2-(4-methylbenzoyl)-4-oxo-4-(p-tolyl)butanenitrile | 117358-56-2

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: 2-(4-methylbenzoyl)-4-oxo-4-(p-tolyl)butanenitrile
• 英文别名: 1,4-dioxo-1,4-bis(4-methylphenyl)-2-cyanobutane；2,3-di(p-toluoyl)propionitrile；2-(4-Methyl-benzoyl)-4-oxo-4-(p-tolyl)-butyronitrile；2-(4-methylbenzoyl)-4-(4-methylphenyl)-4-oxobutanenitrile
• CAS: 117358-56-2
• 化学式: C₁₉H₁₇NO₂
• 分子量: 291.349
• InChiKey: RIPFZTDZBLRYOA-UHFFFAOYSA-N

物化性质

• 熔点：
  148-150 °C(Solvent: Ethanol)
• 沸点：
  520.4±50.0 °C(predicted)
• 密度：
  1.137±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  57.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4-methylbenzoyl)-4-oxo-4-(p-tolyl)butanenitrile 在 肼 作用下， 以 1,4-二氧六环 为溶剂， 反应 3.0h， 以95%的产率得到3,6-di-p-tolyl-2,5-dihydropyridazine-4-carbonitrile
  参考文献：
  名称：

  一锅法合成2-氰基-1,4-二酮：在氰基取代的呋喃，吡咯和二氢哒嗪合成中的应用

  摘要：

  通过经由原位生成的β-酮腈用NaCN对2-溴苯乙酮的亲核取代，已经建立了用于构建官能化的2-氰基-1,4-二酮的方便的合成途径。该方法进一步应用于氰基取代的呋喃，吡咯或二氢哒嗪的合成，这些化合物使用Bi（OTf）3，NH 4 OAc或N 2 H 4以良好至极好的收率获得。通过X射线单晶衍射分析确认了关键结构。

  DOI：

  10.1021/acs.joc.6b01672
• 作为产物：
  描述：

  4,4'-二甲基联苯甲酰 、 丙烯腈 在 三甲基氰硅烷 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以27%的产率得到2-(4-methylbenzoyl)-4-oxo-4-(p-tolyl)butanenitrile
  参考文献：
  名称：

  N-Heterocyclic Carbene-Catalyzed Annulation of α-Cyano-1,4-diketones with Ynals

  摘要：

  In this paper, the first stereoselective annulation reaction between alpha-cyano-1,4-diketones and ynals, mediated by catalytic amounts of a triazolium salt precatalyst and cocatalytic amounts of a weak carboxylate base, is disclosed. The title transformation proceeds smoothly under mild reaction conditions and generates three contiguous stereogenic centers, one of which is a quaternary acetal carbon. This reaction tolerates a wide variety of electronically distinct substituents on both reaction partners and affords privileged bicyclic scaffolds in 61-90% isolated yields and with up to 20:1 diastereomeric preference.

  DOI：

  10.1021/ol3022287

文献信息

• Synthesis of 1,4-Diketones by Michael Addition of O-Aroylmandelonitriles Involving Rearrangement of Aroyl Group and Decyanation.
  作者：Akira MIYASHITA、Yoshiyuki MATSUOKA、Atsushi NUMATA、Takeo HIGASHINO

  DOI：10.1248/cpb.44.448

  日期：——

  The anions derived form O-aroylmendelonitriles 1 reacted with Michael addition acceptors such as acrylonitrile (7) and methyl acrylate (10) to give the corresponding 1, 4-diketones 12, 13, and 15 in moderate to good yields. Under acidic conditions, the 1, 4-diketones 12, 13, and 15 were converted into the furans 17, 18 and 19 in good yields.

  O-aroylmendelonitriles 1 衍生出的阴离子与迈克尔加成受体（如丙烯腈 (7) 和丙烯酸甲酯 (10)）反应，得到相应的 1，4-二酮 12、13 和 15，收率中等至良好。在酸性条件下，1, 4-二酮 12、13 和 15 可以很好地转化为呋喃 17、18 和 19。
• Baghdadchi, Jamil; Chan, Albert P.; Hutchinson, James H., Journal of Heterocyclic Chemistry, 1988, vol. 25, p. 973 - 974
  作者：Baghdadchi, Jamil、Chan, Albert P.、Hutchinson, James H.

  DOI：——

  日期：——
• BAGHDADCHI, JAMIL;CHAN, ALBERT P.;HUTCHINSON, JAMES H., J. HETEROCYCL. CHEM., 25,(1988) N 3, C. 973-974
  作者：BAGHDADCHI, JAMIL、CHAN, ALBERT P.、HUTCHINSON, JAMES H.

  DOI：——

  日期：——
• N-Heterocyclic Carbene-Catalyzed Annulation of α-Cyano-1,4-diketones with Ynals
  作者：Fedor Romanov-Michailidis、Céline Besnard、Alexandre Alexakis

  DOI：10.1021/ol3022287

  日期：2012.9.21

  In this paper, the first stereoselective annulation reaction between alpha-cyano-1,4-diketones and ynals, mediated by catalytic amounts of a triazolium salt precatalyst and cocatalytic amounts of a weak carboxylate base, is disclosed. The title transformation proceeds smoothly under mild reaction conditions and generates three contiguous stereogenic centers, one of which is a quaternary acetal carbon. This reaction tolerates a wide variety of electronically distinct substituents on both reaction partners and affords privileged bicyclic scaffolds in 61-90% isolated yields and with up to 20:1 diastereomeric preference.
• One-Pot Synthesis of 2-Cyano-1,4-diketones: Applications to Synthesis of Cyanosubstituted Furans, Pyrroles, and Dihydropyridazines
  作者：Chieh-Kai Chan、Yi-Ling Chan、Yu-Lin Tsai、Meng-Yang Chang

  DOI：10.1021/acs.joc.6b01672

  日期：2016.9.2

  A convenient synthetic route for the construction of functionalized 2-cyano-1,4-diketones has been established from the nucleophilic substitution of 2-bromoacetophenones with NaCN via the in situ-generated β-ketonitriles. This method was further applied to the synthesis of cyanosubstituted furans, pyrroles, or dihydropyridazines, which were obtained in good to excellent yields using Bi(OTf)3, NH4OAc

  通过经由原位生成的β-酮腈用NaCN对2-溴苯乙酮的亲核取代，已经建立了用于构建官能化的2-氰基-1,4-二酮的方便的合成途径。该方法进一步应用于氰基取代的呋喃，吡咯或二氢哒嗪的合成，这些化合物使用Bi（OTf）3，NH 4 OAc或N 2 H 4以良好至极好的收率获得。通过X射线单晶衍射分析确认了关键结构。