2-benzoyl-4-oxo-4-phenylbutanenitrile | 79892-21-0

• 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-benzoyl-4-oxo-4-phenylbutanenitrile
• 英文别名: 2-Cyano-1,4-diphenyl-butane-1,4-dione
• CAS: 79892-21-0
• 化学式: C₁₇H₁₃NO₂
• 分子量: 263.296
• InChiKey: WCCUZDZUTDHKKU-UHFFFAOYSA-N

物化性质

• 熔点：
  80 °C(Solvent: Ethyl acetate)
• 沸点：
  492.7±40.0 °C(predicted)
• 密度：
  1.177±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 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-benzoyl-4-oxo-4-phenylbutanenitrile 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-diphenyl-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：

  苯甲酰乙腈 、 2-溴苯乙酮 在 N,N-二异丙基乙胺 、 magnesium chloride 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以79%的产率得到2-benzoyl-4-oxo-4-phenylbutanenitrile
  参考文献：
  名称：

  Hunig的碱式氯化镁介导的苯甲酰基乙腈的碳烷基化和氧酰化

  摘要：

  在Hunig碱和无水氯化镁存在下，苯甲酰基乙腈（1）与2-卤代酮和-酯反应生成C-烷基化产物，可以环化成多取代呋喃，而与酰氯反应，则得到e和E的可分离混合物形式的O-酰化产物。 Z异构体。

  DOI：

  10.1016/0040-4039(88)85183-9

文献信息

• Manganese(III)-Based Facile Synthesis of 3-Cyano-4,5-dihydrofurans and 4-Cyano-1,2-dioxan-3-ols Using Alkenes and Acylacetonitrile Building Blocks
  作者：Van-Ha Nguyen、Hiroshi Nishino、Kazu Kurosawa

  DOI：10.1055/s-1997-1282

  日期：1997.8

  New 3-cyano-4,5-dihydrofurans and 4-cyano-1,2-dioxan-3-ols were alternatively synthesized in good yields by the oxidation of acylacetonitrile building blocks with manganese(III) acetate in the presence of alkenes without any byproducts. The reaction at reflux temperature gave 3-cyano-4,5-dihydrofurans under an argon atmosphere, while 4-cyano-1,2-dioxan-3-ols were obtained at 23°C under an air atmosphere except for the reaction of styrene with benzoylacetonitrile which afforded 2-cyano-1,4-diphenylbutane-1,4-dione, and the reaction of 1,1,-diphenylethene with 2-(2-cyano-1-oxoethyl)-5-methylfuran which yielded 2-cyano-4,4-diphenylbutanolide without any cyclic peroxides. The oxidation of benzoylacetonitrile itself at 23°C under an air atmosphere in the absence of alkene gave benzoic acid. Easy conversion of the 1,2-dioxanes to furans was demonstrated, and mechanisms for the formation of dihydrofurans and dioxans as well as the unusual transformation to butanedione and butanolide were also discussed.

  新型3-氰基-4,5-二氢呋喃和4-氰基-1,2-二氧杂环-3-醇通过在烯烃存在下，用醋酸锰(III)对酰基乙腈构建块进行氧化，获得了良好产率且没有副产物。回流温度下的反应在氩气气氛中生成3-氰基-4,5-二氢呋喃，而在空气气氛下23°C下反应则获得4-氰基-1,2-二氧杂环-3-醇，除了苯甲基乙腈与苯乙烯的反应生成了2-氰基-1,4-二苯基丁-1,4-二酮，以及1,1-二苯乙烯与2-(2-氰基-1-氧代乙基)-5-甲基呋喃的反应生成2-氰基-4,4-二苯基丁内酯，没有生成任何环状过氧化物。苯甲基乙腈本身在空气气氛下23°C的氧化反应在缺乏烯烃的情况下产生了苯甲酸。还展示了1,2-二氧杂环转化为呋喃的简便过程，同时讨论了二氢呋喃和二氧杂环的形成机制，以及向丁二酮和丁内酯的不寻常转化。
• Olefin-Insertion Reaction between the Carbonyls of Benzils; Formation of 1,4-Diketones by Michael Additon Catalyzed by Cyanide Ion
  作者：Akira Miyashita、Atsushi Numata、Yumiko Suzuki、Ken-ichi Iwamoto、Takeo Higashino

  DOI：10.1246/cl.1997.697

  日期：1997.8

  Benzils (1) react with Michael addition acceptors (2) in the presence of cyanide ion as a catalyst to give 1,4-diketones (3), which are products of ethylene group insertion between the carbonyls of the benzils. The 1,4-diketones (3) are produced through the formation of the O-aroylmandelonitrile anion, followed by Michael addition and rearrangement of the aroyl group with decyanation.

  在作为催化剂的氰化物离子存在下，苄基 (1) 与迈克尔加成受体 (2) 反应生成 1,4-二酮 (3)，它是苄基羰基之间乙烯基插入的产物。1,4-二酮 (3) 是通过形成 O-芳酰基扁桃腈阴离子，然后进行迈克尔加成和芳酰基重排和脱氰作用而产生的。
• EtOH/Ba(OH)₂ Triggers Self‐Condensation of (<i>E</i>)‐1,4‐Diaryl‐2‐Butene‐1,4‐Diones to Cyclopentanol Derivatives
  作者：H. Surya Prakash Rao、S. P. Senthilkumar

  DOI：10.1081/scc-200061715

  日期：2005.6.1

  Abstract Several stereo‐defined penta‐substituted cyclopentanols were synthesized from EtOH/Ba(OH)2‐induced self‐condensation of (E)‐1,4‐diaryl‐2‐butene‐1,4‐diones formed via domino pathways.

  摘要 从 EtOH/Ba(OH)2 诱导的 (E)-1,4-二芳基-2-丁烯-1,4-二酮通过多米诺途径形成的自缩合合成了几种立体定义的五取代环戊醇。
• 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。
• 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.