(E)-hexanal 2,2-dimethylhydrazone | 72215-74-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (E)-hexanal 2,2-dimethylhydrazone
• 英文别名: hexanal N,N-dimethylhydrazone；Hexenal dimethylhydrazone；hexanal dimethylhydrazone；(E)-Hexanaldimethylhydrazon；N-[(E)-hexylideneamino]-N-methylmethanamine
• CAS: 72215-74-8
• 化学式: C₈H₁₈N₂
• 分子量: 142.244
• InChiKey: KEQDBBYEWHFSRW-CMDGGOBGSA-N

物化性质

• 沸点：
  187.9±23.0 °C(Predicted)
• 密度：
  0.81±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  15.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-hexanal 2,2-dimethylhydrazone 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 反应 96.0h， 以65%的产率得到已腈
  参考文献：
  名称：

  Conversion of Aldehydes into Nitriles via Oxidation of Their Dimethylhydrazones

  摘要：

  芳香醛的二甲基脒经3-氯过氧苯甲酸氧化后，以良好的产率得到相应的腈。还给出了肉桂醛和己醛的另外两个类似的氧化转化的例子。除了己醛脒之外，其他所有的醛脒都可以通过处理与含甲醇的30%双氧水在二氧化硒或更优选的2-硝基苯硒酸催化量的存在下高效转化为腈。

  DOI：

  10.1055/s-1989-27210
• 作为产物：
  描述：

  正己醛 、 偏二甲肼 以 甲醇 为溶剂， 反应 12.0h， 以94%的产率得到(E)-hexanal 2,2-dimethylhydrazone
  参考文献：
  名称：

  Conversion of Aldehydes into Nitriles via Oxidation of Their Dimethylhydrazones

  摘要：

  芳香醛的二甲基脒经3-氯过氧苯甲酸氧化后，以良好的产率得到相应的腈。还给出了肉桂醛和己醛的另外两个类似的氧化转化的例子。除了己醛脒之外，其他所有的醛脒都可以通过处理与含甲醇的30%双氧水在二氧化硒或更优选的2-硝基苯硒酸催化量的存在下高效转化为腈。

  DOI：

  10.1055/s-1989-27210

文献信息

• Highly selective synthesis of hydrazones and indoles from olefins
  作者：Moballigh Ahmed、Ralf Jackstell、Abdul Majeed Seayad、Holger Klein、Matthias Beller

  DOI：10.1016/j.tetlet.2003.11.044

  日期：2004.1

  Reaction of aliphatic olefins with synthesis gas and hydrazines in the presence of rhodium phosphine catalysts leads directly to the corresponding hydrazones. Applying Iphos as ligand good to excellent yields and high chemo- and regioselectivities were obtained in toluene under mild conditions. In case of aromatic hydrazines in situ Fischer indole synthesis can be combined with the new hydrazone preparation

  在铑膦催化剂存在下，脂族烯烃与合成气和肼的反应直接导致相应的。使用Iphos作为配体，在温和的条件下，可在甲苯中获得优异的收率，并获得较高的化学选择性和区域选择性。如果是芳族肼，则可以将Fischer吲哚合成与新的preparation制备方法结合使用，从而直接从烯烃得到取代的吲哚。
• Synthesis of α-phenylselanyl and α-phenylsulfanyl nitriles from aldehyde N,N-dialkylhydrazones
  作者：Michaël Ternon、Xavier Pannecoucke、Francis Outurquin、Claude Paulmier

  DOI：10.1016/s0040-4020(02)00232-6

  日期：2002.4

  dimethylhydrazones 1 (R2=H) and derived from linear aliphatic aldehydes, has led to α-phenylselanyl hydrazones 2. α-Phenylselanyl nitriles 3 were, however, isolated when an excess of base and of PhSeX (X=Cl, Br) were used. Hydrazones 1 bearing an α-alkyl substituent (R2≠H) gave also nitriles 3. SAMP-hydrazones 4 showed the same reactivity and the corresponding nitriles 3 were obtained in a racemic form. The use of

  azaenolates的Phenylselenenylation，通过LDA处理dimethylhydrazones形成1（R 2 = H），并从直链脂族醛衍生的，已经导致α-phenylselanyl腙2。但是，当使用过量的碱和PhSeX（X = Cl，Br）时，会分离出α-苯基硒基腈3。腙1轴承α-烷基取代基（R 2 ≠H），得到也腈3。SAMP-腙4显示了同样的反应性和相应的腈3外消旋形式得到。用PhSCl代替PhSeBr可以从1生成α-苯硫基腈6衍生自α-支化醛（R 2 ≠H）。
• Aza Diels–Alder Reactions of Nitriles, <i>N</i>,<i>N</i>-Dimethylhydrazones, and Oximino Ethers. Application in Formal [2 + 2 + 2] Cycloadditions for the Synthesis of Pyridines
  作者：Philip J. Hamzik、Anne-Sophie Goutierre、Takeo Sakai、Rick L. Danheiser

  DOI：10.1021/acs.joc.7b02503

  日期：2017.12.15

  Metal-free, formal [2 + 2 + 2] cycloaddition strategies for the synthesis of polycyclic pyridine derivatives are described. The overall transformation proceeds via a two-stage pericyclic cascade mechanism. In the first step, an intramolecular propargylic ene reaction generates a vinylallene that is necessarily locked in the s-cis conformation. This vinylallene exhibits exceptional reactivity as a Diels–Alder

  描述了用于合成多环吡啶衍生物的无金属，正式的[2 + 2 + 2]环加成策略。整个转化过程通过两阶段的周环级联机制进行。在第一步中，分子内炔丙基烯反应生成必须锁定在s-顺式构象中的乙烯基丙二烯。该乙烯基丙二烯作为Diels-Alder反应伙伴表现出优异的反应活性，并与通常不反应的氮杂苯亲和剂（包括未激活的氰基和杂取代的亚胺衍生物，如二甲基hydr和肟基醚）参与[4 + 2]环加成反应。以前很少报道过肟基醚Diels–Alder反应的例子，未活化的二烷基hydr的正常电子需求[4 + 2]环加成反应是前所未有的。全面的，
• 1,2-Reduction of α,β-unsaturated hydrazones using dimethylamine–borane/p-toluenesulfonic acid: an easy route to allyl hydrazines
  作者：Maria E Casarini、Franco Ghelfi、Emanuela Libertini、Ugo M Pagnoni、Andrew F Parsons

  DOI：10.1016/s0040-4020(02)00914-6

  日期：2002.9

  alpha,beta-Unsaturated hydrazones can be easily converted into N-allyl hydrazines by reaction with dimethylamine-borane/p-toluenesulfonic acid under mild reaction conditions. The reduction works well for N'-allyhydrazides but N'-allyl-N,N-dimethylhydrazines are rapidly reoxidised by air and so need to be manipulated under an inert atmosphere prior to M-acylation. Competitive conjugate reduction can also be observed and the regioselectivity of the dimethylamine-borane attack is determined by steric and/or electronic factors. The procedure is also effective for the C=N reduction of unconjugated hydrazones. (C) 2002 Elsevier Science Ltd. All rights reserved.
• 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.