Preparation of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine_Kain Industrial Additive

Background and overview^[1]

2,4,6-Tris(4-aminophenyl)-1,3,5-triazine is a heterocyclic organic compound that can be used as a pharmaceutical synthesis intermediate.

Preparation^[1]

Preparation of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine:

Method 1: Add 1.18g (10mmol) of p-aminobenzonitrile to a 50mL four-necked flask, add 25mL of methylene chloride under magnetic stirring to dissolve it, and slowly add 4mL (45mmol) of trifluoromethanesulfonate dropwise in an ice bath. Acid, add N2 to protect the reaction for 24 hours. After the reaction is completed, separate the layers and remove the lower yellow oil layer, add 20 mL of water and adjust the pH to 9-11 with 50% sodium hydroxide solution, precipitate a light yellow solid, filter, wash and dry to obtain products 2, 4, 6 -Tris(4-aminophenyl)-1,3,5-triazine 993 mg, yield 85.0%. Melting point: >300℃. HNMR (400MHz, DMSO): 8.38 (d, J=2.1Hz, 6H, Benzene-H), 6.71 (d, J=8.5Hz, 6H, Benzene-H), 5.90 (s, 6H, NH). Elemental analysis data: C21H18N6, theoretical value: C, 71.17; H, 5.12; N, 23.71. Actual values: C, 71.15; H, 5.13; N, 23.72. IR(KBr): 3321, 3214, 3030, 1637, 1604, 813cm.

Method 2: The preparation of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine is as follows:

P1: Mix 2,5-pyridine dimethanol and selenium dioxide in the 1,4-dioxane solution at a molar ratio of 1:1, stir vigorously under reflux at 100°C, and react with a reaction time of 6 hours, after the reaction is completed, it is filtered and concentrated to obtain a solid, which is then separated by column chromatography (developing solvent: methylene chloride: ethyl acetate = 2:1) to obtain a light pink solid, namely 2,5-dimethyl Acylpyridine.

P2: The mass ratio of p-aminobenzonitrile and trifluoromethanesulfonic acid is 0.18:1, and the reaction is fully stirred at room temperature under nitrogen protection for 24 hours. After that, an appropriate amount of distilled water is added and adjusted with 2M sodium hydroxide solution. pH=7, filter, wash with distilled water several times and dry the resulting light yellow solid, which is 2,4,6-tris(4-aminophenyl)-1,3,5-triazine.

Main reference materials

[1] CN201810684208.8 A kind of helix structure imine iron complex

[2] CN201811373603.0 A covalent organic framework material and its preparation method and application in the synthesis of hindered amines