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Synthesis method based on diaminomaleonitrile asymmetric Schiff base

A technology of diaminomaleonitrile and synthetic method, which is applied in the field of synthesis of asymmetric Schiff base ligands based on diaminomaleonitrile, can solve the problem of low yield of Schiff base, lack of wide applicability, and solvent consumption Large and other problems, to achieve the effect of low cost, easy control of chemical components, and high reactivity

Inactive Publication Date: 2016-05-04
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, methods for synthesizing asymmetric Schiff bases include template method, direct synthesis method, space-occupying method, etc., wherein the template method needs to add a masking agent or precipitant; the direct synthesis method has a low yield of Schiff base and a large amount of solvent consumption, etc. Some factors are subject to certain restrictions; Elder excess diamine method [R.C.Elder, Aust.J.Chem.31 (1978) 35-45], Sinn piperidine method [R.Atkins, G.Brewer, E.Kokot, G.M.Mockler , Inorg.Chem.24 (1985) 127-134] and Yao Kemin's asymmetric diamine method [K.Yao, W.Zhou, G.Lu, Science in China Series B-Chemistry, 42 (1999) 164-169] and other methods are not It has wide applicability and is only effective for the synthesis of a certain Schiff base

Method used

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  • Synthesis method based on diaminomaleonitrile asymmetric Schiff base
  • Synthesis method based on diaminomaleonitrile asymmetric Schiff base
  • Synthesis method based on diaminomaleonitrile asymmetric Schiff base

Examples

Experimental program
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Effect test

Embodiment 1

[0022] (1) Preparation of intermediate Ac-DAMN: Weigh 1.083g (10.0mmol) DAMN into a 50mL round bottom flask, add 10mL ethyl acetate, stir to dissolve. Then weigh 1.000g (13.0mmol) acetyl chloride in a 25mL beaker, add 5mL ethyl acetate to dissolve, transfer the reaction solution to a constant pressure dropping funnel, install the device, add acetyl chloride dropwise to DAMN, and react in ice Stirring was carried out in a water bath. During the reaction, the product gradually changed from brown to brownish yellow. The reaction product was filtered with suction, washed with 10 mL of ethyl acetate and 10 mL of diethyl ether, and dried to obtain wheat yellow powder Ac-DAMN.

[0023] (2) Preparation of asymmetric Schiff base ligand salicylaldehyde acetylated diaminomaleonitrile: Weigh 1.500g (10.0mmol) Ac-DAMN in a 50mL round bottom flask, add 10mL absolute ethanol, stir, Let it dissolve. Then weigh 1.220g (10.0mmol) of salicylaldehyde in a 25mL beaker, add 10mL of absolute ethan...

Embodiment 2

[0025] Preparation of zinc complex: Weigh 0.025g (0.1mmol) L into a 25mL beaker, add 5mL of methanol, stir to dissolve, drop in 0.2mL of DMF, then add 1mL of 0.1mol / L NaOH methanol solution, stir for 0.5h, the ligand Completely dissolved, red. Then weigh 0.030g (0.1mmol) Zn(NO 3 ) 2 ·6H 2 O was dissolved in 4 mL of methanol solution in a 25 mL beaker, and this solution was added to the previous L solution, the color of the solution quickly changed to orange red, stirred for 0.5 h, and the solution remained clear. Filtrate, take the filtrate and let it stand at room temperature, and use the room temperature volatilization method for 5 days to precipitate small orange-yellow cube-shaped crystals.

[0026] X-ray single crystal diffraction test was carried out on the single crystal of the prepared asymmetric Schiff base zinc complex ( Figure 4 ) and thermogravimetric analysis ( Figure 5 ). Table 1 and Table 2 are the crystallographic data, structure revision data and parti...

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Abstract

The invention discloses a synthesis method based on diaminomaleonitrile asymmetric Schiff base. The asymmetric Schiff base synthesis method, namely an acyl chloride occupation method, is efficient, simple and wide in application and is explored by virtue of high acyl chloride reaction activity. The preparation method of the base comprises the following steps: enabling reaction of diaminomaleonitrile and acetyl chloride in an ice water bath to obtain a monoacetylated product Ac-DAMN, and then enabling a condensation reaction with salicylaldehyde to obtain an asymmetric Schiff base ligand; enabling reaction of the ligand and Zn(NO3)2*6H2O in a methanol solution to obtain a coordination crystal. The method is simple in reaction, mild in condition, easy to operate and high in product yield, and is a novel technology for designing and synthesizing the asymmetric Schiff base through the acyl chloride occupation method and further synthesizing the asymmetric Schiff base complex.

Description

technical field [0001] The invention belongs to the field of synthesis of organic functional ligands, in particular to a synthesis method based on diaminomaleonitrile asymmetric Schiff base ligands. Background technique [0002] Schiff bases are a class of important organic molecules containing C=N double bonds based on aldehyde-amine condensation reactions. In view of the abundance of various aldehyde and amine compounds, Schiff bases have developed into a large class of functional organic molecules, especially It is a flexible substituent group on the Schiff base and the N atom in the C=N group of the Schiff base can become a donor interacting with metal ions. Therefore, the Schiff base is another important class of organic ligands. . At present, various Schiff base complexes have been developed and have been applied in the fields of catalytic industry, biopharmaceuticals, and functional materials. Most of these Schiff base ligands and their complexes are symmetrical mol...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C255/30C07F3/06
CPCC07F3/003C07B2200/13C07C253/30C07C255/30
Inventor 李晖常鸽杨建杰郭旭祯
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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