Ammonia → 4,4'-Bis[3-(2-methacryloyloxyethyl)ureido]-3,3'-diaminobiphenyl

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Reaction Steps

Into a one-liter flask equipped with a stirrer, a thermometer, a thermocouple and a dry air inlet tube were charged 26.313 g (0.0959 mole) of 3,3'-dinitrobenzidine and 270 g of N,N-dimethylacetamide under a stream of dry air. After stirring and dissolving the contents of the flask at room temperature, 72.7 g of di-n-butyltin dilaurate was added and dissolved with stirring at 50° C. The contents of the flask were returned to room temperature, and 59.516 g (0.3836 mole) of isocyanatoethyl methacrylate was added, and the resulting solution was stirred at 50° C. for about 80 hours. After the reaction, the reaction mixture was poured into a large quantity of water to deposit a red viscous substance. The deposited material was washed with water and methanol, and then tetrahydrofuran was added thereto, whereby the objective 4,4'-bis[3-(2-methacryloyloxyethyl)ureido]-3,3'-dinitrobiphenyl was deposited as a yellow powdery material. On the other hand, in a 500 ml flask equipped with a stirrer and a thermometer, 61.2 g of powdery metallic tin was suspended into an aqueous solution of acetic acid [acetic acid/water=61.2 g/30.6 g] to prepare a suspension. To the suspension was added a suspension prepared by suspending 17.89 g (0.0306 mole) of the 4,4'-bis[3-(2-methacryloyloxyethyl)ureido]-3,3'-dinitrobiphenyl obtained above into 185 g of acetic acid, and the resulting mixture was stirred at room temperature for about 10 hours. After the reaction, the reaction mixture was poured into a mixed solution consisting of 300 ml of 28% aqueous ammonia and 3 liters of water to deposit a white precipitate. The precipitate was collected by filtration, and the product was extracted therefrom with dimethylacetamide. The extract was poured into an excessive quantity of water to deposit a white precipitate. After thoroughly washing the precipitate with water, it was recrystallized from a methanol/tetrahydrofuran mixed solvent to obtain 4,4'-bis[3-(2-methacryloyloxyethyl)ureido]-3,3'-diamino-biphenyl. The product thus obtained was identified by referring to IR spectrum, 1H-NMR spectrum, mass spectrum and elementary analyses as shown below:

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