4-oxo-2,4-diphenylbutanal dimethylhydrazone

• 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: 4-oxo-2,4-diphenylbutanal dimethylhydrazone
• 英文别名: (4E)-4-(dimethylhydrazinylidene)-1,3-diphenylbutan-1-one
• 化学式: C₁₈H₂₀N₂O
• 分子量: 280.37
• InChiKey: NHHKHINCVYXGNQ-XMHGGMMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  32.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-oxo-2,4-diphenylbutanal dimethylhydrazone 在 aq. MMPP 作用下， 以 甲醇 为溶剂， 反应 0.08h， 以90%的产率得到3-苯甲酰基-2-苯丙腈
  参考文献：
  名称：

  Formaldehyde Dialkylhydrazones as Neutral Formyl Anion and Cyanide Equivalents:  Nucleophilic Addition to Conjugated Enones

  摘要：

  A versatile methodology for the nucleophilic formylation and cyanation of conjugated enones is reported. The procedure is based on the use of formaldehyde dimethylhydrazone, which, acting as a neutral formyl anion equivalent, adds to preformed trialkylsilyl-enone complexes. Both 4-(silyloxy)-3-enal hydrazones 3 or deprotected 4-oxo aldehyde monohydrazones 4 can be obtained as products depending on quenching conditions. In full analogy, an asymmetric version of the reaction using chiral formaldehyde SAMP-hydrazone as a neutral synthon of the chiral formyl anion has been developed, giving rise to the corresponding adducts 5 and 6 in good yields and with excellent diastereoselectivities (de 85-greater than or equal to 98%). Ozonolysis or HCl-mediated hydrolysis of adducts 4 and 6 readily affords racemic and optically enriched 4-oxo aldehydes 7, respectively. Additionally, high-yielding MMPP-oxidative cleavage of 4-oxo hydrazones 4 and 6 has been performed to obtain Li-oxo nitriles 8 in racemic and optically enriched forms, respectively. In this way, interesting chiral bifunctional building blocks, some of them bearing newly created stereogenic quaternary centers, have been efficiently synthesized.

  DOI：

  10.1021/jo970481d
• 作为产物：
  描述：

  N-甲基-N-(亚甲基氨基)甲胺 、 反式-查耳酮 在 四丁基氟化铵 、 (2,3-二甲基-2-丁烷基)(二甲基)硅烷基三氟甲烷磺酸酯 作用下， 生成 4-oxo-2,4-diphenylbutanal dimethylhydrazone
  参考文献：
  名称：

  Formaldehyde Dialkylhydrazones as Neutral Formyl Anion and Cyanide Equivalents:  Nucleophilic Addition to Conjugated Enones

  摘要：

  A versatile methodology for the nucleophilic formylation and cyanation of conjugated enones is reported. The procedure is based on the use of formaldehyde dimethylhydrazone, which, acting as a neutral formyl anion equivalent, adds to preformed trialkylsilyl-enone complexes. Both 4-(silyloxy)-3-enal hydrazones 3 or deprotected 4-oxo aldehyde monohydrazones 4 can be obtained as products depending on quenching conditions. In full analogy, an asymmetric version of the reaction using chiral formaldehyde SAMP-hydrazone as a neutral synthon of the chiral formyl anion has been developed, giving rise to the corresponding adducts 5 and 6 in good yields and with excellent diastereoselectivities (de 85-greater than or equal to 98%). Ozonolysis or HCl-mediated hydrolysis of adducts 4 and 6 readily affords racemic and optically enriched 4-oxo aldehydes 7, respectively. Additionally, high-yielding MMPP-oxidative cleavage of 4-oxo hydrazones 4 and 6 has been performed to obtain Li-oxo nitriles 8 in racemic and optically enriched forms, respectively. In this way, interesting chiral bifunctional building blocks, some of them bearing newly created stereogenic quaternary centers, have been efficiently synthesized.

  DOI：

  10.1021/jo970481d

文献信息

• Direct synthesis of dithioketals from N,N-dialkylhydrazones
  作者：Elena Díez、Ana M López、Carmen Pareja、Eloísa Martín、Rosario Fernández、JoséM Lassaletta

  DOI：10.1016/s0040-4039(98)01728-6

  日期：1998.10

  Direct dithioketalisation of N,N-dialkylhydrazones promoted by BF3. Et2O or p-TsOH and 1,2-ethanedithiol in dry medium affords the corresponding dithiolanes in nearly quantitative yields. A variety of hydrazones derived from several kinds of aldehydes (aliphatic, aromatic, and alpha,beta-unsaturated) and hydrazines [N, N-dimethylhydrazine, 1-aminopyrrolidine, and (S)-1-amino-2- (methoxymethyl)pyrrolidine (SAMP)] were reacted, indicating the generality of the method. The reaction was demonstrated to proceed without racemization of a particularly sensitive chiral substrate. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Formaldehyde Dialkylhydrazones as Neutral Formyl Anion and Cyanide Equivalents:  Nucleophilic Addition to Conjugated Enones
  作者：Elena Díez、Rosario Fernández、Consolación Gasch、José M. Lassaletta、José M. Llera、Eloísa Martín-Zamora、Juan Vázquez

  DOI：10.1021/jo970481d

  日期：1997.7.1

  A versatile methodology for the nucleophilic formylation and cyanation of conjugated enones is reported. The procedure is based on the use of formaldehyde dimethylhydrazone, which, acting as a neutral formyl anion equivalent, adds to preformed trialkylsilyl-enone complexes. Both 4-(silyloxy)-3-enal hydrazones 3 or deprotected 4-oxo aldehyde monohydrazones 4 can be obtained as products depending on quenching conditions. In full analogy, an asymmetric version of the reaction using chiral formaldehyde SAMP-hydrazone as a neutral synthon of the chiral formyl anion has been developed, giving rise to the corresponding adducts 5 and 6 in good yields and with excellent diastereoselectivities (de 85-greater than or equal to 98%). Ozonolysis or HCl-mediated hydrolysis of adducts 4 and 6 readily affords racemic and optically enriched 4-oxo aldehydes 7, respectively. Additionally, high-yielding MMPP-oxidative cleavage of 4-oxo hydrazones 4 and 6 has been performed to obtain Li-oxo nitriles 8 in racemic and optically enriched forms, respectively. In this way, interesting chiral bifunctional building blocks, some of them bearing newly created stereogenic quaternary centers, have been efficiently synthesized.