Cyclohexadienone diazeniumdiolates from nitric oxide addition to phenolates.
Cyclohexadienone diazeniumdiolates from nitric oxide addition to phenolates.
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由一氧化氮加成酚盐生成环己二烯酮二氮烯鎓二醇。
DOI：
10.1021/jo000513o
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
Imonigie,JA
中科院分区：
文献类型：
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作者：
Bohle,DS;Imonigie,JA
位阻酚与一氧化氮在碱性条件下反应生成环己二烯酮二醇二氮烯鎓盐或肟盐。具有2，6-二叔丁基和4-甲基（丁基化羟基甲苯，BHT）、4-乙基或4-甲氧基亚甲基取代基的苯酚产生相应的2，6-二叔丁基-2，5-环己二烯酮-4-烷基-4-二醇二氮烯鎓盐（4-甲基1a，4-乙基3a，4-甲氧基亚甲基5a）。具有2，6-二叔丁基和4-亚甲基（2，6-二叔丁基苯酚）取代基的苯酚产生4-甲氧基亚甲基二氮鎓二醇盐（5a）以及2，6-二叔丁基苯醌肟酸盐（6a），而具有2，6-二叔丁基和4-亚甲基二甲基氨基或氢取代基的苯酚仅产生2，6-二叔丁基苯醌肟酸盐（6a）。1a的银盐的烷基化，或用重氮甲烷处理O2-质子化的二醇二氮烯鎓，都产生O 1-和O2-甲基化异构体的混合物。除了奎宁环鎓盐（1 e，3e，5e）和三亚乙基二铵盐（1f）吸热分解外，所有化合物都表现出放热热分解。其中三种化合物，即“O2-质子化的”（Z）-1-[4-（2-甲氧基苯基）-1-甲基]-2-氧代-N-甲基-N-（2-甲氧基苯基）-N-（2-甲氧基苯基（2，6-二叔丁基-4-甲基-环己二烯酮基）]二氮烯-1-鎓-1，2-二喹啉酸（1b），O2-甲基（Z）-1-[4-（2，6-二叔丁基-4-甲基-环己二烯酮基）]二氮烯-1-鎓-1，2-二醇盐（1c），和“O2-质子化”（Z）-1-[4-[（2，6-二叔丁基-4-甲氧基亚甲基环己二烯酮基）]二氮烯-1-鎓-1，2-二喹啉酸（5 b）的晶体结构经X-射线单晶衍射研究确定。所有结构中的diazeniumdiolate框架都是共面的，在O-N-N-O框架上有相当多的π键离域。
Sterically hindered phenols react with nitric oxide under basic condititons to give either cyclohexadienone diazeniumdiolates or oximates. Phenols with 2,6-di-tert-butyl and 4-methyl (butylated hydroxy toluene, BHT), 4-ethyl, or 4-methoxy methylene substituents yield the corresponding 2,6-di-tert-butyl-2,5-cyclohexadienone-4-alkyl-4-diazeniumdiolate salts (4-methyl1a, 4-ethyl3a, 4-methoxymethylene5a). Phenols with 2,6-di-tert-butyl and 4-methylene (2,6-di-tert-butylphenol) substituents yield 4-methoxymethylenediazeniumdiolate (5a) together with 2,6-di-tert-butyl benzoquinone oximate (6a), while phenols with 2,6-di-tert-butyl and 4-methylenedimethylamino or hydrogen substituents yield exclusively 2,6-di-tert-butyl benzoquinone oximate (6a). Alkylation of the silver salts of1a, or treating the O2-protonated diazeniumdiolate with diazomethane, both yield mixtures of O1- and O2-methylated isomers. All the compounds exhibit exothermic thermal decomposition except the quinuclidinium (1e,3e,5e) and triethylenediammonium (1f) salts which decompose endothermically. Three of the compounds namely “O2-protonated” (Z)-1-[4-(2,6-di-tert-butyl-4-methyl-cyclohexadienonyl)]diazen-1-ium-1,2-diolinic acid (1b),O2-methyl (Z)-1-[4-(2,6-di-tert-butyl-4-methyl-cyclohexadienonyl)]diazen-1-ium-1,2-diolate (1c), and “O2-protonated” (Z)-1-[4-(2,6-di-tert-butyl-4-methoxymethylenecyclohexadienonyl)]diazen-1-ium-1,2-diolinic acid (5b) were characterized by single-crystal X-ray diffraction studies. The diazeniumdiolate framework in all the structures is coplanar with considerable π-bonding delocalized over the O−N−N−O framework.