3-p-bromobenzoyl-2,4-dihydro-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-trione

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 英文名称: 3-p-bromobenzoyl-2,4-dihydro-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-trione
• 英文别名: 3-(4-bromobenzoyl)pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-trione
• 化学式: C₁₈H₈BrNO₅
• 分子量: 398.169
• InChiKey: OTFWZYIPSGLWIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  80.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-p-bromobenzoyl-2,4-dihydro-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-trione 在 水 作用下， 以 1,4-二氧六环 为溶剂， 生成 (Z)-3-(2-(4-bromophenyl)-2-oxoethylidene)-3,4-dihydro-2H-benzo[b][1,4]oxazin-2-one
  参考文献：
  名称：

  Five-membered 2,3-dioxo heterocycles: LXXXVIII. Reaction of 3-aroylpyrrolo[1,2-d][1,4]benzoxazine-1,2,4(4H)-triones with N,N′-dicyclohexylcarbodiimide under thermolysis conditions

  摘要：

  Thermolysis of 3-aroylpyrrolo[1,2-d][1,4]benzoxazine-1,2,4(4H)-triones generates aroyl(2-oxo-1,4-benzoxazin-3-yl)ketenes which react as dienes at the aroylketene fragment in [4 + 2]-cycloaddition at the C=N bond of N,N'-dicyclohexylcarbodiimide with formation of 3-[6-aryl-4-oxo-3-cyclohexyl-2-cyclohexylimino-3,4-dihydro-2H-1,3-oxazin-5-yl]-2H-1,4-benzoxazin-2-ones. Thermolysis of the latter is accompanied by elimination of N,N'-dicyclohexylcarbodiimide, and aroyl(2-oxo-1,4-benzoxazin-3-yl)ketenes thus generated undergo cyclodimerization to produce 7-aroyl-6,10-dioxo-9-(2-oxo-2H-1,4-benzoxazin-3-yl)-6,10-dihydrobenzo[b]pyrido[1,2-d][1,4]oxazin-8-yl benzoates.

  DOI：

  10.1134/s1070428012090151
• 作为产物：
  描述：

  4-(4-bromo-phenyl)-2,4-dioxo-butyric acid 以 异丙醇 、 苯 为溶剂， 反应 3.33h， 生成 3-p-bromobenzoyl-2,4-dihydro-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-trione
  参考文献：
  名称：

  Five-membered 2,3-dioxo heterocycles: XCVIII. [4 + 2]-cycloaddition of alkyl vinyl ethers to 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones. A new synthetic approach to heteroanalogs of 13(14→8)-abeo steroids

  摘要：

  3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones reacted with alkyl vinyl ethers according to the [4 + 2]-cycloaddition pattern with formation of substituted (1S*,16R*)- and (1R*,16R*)-16-alkoxy-14-aryl-3,15-dioxa-10-azatetracyclo[8.7.0.0(1,13).0(4,9)]heptadeca-4,6,8,13-tetraene-2,11,12-triones. The structure of (1S*,16R*)-7-chloro-16-ethoxy-14-phenyl-3,15-dioxa-10-azatetracyclo[8.7.0.0(1,13).0(4,9)]heptadeca-4,6,8,13-tetraene-2,11,12-trione was determined by X-ray analysis. A new synthetic approach was developed to heteroanalogs of 13(14 -> 8)-abeo steroids, substituted 3,15-dioxa-10-azatetracyclo[8.7.0.0(1,13).0(4,9)]heptadecanes.

  DOI：

  10.1134/s1070428013120105

文献信息

• Annulation of 1<i>H</i>-pyrrole-2,3-diones by thioacetamide: an approach to 5-azaisatins
  作者：Aleksandr I Kobelev、Ekaterina E Stepanova、Maksim V Dmitriev、Andrey N Maslivets

  DOI：10.3762/bjoc.15.32

  日期：——

  A novel approach to 1H-pyrrolo[3,2-c]pyridine-2,3-diones (5-azaisatins) has been developed via an unprecedented annulation of pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones by thioacetamide. A new way of C–H functionalization of thioacetamide has been discovered. The reaction proceeds under green catalyst-free conditions.

  已开发出一种新颖的方法，通过噻乙酰胺与吡咯并[2,1-c][1,4]苯并噁嗪-1,2,4-三酮的前所未有的环化反应，合成了1H-吡咯并[3,2-c]吡啶-2,3-二酮（5-氮杂异吲哚）。发现了一种噻乙酰胺的新型C-H官能化方法。该反应在无催化剂的绿色条件下进行。
• Diversity-Oriented Synthesis via Catalyst-Free Addition of Ketones to [e]-Fused 1H-Pyrrole-2,3-diones
  作者：Ekaterina Stepanova、Andrey Maslivets、Svetlana Kasatkina、Maksim Dmitriev

  DOI：10.1055/s-0037-1610647

  日期：2018.12

  pyrrole-based heterocyclic scaffolds has been developed by the interaction of 1H-pyrrole-2,3-diones fused at the [e]-side to a 1,4-benzoxazin-2-one or quinoxalin-2(1H)-one moiety with ketones. The described interaction proceeds either as an aldol reaction or as a Michael addition/intramolecular cyclization depending on the reaction conditions. The disclosed aldol reaction proceeds with good diastereoselectivity

  摘要 通过在[ e ]侧融合的1 H-吡咯-2,3-二酮与1,4-苯并恶嗪-2-one或喹喔啉的相互作用，已经开发出了一种简便的合成方法，可用于两种不同的基于吡咯的杂环骨架-2（1小时）-带有酮的部分。所描述的相互作用根据反应条件以醛醇缩合反应或迈克尔加成/分子内环化的方式进行。当反应在芳烃中进行时，所公开的醛醇缩合反应在无催化剂的条件下以良好的非对映选择性进行。级联迈克尔加成/分子内环化反应的产物主要在无催化剂和无溶剂条件下形成。所提出的策略提供了对药学上有趣的基于吡咯的多杂环药物的便捷访问。 通过在[ e ]侧融合的1 H-吡咯-2,3-二酮与1,4-苯并恶嗪-2-one或喹喔啉的相互作用，已经开发出了一种简便的合成方法，可用于两种不同的基于吡咯的杂环骨架-2（1小时）-带有酮的部分。所描述的相互作用根据反应条件以醛醇缩合反应或迈克尔加成/分子内环化的方式进行。当反应在芳烃中进行时，所
• Cleavage of Pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones with Thiocarbonohydrazide. Synthesis of Substituted 4-Amino-1,2,4-triazines
  作者：A. I. Kobelev、E. E. Stepanova、M. V. Dmitriev、A. N. Maslivets

  DOI：10.1134/s1070428019070182

  日期：2019.7

  4-dihydro-1,2,4-triazin-5(2H)-ones and 6-substituted 1,4-benzoxazine-2,3-diones which can be separated by fractional crystallization directly from the reaction mixture. The reaction is likely to involve a sequence of nucleophilic transformations with intermediate formation of spiro[pyrrole-2,6′-[1,2,4]triazines] which undergo cleavage of the C2-N1 bond in the pyrrole ring. The structure of the products

  3-酰基吡咯并[ 2,1- c ] [1,4]苯并恶嗪-1,2,4-三酮与硫代碳酰肼反应生成4-氨基-6-（酰基甲基）-3-亚磺酰基-3,4-二氢的混合物-1,2,4-三嗪-5（2 H）-ones和6-取代的1,4-苯并恶嗪-2,3-二酮可以通过分级结晶直接从反应混合物中分离出来。该反应可能涉及亲核转化的序列，中间形成螺[吡咯-2,6'-[1,2,4]三嗪]，该中间体经历C 2 -N 1的裂解在吡咯环上键合。通过X射线分析确定产物的结构，并通过UPLC / MS鉴定中间产物。1,2,4-三嗪衍生物也可以独立地与2,4-二氧代丁酸烷基酯或2-氧代丁二酸和硫代碳酰肼合成。由4-芳基-2,4-二氧代丁酸和硫代碳酰肼合成4-氨基-1,2,4-三嗪的已知程序已得到改进，以满足“绿色化学”原理。开发了两种合成取代的4-氨基-1,2,4-三嗪的新方法。所获得的化合物引起了药物化学，药理学和精细有机合成的兴趣。
• Organocatalytic γ-oxidation of α,β-unsaturated aldehydes
  作者：Mikołaj Chromiński、Maciej Giedyk、Dorota Gryko

  DOI：10.3998/ark.5550190.p008.394

  日期：——

  Direct, organocatalytic γ-oxidation of α,β-unsaturated aldehydes via dienamine catalysis has been developed. The reaction of 2-hexenal with dibenzoyl peroxide (BPO) catalyzed by the MacMillan catalyst gave desired γ-benzoyloxy aldehyde in a moderate yield, notably the formation of α-substituted product was greatly suppressed. γ-Benzoyloxy-α,β-unsaturated aldehyde turned out to be a useful building

  已经开发了通过二烯胺催化的 α,β-不饱和醛的直接有机催化 γ-氧化。2-己烯醛与过氧化二苯甲酰（BPO）在麦克米伦催化剂的催化下反应，以中等产率得到所需的γ-苯甲酰氧基醛，显着抑制了α-取代产物的形成。γ-苯甲酰氧基-α,β-不饱和醛被证明是合成高度官能化分子的有用构件。
• Facile regiodivergent synthesis of spiro pyrrole-substituted pseudothiohydantoins and thiohydantoins via reaction of [<i>e</i>]-fused 1<i>H</i>-pyrrole-2,3-diones with thiourea
  作者：Aleksandr I Kobelev、Nikita A Tretyakov、Ekaterina E Stepanova、Maksim V Dmitriev、Michael Rubin、Andrey N Maslivets

  DOI：10.3762/bjoc.15.280

  日期：——

  A highly divergent synthesis of regioisomeric thiohydantoins and pseudothiohydantoins spiro-fused to a pharmacologically valuable pyrrole-2-one fragment involving the reaction of [e]-fused 1H-pyrrole-2,3-diones with thioureas was developed. The obtained spiro pseudothiohydantoin derivatives were found to undergo a pseudothiohydantoin-thiohydantoin rearrangement. The reactions were shown to proceed

  研发了一种高度分散的合成，其是将与[e]-融合的1H-吡咯-2,3-二酮与硫脲反应的药理学上有价值的吡咯-2-酮片段螺合稠合的区域异构硫代乙内酰脲和假硫代乙内酰脲。发现所获得的螺假硫代乙内酰脲衍生物进行了假硫代乙内酰脲-硫代乙内酰脲重排。显示反应在无催化剂条件下以良好的产率进行，并且无需应用制备色谱法就可以分离出产物。