2-甲基-3-(乙酰基氨基)丙醛 | 24431-53-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 2-甲基-3-(乙酰基氨基)丙醛
• 英文名称: 2-methyl-3-(acetylamino)propanal
• 英文别名: 2-methyl-3-acetamidopropanal；3-acetamido-2-methylpropanal；N-(2-methyl-3-oxopropyl)acetamide
• CAS: 24431-53-6
• 化学式: C₆H₁₁NO₂
• mdl: MFCD17170550
• 分子量: 129.159
• InChiKey: OPXQPMSORHSYMU-UHFFFAOYSA-N

物化性质

• 沸点：
  290.4±23.0 °C(Predicted)
• 密度：
  0.984±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.666
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-甲基-3-(乙酰基氨基)丙醛 在 potassium permanganate 作用下， 以 丙酮 为溶剂， 生成 methyl 3-acetamido-2-methylpropanoate
  参考文献：
  名称：

  Asymmetric hydroformylation and hydrocarboxylation of enamides. Synthesis of alanine and proline

  摘要：

  DOI：

  10.1021/jo01299a022
• 作为产物：
  描述：

  N-烯丙基乙酰胺 、 一氧化碳 在 三(三苯基膦)羰基氢化铑 氢气 作用下， 以 苯 为溶剂， 40.0 ℃ 、3.45 MPa 条件下， 反应 30.0h， 生成 N-[(甲基)羰基]-2-吡咯啉 、 2-甲基-3-(乙酰基氨基)丙醛
  参考文献：
  名称：

  Asymmetric hydroformylation and hydrocarboxylation of enamides. Synthesis of alanine and proline

  摘要：

  DOI：

  10.1021/jo01299a022

文献信息

• Amide-directed hydrocarbonylation of N-alkenylamides and α-alkenyllactams
  作者：Iwao Ojima、Zhaoda Zhang

  DOI：10.1016/0022-328x(91)80177-l

  日期：1991.10

  N-benzoyl-2-hydroxy-4-methylpyrrolidine, the key intermediate for the double carbonylation and the reductive annulation, is obtained selectivity in a Rh4(CO)12-catalyzed reaction of N-methallylamide. The hydrocarbonylations of this cyclic hemiamidal catalyzed by RhCl(PPh3)3, Co2Rh2(CO)12, and Co2(CO)8 give the corresponding double carbonylation product (2-formylpyrrolidine), reductive annulation product (pyrrolidine)

  N-烯丙基酰胺的酰胺导向的Rh催化的加氢甲酰化和Pd催化的加氢酯化分别得到具有良好区域选择性的异醛和酯。N-甲基烯丙基酰胺的Rh-和Co 2 Rh 2（CO）12催化反应分别通过新颖的双羰基化反应生成1-酰基-2-甲酰基吡咯烷，并通过还原环化分别生成1-酰基吡咯烷，选择性极好。在Rh 4（CO）12催化的N反应中，具有选择性的环状半缩醛N-苯甲酰基-2-羟基-4-甲基吡咯烷酮是双羰基化和还原性环化反应的关键中间体-甲基烯丙基酰胺。RhRh（PPh 3）3，Co 2 Rh 2（CO）12和Co 2（CO）8催化的环状环乙酰胺的羰基化反应产生相应的双羰基化产物（2-甲酰基吡咯烷），还原环化产物（吡咯烷），和酰胺羰基化产物（脯氨酸）的收率和选择性极好。在氘标记实验的基础上研究了新型双羰基化和还原性环化反应的机理，发现这些反应是通过烯酰胺中间体进行的，然后向烯酰胺中添加极富区域选择性的金属氢化物。
• Selective hydroformylation of N-allylacetamide in an inverted aqueous two-phase catalytic system, enabling a short synthesis of melatonin
  作者：Göran Verspui、Guido Elbertse、Frank A. Sheldon、Michiel A. P. J. Hacking、Roger A. Sheldon

  DOI：10.1039/b003715j

  日期：——

  Water increases the selectivity in the Rh–phosphine catalysed hydroformylation of N-allylacetamide; an aqueous–organic biphasic system, containing a hydrophobic Rh-catalyst, provided facile catalyst/product separation, after which the aqueous product phase could be used in a one-pot synthesis of N-acetyl-5-methoxytryptamine (melatonin).

  水增加了Rh-膦催化的N-烯丙基乙酰胺加氢甲酰化的选择性；含有疏水性 Rh 催化剂的水-有机双相体系提供了简便的催化剂/产物分离，之后水相产物可用于 N-乙酰基-5-甲氧基色胺（褪黑激素）的一锅法合成。
• Enantioselective Hydroformylation of <i>N</i>-Vinyl Carboxamides, Allyl Carbamates, and Allyl Ethers Using Chiral Diazaphospholane Ligands
  作者：Richard I. McDonald、Gene W. Wong、Ram P. Neupane、Shannon S. Stahl、Clark R. Landis

  DOI：10.1021/ja106674n

  日期：2010.10.13

  Rhodium complexes of diazaphospholane ligands catalyze the asymmetric hydroformylation of N-vinyl carboxamides, allyl ethers, and allyl carbamates; products include 1,2- and 1,3-aminoaldehydes and 1,3-alkoxyaldehydes. Using glass pressure bottles, short reaction times (generally less than 6 h), and low catalyst loading (commonly 0.5 mol %), 20 substrates are successfully converted to chiral aldehydes

  二氮杂磷烷配体的铑配合物催化 N-乙烯基羧酰胺、烯丙基醚和烯丙基氨基甲酸酯的不对称加氢甲酰化；产品包括 1,2- 和 1,3- 氨基醛和 1,3- 烷氧基醛。使用玻璃压力瓶、较短的反应时间（通常小于 6 小时）和低催化剂负载（通常为 0.5 mol%），20 种底物成功转化为具有有用的区域选择性和高对映选择性（高达 99% ee）的手性醛。手性罗氏醛是通过烯丙基甲硅烷基醚的加氢甲酰化得到 97% ee 的。通常困难的底物，如 1,1- 和 1,2- 二取代烯烃，在六个例子中进行了有效的加氢甲酰化，ee 为 89-97%，并完全转化。
• Novel amide-directed hydrocarbonylations and double carbonylation of N-allylamides
  作者：Iwao Ojima、Zhaoda Zhang

  DOI：10.1021/jo00253a051

  日期：1988.9
• Catalytic conversions in water
  作者：Göran Verspui、Guido Elbertse、Georgios Papadogianakis、Roger A. Sheldon

  DOI：10.1016/s0022-328x(00)00751-8

  日期：2001.3

  The Rh/tppts (tppts = P(C6H4-m-SO3Na)(3)) catalysed hydroformylation of N-allylacetamide in water proceeds at a much faster rate and in a much higher selectivity (> 99%) towards the aldehydes, 4-acetamidobutanal and 2-methyl-3-acetamidopropanal, than the Rh/PPh3 catalysed reaction in organic solvents, such as THF, toluene and methanol. In water, at 90 degreesC and 50 bar H-2/CO, turnover frequencies (TOF) > 10.700 h(-1) were observed. Unfortunately, both catalysts exhibited a rather low regioselectivity (linear/branched (l/b) ratio = 1.1-1.5) which for Rh/tppts was found not to depend on the temperature, pressure, or ligand concentration. By using phosphate buffers the optimum pH of the aqueous reaction mixture was found to be pH 7.0. Under basic conditions (pH 11.0), the l/b ratio increased to l/b = 6.5, while the overall selectivity towards the aldehydes decreased to 41%. in a toluene/water biphasic system, due to the presence of water, the selectivity towards the aldehydes remained > 99%. Although Rh:PPh3 (operating in the organic phase) was less active compared to Rh/tppts (operating in the aqueous phase), Rh/PPh3 could easily be separated from the aqueous product layer. The hydrophobic Rh/Xantphos catalyst (Xantphos = 4.5-bis(diphenylphosphino)-9,9-dimethylxanthene) afforded a product mixture with l/b ratios up to 20 and could be recycled in five consecutive runs without loss in activity. (C) 2001 Elsevier Science B.V. All rights reserved.