6,6-dimethoxy-4-fluorocyclohexa-2,4-dienone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,6-dimethoxy-4-fluorocyclohexa-2,4-dienone
• 英文别名: 4-Fluoro-6,6-dimethoxycyclohexa-2,4-dien-1-one；4-fluoro-6,6-dimethoxycyclohexa-2,4-dien-1-one
• 化学式: C₈H₉FO₃
• 分子量: 172.156
• InChiKey: AVOQMXPGWLYBIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6,6-dimethoxy-4-fluorocyclohexa-2,4-dienone 在 盐酸 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 0.03h， 以90%的产率得到2-chloro-4-fluoro-6-methoxyphenol
  参考文献：
  名称：

  Unanticipated participation of HCl in nucleophilic chlorination reaction: expedient route to meta chlorophenols

  摘要：

  o-Quinone monoketals participated in a 1,4-addition reaction with HCl furnishing m-chlorophenols in high yields. Several readily available o-quinone monoketals were selected to display the generality of this serendipitous and unprecedented reaction and the results are presented herein. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2015.11.012
• 作为产物：
  描述：

  甲醇 、 4-氟-2-甲氧基苯酚 在 碘苯二乙酸 作用下， 反应 0.17h， 以89%的产率得到6,6-dimethoxy-4-fluorocyclohexa-2,4-dienone
  参考文献：
  名称：

  4-卤代邻苯并醌的狄尔斯-阿尔德反应。实验和理论研究†

  摘要：

  描述了6,6-二甲氧基环己-2,4-二壬烯的4-卤代衍生物的[4 + 2]环加成反应的研究，称为邻醌单缩酮/被掩盖的邻苯并醌。4-氟，4-氯-和4-碘-掩蔽的邻苯二醌具有足够的稳定性，足以对其进行分离和表征。这些共轭二烯酮以高度区域和立体选择性的方式与几种缺电子和富电子的亲二烯物环合，从而以高至优异的化学产率提供相应的卤代双环[2.2.2]辛烯酮衍生物。光环蒙面o-苯醌在反应条件下不进行二聚。为了评估观察到的这些Diels–Alder反应的选择性，我们在B3LYP / 6-31G **理论水平上对掩蔽的邻位邻苯二醌与甲基乙烯基酮和乙基乙烯基醚之间的反应进行了量子力学计算。HOMO和LUMO能隙的差异表明，这些反应可以归类为反电子需求Diels–Alder反应。在许多情况下，计算得到的过渡态能量和整体电子指数支持了实验观察到的反应选择性。

  DOI：

  10.1039/c4ob00856a

文献信息

• Substituent effect on di-π-methane reactions of benzopyrazinobarrelenes and benzoquinoxalinobarrelenes
  作者：Gary J. Chuang、Chun-Chen Liao

  DOI：10.1016/j.tet.2016.01.021

  日期：2016.3

  To examine the substituent effect on the di-π-methane (DPM) rearrangement of barrelene-like skeleton, benzopyrazinobarrelene (BPB) and benzoquinoxalinobarrelene (BQB) were utilized as the photoreaction experimental platforms. By the installation of the pyrazine, the DPM reaction was limited to aza-di-π-methane reaction only, in terms of chemoselectivity. The results of the induced regioselectivity

  为了检查取代基对桶状骨架的二π-甲烷（DPM）重排的影响，将苯并吡嗪并戊烯酮（BPB）和苯并喹喔啉并戊烯酮（BQB）用作光反应实验平台。通过安装吡嗪，就化学选择性而言，DPM反应仅限于氮杂-二-π-甲烷反应。检查了诱导的BPM和BQB的DPM重排的区域选择性的结果，该BPB和BQB具有连接到烯烃/桥头位置的多种不同取代基。
• Diels–Alder reactions of 4-halo masked o-benzoquinones. Experimental and theoretical investigations
  作者：Seshi Reddy Surasani、Santosh Kumar Reddy Parumala、Rama Krishna Peddinti

  DOI：10.1039/c4ob00856a

  日期：——

  undergo dimerization under the reaction conditions. To evaluate the observed selectivities of these Diels–Alder reactions, we have performed quantum mechanical calculations for the reactions between halo masked o-benzoquinones and methyl vinyl ketone and ethyl vinyl ether at the B3LYP/6-31G** theory level. The differences in HOMO and LUMO energy gaps suggest that these reactions can be classified as inverse

  描述了6,6-二甲氧基环己-2,4-二壬烯的4-卤代衍生物的[4 + 2]环加成反应的研究，称为邻醌单缩酮/被掩盖的邻苯并醌。4-氟，4-氯-和4-碘-掩蔽的邻苯二醌具有足够的稳定性，足以对其进行分离和表征。这些共轭二烯酮以高度区域和立体选择性的方式与几种缺电子和富电子的亲二烯物环合，从而以高至优异的化学产率提供相应的卤代双环[2.2.2]辛烯酮衍生物。光环蒙面o-苯醌在反应条件下不进行二聚。为了评估观察到的这些Diels–Alder反应的选择性，我们在B3LYP / 6-31G **理论水平上对掩蔽的邻位邻苯二醌与甲基乙烯基酮和乙基乙烯基醚之间的反应进行了量子力学计算。HOMO和LUMO能隙的差异表明，这些反应可以归类为反电子需求Diels–Alder反应。在许多情况下，计算得到的过渡态能量和整体电子指数支持了实验观察到的反应选择性。
• A fluorinated masked o-benzoquinone
  作者：Timothy B. Patrick、Hong Yu、Demitri Taylor、Keith Gorrell

  DOI：10.1016/j.jfluchem.2004.06.007

  日期：2004.12

  A fluorinated masked o-benzoquinone has been prepared by oxidation 4-fluoro-2-methoxyphenol in methanol with phenyliodine diacetate. The fluorinated diene reacts in situ in normal Diels–Alder reactions with various dienophiles. The sequence provides new fluorinated building blocks for the synthesis of a variety of fluorinated compounds.

  氟代掩蔽的邻苯并醌是通过将4-氟-2-甲氧基苯酚在甲醇中用苯基碘二乙酸酯氧化制得的。氟化二烯在正常Diels-Alder反应中与各种亲二烯体原位反应。该序列为合成各种氟化化合物提供了新的氟化结构单元。
• Diels–Alder reactions of halogenated masked o-benzoquinones: synthesis of halogen-substituted bicyclo[2.2.2]octenones
  作者：Seshi Reddy Surasani、Virendra Singh Rajora、Naganjaneyulu Bodipati、Rama Krishna Peddinti

  DOI：10.1016/j.tetlet.2008.11.117

  日期：2009.2

  Intermolecular Diels–Alder reactions of 4-halo masked o-benzoquinones generated from hypervalent iodine-mediated oxidation of 4-halo-2-methoxyphenols, with electron-deficient dienophiles—methyl acrylate, methyl methacrylate and methyl vinyl ketone—leading to halo-substituted bicyclo[2.2.2]octenones, are described. The halo-benzoquinone monoketals can be isolated and characterized. The dimerization

  分子间狄尔斯-由高价碘介导的4-卤-2-甲氧基苯酚的氧化反应生成的4-卤代掩蔽的邻苯甲醌与电子不足的亲二烯体（丙烯酸甲酯，甲基丙烯酸甲酯和甲基乙烯基酮）的der代反应导致卤素取代描述了双环[2.2.2]辛烯酮。卤代-苯醌单缩酮可以被分离和表征。在反应条件下未观察到这些中间体的二聚化。
• Reversal of Polarity in Masked <i>o</i>-Benzoquinones: Rapid Access to Unsymmetrical Oxygenated Biaryls
  作者：Santosh Kumar Reddy Parumala、Rama Krishna Peddinti

  DOI：10.1021/ol401341s

  日期：2013.7.19

  An unprecedented diacetoxyiodobenzene induced direct arylation of guaiacol derivatives and electron-rich arenes using a Lewis acid as an activator furnishes unsymmetrical biaryls without prefunctionalization of both coupling partners. The addition of electron-rich arenes on the a-position of electrophilic masked o-benzoquinones in an anti-Michael addition fashion affords the highly oxygenated unsymmetrical biaryls in good to excellent yields.