Hartmann R W, Bayer H, Grün G
Fachrichtung 12.1 Pharmazeutische Chemie, Universität des Saarlandes, Saarbrücken, Germany.
J Med Chem. 1994 Apr 29;37(9):1275-81. doi: 10.1021/jm00035a007.
The (E)-2-(4-pyridylmethylene)-1-indanones(E)-1-(E)-5[(E)-1,H;(E)-2,4- OCH3; (E)-3,5-OCH3; (E)-4,4-OH;(E)-5,5-OH] were obtained by aldol condensation of the corresponding 1-indanones with 4-pyridinecarboxaldehyde, and in case of the OH compound (E)-4 subsequent ether cleavage of (E)-2. The synthesis of the (Z)-isomers (Z)-1-(Z)-3[(Z)-1,H;(Z)-2,4-OCH3; (Z)-3,5-OCH3] was accomplished by UV irradiation of the corresponding (E)-isomers. Catalytic hydrogenation of (E)-1-(E)-3 gave the 2-(4-pyridylmethyl)-1-indanones 6-8 (6, H; 7,4-OCH3; 8,5-OCH3). The 2-(4-pyridylmethyl)-substituted indans 11-13 (11,H; 12,4-OCH3; 13,5-OCH3) and the tetralins 16-19 (16,H;17,5-OCH3;18,6-OCH3;19,7-OCH3) were obtained by reduction of the corresponding ketones using N2H4/KOH. The 2-(4-pyridylmethyl)-substituted indanones 9 (4-OH) and 10 (5-OH), indans 14 (4-OH) and 15 (5-OH), and tetralins 20-22 (20,5-OH; 21,6-OH; 22,7-OH) were synthesized by ether cleavage of the corresponding OCH3 compounds. All compounds showed inhibition of human placental aromatase exhibiting relative potencies from 0.9 [(E)-4] to 163 [18; aminoglutethimide (AG) potency identical to 1]. Compounds 13 and 18 showed competitive type of inhibition and a type II difference spectrum, indicating the interaction of the pyridyl-N with the central Fe(III) ion of the cytochrome P450 heme component.(ABSTRACT TRUNCATED AT 250 WORDS)
通过相应的茚满酮与4-吡啶甲醛进行羟醛缩合反应制得(E)-2-(4-吡啶基亚甲基)-1-茚满酮(E)-1-(E)-5[(E)-1,H;(E)-2,4-OCH₃;(E)-3,5-OCH₃;(E)-4,4-OH;(E)-5,5-OH],对于含羟基的化合物(E)-4,后续对(E)-2进行醚键裂解。(Z)-异构体(Z)-1-(Z)-3[(Z)-1,H;(Z)-2,4-OCH₃;(Z)-3,5-OCH₃]的合成是通过对相应的(E)-异构体进行紫外线照射实现的。(E)-1-(E)-3的催化氢化反应得到2-(4-吡啶基甲基)-1-茚满酮6-8(6,H;7,4-OCH₃;8,5-OCH₃)。2-(4-吡啶基甲基)取代的茚满11-13(11,H;12,4-OCH₃;13,5-OCH₃)和四氢萘16-19(16,H;17,5-OCH₃;18,6-OCH₃;19,7-OCH₃)是通过使用水合肼/氢氧化钾还原相应的酮制得的。2-(4-吡啶基甲基)取代的茚满酮9(4-OH)和10(5-OH)、茚满14(4-OH)和15(5-OH)以及四氢萘20-22(20,5-OH;21,6-OH;22,7-OH)是通过对相应的OCH₃化合物进行醚键裂解合成的。所有化合物均表现出对人胎盘芳香化酶的抑制作用,相对效力从0.9[(E)-4]到163[18;氨鲁米特(AG)效力等同于1]。化合物13和18表现出竞争性抑制类型以及II型差示光谱,表明吡啶基-N与细胞色素P450血红素成分的中心铁(III)离子相互作用。(摘要截短于250字)