1,3-二(4-甲基苯基)丙烷-1,3-二酮 | 3594-36-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 中文名称: 1,3-二(4-甲基苯基)丙烷-1,3-二酮
• 英文名称: 1,3-bis(p-methylphenyl)-1,3-propanedione
• 英文别名: bis(p-methylbenzoyl)methane；1,3-di-p-tolylpropane-1,3-dione；1,3-Propanedione, 1,3-bis(4-methylphenyl)-；1,3-bis(4-methylphenyl)propane-1,3-dione
• CAS: 3594-36-3
• 化学式: C₁₇H₁₆O₂
• mdl: MFCD00227715
• 分子量: 252.313
• InChiKey: XKFZOWRFWMXGQG-UHFFFAOYSA-N

物化性质

• 熔点：
  125-127 °C
• 沸点：
  425.3±33.0 °C(Predicted)
• 密度：
  1.099±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.176
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2914399090

反应信息

• 作为反应物：
  描述：

  1,3-二(4-甲基苯基)丙烷-1,3-二酮 在 一水合肼 作用下， 以 乙醇 为溶剂， 生成 3,5-双(4-甲基苯基)-1H-吡唑
  参考文献：
  名称：

  Synthesis, spectroscopic characterization and quantum chemical computational studies on 1-acetyl-3,5-di(4-methylphenyl)-1H-pyrazole

  摘要：

  The pyrazole compound 1-acetyl-3,5-di(4-methylphenyl)-1H-pyrazole, (C19H18N2O), was characterized by X-ray single crystal diffraction technique, IR-NMR spectroscopy and quantum chemical computational methods as both experimental and theoretically. The compound crystallizes in the monoclinic space group C 2/c with a = 32.5334 (1) angstrom, b = 5.8060 (1) angstrom, c = 23.6519 (8) angstrom, beta = 134.572 (2)degrees, and Z = 8. The molecular geometry was also optimized using the Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods with the 6-311G(d,p) basis set and compared with the experimental data. To determine conformational flexibility, molecular energy profile of the tittle compound was obtained by semi-empirical (AM1) with respect to selected degree of torsional freedom, which was varied from -180 degrees to +180 degrees in steps 10 degrees. From the optimized geometry of the molecule, vibrational frequencies, gauge-independent atomic orbital (GIAO) H-1 and C-13 NMR chemical shift values, molecular electrostatic potential (MEP) distribution, non-linear optical properties, frontier molecular orbitals (FMOs) of the title compound have been calculated in the ground state theoretically. The theoretical result showed good agreement with the experimental values (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2012.06.013
• 作为产物：
  描述：

  1,3-di(4-methylphenyl)propane-1,3-dione 以 乙腈 为溶剂， 生成 1,3-二(4-甲基苯基)丙烷-1,3-二酮
  参考文献：
  名称：

  烯醇化速率控制1，3-二羰基衍生物的单氟化与二氟化。

  摘要：

  含氟的1,3-二羰基衍生物是药物发现和制造的基本组成部分。为了了解决定1，3-二羰基系统单氟化和二氟化之间选择性的因素，我们进行了酮-烯醇互变异构和氟化过程的动力学研究。1,3-二芳基-1,3-二羰基衍生物及其2-氟类似物的光酮化与弛豫动力学耦合，以确定烯醇化速率。反应添加剂（例如水）会加快烯醇化过程，特别是2-氟-1,3-二羰基体系的烯醇化过程。用Selectfluor™和NFSI进行烯醇氟化的动力学研究表明，2-氟化对烯醇亲核性与亲电子性显着不同的试剂的定量影响。我们的发现对α的合成具有重要意义，

  DOI：

  10.1039/c9sc04185k

文献信息

• Reinventing the De Mayo reaction: synthesis of 1,5-diketones or 1,5-ketoesters <i>via</i> visible light [2+2] cycloaddition of β-diketones or β-ketoesters with styrenes
  作者：Rebeca Martinez-Haya、Leyre Marzo、Burkhard König

  DOI：10.1039/c8cc07044j

  日期：——

  reaction between 1,3-diketones and styrenes following a [2+2] cycloaddition pathway via a photosensitization mechanism gives access to 1,5-diketones. The reaction has been applied to substituted styrenes and aryl- and alkyl-substituted ketones. Moreover, the method converts β-ketoesters, β-amido esters, and β-cyano ketones. Seven membered rings, a frequent structural motif of natural products, are also

  1，3-二酮与苯乙烯之间的可见光介导的De Mayo反应通过光敏化机理遵循[2 + 2]环加成途径，从而可以接近1,5-二酮。该反应已应用于取代的苯乙烯以及芳基和烷基取代的酮。此外，该方法转化了β-酮酸酯，β-酰氨基酯和β-氰基酮。七元环是天然产物的常见结构基序，也可以使用这种方法获得。
• Tris-(2-pyridylmethyl)amine-ligated Cu(<scp>ii</scp>) 1,3-diketonate complexes: anaerobic retro-Claisen and dehalogenation reactivity of 2-chloro-1,3-diketonate derivatives
  作者：Josiah G. D. Elsberg、Stephen N. Anderson、David L. Tierney、Eric W. Reinheimer、Lisa M. Berreau

  DOI：10.1039/d0dt04074f

  日期：——

  We report synthetic, structural and reactivity investigations of tris-(2-pyridylmethyl)amine (TPA)-ligated Cu(II) 1,3-diketonate complexes. These complexes exhibit anaerobic retro-Claisen type C–C bond cleavage reactivity which exceeds that found in analogs supported by chelate ligands with fewer and/or weaker pyridyl interactions.

  我们报告了三(2-吡啶甲基)胺(TPA)连接的Cu( II )1,3-二酮络合物的合成、结构和反应性研究。这些配合物表现出厌氧逆克莱森型 C-C 键裂解反应性，超过了由具有较少和/或较弱吡啶基相互作用的螯合配体支持的类似物中发现的反应性。
• Cu(OTf)₂-Catalyzed Pummerer Coupling of β-Ketosulfoxides
  作者：Regev Parnes、Hagai Reiss、Doron Pappo

  DOI：10.1021/acs.joc.7b02708

  日期：2018.1.19

  The copper(II) trifluoromethanesulfonate-catalyzed Pummerer reaction of β-ketosulfoxides with 1,3-dicarbonyl compounds or π-nucleophiles such as phenols, arenes, and tetraallylsilane is reported. The mild conditions provide an efficient entry to a novel class of polysubstituted 3-alkylthiofuran and polysubstituted 3-thiobenzofuran heterocycles from readily available materials.

  据报道，β-酮亚砜与1,3-二羰基化合物或π-亲核试剂（例如苯酚，芳烃和四烯丙基硅烷）的三氟甲磺酸铜（II）催化Pummerer反应。温和的条件从容易获得的材料中有效地进入了新型的多取代的3-烷基硫呋喃和多取代的3-硫代苯并呋喃杂环。
• Synthesis and Characterization of Ruthenium and Rhenium Nucleosides
  作者：Peijiao Wang、Jeremiah E. Miller、Lawrence M. Henling、Charlotte L. Stern、Natia L. Frank、Amanda L. Eckermann、Thomas J. Meade

  DOI：10.1021/ic701250r

  日期：2007.11.1

  and characterization of new ruthenium and rhenium nucleosides [Ru(tolyl-acac)2(IMPy)-T] (tolyl-acac=di(p-methylbenzonatemethane), IMPy=2'-iminomethylpyridine, T=thymidine) (5) and [Re(CO)3(IMPy)-T]Cl (9), respectively. Structural analysis of 9 shows that the incorporation of this metal complex causes minimal perturbation to the sugar backbone and the nucleobase. Eletrochemical (5, E1/2=0.265 V vs NHE;

  我们报告了新的钌和rh核苷[Ru（tolyl-acac）2（IMPy）-T]（tolyl-acac = di（p-methylbenzonatemethane），IMPy = 2'-iminomethylpyridine，T = thymidine）的合成和表征5）和[Re（CO）3（IMPy）-T] Cl（9）。9的结构分析表明，这种金属配合物的掺入对糖主链和核碱基的扰动最小。电化学（5，E1 / 2 = 0.265 V vs NHE; 9，E1 / 2 = 1.67 V vs NHE），吸收（5，lambdamax = 600，486 nm; 9，lambdamax = 388 nm）和发射（9，lambdamax = 770 nm，pi = 17 ns）数据表明5和9是用于DNA介导的基态电子转移研究的合适探针。报告了5和基于联吡啶的钌核苷[Ru（bpy）2（IMPy）-T] 2+（7）的非对映异构体的分离和表征。
• Enantioselective Borohydride Reduction Catalyzed by Optically Active Cobalt Complexes
  作者：Tohru Yamada、Takushi Nagata、Kiyoaki D. Sugi、Kiyotaka Yorozu、Taketo Ikeno、Yuhki Ohtsuka、Daichi Miyazaki、Teruaki Mukaiyama

  DOI：10.1002/chem.200304794

  日期：2003.9.22

  enantioselective borohydride reduction of aromatic ketones or imines to the corresponding alcohols was developed in the presence of a catalytic amount of an optically active cobalt(II) complex catalyst. This enantioselective reduction is carried out using a precisely premodified borohydride with alcohols such as tetrahydrofurfuryl alcohol, ethanol and methanol. High optical yields are obtained by choosing

  在催化量的光学活性钴（II）络合物催化剂的存在下，芳香族酮或亚胺对映体的高度对映选择性硼氢化物还原。该对映选择性还原是使用精确预改性的硼氢化物与醇（例如四氢糠醇，乙醇和甲醇）进行的。通过选择合适的醇作为改性剂和合适的催化剂β-酮亚氨基配体，可以获得高的光学收率。对映选择性硼氢化物还原已成功应用于光学活性的1,3-二醇的制备，双酰基二茂铁的立体选择性还原以及1,3-二羰基化合物的动态和/或动力学拆分。