2,2-dimethyl-7-hydroxy-5-methoxychroman | 50386-17-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 2,2-dimethyl-7-hydroxy-5-methoxychroman
• 英文别名: 3,4-Dihydro-7-hydroxy-5-methoxy-2,2-dimethyl-2H-1-benzopyran；5-methoxy-2,2-dimethyl-7-chromanol；7-hydroxy-5-methoxy-2,2-dimethylchroman；sophoflavanone H；5-methoxy-2,2-dimethyl-chroman-7-ol；5-Methoxy-2,2-dimethyl-3,4-dihydrochromen-7-ol
• CAS: 50386-17-9
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: HAMYSTQPVKFIRF-UHFFFAOYSA-N

物化性质

• 熔点：
  103-104 °C
• 沸点：
  350.0±42.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-7-hydroxy-5-methoxychroman 在 palladium diacetate 、 甲酸 、 sodium acetate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 苯 为溶剂， 反应 28.0h， 生成 黄木亭
  参考文献：
  名称：

  Atom Economy. Palladium-Catalyzed Formation of Coumarins by Addition of Phenols and Alkynoates via a Net C−H Insertion

  摘要：

  A strategy to achieve ortho substitution of phenols initiated by an ortho-palladation to create coumarins was examined. Indeed, treatment of alkynoates with electron-rich phenols in the presence of a palladium catalyst and an acid does generate coumarins. The scope of the reaction with respect to the phenol and the alkynoates is defined. With unsymmetrical aromatic substrates, generally good regioselectivity that reflects the HOMO coefficients can be observed. In the course of these studies, numerous important naturally occurring coumarins have been synthesized, including fraxinol methyl ether, ayapin, herniarin, xanthoxyletin, and alloxanthoxyletin. The fact that a Pd(0) is the precatalyst rather than a Pd(+2) species and that an acid that reduces Pd(+2) salts, formic acid, functions better than other carboxylic acids raises doubts about the initial working hypothesis. A novel mechanism involving a palladium phenoxide formed from a hydridopalladium carboxylate and phenol is invoked to rationalize the results.

  DOI：

  10.1021/ja0286573
• 作为产物：
  描述：

  3,3-二甲基丙烯酸 在 盐酸 、 氢氧化钾 、 potassium carbonate 、 zinc(II) chloride 、 锌 、 三氯氧磷 作用下， 以 乙醇 、 丙酮 为溶剂， 反应 44.0h， 生成 2,2-dimethyl-7-hydroxy-5-methoxychroman
  参考文献：
  名称：

  Atom Economy. Palladium-Catalyzed Formation of Coumarins by Addition of Phenols and Alkynoates via a Net C−H Insertion

  摘要：

  A strategy to achieve ortho substitution of phenols initiated by an ortho-palladation to create coumarins was examined. Indeed, treatment of alkynoates with electron-rich phenols in the presence of a palladium catalyst and an acid does generate coumarins. The scope of the reaction with respect to the phenol and the alkynoates is defined. With unsymmetrical aromatic substrates, generally good regioselectivity that reflects the HOMO coefficients can be observed. In the course of these studies, numerous important naturally occurring coumarins have been synthesized, including fraxinol methyl ether, ayapin, herniarin, xanthoxyletin, and alloxanthoxyletin. The fact that a Pd(0) is the precatalyst rather than a Pd(+2) species and that an acid that reduces Pd(+2) salts, formic acid, functions better than other carboxylic acids raises doubts about the initial working hypothesis. A novel mechanism involving a palladium phenoxide formed from a hydridopalladium carboxylate and phenol is invoked to rationalize the results.

  DOI：

  10.1021/ja0286573

文献信息

• Regioselective total synthesis of edulane and its angular analogue
  作者：Kandasamy Subburaj、Modachur G. Murugesh、Girish K. Trivedi

  DOI：10.1039/a608227k

  日期：——

  Herein we describe a 10-step total synthesis of edulane 3 and its angular analogue 18 from phloroglucinol. The key step involves ZnCl2-catalysed condensation of the appropriately substituted 2H-chromenes 8, 9 and 10 with the 2-alkoxy-1,4-benzoquinones 11 and 12, respectively.

  在此，我们介绍了一种通过 10 个步骤从氯代葡萄糖醇全盘合成 edulane 3 及其角类似物 18 的方法。关键步骤包括 ZnCl2 催化适当取代的 2H-色烯 8、9 和 10 分别与 2-烷氧基-1,4-苯醌 11 和 12 的缩合。
• Microwave-Assisted Rate-Enhanced Method for the Synthesis of 2,2-Dimethyl-2<i>H</i>-chromenes
  作者：Kandasamy Subburaj、Girish K. Trivedi

  DOI：10.1246/bcsj.72.259

  日期：1999.2

  Herein we describe a simple and facile method for the synthesis of chromenes by base catalyzed condensation of phenols with 3-methyl-2-butenal under microwave irradiation.

  在此，我们介绍了一种在微波辐照下通过碱催化苯酚与 3-甲基-2-丁烯醛缩合合成色烯的简单易行的方法。
• Regioselective total synthesis of (±) Neorautane, (±) Neorautanin and their analogs. Microwave mediated synthesis of 2H-chromenes from propargyl phenyl ethers
  作者：Kandasamy Subburaj、Rita Katoch、Modachur G. Murugesh、Girish K. Trivedi

  DOI：10.1016/s0040-4020(97)00783-7

  日期：1997.9

  Herein we describe the total synthesis of (±) Neorautane 1, (±) Neorautanin 2 and their analogs 15–18. The key intermediates Chromenes 10–13 were synthesised by microwave irradiation of propargyl phenyl ethers 8 and 9 in DMF under pressure.

  在这里，我们描述了（±）Neorautane 1，（±）Neorautanin 2及其类似物15–18的总合成。通过在压力下于DMF中微波照射炔丙基苯基醚8和9合成关键中间体Chromenes 10-13。
• Valorisation of phenols to coumarins through one-pot palladium-catalysed double C–H functionalizations
  作者：Giulia Brufani、Federica Valentini、Flavio Sabatelli、Benedetta Di Erasmo、Anastasiia M. Afanasenko、Chao-Jun Li、Luigi Vaccaro

  DOI：10.1039/d2gc03579k

  日期：——

  chemical production. Among the transformation of phenols, C–H functionalization is limited to a few examples with homogeneous metal-based catalysts. Herein, a robust one-pot approach for constructing C8 alkyl substituted coumarins starting from simple phenols through the palladium-catalysed double C–H functionalizations is presented. In such a combined protocol, a Pd/C was used as a heterogeneous catalyst

  酚类通过步骤和原子效率协议对于向可持续化学品生产的过渡非常重要。在酚类的转化中，C-H 官能化仅限于使用均相金属基催化剂的少数例子。本文提出了一种稳健的一锅法，用于从简单的酚类开始通过钯催化的双 C-H 官能化构建 C8 烷基取代的香豆素。在这样的组合方案中，Pd/C 首次用作非均相催化剂。所开发的方法能够使用潜在的生物质衍生酚以良好的分离产量合成结构多样的香豆素，包括天然产物。
• Lahey, University of Queensland Papers, Department of Chemistry, 1942, vol. 1, # 20, p. 2,10
  作者：Lahey

  DOI：——

  日期：——