异黄酮衍生物的合成Ⅱ.7-氯和6-氯-7-甲氧基-3′-(N,N-二乙胺甲基)-4′-羟基异黄酮的合成

SYNTHESIS OF ISOFLAVONE DERIVATIVES Ⅱ. 7-Chloro and 6-chloro-7-methoxy-3′-N,N-diethylaminomethyl-4′-hydroxy isoflavones

合成了7-氯和-6-氯-7-甲氧基-3′-(N,N-二乙胺甲基)-4′-羟基异黄酮(1478和1481)。它们的合成是由间-氯苯酚或3-羟基-4-氯苯酚与对-硝基苯乙酰氯反应,制得取代的脱氧安息香。它们与原甲酸乙酯环合得到取代的-4′-硝基异黄酮,再将化合物中的硝基用锌粉还原成氨基,再经重氮化和水解,得到取代的-4′-羟基异黄酮。它们经Mannich反应,最后制得7-氯和6-氯-7-甲氧基-3′-(N,N-二乙胺甲基)-4′-羟基异黄酮。它们耐氧作用不如已合成的7-甲氧基-3′-(N,N-二烷胺甲基)-4′-羟基异黄酮。

7-Chloro and 6-chloro-7-methoxy-3'-N, N-diethylaminomethyl-4'-hydroxy isoflavones were synthesized. M-chlorocresol or 3-hydroxy-4-chlorophe- nol on treatment with p-nitrobenzoyl chloride was prepared and conyerted into substituted p-nitrobezyl ketone. These compounds were cyclized with ethyl orthoformate to give substituted-4-nitroisoflavones. Then their nitro group was reduced by Zn in CH_3COOH into an amino group. It was diazotized and hydrolyzed to be converted into substituted-4-hytroxy isoflavones, 7-chloro and 6-chloro-7-methoxy-3-N, N-diethylaminomethyl-4-hydroxy isoflavones were prepared by the Mannich reaction of di (ethylamino) methane with 7-chloro and 6-chloro-7-methoxy-4-hydroxy isoflavones. The two compounds of isoflavone have been tested for resistance to hypoxia, in mice and found not as effective as the 7-methoxy-3'-N,N-dialkylaminomethy-4'-hydroxy isoflavone.