摘要
以豆腐果苷为原料,与4-取代苯乙酮发生Schmidt-Claisen反应,得到一系列查尔酮结构的E-4-β-D-吡喃阿洛糖苷-苯乙烯基-4-取代苯乙酮衍生物3a～3h,其中3c,3e,3f为新化合物.3a～3h在甲醇钠存在下,与1,3-丙二腈发生1,4-Michael加成,经关环、重排、氧化,得到4-(4-β-D-吡喃阿洛糖苷-苯基)-2-芳基-5-腈基-6-甲氧基吡啶系列豆腐果苷衍生物10a～10h,联氨催化还原10e而得到10i.共获得12个未见文献报道的新化合物,其结构经HNMR,IR和1HRMS确证,并进行了药理活性筛选.结果表明,部分化合物具有比母体化合物更好的镇静催眠活性.同时,对Schmidt-Claisen反应存在的主要副反应进行了分析;对查尔酮与1,3-丙二腈在甲醇钠存在下反应生成吡啶衍生物反应机理进行了推导,提出了氧化脱氢形成吡啶的新机理.
（E）-3-[4-β-D-Allopyranosyloxyphenyl]acrophenones （3a-3h） with a structure of chalcone were synthesized by Schmidt-Claisen reaction of 4-substituted hypnone with helicid, among which 3c, 3e and 3f are three new compounds. The chalcone was then reacted with malononitrile and sodium methoxide to obtain the pyridine derivatives 10a-10h of helicid by Michael addition, followed by cyclization, Dimroth rearrangement, and oxidation. Catalytic reduction of 10e with hydrazine led to 10i. All together twelve new compounds were obtained, and structurally confirmed by ^1H NMR, IR and HRMS data. The preliminary bioassay tests of 10a-10i show that some of the compounds have a better sedative and hypnotic activity. The major side reaction of Schimdt-Claisen condensation was analyzed. And the mechanism of oxydehydrogenation that leads to the formation of pyridine derivatives by the reaction of chalcone with malononitrile and sodium methoxide was firstly revealed.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
2009年第11期1768-1773,共6页
Chinese Journal of Organic Chemistry
