1,3-Bis(4-methoxyphenyl)-2,2-dimethyl-1,3-propandion | 95581-17-2

• 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
• 英文名称: 1,3-Bis(4-methoxyphenyl)-2,2-dimethyl-1,3-propandion
• 英文别名: 1,3-Propanedione, 1,3-bis(4-methoxyphenyl)-2,2-dimethyl-；1,3-bis(4-methoxyphenyl)-2,2-dimethylpropane-1,3-dione
• CAS: 95581-17-2
• 化学式: C₁₉H₂₀O₄
• 分子量: 312.365
• InChiKey: NEJWJDWXMDYQQL-UHFFFAOYSA-N

物化性质

• 熔点：
  89 °C(Solv: methanol (67-56-1))
• 沸点：
  472.5±30.0 °C(Predicted)
• 密度：
  1.123±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 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：

  1,3-Bis(4-methoxyphenyl)-2,2-dimethyl-1,3-propandion 在 氧气 、 肼 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 21.0h， 生成 3-hydroperoxy-3,5-bis(4-methoxyphenyl)-4,4,5-trimethylpyrazole
  参考文献：
  名称：

  Oxygen-atom transfer reagents: New, reactive α-azohydroperoxides

  摘要：

  DOI：

  10.1016/s0040-4039(00)96020-9
• 作为产物：
  描述：

  1,3-双(4-甲氧基苯基)1,3-丙二酮 、 碘甲烷 在 potassium carbonate 作用下， 以 氯仿 、 二甲基亚砜 为溶剂， 以58%的产率得到1,3-Bis(4-methoxyphenyl)-2,2-dimethyl-1,3-propandion
  参考文献：
  名称：

  Electronic Substituent Effects on the Acid-Catalyzed [4+ + 2] Cycloaddition of Isopyrazoles with Cyclopentadiene and the Photochemical and Thermal Denitrogenation of the Resulting 1,4-Diaryl-7,7-dimethyl-2,3-diazabicyclo[2.2.1]hept-2-ene Azoalkanes to Bicyclo[2.1.0]pentanes

  摘要：

  Eight symmetrically disubstituted 3,5-diaryl-4,4-dimethylisopyrazoles 6 with para and meta substituents (OMe, Me, H, F, Cl, Br, CN, NO2) and two unsymmetrically para-substituted derivatives (OMe and NO2; Me and CO(2)Me) were synthesized from the corresponding 1,3-diaryl-2,2-dimethyl-1,3-propanediones 5, which in turn were readily available by 2,2-dimethylation of the diones 4. The acid-catalyzed cycloaddition of cyclopentadiene to the isopyrazoles 6, a Diels-Alder reaction with inverse electron demand, afforded the 1,4-diaryl-substituted gem-dimethyl azoalkanes 7 of the diazabicyco[2.2.1]hept-2-ene (DBH) type. The cycloadduct yields were strongly dependent on the nature of the aryl substituents and highest for the electron-withdrawing substituents. In acidic solution, the azoalkanes showed cycloreversion to generate an equilibrium between isopyrazole 6, cyclopentadiene, and azoalkane 7. For the p-methoxy derivative, cycloreversion was essentially quantitative, whereas only 20% cycloreversion occurred for the para nitro compound. A positive Hammett rho value (rho = 3.24 for 2 equiv of CF3COOH) was determined for the equilibrium constants of the acid-catalyzed [4(+) + 2] cycloaddition. The unsymmetrically substituted isopyrazoles gave two regioisomeric cycloadducts with a slight excess of one isomer. The direct and triplet-sensitized photochemical and thermal denitrogenation of the azoalkanes 7 gave in quantitative yields the 1,4-diaryl-substituted bicyclo[2.1.0]pentanes (BCP) 8 with retention of configuration. The azoalkanes 7 and the housanes 8 are more persistent than the related 1,4-diaryl-substituted DBH and BCP derivatives. The stabilizing effect is rationalized in terms of less favorable benzylic conjugation in the transition states for C-N (azoalkanes) and C-C (housanes) bond cleavage due to steric interactions between the geminal methyl groups at the methane bridge and the diaryl substituents at the bridgehead sites.

  DOI：

  10.1021/jo00093a010

文献信息

• Astonishing Alkylation and Unusual Reduction Reactions of Anionic Titanium(II) Isopropoxide Complexes: Evidence for SET Processes in Transition-Metal Oxidative Additions
  作者：John J. Eisch、John N. Gitua

  DOI：10.1002/1099-0682(200212)2002:12<3091::aid-ejic3091>3.0.co;2-y

  日期：2002.12

  mixture of titanium(II) isopropoxide and lithium isopropoxide (1:2), generated in THF by the treatment of titanium(IV) isopropoxide with two equivalents of n-butyllithium, has been shown to be an unexpected alkylating agent as well as an unusual reducing agent for a wide variety of organic substrates. Since titanium(II) isopropoxide, which is free of any lithium isopropoxide, neither causes alkylation

  异丙醇钛 (II) 和异丙醇锂 (1:2) 的混合物，通过用两当量的正丁基锂处理异丙醇钛 (IV) 在 THF 中生成，已被证明是一种意想不到的烷化剂以及适用于各种有机底物的不寻常还原剂。由于不含任何异丙醇锂的异丙醇钛 (II) 既不会引起任何相同底物的烷基化，也不是如此强大的还原剂，因此建议异丙醇锂通过以下方式激活异丙醇钛 (II) 以进行此类不寻常的反应形成锂盐配位络合物 Li2Ti[OiPr]4。前所未有的烷基化反应的例子是水解后，各种取代的苯甲腈转化为异丙基取代的苯基酮，（二氯甲基）苯转化为，主要是 2-甲基-1-苯基-1-丙烯和（三氯甲基）苯转化为异丙基苯基酮。通过分别比较 Li2Ti[OiPr]4 和 Ti[OiPr]2 的还原作用，已经表明，通常，锂盐是环氧化物、苄基卤化物和共轭烯烃的更强大的还原剂。从 Li2Ti[OiPr]4 与苯甲腈、苯乙烯、异构二苯乙烯氧化物和顺式二苯乙烯的反应中，为
• Maier, Guenther; Roth, Cornelia; Schmitt, Reinhart K., Chemische Berichte, 1985, vol. 118, # 2, p. 704 - 721
  作者：Maier, Guenther、Roth, Cornelia、Schmitt, Reinhart K.

  DOI：——

  日期：——
• Diastereoselectivity in the Reduction of Acyclic Carbonyl Compounds with Diisopropoxytitanium(III) Tetrahydroborate
  作者：K. S. Ravikumar、Surajit Sinha、S. Chandrasekaran

  DOI：10.1021/jo9902906

  日期：1999.8.1

  Diisopropoxytitanium(III) tetrahydroborate, ((PrO)-Pr-i)(2)TiBH4, formed in situ in dichloromethane from diisopropoxytitanium dichloride and benzyltriethylammonium tetrahydroborate (1:2) reduces alpha-hydroxyketones/1,2-diketones and beta-hydroxyketones/1,3-diketones to the corresponding diols with high stereoselectivity. In the case of alpha-hydroxyketones and 1,2-diketones, the anti isomer is the major product while reduction of beta-hydroxyketones and 1,3-diketones leads to the syn isomer as the major product.
• Maier, Guenther; Schmitt, Reinhart K.; Seipp, Ulrich, Chemische Berichte, 1985, vol. 118, # 2, p. 722 - 728
  作者：Maier, Guenther、Schmitt, Reinhart K.、Seipp, Ulrich

  DOI：——

  日期：——
• MAIER, G.;SCHMITT, R. K.;SEIPP, U., CHEM. BER., 1985, 118, N 2, 722-728
  作者：MAIER, G.、SCHMITT, R. K.、SEIPP, U.

  DOI：——

  日期：——