the unit cell parameters are a=9.258(2) angstrom, b=12.881(3) angstrom, c=17.405(4) angstrom, alpha=69.301(3) degrees, beta=88.193(4) degrees, gamma=81.061(3) degrees, V=1917.3(7) angstrom<3>, and Z=2.

Description

technical field [0001] The invention relates to the preparation of Pincer type metal organic compounds, in particular to a pincer skeleton ligand containing a phosphonic bond, its preparation and a method for preparing the Pincer type organic compound. Background technique [0002] The pincer skeleton ligands can coordinate with metal atoms to form Pincer-type metal organic compounds, in which the pincer ligands provide a highly stable chemical environment for the metal atoms and can precisely adjust the properties of the metal atoms, thereby effectively controlling the organic compounds. reactivity. The formed Pincer-type organometallic compounds are widely used in the fields of coordination chemistry, organic chemistry and homogeneous catalysis. The current Pincer-type skeleton complexes mainly include NNN, NCN, PCP and other types. Designing and synthesizing new pincer ligands to enrich the types of Pincer-type metal-organic compounds has become an indispensable research...

Claims

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Application Information

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IPC IPC(8): C07F9/53C07F15/06
Inventor 赵学波蒋敏李良军许贤瑞邢艳珑
Owner QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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