Substituted deuteroporphyrins. I. Reactions at the periphery of the porphyrin ring.
Substituted deuteroporphyrins. I. Reactions at the periphery of the porphyrin ring.
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取代的次卟啉。
DOI：
10.1021/jo01346a042
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发表时间：
1966
期刊：
影响因子：
--
通讯作者：
J. York
中科院分区：
文献类型：
--
作者：
W. Caughey;J. O. Alben;W. Y. Fujimoto;J. York
从原卟啉IX或其氯化铁（protohemin）出发，采用外围取代基反应或直接在卟啉环上取代的制备方法，得到了不同取代的次卟啉IX。包括乙烯基的氧化，加成和置换反应;与早期的报道相反，观察到2-和4-乙烯基的反应性没有显着差异。亲电取代反应（酰化，溴化，硝化）在所选择的环位置不同。已发现次血红素的酰化和次卟啉IX二甲酯的溴化主要发生在2和4位，而酯在硝酸-硫酸中的硝化优先发生在α和β位。未观察到α和β之间或2和4个位置之间的选择性。结果表明，相对于2，4位，质子化物种中的内消旋位比中性物种或氯化血红素中的内消旋位更容易受到亲电攻击。
Variously substituted deuteroporphyrins IX havebeen obtained from protoporphyrin IX or its iron (III) chloride (protohemin) employing preparative methods which involve reactions of peripheral substituents or substitution directly on the porphyrin ring. Included were oxidation, addition, and displacement reactions of vinyl groups; in contrast to earlier reports no significant differences in the reactivities of the 2-and 4-vinyl groups were observed. Electrophilic substitution reactions (acylation, bromination, nitration) differed in the ring positions selected. Both acylations of deuterohemin and bromination of deuteroporphyrin IX dimethyl ester have been found to take place predominately at the 2 and 4 positions, whereas nitration of the ester in nitric acid-sulfuric acid occurred preferentially at the a and ß positions. Selectivity between a and ß or between 2 and 4 positions was not noted. It is suggested that relativeto the 2, 4 positions the meso positions are more susceptible to electrophilic attack in the protonated species than in either the neutral species or the hemin.