In the investigation of novel baicalein derivatives with bioactivity, a series of Mannich base derivatives of baicalein were designed and synthesized at C-8 in A-ring through Mannich reaction. The characteristic of this reaction was mild condition, easier purification and good yield (>80%). Furthermore, two new six-ring dihydrobenzoxazine compounds 5h and 5i were obtained when the ratio of primary amine and HCHO was 1∶2. Mannich base hydrochloride compounds 4b and 4j were prepared in hydrochloric acid for t...