2-Phenyl-1,4-dioxa-spiro[4,5]deca-6,9-dien-8-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Phenyl-1,4-dioxa-spiro[4,5]deca-6,9-dien-8-one
• 英文别名: 2-phenyl-1,4-dioxaspiro[4.5]deca-6,9-dien-8-one；3-Phenyl-1,4-dioxaspiro[4.5]deca-6,9-dien-8-one；3-phenyl-1,4-dioxaspiro[4.5]deca-6,9-dien-8-one
• 化学式: C₁₄H₁₂O₃
• 分子量: 228.247
• InChiKey: BVULXGNODZYVBO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  苯基乙二醇 、 4-甲氧基苯酚 在 [双(三氟乙酰氧基)碘]苯 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 以77%的产率得到2-Phenyl-1,4-dioxa-spiro[4,5]deca-6,9-dien-8-one
  参考文献：
  名称：

  New Cyclohexadienone Derivatives: Preparation and Chiral Discrimination in High-Pressure Diels-Alder Cycloadditions

  摘要：

  A wide range of cyclohexadienones has been synthesised in order to study their reactivity and their regio- and stereoselectivity with the enantiopure diene 1 under high-pressure conditions. Computational investigations were used to point out some parameters which affect the reactivity in this high chiral discrimination process. In addition, the resulting [4+2] cycloadducts allowed the preparation of new polyfunctional cyclohexenone derivatives.

  DOI：

  10.1002/1521-3765(20010601)7:11<2349::aid-chem23490>3.0.co;2-c

文献信息

• Oxidation of non-phenolic β-O-aryl-lignin model dimers catalysed by lignin peroxidase. Comparison with the oxidation induced by potassium 12-tungstocobalt(III)ate
  作者：Enrico Baciocchi、Massimo Bietti、Maria Francesca Gerini、Osvaldo Lanzalunga、Simona Mancinelli

  DOI：10.1039/b101362i

  日期：——

  The H2O2-promoted oxidations of the non-phenolic β-O-aryl-lignin model dimers 1-(3,4-dimethoxyphenyl)-2-phenoxyethanol (1) and 2-(4-methoxyphenoxy)-1-phenylethanol (2) catalysed by LiP at pH = 4.0 have been studied. The oxidation of 1 mainly leads to the corresponding ketone, indicating that the prevailing reaction of the intermediate radical cation 1+˙ is Cα–H deprotonation. The oxidation of 2 forms 2-(4-methoxyphenoxy)-2-phenylethanol (7, an isomer of 2), 2-phenyl-1,4-dioxaspiro[4.5]deca-6,9-dien-8-one (8) and products coming from the cleavage of the C–C bond γ to the more electron rich ring. The formation of all these products can be rationalised by assuming that the main reaction of the intermediate 2+˙ is a nucleophilic attack of the alcoholic OH group on the ring bearing the positive charge. This leads to a spirocyclohexadienyl radical, which either is then oxidised to the dioxaspirodecadienone 8 or undergoes ring opening to give an alkoxyl radical from which the isomer of 2 and the C–C bond cleavage products may form. Support for this mechanism has been provided by a study of the oxidation of 4-MeOC6H4OCH2CD2OH and by comparing the results with those obtained when the alkoxyl radical 4-MeOC6H4OCH2CD2O˙ was generated from 4-MeOC6H4OCH2CD2OOt-Bu. The oxidation of 1 induced by the genuine one-electron oxidant potassium 12-tungstocobalt(III)ate at pH = 4.0 confirms the results obtained with LiP. However, under the same conditions, no fragmentation products were observed in the oxidation of 2, probably due to a fast oxidation, by potassium 12-tungstocobalt(III)ate, of the spirocyclohexadienyl radical.

  研究了 pH= 4.0 条件下 LiP 催化的 H2O2 促进的非酚类δ-O-芳基木质素模型二聚体 1-(3,4-二甲氧基苯基)-2-苯氧基乙醇 (1) 和 2-(4-甲氧基苯氧基)-1-苯乙醇 (2) 的氧化作用。1 的氧化主要生成相应的酮，表明中间自由基阳离子 1+Ë 的主要反应是 CαâH 去质子化。2 的氧化反应生成 2-（4-甲氧基苯氧基）-2-苯乙醇（7，2 的异构体）、2-苯基-1,4-二氧杂螺[4.5]癸-6,9-二烯-8-酮（8）以及由 CâC 键 δ³ 裂解到电子更丰富的环上的产物。假设中间体 2+Ë 的主要反应是带有正电荷的环上的醇羟基发生亲核反应，则所有这些产物的形成都是合理的。这将产生一个螺环己二烯基，然后将其氧化为二氧杂螺癸二烯酮 8，或者进行开环反应，产生一个烷氧基基，并由此形成 2 的异构体和 CâC 键裂解产物。通过研究 4-MeOC6H4OCH2CD2OH 的氧化过程，并将结果与从 4-MeOC6H4OCH2CD2OOt-Bu 生成烷氧基自由基 4-MeOC6H4OCH2CD2OË 时的结果进行比较，为这一机理提供了支持。 在 pH= 4.0 的条件下，真正的单电子氧化剂 12-钨钴(III)ate钾诱导的 1 的氧化过程证实了使用 LiP 得到的结果。不过，在相同的条件下，2 的氧化过程中没有观察到碎片产物，这可能是由于 12-钨钴(III)ate钾快速氧化了螺环己二烯基。
• New Cyclohexadienone Derivatives: Preparation and Chiral Discrimination in High-Pressure Diels-Alder Cycloadditions
  作者：Marie-Elise Trân-Huu-Dâu、Rudolf Wartchow、Ekkehard Winterfeldt、Yung-Sing Wong

  DOI：10.1002/1521-3765(20010601)7:11<2349::aid-chem23490>3.0.co;2-c

  日期：2001.6.1

  A wide range of cyclohexadienones has been synthesised in order to study their reactivity and their regio- and stereoselectivity with the enantiopure diene 1 under high-pressure conditions. Computational investigations were used to point out some parameters which affect the reactivity in this high chiral discrimination process. In addition, the resulting [4+2] cycloadducts allowed the preparation of new polyfunctional cyclohexenone derivatives.