benzylidene pyruvic acid | 17451-19-3

• 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: benzylidene pyruvic acid
• 英文别名: Cinnamoyl-ameisensaeure；phenylmethylidenepyruvic acid；Benzyliden-brenztraubensaeure；3-Butenoic acid, 2-oxo-4-phenyl-；2-oxo-4-phenylbut-3-enoic acid
• CAS: 17451-19-3
• 化学式: C₁₀H₈O₃
• 分子量: 176.172
• InChiKey: YQOUMBVFEWZLME-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 海关编码：
  2918300090
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335

反应信息

• 作为反应物：
  描述：

  benzylidene pyruvic acid 在 盐酸 作用下， 生成 (2,4-diphenyl-cyclobutane-1,3-diyl)-di-glyoxylic acid dimethyl ester
  参考文献：
  名称：

  Reimer, Journal of the American Chemical Society, 1924, vol. 46, p. 785

  摘要：

  DOI：
• 作为产物：
  描述：

  potassium 4-phenyl-2-oxo-but-3-enoate 在 盐酸 作用下， 以 水 为溶剂， 反应 12.0h， 生成 benzylidene pyruvic acid
  参考文献：
  名称：

  α-酮酰胺类化合物的不对称氢化方法

  摘要：

  本发明属于不对称催化领域，公开了一种α‑酮酰胺类化合物的不对称氢化方法，包括以下步骤：在催化剂、碱、溶剂的存在下，α‑酮‑β‑烯酰胺类化合物在氢气氛围中还原得到手性α‑羟基‑β烯酰胺类化合物；所述催化剂是由金属铱盐与手性配体络合得到，所述手性配体选自以下化合物：本发明操作简单，转化率和选择性高，成本低廉，具有原子经济性高、环境友好等优点，具有非常良好的工业化应用前景。

  公开号：

  CN108546238B
• 作为试剂：
  描述：

  sodium pyruvate 、 、 苯甲醛 、 盐酸 在 benzylidene pyruvic acid 、 乙酸乙酯 作用下， 以 sodium hydroxide 为溶剂， 反应 4.0h， 生成 benzylidene pyruvic acid
  参考文献：
  名称：

  Process for preparing benzylpyruvic acids and esters

  摘要：

  公开了一种连续的、非隔离的制备苯甲基丙酮酸和苯甲基丙酮酸酯的方法。所得的苯甲基丙酮酸和酯可用作中间体，制备用于治疗高血压的羧基烷基二肽化合物，这些化合物用作血管紧张素转换酶（ACE）抑制剂。

  公开号：

  US04956490A1

文献信息

• Arylidene pyruvic acids motif in the synthesis of new thiopyrano[2,3-<i>d</i>]thiazoles as potential biologically active compounds
  作者：Andrii Lozynskyi、Borys Zimenkovsky、Ihor Nektegayev、Roman Lesyk

  DOI：10.1515/hc-2014-0204

  日期：2015.2.1

  Novel rel-(5R,6S,7S)-2-oxo-5,7-diaryl-3,5,6,7-tetrahydro-2H-thiopyrano[2,3-d]thiazol-6-yl-oxo-acetic acids were synthesized in 52–70% yields via regioselective and diastereoselective hetero-Diels-Alder reaction of 5-arylidene-4-thioxo-2-thiazolidinones with a series of arylidene pyruvic acids. The synthesized compounds were evaluated for anticancer activity in NCI60 cancer cell lines and for antiexudative activity on the carrageenan edema model in rats. Biological screening data led to identification of 3e as having moderate antitumor activity on the colon cancer HT-29 cell line and of 3b as having promising antiexudative effect.

  新型rel-(5R,6S,7S)-2-氧代-5,7-二芳基-3,5,6,7-四氢-2H-噻吩并[2,3-d]噻唑-6-基-氧代-乙酸在52-70%的产率下通过5-芳基亚亚甲基-4-硫代-2-噻唑烷酮与一系列芳基亚亚甲基丙酮酸的区域选择性和对映选择性异-Diels-Alder反应合成。合成的化合物在NCI60癌细胞系中进行了抗癌活性评价，并在大鼠卡拉胶水肿模型上进行了抗渗出活性评价。生物筛选数据表明3e在结肠癌HT-29细胞系中具有中等抗肿瘤活性，3b具有有希望的抗渗出效果。

• Phenyl-substituted 2,2′:6′,2″-terpyridine as a new series of fluorescent compounds—their photophysical properties and fluorescence tuning
  作者：Toshiki Mutai、Jin-Dong Cheon、Shinpei Arita、Koji Araki

  DOI：10.1039/b102685m

  日期：——

  Several phenyl-substituted 2,2′:6′,2″-terpyridines (tpy) were synthesized and it was found that 4′-phenyl tpy (ptp, 3) exhibited the most effective fluorescence, whose quantum yield was up to 0.64 in cyclohexane. For further study on tuning the fluorescence properties of ptp, different substituents were introduced into the p-position of the phenyl group. While Br- 10, Cl- 11, and CH3-ptp 12 showed their absorption and fluorescence in the same region as 3, those of NH2- 14 and Me2N-ptp 15 were observed at much longer wavelengths. In addition, fluorescence maxima of 14 and 15 showed large (>130 nm) solvent dependence. The difference between ground and excited state dipole moment (Δμ) for 15 was estimated to be 15.2 D by the Lippert–Mataga equation, indicating the intramolecular charge transfer (ICT) process. Semi-empirical MO calculation (MOPAC/AM1) demonstrated that the HOMO-1, HOMO and LUMO of 3, 10–12 were mainly localized on the phenyl (πph), tpy (πtpy) and tpy (π*tpy) part, respectively, indicating that the lowest energy absorption band of 3, 10–12 was the local excitation (πtpy–π*tpy). In the case of 14 and 15, which have an electron-donating substituent, πph instead of πtpy became the HOMO. Thus, the lowest energy absorption of 14 and 15 was an ICT transition (πph–π*tpy), and a large red shift of the fluorescence occurred. In these compounds, the energy level of πph is controlled without affecting that of πtpy and π*tpy, suggesting a novel approach for tuning the color of fluorescence.

  合成了几种苯基取代的2,2':6',2''-三联吡啶（tpy），发现4'-苯基tpy（ptp，3）具有最有效的荧光，其在环己烷中的量子产率高达0.64。为了进一步研究调节ptp的荧光性质，将不同的取代基引入苯环的p位。Br-10，Cl-11和CH3-ptp 12显示与3相同的吸收和荧光区域，而NH2-14和Me2N-ptp 15的吸收和荧光则在更长的波长处被观察到。此外，14和15的荧光最大值显示了大于130 nm的溶剂依赖性。根据Lippert-Mataga方程，15的基态和激发态偶极矩差（Δμ）估计为15.2 D，表明存在分子内电荷转移（ICT）过程。半经验MO计算（MOPAC/AM1）表明，3、10-12的HOMO-1、HOMO和LUMO主要分别定域在苯基（πph）、tpy（πtpy）和tpy（π*tpy）部分，表明3、10-12的最低能量吸收带是局部激发（πtpy-π*tpy）。对于具有电子给体取代基的14和15，πph而非πtpy成为HOMO。因此，14和15的最低能量吸收是ICT跃迁（πph-π*tpy），并发生了大幅度的荧光红移。在这些化合物中，πph的能级可以在不影响πtpy和π*tpy能级的情况下进行调控，这为调节荧光颜色提供了一种新方法。
• Heterocyclization Reactions of 3-methylisoxazol-5-amine with Pyruvic Acid Derivatives Using Classical and Non-classical Methods of Activation
  作者：Alisa D. Morozova、Elena A. Muravyova、Sergey M. Desenko、Vladimir I. Musatov、Daria V. Yedamenko、Valentin A. Chebanov

  DOI：10.1007/s10593-017-1989-9

  日期：2016.11

  between 3-methylisoxazol-5-amine and pyruvic acid derivatives were studied both by using classical methods of activation, as well as under microwave irradiation and ultrasonication. It was shown that the reactions with esters of arylidene pyruvic acids could lead to the formation of three different types of heterocyclic systems, while in the case of arylidene pyruvic acid a very insignificant conversion

  通过使用经典的活化方法，以及在微波辐射和超声处理下，研究了3-甲基异恶唑-5-胺与丙酮酸衍生物之间的双组分和多组分相互作用。结果表明，与亚芳基丙酮酸的酯反应可导致形成三种不同类型的杂环系统，而在亚芳基丙酮酸的情况下，起始化合物向异恶唑[5,4- b ]的转化非常微不足道。由于3-甲基异恶唑-5-胺的低稳定性，观察到吡啶羧酸。
• Nucleophilic displacements of N-aryl and heteroaryl groups. Part 4. Pyrylium-mediated transformations of heteroarylamines into pyridinium salts and their inter- and intra-molecular displacement
  作者：Alan R. Katritzky、Bushra J. Agha、Radi Awartani、Ranjan C. Patel

  DOI：10.1039/p19830002617

  日期：——

  idinium salts. Hydrolysis and decarboxylation afford 1-(2-pyridyl)-2,4-diphenyl- and 1-(2-pyridyl)-4-phenyl-pyridinium salts. Neither these, nor their 2,4,6-triphenyl analogues underwent smooth nucleophilic substitution.

  杂芳基胺和合适的吡啶鎓盐得到1-杂芳基-2-乙氧基羰基-4,6-二苯基吡啶鎓和1-（2-吡啶基）-2,6-二乙氧基羰基-4-苯基吡啶鎓盐。水解和脱羧得到1-（2-吡啶基）-2，4-二苯基-和1-（2-吡啶基）-4-苯基-吡啶鎓盐。这些或它们的2,4,6-三苯基类似物均未进行平滑的亲核取代。
• X=Y-ZH systems as potential 1,3-dipoles
  作者：Moustafa F. Aly、Ronald Grigg

  DOI：10.1016/s0040-4020(01)86099-3

  日期：1988.1

  α-Imino acids, prepared from α-keto acids and primary amines, undergo facile decarboxylation to the corresponding imines on heating at ⩽,80°C in benzene or methylene chloride. Decarboxylation proceeds via a 1,2-ylide which can be trapped by sulphur to give the corresponding secondary thioamides in good yield. 1,2-Ylides from secondary amines and ∞-keto acids can be generated in situ and trapped with

  由α-酮酸和伯胺制得的α-氨基酸在⩽80℃下于苯或二氯甲烷中加热时，容易脱羧成相应的亚胺。脱羧反应通过1,2-ylide进行，可以被硫捕获，从而以高收率得到相应的仲硫代酰胺。来自仲胺和∞-酮酸的1,2-内酯可以原位生成并用硫捕获，从而以优异的收率得到叔硫酰胺。