Preparation method of 4, 4'-dinitrobibenzyl

A technology of dinitrobibenzyl and p-nitrotoluene, which is applied in the field of fine chemicals, can solve the problems of poor recycling of waste alkali, high industrialization cost, troublesome reaction operation, etc., and achieve a green and efficient reaction system and a safe and clean oxidant , the effect of mild reaction conditions

Active Publication Date: 2021-11-12
CHINA THREE GORGES UNIV
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Problems solved by technology

The reductive coupling method mainly uses p-nitrobenzyl halides as raw materials, organic solvents, inorganic solvents or ionic liquids as solvents, and transition metals, metal salts, metal complexes, etc. as catalysts for catalytic reactions (Tetrahedron Lett., 2015, 56 (19), 2480-2487; New J.Chem., 2016, 40(12), 9912-9916; Catal.Sci.Technol., 2015, 5(9), 4336-4340; Chem.Commun., 2014, 50(36), 4674-4676), the product yield of this process is high, but a large amount of halogen-containing by-products will cause environmental pollution and corrode equipment during the reaction process, and the catalyst cannot be recovered well, and the operating cost is high
The diphenylethane nitration method mainly uses diphenylethane as a raw material, and the nitric acid with a specific gravity of 1.42 is used as a nitrating reagent or a mixed acid for nitration reaction (Ind.Eng.Chem.Prod.Res.Dev., 1977,16,309-311), The product yield of this process is high, but the selectivity of the reaction process is low, and a large amount of waste acid will be produced, the post-treatment is troublesome, the operation cost is high, and it is not environmentally friendly.
Oxidative coupling is a very promising method. The oxidation...

Method used

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  • Preparation method of 4, 4'-dinitrobibenzyl
  • Preparation method of 4, 4'-dinitrobibenzyl
  • Preparation method of 4, 4'-dinitrobibenzyl

Examples

Experimental program
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Effect test

Embodiment 1

[0038] The preparation method of metal-modified mesoporous material supported guanidinium salt ionic liquid catalyst comprises the following steps:

[0039] (1) Tetrabutylurea (0.5mol) and phosphorus oxychloride (0.6mol) react in toluene (200mL) solvent at 65°C for 24 hours, then add n-hexylamine (1.25mol) and continue the reaction for 22 hours, then add mass Adjust the pH to neutral with a fraction of 20% NaOH aqueous solution, extract the mixture with dichloromethane (400 mL), recover the solvent, and dry to obtain intermediate a;

[0040] (2) Then react intermediate a (0.3mol) with 3-chloropropyltriethoxysilane (0.3mol) in toluene (180mL) at 100°C for 24 hours, recover the solvent and dry to obtain intermediate b;

[0041] (3) intermediate b (0.15mol) in acetonitrile (180mL) solvent and CoCl 2 , CuCl or CeCl 3 (0.2mol) was reacted at 70°C for 24 hours, washed with acetonitrile, and dried to obtain ionic liquid c;

[0042] (4) Ionic liquid c (6 g) was reacted with transit...

Embodiment 2

[0046] In the reactor, add p-nitrotoluene (0.1mol), ethanol (100mL), Ir-FDU-12@ILCuCl 2 (0.4g), oxygen was introduced under stirring, and the oxygen flow rate was 3mL / min, and then the stirring reaction was continued at 45°C for 2 hours. The product phase and the catalyst phase can be separated by pouring it while it is hot, and the filtrate is cooled to room temperature, and the product is precipitated from the filtrate, filtered, and dried to obtain the pure product 4,4'-dinitrobibenzyl with a yield of 94%. figure 1 The HPLC analysis results showed that the purity of 4,4'-dinitrobibenzyl was 99.2%.

Embodiment 3

[0048] In the reactor, add p-nitrotoluene (0.1mol), ethanol (100mL), Ir-FDU-12@ILCoCl 3 (0.6g), feed oxygen under stirring, the oxygen flow rate is 5mL / min, then continue to stir and react at 50°C for 3 hours. The product phase and the catalyst phase can be separated by pouring it while it is hot, and the filtrate is cooled to room temperature, and the product is precipitated from the filtrate, filtered, and dried to obtain the pure product 4,4'-dinitrobibenzyl with a yield of 78%. HPLC analysis is the same as in Example 2, only the purity of 4,4'-dinitrobibenzyl is 95.7%.

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Abstract

The invention discloses a novel preparation method of 4, 4'-dinitrobibenzyl. According to the method, p-nitrotoluene is used as a reactant, oxygen is used as an oxidizing agent, ethanol is used as a solvent, transition metal doped FDU-12 mesoporous molecular sieve supported guanidine salt ionic liquid is used as a catalyst, and 4, 4 '-dinitrobibenzyl is prepared through high-selectivity oxidative dehydrogenation coupling reaction. After the reaction is finished, the catalyst phase and the product phase are easily subjected to heterogeneous separation and can be well recycled. The method has the advantages of simple operation, mild reaction conditions, small catalyst dosage, high reaction efficiency and selectivity, and small discharge of three wastes, and is a novel green and clean preparation method.

Description

technical field [0001] The invention relates to a method for preparing 4,4'-dinitrobibenzyl through the oxygen-selective oxidative dehydrogenation coupling of p-nitrotoluene catalyzed by a mesoporous molecular sieve-loaded guanidinium salt ionic liquid, which belongs to the technical field of fine chemicals. [0002] technical background [0003] 4,4'-Dinitrobibenzyl is an important fine organic synthesis intermediate, which can be used in the production of medicines, pesticides, dyes, polymers, etc. At present, there are mainly three synthetic methods for preparing 4,4’-dinitrobibenzyl at home and abroad, namely reductive coupling method, diphenylethane nitration method and oxidative coupling method. The reductive coupling method mainly uses p-nitrobenzyl halides as raw materials, organic solvents, inorganic solvents or ionic liquids as solvents, and transition metals, metal salts, metal complexes, etc. as catalysts for catalytic reactions (Tetrahedron Lett., 2015, 56 (19),...

Claims

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Application Information

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IPC IPC(8): C07C201/12C07C205/06B01J31/02B01J29/04
CPCC07C201/12B01J31/0295B01J31/0279B01J29/043B01J29/045B01J2229/186B01J2231/46C07C205/06Y02P20/584
Inventor 胡玉林戎启李精锐刘杨
Owner CHINA THREE GORGES UNIV
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