3,3-dimethyl-3,4-dihydro-1H-benzo[c]chromene-1,6(2H)-dione | 6315-06-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 异香豆素及其衍生物
• 英文名称: 3,3-dimethyl-3,4-dihydro-1H-benzo[c]chromene-1,6(2H)-dione
• 英文别名: 3,3-dimethyl-2,4-dihydrobenzo[c]chromene-1,6-dione
• CAS: 6315-06-6
• 化学式: C₁₅H₁₄O₃
• 分子量: 242.274
• InChiKey: HSAUHTNZZYCVSU-UHFFFAOYSA-N

物化性质

• 熔点：
  143-145 °C(Solv: ethanol (64-17-5))
• 沸点：
  393.3±42.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,3-dimethyl-3,4-dihydro-1H-benzo[c]chromene-1,6(2H)-dione 在 N-碘代丁二酰亚胺 作用下， 以 二甲基亚砜 为溶剂， 以63%的产率得到2-iodo-3,3-dimethyl-3,4-dihydro-1H-benzo[c]chromene-1,6(2H)-dione
  参考文献：
  名称：

  Rh(III)-催化烯胺酮导向 C-H 偶联重氮二羰基用于异香豆素和萘的骨架发散合成

  摘要：

  面向多样性的合成对于扩展可探索的化学空间非常有用，但受到骨架多样化化学可用工具箱的限制。我们在此报告了 Rh(III) 催化的烯胺酮和重氮二羰基偶联，用于异香豆素和萘的骨架发散合成。骨架形成过程的重氮二羰基环大小和 pH 依赖性证明了在单一类型的系统中实现了底物和试剂控制的骨架多样性产生。有趣的 C-C 键裂解反应性对于能够轻松合成获得异香豆素至关重要。

  DOI：

  10.1021/acs.orglett.2c03288
• 作为产物：
  描述：

  2-溴苯乙酮 在 tris(acetonitrile)(η5-pentamethylcyclopentadienyl)rhodium(III) hexafluoroantimonate 、 cesium acetate 作用下， 以 乙醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 66.0h， 生成 3,3-dimethyl-3,4-dihydro-1H-benzo[c]chromene-1,6(2H)-dione
  参考文献：
  名称：

  Divergent Access to 1-Naphthols and Isocoumarins via Rh(III)-Catalyzed C–H Activation Assisted by Phosphonium Ylide

  摘要：

  Rh-catalyzed C-H activation of phenacyl phosphoniums in coupling with alpha-diazocarbonyl compounds has been realized with the assistance of a mutifunctional phosphonium ylidic directing group, providing expedient accesses to 1-naphthols and isocoumarins. Switchable synthesis of 1-naphthols and isocoumarins was realized by substrate control, where these transformations were enabled by initial C-H activation and subsequent intramolecular Wittig reaction or nucleophilic C-O formation.

  DOI：

  10.1021/acs.orglett.7b01365

文献信息

• Regioselective synthesis of multisubstituted isoquinolones and pyridones via Rh(<scp>iii</scp>)-catalyzed annulation reactions
  作者：Liangliang Shi、Ke Yu、Baiquan Wang

  DOI：10.1039/c5cc05977a

  日期：——

  A mild and efficient Rh(III)-catalyzed regioselective synthesis of isoquinolones and pyridones has been developed. The protocol uses readily available N-methoxybenzamide or N-methoxymethacrylamide and diazo compounds as the starting materials. The...

  已经开发了温和有效的Rh（III）催化的异喹诺酮和吡啶酮的区域选择性合成。该方案使用容易获得的N-甲氧基苯甲酰胺或N-甲氧基甲基丙烯酰胺和重氮化合物作为起始原料。这...
• Rh(III)-catalyzed C-H activation of primary benzamides and tandem cyclization with cyclic 2-diazo-1,3-diketones for the synthesis of isocoumarins
  作者：Xinwei He、Guang Han、Youpeng Zuo、Yongjia Shang

  DOI：10.1016/j.tet.2018.10.045

  日期：2018.12

  A simple and efficient Rh(III)-catalyzed C-H activation and tandem intramolecular cyclization for the synthesis of isocoumarins has been developed. The protocol uses easily available primary benzamides and cyclic 2-diazo-1,3-diketones as starting materials. This reaction proceeds via C-C and C-O bond formation in a single reaction vessel, and the corresponding isocoumarins were obtained in moderate

  已经开发了一种简单有效的Rh（III）催化的CH活化和串联分子内环化反应合成异香豆素。该方案使用容易获得的伯甲酰胺和环状2-重氮-1,3-二酮作为起始原料。该反应通过在单个反应容器中形成CC和CO键而进行，并以中等至极好的收率（58％–97％）获得了相应的异香豆素。完善的方案显示出较高的官能团耐受性，为异香豆素主链提供了有效的替代途径。
• Rh( <scp>III</scp> )‐Catalyzed Diverse C—H Functionalization of Iminopyridinium Ylides
  作者：Zhenzhen Dong、Pengfei Li、Xingwei Li、Bingxian Liu

  DOI：10.1002/cjoc.202100203

  日期：2021.9

  Divergent synthesis of useful skeletons has been realized via rhodium(III)-catalyzed C—H activation of iminopyridinium ylides and coupling with various unsaturated coupling reagents. Isocoumarins and isoquinolones were obtained via cleavage of the C—N or N—N bond in the ylidic directing group, while fluorinated alkenes were delivered with the directing group intact. The reactions occurred with wide

  通过铑（III）催化的亚氨基吡啶鎓叶立德的CH活化并与各种不饱和偶联剂偶联，已经实现了有用骨架的发散合成。异香豆素和异喹诺酮获得经由所述C-N或N-N键的ylidic导向基团中的裂解，而氟化烯烃用的导向基团完整递送。该反应在氧化还原中性和耐空气条件下以广泛的底物范围和良好的效率发生。代表性产品表现出固态荧光特性和对人类癌细胞的抑制生物活性。
• Tandem Reactions Leading to Benzo[c]chromen-6-ones and 3-Substituted Isocoumarins
  作者：Xuesen Fan、Yan He、Liangyan Cui、Shenghai Guo、Jianji Wang、Xinying Zhang

  DOI：10.1002/ejoc.201101559

  日期：2012.2

  A simple and convenient protocol for the synthesis of benzo[c]chromen-6-ones and 3-substituted isocoumarins through a CuI-catalyzed tandem reaction of 2-bromobenzoates withcyclohexane-1,3-diones or acyclic 1,3-diones is developed. This strategy can also be extended to the one-pot synthesis of isoquinolin-1(2H)-one and 3,4-dihydrophenanthridine-1,6(2H,5H)-dione.

  开发了一种通过 CuI 催化的 2-溴苯甲酸酯与环己烷-1,3-二酮或无环 1,3-二酮的串联反应合成苯并 [c] chromen-6-ones 和 3-取代异香豆素的简单方便的方案. 这种策略也可以扩展到异喹啉-1(2H)-one 和 3,4-二氢菲啶-1,6(2H,5H)-二酮的一锅法合成。
• Harnessing hypervalent iodonium ylides as carbene precursors: C–H activation of <i>N</i>-methoxybenzamides with a Rh(<scp>iii</scp>)-catalyst
  作者：Sivakalai Mayakrishnan、Masilamani Tamizmani、Naryanan Uma Maheswari

  DOI：10.1039/d0cc06038k

  日期：——

  Hypervalent iodonium ylides expeditiously generate carbenes which undergo domino intermolecular C–H activation followed by intramolecular condensation in the presence of N-methoxybenzamide as a starting material and a Rh(III)-catalyst to afford dihydrophenanthridines. KIE studies and DFT calculations were performed to substantiate the mechanistic pathway. To extend the synthetic utilisation, fluorescent

  高价碘鎓叶立德迅速生成碳烯，这些碳烯经过多米诺骨牌分子间CH活化，然后在以N-甲氧基苯甲酰胺为起始原料和Rh（III）催化剂存在下进行分子内缩合，得到二氢菲啶。进行了KIE研究和DFT计算，以证实机理途径。以延长合成利用率，荧光pyranoisocoumarins通过使用的Rh（实现III）催化围-C-H / O-H活化/环反应。