Synthesis Of Bryoanthrathiophene's Analogues

The aim of this dissertation is to synthesize the Bryoanthrathiophene's analogues possessing 6H-anthra[1,9-bc]thiophene structure occuring rarely in nature with potential anticancer activity .First of all, the synthesis of Methylcarboxylate Bryoanthrathiophene was improved in the total yield of 56% with 1,8-dihydroxyl-9,10-anthraquinone as the starting material in 4 steps including protection, nitration, one pot-two step cyclization and deprotection.Second, the synthesis of Demethyl Bryoanthrathiophene, 5,7-dihydroxyl-6-oxo-6H- anthra[1,9-bc]thiophene, was achieved in the total yield of 52% employing 1,8-dihydroxyl- 9,10- anthraquinone as the starting material in 6 steps including protection, nitration, one pot-two step cyclization, deprotection, and decarboxylization.Third, the reactions of electrophilic substitution on the substrates including Methylcar- boxylate Bryoanthrathiphene, Demethyl Bryoanthrathiophene, Bryoanthrathiophene,shown that 1-methylcarboxylate in Methylcarboxylate Bryoanthrathiophene makes the 6H-anthra [1,9-bc]thiophene ring deactivating while 1-methyl in Bryoanthrathiophene activates the ring, using 1-H in Demethyl Bryoanthrathiophene as the standard substitution; and also shown that compared the activity of A,B,C,D rings in 6H-anthra [1,9-bc]thiophene, the result is A>C>D>B.Fourth, the reactions of Zn/HOAc reduction on Bryoanthrathiophene's analogues were applied, shown that selective reduction of these analogues remaining 6-oxo-6H-anthra [1,9-bc]thiophene skeleton must take place in the existance of proton donor by formation of the intramolecular hydrogen bond between 5-hydroxyl or 7-hydroxyl and 6-oxo.Fifth, a several new compounds with 6H-anthra[1,9-bc]thiophene ring structure were synthesized and a serial of oxidizing reaction upon these analogues were also studied.In conclusion, this dissertation has synthesized a serial of Bryoanthrathiophene's analogues, and studied reactions of reduction, oxidation and electrophilic substitution, which lays the foundation of the investigation of their physico-chemical properties and modification of their substitutions.