Vinylformamide Derivatives, Polymers Formed Therefrom and Synthesis Thereof

Title A -Vinylformamide Derivatives, Polymers Formed Therefrom and Synthesis Thereof 

A-Vinylformamide was converted into A-alkyl-A-vinylformamide derivatives by reacting it with an alkyl bromide in the presence of base. When A-vinylformamide intermediates were reacted with 2,2 -azobisisobutyronitrile, the polymer was obtained. Hydrolysis of poly(A-vinylformamide) generated an A-alkyl polyvinyla-mine, a versatile synthetic intermediate. 

A reactor was charged with A-vinylformamide (0.164 mol) and 200 ml of anhydrous THF and then cooled to 15°C using an ice bath. The solution was next treated with potassium t-butoxide (0.167 mol) in three portions over 45 minutes followed by the dropwise addition of 1-bromo-hexane (0.179 mol) over 30 minutes. The reaction was slowly warmed to ambient temperature and stirred overnight. The mixture was filtered to remove KBr and then concentrated, and the residue was diluted with 200 ml of water. 

The organic layer was extracted three times with diethyl ether, and the combined extractions were washed twice with water and dried using MgS04. The mixture was reconcentrated and then purified by chromatography on silica using diethyl ether/ petroleum ether, 3 7, respectively the product was isolated in 63% yield. Other aliphatic derivatives were prepared according to this procedure and are provided in Table 1. 

The Step 1 product (1.0 g) and 2,2 -azobisisobutyronitrile (18 mg) were added to an ampoule and degassed before sealing. The polymerization was carried out in an oil bath at 65°C for 15 hours. The polymer was purified by Soxhlet extraction using petroleum ether for 8 hours and dried under reduced pressure at 60°C for 12 hours. Polymer properties of derivatives are provided in Table 2. 

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