3-chloro-1-methyl-4-phenyl-1-azaspiro[4.5]deca-3,6,9-triene-2,8-dione | 1078120-47-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-chloro-1-methyl-4-phenyl-1-azaspiro[4.5]deca-3,6,9-triene-2,8-dione
• 英文别名: 3-Chloro-1-methyl-4-phenyl-1-azaspiro[4.5]deca-3,6,9-triene-2,8-dione
• CAS: 1078120-47-4
• 化学式: C₁₆H₁₂ClNO₂
• 分子量: 285.73
• InChiKey: QKIXESVDDOTPQN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  N-甲基-P-氨基苯甲醚 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 potassium chloride 、 sodium acetate 、 三乙胺 、 N,N'-二环己基碳二亚胺 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 2.0h， 生成 3-chloro-1-methyl-4-phenyl-1-azaspiro[4.5]deca-3,6,9-triene-2,8-dione
  参考文献：
  名称：

  用PhI（OCOCF3）2和KBr / KCl光导合成N-芳基炔酰胺的卤代螺[4,5]三烯酮。

  摘要：

  已经开发出新颖且方便的N-（对甲氧基芳基）丙酰胺的光介导的卤代螺环化。苯碘双（三氟乙酸盐）（PIFA）作为碘化试剂的光解在氙灯的照射下导致碘化ipso环化，而溴化的ipso环化或氯化的ipso环化则通过照射PIFA和KBr / KCl在蓝色LED下。本协议只是利用光作为安全，清洁的能源，不需要任何外部光催化剂即可提供各种3-卤代螺[4,5]三烯酮，产率高至优异（高达93％）。

  DOI：

  10.1039/d0ob00057d

文献信息

• Electrochemical Oxidative Halogenation of <i>N</i>-Aryl Alkynamides for the Synthesis of Spiro[4.5]trienones
  作者：Ke Yu、Xianqiang Kong、Jiajun Yang、Guodong Li、Bo Xu、Qianjin Chen

  DOI：10.1021/acs.joc.0c02429

  日期：2021.1.1

  We developed a green method for the synthesis of spiro[4.5]trienones through an electrochemical oxidative halocyclization with N-aryl alkynamides. This reaction was conducted under metal-catalyst- and exogenous-oxidant-free conditions at room temperature. Using readily available LiCl, LiBr, and LiI as the halogen source, a variety of dearomative halo-spirocyclization products were obtained in good

  我们开发了一种通过N-芳基炔酰胺的电化学氧化卤代环化合成螺[4.5]三烯酮的绿色方法。该反应在室温下在无金属催化剂和无外源氧化剂的条件下进行。使用现成的LiCl，LiBr和LiI作为卤素源，可以得到具有良好收率或优异收率的多种脱芳族卤代-螺环化产品，并具有广泛的范围和官能团耐受性。
• Synthesis of 3‐Halogenated Quinolin‐2‐Ones from <i>N</i> ‐Arylpropynamides <i>via</i> Hypervalent Iodine(III)−Mediated Umpolung Process
  作者：Xiaoxian Li、Beibei Zhang、Bingyue Zhao、Xiaofan Wang、Lingzhi Xu、Yunfei Du

  DOI：10.1002/adsc.202200131

  日期：2022.4.12

  The selective synthesis of 3-halogenated quinolin-2-ones from N-arylpropynamides was realized via umpolung process mediated by phenyliodine(III) diacetate (PIDA) and MX (LiCl, LiBr, CuI). Differing from most previous electrophilic cyclization/halogenation processes that afforded spiro[4,5]trienones, 3-halogenated quinolin-2-ones were obtained through this method with high selectivity.

  通过由二乙酸苯碘 (III) (PIDA) 和 MX (LiCl、LiBr、CuI) 介导的 umpolung 过程实现了从N-芳基丙酰胺选择性合成 3-卤代 quinolin-2-ones 。与以往大多数得到螺[4,5]三烯酮的亲电环化/卤化过程不同，通过该方法获得了高选择性的3-卤代喹啉-2-酮。
• Metal‐Free ipso‐Halocyclization of N‐Arylpropynamides Using Hypervalent Iodine(III) Reagents under Aqueous Condition
  作者：Pankaj Jangir、Kalu Ram Bajya、Akshay S. Pathare、Mohammad Sodoor、Rinku Saini、Mukesh Purohit、Sermadurai Selvakumar

  DOI：10.1002/ejoc.202400203

  日期：2024.5.27

  An efficient intramolecular ipso-halocyclization of para-unsubstituted N-arylpropynamides proceeds using readily available hypervalent iodine reagents as oxidant and potassium halides as halogen source under aqueous medium. This method shows a broad substrate scope and doesn't require any metal catalysts.

  使用容易获得的高价碘试剂作为氧化剂和卤化钾作为卤素源，在水性介质下对未取代的N-芳基丙酰胺进行有效的分子内卤环化。该方法显示了广泛的底物范围并且不需要任何金属催化剂。
• Intramolecular <i>ipso</i>-Halocyclization of 4-(<i>p</i>-Unsubstituted-aryl)-1-alkynes Leading to Spiro[4,5]trienones: Scope, Application, and Mechanistic Investigations
  作者：Bo-Xiao Tang、Yue-Hua Zhang、Ren-Jie Song、Dong-Jun Tang、Guo-Bo Deng、Zhi-Qiang Wang、Ye-Xiang Xie、Yuan-Zhi Xia、Jin-Heng Li

  DOI：10.1021/jo300037n

  日期：2012.3.16

  A new, general method for the synthesis of spiro[4,5]trienores is described by the intramolecular ipso-halocyclization of 4-(p-unsubstituted-aryl)-1-alkynes. In the presence of halide electrophiles, a variety of 4-(p-unsubstituted-aryl)-1-alkynes underwent the intramolecular ipso-halocyclization with water smoothly, affording the corresponding halo-substituted spiro[4,5]trienones in moderate to good yields. The obtained spiro[4,5]trienones can be applied in constructing the azaquaternary tricyclic skeleton via Pd-catalyzed Heck reaction. Notably, the prepared spiro[4,5]trienones and azaquaternary tricycles are of importance in the areas of pharmaceuticals and agrochemicals. The mechanism of the intramolecular ipso-halocyclization reaction is also discussed according to the O-18-labeling experiments and DFT calculations.
• Electrophilic <i>ipso</i>-Cyclization of <i>N</i>-(<i>p</i>-Methoxyaryl)propiolamides Involving an Electrophile-Exchange Process
  作者：Bo-Xiao Tang、Qin Yin、Ri-Yuan Tang、Jin-Heng Li

  DOI：10.1021/jo8018297

  日期：2008.11.21

  A novel electrophilic ipso-cyclization involving an electrophile-exchange process has been developed. In the presence of CuX (X = I, Br, SCN) and electrophilic fluoride reagents, a variety of N-(p-methoxyaryl)propiolamides and 4-methoxyphenyl 3-phenylpropiolate were cyclized to selectively afford the corresponding spiro[4.5]decenones in moderate to good yields. It is noteworthy that two azaquaternary tricyclic products were synthesized through a two-step pathway involving an electrophilic ipso-cyclization and then an intramolecular Heck reaction.