o-Phenanthroline CAS 66-71-7

Synthesis of 2-hydroxy-1,10-o-phenanthroline
Starting with l,10-phenanthroline, and then adding structural modifications on this basis, it is an important method to synthesize l,10-phenanthroline derivatives. The derivatives obtained in this way are mainly concentrated in 5, The 6-position, 3,8-position, 2,9-position, and the 5,6-position produced the highest number of derivatives. Derivatives of phenanthroline, as good metal ligands, are widely used in antibacterial and antitumor, catalytic reactions, supramolecular chemistry, DNA probes, molecular switches, etc. 2-Hydroxy-1,10-o-phenanthroline is an important 2-position derivative in 1,10-o-phenanthroline derivatives. The main synthesis method is through 2-halogenated-1,10-o-phenanthroline. The hydrolysis reaction is obtained. Due to the lack of access routes, there are relatively few studies on the properties and applications of 2-hydroxy-1,10-phenanthroline reported in the literature. CN201710460068.1 provides a kind of synthetic method of 2-hydroxyl-1,10-o-phenanthroline, and increases the source route of target product. For this reason, the present invention adopts the following route to synthesize 2-hydroxy-1,10-o-phenanthroline:

The reaction method takes 1,10-o-phenanthroline (2) as a starting material, reacts with benzyl halide to obtain an intermediate quaternary ammonium salt (3), and then oxidizes it with potassium ferricyanide to obtain 1-benzyl-1,10 -o-phenanthroline-2-one (4), then debenzylated under palladium-carbon catalysis to obtain 2-hydroxy-1,10-o-phenanthroline (1).

The preparation scheme of 2-hydroxy-1,10-o-phenanthroline is as follows: 1,10-o-phenanthroline (2) and benzyl halide are heated to obtain 1-benzyl-1,10-o-phenanthroline halide salt (3 ), 1-benzyl-1,10-o-phenanthroline halide salt (3) was oxidized by potassium ferricyanide in cold aqueous solution to obtain 1-benzyl-1,10-o-phenanthroline-2-one (4) ), and finally low-pressure hydrogenation in the presence of palladium-carbon catalyst to obtain 2-hydroxy-1,10-o-phenanthroline (1). The benzyl halide used in this scheme can be selected from benzyl chloride or benzyl bromide, and can also be a derivative of benzyl chloride or benzyl bromide; it is better to control the temperature at -5 to 5°C when potassium ferricyanide is oxidized; The hydrogen pressure in the case of the benzyl group may be normal pressure or a hydrogen pressure not higher than 1 MPa.

CN201410517030.X provides an organic-silica gel hybrid capillary monolithic column modified by o-phenanthroline and its application. The organic-silica gel hybrid capillary monolithic column not only eliminates the complicated and tedious operations such as traditional packing column packing, and sintered plugs It also overcomes the shortcomings of low open-column capacity and small comparison, and its chemical properties are stable, reproducible, and have more sites of action with the sample. Good separation effect. In order to achieve the above object, the present invention adopts the following technical scheme: an organic-silica gel hybrid capillary monolithic column modified by o-phenanthroline, using o-phenanthroline as an ionic liquid, subjected to capillary pretreatment, column bed preparation, and column bed modification The organo-silica hybrid capillary monolithic column was prepared.

Its preparation method comprises the following steps:

1. Capillary pretreatment: take a capillary column of appropriate length, pass water for 0.5 h, 1 M hydrochloric acid for 1 h, water for 0.5 h, and 1 M sodium hydroxide for 0.5 h, plug both ends and react at 100 °C for 3 h; Water for 0.5 h, 0.1 M hydrochloric acid for 0.5 h, water for 0.5 h, methanol for 0.25 h, acetone for 0.25 h, and then nitrogen blowing at 180 °C for 3 h.
2. Preparation of column bed: Dissolve polyethylene glycol and urea in 0.01 mol/L acetic acid solution, stir until completely dissolved, place in an ice bath at 0 °C, and add tetramethoxysilane and chloropropyltrimethoxysilane dropwise silane, vigorously stirred for 4 h to obtain a transparent and uniform sol mixture; the sol mixture was ultrasonically oscillated for 5 min and then injected into the pretreated capillary, both ends of the capillary were sealed, reacted in a water bath at 55 °C for 12 h, and then distilled water respectively. Rinse with methanol to obtain chloropropyl-silica hybrid capillary monolithic column.
3. Column bed modification: After ultrasonically treating the methanol aqueous solution containing o-phenanthroline and sodium iodide for 5 min, inject it into the prepared capillary, bath in 80 °C water for 12 h, and then rinse with double distilled water and methanol respectively to obtain Modified organo-silica hybrid capillary monolithic column.

The significant advantages of the present invention are:

1. The present invention uses o-phenanthroline to modify the organic-silica gel hybrid capillary monolithic column, because the positive charge of o-phenanthroline can provide ion exchange sites, and at the same time, it has a pyridine ring with a large π-conjugated system and has a symmetrical structure, The monolithic column prepared with it has various forces such as π-π interaction, hydrogen bonding and electrostatic interaction, which can improve the separation effect.
2. The present invention utilizes the organic-silica gel hybrid capillary monolithic column modified by o-phenanthroline, which not only eliminates the complicated and tedious operations such as traditional packed column packing, and the generation of air bubbles caused by sintered plugs, but also overcomes the problem of opening the column. The disadvantages of low capacity and relatively small size have the advantages of stable structure and good reproducibility.