An efficient and facile one pot synthesis of (E,E)‐4,6‐bis(styryl)‐pyrimidines has been developed. It involves one pot two step reactions in environmentally benign solvent water, where first step involves pyrimidine ring formation from acetylacetone and urea via [3+3] annulation, followed by aldol condensation with differently substituted aromatic aldehyde to give desired (E,E)‐4,6‐bis(styryl)‐pyrimidines in moderate to good yields.
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