4-formylphenyl cinnamate | 85238-61-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 4-formylphenyl cinnamate
• 英文别名: 4-formyl cinnamate；2-Propenoic acid, 3-phenyl-, 4-formylphenyl ester；(4-formylphenyl) 3-phenylprop-2-enoate
• CAS: 85238-61-5
• 化学式: C₁₆H₁₂O₃
• mdl: MFCD00430474
• 分子量: 252.269
• InChiKey: ASHIAZHAFARVET-UHFFFAOYSA-N

物化性质

• 熔点：
  95-96 °C
• 沸点：
  437.3±34.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  4-formylphenyl cinnamate 在 氢氧化钾 、 sodium hydroxide 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 24.0h， 生成 [4-(2-amino-4-thiophen-2-yl-6H-1,3-oxazin-6-yl)phenyl] 3-phenylprop-2-enoate
  参考文献：
  名称：

  Vasavada, Jaladhi A.; Parekh, Journal of the Indian Chemical Society, 2003, vol. 80, # 1, p. 55 - 56

  摘要：

  DOI：
• 作为产物：
  描述：

  肉桂酸 在 氯化亚砜 、 三乙胺 作用下， 以 氯仿 为溶剂， 反应 9.25h， 生成 4-formylphenyl cinnamate
  参考文献：
  名称：

  ACYLOXY SUBSTITUTED PHENYL DITHIANE DERIVATIVES

  摘要：

  Para-酰基取代的二氮杂环己烯，其医药配方和制备和使用方法。

  公开号：

  US20220235024A1

文献信息

• The α-Effect in Nucleophilic Substitution Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Butane-2,3-dione Monoximate
  作者：Min-Young Kim、Yu-Jin Son、Ik-Hwan Um

  DOI：10.5012/bkcs.2013.34.10.2877

  日期：2013.10.20

  Second-order rate constants ($k_Ox^-}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl X-substituted-cinnamates (7a-7e) and Y-substituted-phenyl cinnamates (8a-8e) with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0\pm}0.1^\circ}C$. The Hammett plot for the reactions of 7a-7e consists of two intersecting straight lines while the Yukawa-Tsuno plot exhibits an excellent linearity with $\rho}_X$=0.85 and r=0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step but is caused by resonance stabilization of the ground state (GS) of the substrate possessing an electron-donating group (EDG). The Br$\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (8a-8e) is linear with $\beta}_lg}$ = -0.64, which is typical of reactions reported previously to proceed through a concerted mechanism. The $\alpha}$-nucleophile ($Ox^-$) is more reactive than the reference normal-nucleophile ($4-ClPhO^-$). The magnitude of the $\alpha}$-effect (i.e., the $k_Ox^-}/k_4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent X in the nonleaving group but increases linearly as the substituent Y in the leaving group becomes a weaker electron-withdrawing group (EWG). It has been concluded that the difference in solvation energy between $Ox^-$ and $4-ClPhO^-$ (i.e., GS effect) is not solely responsible for the $\alpha}$-effect but stabilization of transition state (TS) through a cyclic TS structure contributes also to the Y-dependent $\alpha}$-effect trend (i.e., TS effect).

  二阶速率常数（$k_Ox^-}$）通过分光光度法测定，用于4-硝基苯基X-取代肉桂酸酯（7a-7e）和Y-取代苯基肉桂酸酯（8a-8e）与丁烷-2,3-二酮单肟盐（$Ox^-$）在$25.0\pm}0.1^\circ}C$下80 mol % $H_2O$/20 mol % DMSO中的亲核取代反应。7a-7e反应的Hammett图由两条相交直线组成，而Yukawa-TSuno图显示出极佳的线性，$\rho}_X$=0.85，r=0.58，表明非线性Hammett图并非由于速率决定步骤变化所致，而是由具有供电子基团（EDG）的底物基态（GS）共振稳定化引起。Y-取代苯基肉桂酸酯（8a-8e）反应的Br$\o}$nsted型图线性，$\beta}_lg}$ = -0.64，这与先前报道的通过协同机制进行的反应一致。$\alpha}$-亲核试剂（$Ox^-$）比参考正常亲核试剂（$4-ClPhO^-$）更具反应活性。$\alpha}$-效应（即$k_Ox^-}/k_4-ClPhO^-}$比值）的大小与非离去基团中取代基X的电子性质无关，但随着离去基团中取代基Y变为更弱的吸电子基团（EWG）而线性增加。结论是，$Ox^-$与$4-ClPhO^-$之间的溶剂化能差异（即GS效应）并非$\alpha}$-效应的唯一原因，过渡态（TS）通过环状TS结构稳定化也对依赖于Y的$\alpha}$-效应趋势（即TS效应）有贡献。
• Structure-Reactivity Correlations in Nucleophilic Displacement Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Z-Substituted-Phenoxides
  作者：Yu-Jin Son、Eun-Hee Kim、Ji-Sun Kang、Ik-Hwan Um

  DOI：10.5012/bkcs.2013.34.8.2455

  日期：2013.8.20

  linear correlation with ρX = 0.89 and r = 0.58. The Bronsted-type plot for the reactions of 4-nitrophenyl cinnamate (4c) with Z-substituted-phenoxides is linear with βnuc = 0.76. The Bronsted-type plot for the reactions of Y-substituted-phenyl cinnamates (5a-5d) with 4-chlorophenoxides (4ClPhO – ) is also linear with βlg = –0.72. The Hammett plot correlated with σ – constants for the reactions of 5a5d

  已经通过分光光度法测量了 4-硝基苯基 X-取代肉桂酸酯 (4a-4e) 和 Y-取代苯基肉桂酸酯 (5a-5e) 与 Z-取代苯氧基阴离子的亲核置换反应的二级速率常数 (kN)在 80 mol % H2O/20 mol % DMSO 中，温度为 25.0 ± 0.1 o C。 4a-4e 与 4-氯酚 (4-ClPhO – ) 反应的 Hammett 图由两条相交的直线组成，可将其视为速率决定步骤 (RDS) 的变化。然而，已经得出结论，非线性哈米特图不是由于 RDS 的变化，而是由于通过共振相互作用在肉桂酰基部分具有吸电子基团的底物的基态稳定引起的，因为 Yukawa-Tsuno图与 ρX = 0.89 和 r = 0.58 表现出极好的线性相关性。肉桂酸 4-硝基苯酯 (4c) 与 Z-取代的酚盐反应的布朗斯台德型图是线性的，βnuc = 0.76。Y-取代的肉桂酸苯酯 (5a-5d)
• Selective Synthesis of 3,4-Dihydrocoumarins and Chalcones from Substituted Aryl Cinnamic Esters
  作者：Jae-Ho Jeon、Deok-Mo Yang、Jong-Gab Jun

  DOI：10.5012/bkcs.2011.32.1.65

  日期：2011.1.20

  Coumarins are ubiquitous in plant kingdom and have been used as antitumor, antifungals, anticoagulants, insecticides. Chalcones are also widespread in plant kingdom and have been known to possess diverse biological activities; antibacterial, antifungal, antitumor and anti-inflammatory, etc. As they are considered as important natural products, numerous synthetic approaches have been reported up to the present. We devise a new selective method of preparing dihydrocoumarins and chalcones from aryl cinnamates by the selection of reagents. Dihydrocoumarin derivatives were prepared selectively by using intramolecular cyclization catalyzed by p-toluene sulfonic acid. Also, chalcones were prepared by Fries-rearrangement catalyzed by $TiCl_4$. This method can be used for preparing various coumarin & chalcone compounds.

  香豆素广泛存在于植物王国中，并已被用作抗癌剂、抗真菌剂、抗凝血剂和杀虫剂。查尔酮也在植物王国中广泛分布，并且已知具有多种生物活性，包括抗菌、抗真菌、抗癌和抗炎等。由于它们被认为是重要的天然产物，迄今为止已经报道了许多合成方法。我们设计了一种新的选择性方法，通过选择试剂，从芳基肉桂酸制备二氢香豆素和查尔酮。通过使用对甲苯磺酸催化的分子内环化反应，选择性地制备了二氢香豆素衍生物。此外，还通过三氯化钛催化的Fries重排反应制备了查尔酮。这种方法可以用于制备各种香豆素和查尔酮化合物。
• Kinetic study on aminolysis of aryl X-substituted-cinnamates in acetonitrile: differential medium effect determines reactivity and reaction mechanism
  作者：Ik-Hwan Um、Ae-Ri Bae、Julian M. Dust

  DOI：10.1139/cjc-2018-0310

  日期：2019.1

  A kinetic study on nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted-cinnamates (1a–1f) and Y-substituted-phenyl cinnamates (2a–2g) with a series of alicyclic secondary amines in MeCN at 25.0 ± 0.1 °C is reported. The Bronsted-type plots for the reactions of 1a–1f are linear with βnuc = 0.47∼0.50, indicating that the bond formation between the amine nucleophile and the electrophilic

  2,4-二硝基苯基X-取代肉桂酸酯（1a-1f）和Y-取代-苯基肉桂酸酯（2a-2g）与一系列脂环族仲胺在MeCN中25.0±0.1°C的亲核取代反应动力学研究被报道。1a-1f 反应的布朗斯台德型曲线是线性的，βnuc = 0.47∼0.50，表明胺亲核试剂和亲电子中心之间的键形成在过渡态略微提前。2a-2g 与哌啶反应的 Bronsted 型图也是线性的，βlg = –0.66，这是先前报道的反应通过协同机制进行的典型 βlg 值。此外，与 σ– 常数相关的哈米特图比与 σo 常数相关的线性关系好得多，这意味着离去基团的排出在速率决定步骤 (RDS) 中进行。因此，反应被总结为通过协同机制进行。1a-1f 反应的哈米特图包括...
• Cytotoxic 1,3-diarylidene-2-tetralones and related compounds
  作者：Jonathan R Dimmock、Maniyan P Padmanilyam、Gordon A Zello、J Wilson Quail、Eliud O Oloo、Jared S Prisciak、Heinz-Bernhard Kraatz、Arten Cherkasov、Jeremy S Lee、Theresa M Allen、Cheryl L Santos、Elias K Manavathu、Erik De Clercq、Jan Balzarini、James P Stables

  DOI：10.1016/s0223-5234(02)01402-2

  日期：2002.10

  demonstrated cytotoxic activity towards murine P388 and L1210 cells as well as human Molt 4/C8 and CEM T-lymphocytes. In general, the related 1-arylidene-2-tetralones 3 possessed lower potencies in these screens than the compounds in series 1 and 4. Approximately, half of the compounds were evaluated against a panel of human tumour cell lines. In this screen, most of the enones were more cytotoxic than the

  合成了许多1，3-亚芳基-2-四氢萘酮1、2和4，它们对鼠P388和L1210细胞以及人类Molt 4 / C8和CEM T淋巴细胞具有细胞毒活性。一般而言，相关的1-芳基-2-四氢萘酮3在这些筛选中的效力低于系列1和4中的化合物。大约一半的化合物是针对一组人类肿瘤细胞系进行评估的。在该筛选中，大多数烯酮比已确立的抗癌药美法仑具有更高的细胞毒性，并且其中一些已证明对白血病和结肠癌细胞具有选择性毒性。代表性化合物的作用方式包括干扰核酸和蛋白质的生物合成以及改变氧化还原电位。当对小鼠腹膜内给药时，该化合物具有良好的耐受性。