Preparation methods and applications of tetraethylcyanocopper tetrafluoroborate hexafluorophosphate_Industrial additives

Background and overviewQuenching agent^[1]

Tetraethylcyanocopper hexafluorophosphate tetrafluoroborate, namely tetra(acetonitrile) copper (I) tetrafluoroborate, can be prepared in one step from HBF4 and Cu2O. There are reports in the literature that it can be used to prepare a 5-fluorouracil-1-ylacetate phenanthroline copper tetrafluoroborate anti-cancer functional complex.

Preparation^[1]

Add 13 mL of 48-50% HBF4 slowly to a stirred suspension of 4.0 g (28 mmol) Cu2O in 80 mL CH3CN. The reaction is exothermic. When the addition is complete, stir the solution for approximately 5 minutes. Filter the solution while hot to remove undissolved solids. Add an equal volume of diethyl ether to the light blue filtrate. The solution was cooled to 0°C for 2 hours and white crystallites formed. The solid was collected by filtration under nitrogen. The solid was washed with diethyl ether. The solid was then immediately dried under vacuum.

Apply^[2]

Tetrakis (acetonitrile) copper (I) tetrafluoroborate can be used to prepare a 5-fluorouracil-1-ylacetate phenanthroline copper tetrafluoroborate anti-cancer functional complex. The method is as follows:

(1) Dissolve 51.2g (92mmol) sodium hydroxide solid in 160mL aqueous solution, and then dissolve 31.2g (92mmol) 5-fluorouracil in the aqueous sodium hydroxide solution;

(2) At 40°C, slowly add 80 mL of a solution containing 50 g (360 mmol) bromoacetic acid to the above solution dropwise over 120 minutes, and stir at this temperature overnight;

(3) After cooling to normal temperature, use concentrated HCl to adjust the pH value of the solution to 5.5, and then place the solution in the refrigerator for 2 hours;

(4) If precipitate precipitates, filter to remove the precipitate, then add concentrated hydrochloric acid to adjust the pH value of the solution to 2, and then refrigerate it in the refrigerator for 8 hours until the white precipitation is complete Precipitate;

(5) Wash the filtered white precipitate three times with high-purity water, and finally dry it to obtain the compound 5-fluorouracil-1-ylacetic acid, the expression is 5-FUAA, recorded as L1;

(6) Dissolve 0.0945g (0.3mmol) tetrafluoroborate (acetonitrile) copper (I) and 0.0564g (0.3mmol) 5-FUAA in 5 mL methanol, and sonicate to dissolve;

(7) Then add 0.1189g (0.6mmol) 1,10-phenanthroline. After a constant temperature reaction of 70°C for 20 hours under sealed conditions, and cooling to room temperature, blue block crystals of [Cu(phen)2L1]BF4·H2O can be obtained.

Structural characterization of 5-fluorouracil-1-ylacetate-phenanthroline copper tetrafluoroborate anti-cancer functional complex. The [Cu(phen)2L1]BF4·H2O belongs to the tetragonal crystal system and the space group is I4(1)/a, the central metal copper is coordinated with the nitrogen atoms in two 1,10-phenanthroline molecules and the 5-fluorouracil-1-yl acetic acid anion to form a five-coordinate compound.

The application of 5-fluorouracil-1-ylacetate phenanthroline copper tetrafluoroborate anti-cancer functional complex. The [Cu(phen)2L1] BF4·H2O has a certain stability at ambient temperature. The interaction mode with DNA is electrostatic interaction, which can effectively inhibit the growth of human breast cancer cells and human colon cancer cells, and has certain anti-cancer activity.