diethyl 2-(naphthalen-1-yl)methylenemalonate | 52505-38-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: diethyl 2-(naphthalen-1-yl)methylenemalonate
• 英文别名: diethyl 1-naphthylmethylenemalonate；Diethyl [(naphthalen-1-yl)methylidene]propanedioate；diethyl 2-(naphthalen-1-ylmethylidene)propanedioate
• CAS: 52505-38-1
• 化学式: C₁₈H₁₈O₄
• 分子量: 298.339
• InChiKey: AFBQSUUVVNVVTR-UHFFFAOYSA-N

物化性质

• 熔点：
  175-177 °C(Solv: chloroform (67-66-3))
• 沸点：
  203-205 °C(Press: 2 Torr)
• 密度：
  1.175±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 2-(naphthalen-1-yl)methylenemalonate 在 吡啶 、 lithium aluminium tetrahydride 、 magnesium 作用下， 以 乙醚 为溶剂， 生成 2-(Di-naphthylmethyl)propane-1,3-diol bismethanesulfonate
  参考文献：
  名称：

  Synthesis of Helical Molecules Based on 5,6,6a,7,8,12b-Hexahydrobenzo[c]phenanthrene-5,8-dione

  摘要：

  在纽曼 1-7 合成一些多环芳香烃的基础上，对合成路线进行了修改和发展，从而方便地制备出 11 种正式基于己二酮 (1) 的螺旋分子（方案 1）。与纽曼的工作不同的是，我们确定了 (1a-k) 中 C6a-C12b 的立体化学结构，并在某些情况下能够对其进行控制。我们还研究了在生成六环衍生物（1d, e）的反应中，六元环和七元环的竞争性形成。此外，我们还报告了在合成(1h)的过程中出现的一种不寻常的裂解（方案 2），由此产生了意想不到的副产物 4-甲氧基苯乙酮 (16)。

  DOI：

  10.1071/ch9951707
• 作为产物：
  描述：

  1-萘甲醛 、 丙二酸二乙酯 在 哌啶 、 溶剂黄146 作用下， 以 乙醇 为溶剂， 以75%的产率得到diethyl 2-(naphthalen-1-yl)methylenemalonate
  参考文献：
  名称：

  的不对称迈克尔加成ñ -叔-Butanesulfinyl亚氨酸酯与α，β不饱和二酯：范围和适用于茚酮衍生物的合成

  摘要：

  使用LDA作为碱，已经开发出了N-叔丁亚磺酰亚胺基亚氨酸酯与α，β-不饱和二酯的无添加剂和高度非对映选择性的迈克尔加成反应，具有良好或优异的收率。该化学的实用性通过具有高对映体过量的3-取代的茚满酮衍生物8a，8d，8e和8i的不对称合成进一步证明，它们是制备生物活性铅化合物的潜在组成部分。

  DOI：

  10.1021/ol400277h

文献信息

• 2-Amino-quinazolin-5-ones
  申请人：Bellamacina R. Cornelia

  公开号：US20070027150A1

  公开（公告）日：2007-02-01

  2-Amino-quinazolin-5-one compounds, stereoisomers, tautomers, pharmaceutically acceptable salts, and prodrugs thereof; compositions that include a pharmaceutically acceptable carrier and one or more of the 2-amino-quinazolin-5-one compounds, either alone or in combination with at least one additional therapeutic agent. Methods of using the 2-amino-quinazolin-5-one compounds, either alone or in combination with at least one additional therapeutic agent, in the prophylaxis or treatment of cell proliferative diseases.

  2-氨基喹唑啉-5-酮化合物，立体异构体，互变异构体，药学上可接受的盐及其前药；包括药学上可接受的载体和一种或多种2-氨基喹唑啉-5-酮化合物的组合物，可以单独使用或与至少一种额外治疗剂结合使用。使用2-氨基喹唑啉-5-酮化合物的方法，可以单独使用或与至少一种额外治疗剂结合使用，用于预防或治疗细胞增殖性疾病。
• Synthesis and structure-activity relationships of human renin inhibitors designed from angiotensinogen transition state.
  作者：Kinji IIZUKA、Tetsuhide KAMIJO、Hiromu HARADA、Kenji AKAHANE、Tetsuhiro KUBOTA、Yasuo ETOH、Iwao SHIMAOKA、Atsushi TSUBAKI、Makoto MURAKAMI、Toshiaki YAMAGUCHI、Akira IYOBE、Hideaki UMEYAMA、Yoshiaki KISO

  DOI：10.1248/cpb.38.2487

  日期：——

  The synthesis and the structure-activity relationships of renin inhibitors designed from the angiotensinogen transition state are described. These inhibitors contained residues modified at P1-P1, , P2, and P4-P3. Decrease in the size of side chain alkyl group in norstatine analog at P1 diminished the inhibitory activities of the compounds. Compound 5j, which contained valine residue instead of histidine residue at P2, inhibited potently cathepsin D (IC50=6.0×10-9 M) and pepsin (IC50=3.5×10-7 M) to the same extent as renin (IC50=8.5×10-10 M), and thus was not specific for renin. The reduction of the β-carbonyl group to methylene group in β-carbonylpropionyl residue at P4-P3 decreased the potency about 2 orders against human renin (5i : IC50=1.1×10-7 M vs. 1 : IC50=2.4 ×10-9 M). These results confirmed the rationality of our analysis of the interaction between an orally potent human renin inhibitor 1 and the active site of human renin using modeling techniques, showing that 1 fits the active site of renin favorably. The experimental details of the synthesis are presented.

  描述了基于血管紧张素原过渡态设计的肾素抑制剂的合成及其构效关系。这些抑制剂在P1-P1、P2和P4-P3位点含有修饰的残基。在P1位点，诺斯他酮类似物侧链烷基基团的尺寸减小，降低了化合物的抑制活性。化合物5j在P2位点含有缬氨酸残基而非组氨酸残基，能有效抑制猫hepsin D（IC50=6.0×10⁻⁹ M）和胃蛋白酶（IC50=3.5×10⁻⁷ M），其抑制活性与肾素相当（IC50=8.5×10⁻¹⁰ M），因此并非特异性针对肾素。P4-P3处β-羰基基团减少为亚甲基基团，使其对人肾素的效能下降了约两个数量级（5i: IC50=1.1×10⁻⁷ M vs. 1: IC50=2.4×10⁻⁹ M）。这些结果证实了我们对口服有效的人肾素抑制剂1与人肾素活性位点间相互作用的分析合理性，显示出1与肾素活性位点的适配良好。合成的实验细节也已呈现。
• The Employment of Sodium Hydride as a Michael Donor in Palladium‐catalyzed Reductions of α, β‐Unsaturated Carbonyl Compounds
  作者：Ye Liu、Yujian Mao、Yanwei Hu、Jingjing Gui、Liang Wang、Wei Wang、Shilei Zhang

  DOI：10.1002/adsc.201801676

  日期：2019.4

  Sodium hydride was employed as a Michael donor under the catalysis of PdCl2 for 1,4‐conjugate reductions of α, β‐unsaturated carbonyl compounds, which features operational simplicity, mild conditions and high atom‐economy. The merits of NaH as a reductant were demonstrated by the one‐pot or cascade reactions for the syntheses of complex molecules.

  在PdCl 2催化下，氢化钠被用作Michael供体，以减少α，β-不饱和羰基化合物的1,4-共轭还原，其具有操作简便，条件温和和高原子经济性的特点。NaH作为还原剂的优点通过合成复杂分子的一锅法或级联反应得到了证明。
• An efficient hydrocyanation of α, β-unsaturated diesters with TMSCN catalyzed by MgI₂ etherate
  作者：Haokun Pan、Hua Li、Huijun Liu、Xingxian Zhang

  DOI：10.1080/10426507.2019.1700377

  日期：2020.5.3

  Abstract A mild, efficient and highly regioselective addition of trimethylsilyl cyanide (TMSCN) to α,β-unsaturated diesters has been achieved by using MgI2 etherate as catalyst under solvent-free conditions. This protocol provides the corresponding β-cyano esters in high yields. Graphical Abstract

  摘要 以MgI2 醚合物为催化剂，在无溶剂条件下，实现了三甲基氰化硅烷(TMSCN) 温和、高效和高区域选择性加成到α,β-不饱和二酯的过程。该协议以高产率提供相应的 β-氰基酯。图形概要
• The synthesis of singlet ground state derivatives of non-Kekulé polynuclear aromatics
  作者：Graeme Allinson、Richard J. Bushby、Malini V. Jesudason、Jean-Louis Paillaud、Norman Taylor

  DOI：10.1039/a606932k

  日期：——

  It is known that a two-electron reduction of tetrabutylammonium 3,4-dioxo-4H,8H-dibenzo[cd,mn]pyren- 12-olate gives a trioxy (tri-O-) derivative of the non-Kekulé polynuclear aromatic compound dibenzo[cd,mn]pyrene (triangulene). This derivative is stable in solution and, like triangulene itself, has a triplet ground state. In exploring the generality of this strategy for the synthesis of high-spin derivatives of non-Kekulé polynuclear aromatic compounds we have investigated two electron reductions of 4,8-dioxo-4H,8H-dibenzo[cd,mn]pyrene (to give a dioxy derivative of triangulene), 7,8-dioxo-7H,8H-dibenzo[de,hi ]naphthacene (to give a dioxy derivative of dibenzo[de,hi]naphthacene) and 7,9-dioxo-7H,9H-dibenzo[de,jk ]pentacene (to give a dioxy derivative of dibenzo[de,jk]pentacene). Dibenzo[cd,mn]pyrene (triangulene), dibenzo[de,hi]naphthacene and dibenzo[de,jk]pentacene should all have triplet ground states, but the presence of two O- substituents on these aromatic nuclei will (just) lift the degeneracy of the putative singly occupied molecular orbitals. We have shown that the splitting this produces is sufficient to ensure that all of these dioxy derivatives have singlet ground states. Hence the strategy employed for making and stabilising triplet triangulene as its trioxy derivative does not provide a paradigm for other high-spin non-Kekulé polynuclear aromatics. The reduction reactions were studied by cyclic voltammetry, by UV–VIS spectroscopy, and by EPR spectroscopy. Improved synthetic routes are described for 7,8-dioxo-7H,8H-dibenzo[de,hi ]naphthacene and for 7,9-dioxo-7H,9H-dibenzo[de,jk ]pentacene. Violent explosions were encountered in attempts to repeat the literature procedure for the synthesis of 4,6-dichlorobenzene-1,3-dicarboxylic acid.

  已知，四丁基铵3,4-二氧-4H,8H-二苯并[cd,mn]芘-12-olate的二电子还原反应产生非Kekulé多核芳香化合物二苯并[cd,mn]芘（三角烯）的三氧（tri-O-）衍生物。这种衍生物在溶液中稳定，并且像三角烯本身一样，具有三重态基态。在探索这种策略合成非Kekulé多核芳香化合物的高自旋衍生物的普遍性时，我们研究了4,8-二氧-4H,8H-二苯并[cd,mn]芘（产生三角烯的二氧衍生物）、7,8-二氧-7H,8H-二苯并[de,hi]萘并萘（产生二苯并[de,hi]萘并萘的二氧衍生物）和7,9-二氧-7H,9H-二苯并[de,jk]戊搭烯（产生二苯并[de,jk]戊搭烯的二氧衍生物）的二电子还原反应。二苯并[cd,mn]芘（三角烯）、二苯并[de,hi]萘并萘和二苯并[de,jk]戊搭烯都应该具有三重态基态，但这些芳香核上有两个O取代基的存在（恰好）会解除假定的单占据分子轨道的简并性。我们已经证明，这种分裂产生的分裂足以确保所有这些二氧衍生物具有单重态基态。因此，用于制造和稳定三重态三角烯作为其三氧衍生物的策略并不为其他高自旋的非Kekulé多核芳香化合物提供范例。还原反应通过循环伏安法、紫外-可见光谱和电子顺磁共振光谱进行了研究。还描述了7,8-二氧-7H,8H-二苯并[de,hi]萘并萘和7,9-二氧-7H,9H-二苯并[de,jk]戊搭烯的改进合成路线。在尝试重复文献中4,6-二氯苯-1,3-二羧酸的合成步骤时，遭遇了剧烈的爆炸。