3-[1-(4-Bromo-phenyl)-meth-(E)-ylidene]-2-phenyl-chroman-4-one | 77015-48-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 黄酮类化合物
• 英文名称: 3-[1-(4-Bromo-phenyl)-meth-(E)-ylidene]-2-phenyl-chroman-4-one
• 英文别名: (3E)-3-[(4-bromophenyl)methylidene]-2-phenylchromen-4-one
• CAS: 77015-48-6
• 化学式: C₂₂H₁₅BrO₂
• 分子量: 391.264
• InChiKey: BOYUWRVHTCLLJC-RGEXLXHISA-N

物化性质

• 沸点：
  547.7±50.0 °C(Predicted)
• 密度：
  1.438±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-[1-(4-Bromo-phenyl)-meth-(E)-ylidene]-2-phenyl-chroman-4-one 在 二甲基二环氧乙烷 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 408.0h， 以82%的产率得到trans,trans-(+/-)-3'-(4-Bromophenyl)-2-phenylspiro-4-one
  参考文献：
  名称：

  Dioxirane Oxidation of 3-Arylideneflavanones: Diastereoselective Formation of trans,trans Spiroepoxides from the E Isomers

  摘要：

  Oxidation of the E isomers of the 3-arylideneflavanones 1 by dimethyldioxirane in acetone solution at ambient temperature led to spiroepoxides trans,trans-2 in high yields (greater than or equal to 170%) and complete diastereoselectivity. Steric interaction with the axial aryl group in the 3-arylideneflavanone E-1. directs the attack of the dioxirane to the opposite side during the oxygen transfer to afford exclusively the trans,trans-2 epoxides, which clearly demonstrates the advantage of dimethyldioxirane as oxidant. In comparison, these substrates give under Weitz-Scheffer conditions (alkaline hydrogen peroxide) both diastereomeric epoxides (dr ca. 3:1) in poor yields (less than or equal to 130%), while m-CPBA produces trans,trans-2 spiroepoxides preferentially, but also in low yields (less than or equal to 140%).(1,2) Attempted epoxidation of the Z isomers afforded instead the 3-benzoylflavones 3 and/or 3-benzoylflavanones 4 in low yields. With the much more reactive methyl(trifluoromethyl)dioxirane, the E-1 isomers also gave the trans,-trans-2 spiroepoxides diastereoselectively in high yields, but the Z isomers suffered complete decomposition. Presumably the sterically hindered Z isomers encumber the oxygen atom transfer by the dioxirane and radical-type oxidation dominates for these reluctant substrates.

  DOI：

  10.1021/jo00083a035
• 作为产物：
  描述：

  (3Z)-3-[(4-bromophenyl)methylidene]-2-phenylchromen-4-one 以 氘代吡啶 为溶剂， 以100%的产率得到3-[1-(4-Bromo-phenyl)-meth-(E)-ylidene]-2-phenyl-chroman-4-one
  参考文献：
  名称：

  类黄酮。第6部分。3-芳基黄烷酮的碱催化异构化反应的动力学和机理

  摘要：

  3-芳基黄烷酮的碱催化Z → E转化提供了一个适用于1 H nmr光谱动力学研究的独特系统。在[ 2 H 5 ]吡啶中对10个烯酮进行异构化研究表明，正在发生一阶单分子反应。哈米特σ-ρ关系不足以适应的情况下，上速率的取代基影响p -和米硝基-3-亚苄基衍生物。讨论了硝基取代基的异常情况。

  DOI：

  10.1039/p29870000449

文献信息

• Simple Diastereoselective Synthesis of (2<i>S</i>*,2′<i>R</i>*,3′<i>R</i>*,4<i>S</i>*)-2,3′-Diphenylspiro[chroman-3,2′-oxiran]-4-ols and (2<i>S</i>*,2′<i>S</i>*,3′<i>S</i>*,4<i>S</i>*)-2,3′-Diphenylspiro[chroman-3,2′-oxiran]-4-ols
  作者：Tapas K. Mandal、Falguni Chattopadhyay、Chayan Guha、Nayim Sepay、Haimanti Mallik、Asok K. Mallik

  DOI：10.1080/00304948.2018.1405335

  日期：2018.1.2

  lead to interesting compounds having three contiguous stereogenic centers. This fascinating aspect is the key factor for their use as precursors for the synthesis of a wide range of important and useful organic molecules. Two main routes for synthesis of 2,3-epoxyalcohols are i) epoxidation of allyl alcohols, and ii) chemoselective ketone reduction of a,b-epoxyketones. Both allyl alcohols and a,b-epoxyketones

  环氧乙烷（环氧化物）是有机合成中非常通用的构件，它们可以与各种亲核试剂一起打开。环氧化物的亲核加成在 1,2-双官能化合物的立体选择性制备中起着关键作用。它是环氧化物反应最深入研究的反应之一，为此开发了不同的促进剂和条件。1,3-二取代和 1,2,3-三取代的 2,3-环氧醇属于一类重要的环氧化合物，因为它们的环氧环开环可以产生具有三个连续立体中心的有趣化合物。这个迷人的方面是它们用作合成各种重要和有用的有机分子的前体的关键因素。合成 2,3-环氧醇的两条主要途径是 i) 烯丙醇的环氧化，和 ii) a,b-环氧酮的化学选择性酮还原。烯丙醇和a,b-环氧酮都是容易获得的化合物，属于后一类的那些通常通过非常简单的反应制备，即a,b-不饱和酮与过氧化氢和碱的环氧化。这里值得一提的是，对于 a,b-环氧酮的还原以及化学选择性，反应的立体选择性在实现目标合成所需的转化步骤中起着非常重要的作用。这导
• Structure–cytotoxic activity relationship of 3-arylideneflavanone and chromanone (E,Z isomers) and 3-arylflavones
  作者：Bogumiła Kupcewicz、Grażyna Balcerowska-Czerniak、Magdalena Małecka、Piotr Paneth、Urszula Krajewska、Marek Rozalski

  DOI：10.1016/j.bmcl.2013.05.044

  日期：2013.7

  The E,Z-isomers of 3-arylidene substituted flavanone, chromanone and 3-aryl substituted flavone derivatives were tested in vitro for their cytotoxic activity against three cancer cell lines (HL-60, NALM-6, WM-115) and normal cell line (HUVEC). It was observed that substitution at C-3 position led to significant enhance in cytotoxicity. Isomeric configuration of 3-arylideneflavanones had an influence on the cytotoxic potential. Multiple regression analysis combined with variable selection by genetic algorithm was used to model relationships between molecular descriptors and the cytotoxic activity. The most accurate QSAR models were based on a combination between energy of LUMO, experimental value of logP and partial charge on carbonyl oxygen (delta O-2). (C) 2013 Elsevier Ltd. All rights reserved.
• Flavanoids. Part 6. The kinetics and mechanism of base-catalysed isomerisation of 3-arylideneflavanones
  作者：Dilip Dattatraya Dhavale、Poonam Joshi、Keshav Gangadhar Marathe

  DOI：10.1039/p29870000449

  日期：——

  Base-catalysed Z→E conversion of 3-arylideneflavanones provide a unique system suitable for kinetic studies by 1H n.m.r. spectroscopy. Isomerisation studies of 10 enones in [2H5] pyridine showed that a first-order unimolecular reaction was taking place. The Hammett σ–ρ relationship is not adequate to accommodate the substituent effect on rate in the case of p- and m-nitro-3-benzylidene derivatives

  3-芳基黄烷酮的碱催化Z → E转化提供了一个适用于1 H nmr光谱动力学研究的独特系统。在[ 2 H 5 ]吡啶中对10个烯酮进行异构化研究表明，正在发生一阶单分子反应。哈米特σ-ρ关系不足以适应的情况下，上速率的取代基影响p -和米硝基-3-亚苄基衍生物。讨论了硝基取代基的异常情况。
• Dioxirane Oxidation of 3-Arylideneflavanones: Diastereoselective Formation of trans,trans Spiroepoxides from the E Isomers
  作者：Csaba Nemes、Albert Levai、Tamas Patonay、Gabor Toth、Sandor Boros、Judit Halasz、Waldemar Adam、Dieter Golsch

  DOI：10.1021/jo00083a035

  日期：1994.2

  Oxidation of the E isomers of the 3-arylideneflavanones 1 by dimethyldioxirane in acetone solution at ambient temperature led to spiroepoxides trans,trans-2 in high yields (greater than or equal to 170%) and complete diastereoselectivity. Steric interaction with the axial aryl group in the 3-arylideneflavanone E-1. directs the attack of the dioxirane to the opposite side during the oxygen transfer to afford exclusively the trans,trans-2 epoxides, which clearly demonstrates the advantage of dimethyldioxirane as oxidant. In comparison, these substrates give under Weitz-Scheffer conditions (alkaline hydrogen peroxide) both diastereomeric epoxides (dr ca. 3:1) in poor yields (less than or equal to 130%), while m-CPBA produces trans,trans-2 spiroepoxides preferentially, but also in low yields (less than or equal to 140%).(1,2) Attempted epoxidation of the Z isomers afforded instead the 3-benzoylflavones 3 and/or 3-benzoylflavanones 4 in low yields. With the much more reactive methyl(trifluoromethyl)dioxirane, the E-1 isomers also gave the trans,-trans-2 spiroepoxides diastereoselectively in high yields, but the Z isomers suffered complete decomposition. Presumably the sterically hindered Z isomers encumber the oxygen atom transfer by the dioxirane and radical-type oxidation dominates for these reluctant substrates.