Korytnyk W, Ghosh A C, Potti P G, Srivastava S C
J Med Chem. 1976 Aug;19(8):999-1002. doi: 10.1021/jm00230a003.
4-Amino-4-norpyridoxol, a new key intermediate for the modification of the 4 position of vitamin B6, has been obtained by an unusual photochemical rearrangement of pyridoxal oxime. It has also been synthesized starting from 3,-alpha5-O-dibenzylpyridoxal, which was converted to 3,alpha5-O-dibenzylpyridoxamide. The latter, on Hoffman reaction, gave the desired 3,5-blocked 4-amino derivative. Several derivatives of this analogue have been prepared, and its existence in the amino tautomeric form has been established by NMR spectroscopy. A modified Sandmeyer reaction on 4-amino-4-norpyridoxol gave the 4-bromo analogue, which was found to be moderately active as an inhibitor of mouse mammary adenocarcinoma cells grown in cell culture, whereas the 4-amino analogue was not active at 10(-4)M. Other analogues containing electron-withdrawing and electron-donating substituents in the 4 position of pyridoxine were also tested.
4-氨基-4-去甲吡哆醇是一种用于修饰维生素B6第4位的新型关键中间体，它是通过吡哆醛肟的一种不寻常的光化学重排反应得到的。它也可以从3-α,5-O-二苄基吡哆醛开始合成，该化合物被转化为3-α,5-O-二苄基吡哆酰胺。后者经霍夫曼反应得到所需的3,5-封闭的4-氨基衍生物。已经制备了该类似物的几种衍生物，并且通过核磁共振光谱确定了其氨基互变异构形式的存在。对4-氨基-4-去甲吡哆醇进行改良的桑德迈尔反应得到了4-溴类似物，发现该类似物作为细胞培养中生长的小鼠乳腺腺癌细胞的抑制剂具有中等活性，而4-氨基类似物在10^(-4)M时无活性。还测试了在吡哆醇第4位含有吸电子和供电子取代基的其他类似物。
