Study On New Methods Of Synthesis Isoflavonoids And 3,4-dihydro-2(1H) Quinolinone Derivatives

This dissertation studies on new methods of synthesis isoflavonoids and 3,4-dihydro-2(lH)quinolinone derivatives with higher yield and simpler operation. It covers nine chapters which can be divided into two parts.The first part which contains six chapters gives the comments on the synthesis of isoflavonoids. This part not only designs and synthesizes genistein, daidzein, 5,7-dihydroxyisoflavone, 6-bromo-4',7-dimethoxyisoflavone and their derivatives, but also discusses the technical conditions.Firstly, we replace expensive material l,3,5-trihydroxybenzene(produced from TNT, whose price is about 600,000 yuan/t) with cheap material 1,3,5-trimethoxybenzene (160,000 yuan/t) and get 4',5,7-trihydroxyisofiavone or 5,7-dihydroxyisoflavone by demethylation reaction of 4',5,7-trimethoxyisoflavone or 5,7-dimethoxyisoflavone which can be gotten via cyclizing of phenyl benzyl ketone. This way not only costs less but also yields higher, the total yield can reach 60-75%. Secondly, two new compounds are found in this part: 2-hydroxy-4,4'-dimethoxy-5-bromodeoxy-benzoin and 6-bromo-4',7-dimethoxy-isoflavone. They are prepared in synthesis of 6-bromo-4',7-dimethoxyisoflavone. Then, the part puts forward the system of demethylation reaction which is hydrobromic acid(2000~5200yuan/t) or hydrobromic acid/PTC for the first time, and it is much cheaper than hydroiodic acid(l 80000 ~200000yuan/t), the common demethyl reagent in references. We use this method to take off all the methyl and get genistein, daidzein and 5,7-dihydroxyisoflavone in one time. At last, we investigate the order and mechanism of the demethylation of 4',5,7-dimethoxyisoflavone, and testify them by 'HNMR spectrum of genistein, daidzein, 5,7-dihydroxyisoflavone, 5-hydroxy-4',7-dimethoxyisoflavone, 4',5-dihydroxy-7-methoxyisoflavone, 4'-hydr-oxy-7-methoxyisoflavone and 5-hydroxy-7-methoxyisoflavone.ABSTRACTThe second part, which contains two chapters, designs and synthesizes 3,4-dihydro-2(lH)quinolinone derivatives. In this part, a new mehod of synthesis 6-hydroxy-3,4-dihydro-2(lH)quinolinone is brought forward, and the total yield gets upwards of 65%. On the one hand, the total yield of 6-amino-3,4-dihydro-2(lH)quinolinone can reach 78% (from aniline), which is more than 58.6% total yield(from aniline) that mentioned in references. On the other hand, we get a new compound in the reaction of synthesis 3,4-dihydro-2(lH)quinolinone derivatives, which is 6-amhio-8-nitro-3,4-dihydro-2(lH)quinolinone. Furthermore, the yields of reduction are very high, those of 6-amino-3,4-dihydro-2(lH)quinolinone and 6,8-diamino-3,4-dihydro- 2(lH)quinolinone are basically quantitation.Generally speaking, the methods of synthesis isoflavonoids and 3,4-dihydro-2(lH)quinolinone derivatives in this paper cost less, operate simpler, yield higher and postprocess easier with gentle reaction condition. They are fit for mass production compared with other current ways.