2-(2-HYDROXYPHENOXY)-BENZOIC ACID LACTONE, A SIMPLE ANALOG OF THE DEPSIDONES
2-(2-HYDROXYPHENOXY)-BENZOIC ACID LACTONE, A SIMPLE ANALOG OF THE DEPSIDONES
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DOI：
10.1021/ja01122a034
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发表时间：
1952-01-01
影响因子：
15
通讯作者：
WELDON, JW
中科院分区：
文献类型：
--
作者：
NOYCE, DS;WELDON, JW
已经从地衣中分离出多种化合物。许多已被证明是2-（2-羟基苯氧基）-苯甲酸内酯（I）的高度取代的衍生物，并被给予通用名称“缩酚西酮”。2最近报道了地衣中的一些化合物的抑菌活性，3，4 '5包括松萝酸3和depolipones，diploicin 4和physodic acid。5.由于显然还没有合成出具有缩酚酮基本核的化合物，我们已着手研究合成这类系统的适用方法。最有吸引力的方法可能是氧杂蒽酮的过氧酸氧化。然而，这种氧化在各种各样的实验条件下失败。这种失败至少部分地归因于氧杂蒽酮的羰基受共轭醚桥的影响缺乏反应活性，因为芴酮被顺利地氧化成2-（2-羟基苯基）-苯甲酸内酯。7用过氧乙酸氧化3-甲氧基口山酮和2-硝基口山酮也失败了。另一种合成方法是将适当的羟基酸内酯化。另外两个七元二苯并内酯先前已通过闭环制备。Orndorff和Kline 8用乙酸酐制备了2-（2，4-二羟基苯甲酰基）-苯甲酸的内酯，而Galbraith和Smiles 9用类似的方法制备了2-（2-羟基-5-甲基苯巯基）-5-硝基苯甲酸的内酯。以邻氯苯甲酸甲酯和愈创木酚钠为原料，
A wide variety of compounds have been isolated from lichens. Many have been shown to be highly substituted derivatives of 2-(2-hydroxyphenoxy)-benzoic acid lactone (I) and have been given the generic name“depsidone.” 2 Bacteriostatic activ-ity has recently been reported for a number of compounds from lichens, 3, 4'5 including usnic acid3 and the depsidones, diploicin4 and physodic acid. 5 Since no compounds possessing the basic nucleus of the depsidones have apparently been synthesized, we have undertaken an investigation of applicable methods for synthesis of such systems. The most attractive method might appear to be the peroxy acid oxidation6 of xanthone. However, this oxida-tion failed under a wide variety of experimental conditions. This failure must be attributed at least partially to thelack of reactivity of the carbonyl group of xanthone as influenced by the conjugated ether bridge, since fluorenone is oxidizedsmoothly to 2-(2-hydroxyphenyl)-benzoic acid lactone. 7 Simi-lar attempts to oxidize 3-methoxyxanthone and 2-nitroxanthone with peracetic acid also failed. The alternate approach to I involved lactoniza-tion of the appropriate hydroxy acid. Two other seven-membered dibenzlactones have been previously prepared by ring closure. Orndorff and Kline8 have prepared the lactone of 2-(2, 4-dihydroxybenzoyl)-benzoic acid using acetic anhydride, while Galbraith and Smiles9 have prepared the lac-tone of 2-(2-hydroxy-5-methylphenylmercapto)-5-nitrobenzoic acid by a similar procedure. In the present investigation condensation of methyl o-chlorobenzoate with sodium guaiacolate