N-allylbutyramide | 2978-29-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N-allylbutyramide
• 英文别名: N-allyl butyramide；N-prop-2-enylbutanamide
• CAS: 2978-29-2
• 化学式: C₇H₁₃NO
• mdl: MFCD03391296
• 分子量: 127.186
• InChiKey: KTJYOKLCBAFHDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.571
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-allylbutyramide 在 四氯化碳 、 三乙胺 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以36%的产率得到1-ethylbut-3-enyl cyanide
  参考文献：
  名称：

  Rearrangements of Substituted 3-Aza-1,2,5-hexatrienes. 3. The Scope and Versatility of an Extremely Mild 3-Aza-Cope Reaction

  摘要：

  An investigation of the [3,3]-sigmatropic reaction of substituted 3-aza-1,2,5-hexatrienes to give 4-pentenenitriles is presented. This reaction has been found to occur under a wide variety of reactions conditions (10 are reported) starting from readily available N-allylamides. In contrast to other 3-aza-Cope reactions, this process occurs at room temperature, under essentially neutral conditions, allowing for the facile preparation of substituted nitrile products in moderate to excellent yields. The scope and versatility of this reaction are demonstrated by its use on a wide variety of substrates, including nitrogen- and oxygen-substituted amides. The rearrangements of cis- and trans-4-tert-butyl-N-allylcyclohexanecarboxamides 16a and 16b are reported and were found to give a ratio of axial to equatorial (A:E) products consistent with A:E ratios found for other related sigmatropic reactions. The stereochemical requirements for this reaction appear to be similar to other [3,3]-rearrangements even though the transition state for this rearrangement is most likely neither boat nor chairlike.

  DOI：

  10.1021/jo951587g
• 作为产物：
  描述：

  丁腈 、 丙烯胺 在 Iron(III) nitrate nonahydrate 作用下， 反应 24.0h， 以100%的产率得到N-allylbutyramide
  参考文献：
  名称：

  An iron-catalysed synthesis of amides from nitriles and amines

  摘要：

  The cheap, commercially available iron complex, Fe(NO3)(3)center dot 9H(2)O, has been used to catalyse the formation of amides by the addition of amines to nitriles. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.05.021

文献信息

• Sterically Demanding Oxidative Amidation of α-Substituted Malononitriles with Amines Using O₂
  作者：Jing Li、Martin J. Lear、Yujiro Hayashi

  DOI：10.1002/anie.201603399

  日期：2016.7.25

  An efficient amidation method between readily available 1,1-dicyanoalkanes and either chiral or nonchiral amines was realized simply with molecular oxygen and a carbonate base. This oxidative protocol can be applied to both sterically and electronically challenging substrates in a highly chemoselective, practical, and rapid manner. The use of cyclopropyl and thioether substrates support the radical

  简单地使用分子氧和碳酸盐碱即可实现易于获得的1,1-二氰基烷烃与手性或非手性胺之间的高效酰胺化方法。该氧化方案可以高度化学选择性，实用和快速的方式应用于空间和电子挑战性底物。环丙基和硫醚底物的使用可支持α-过氧丙二腈物种的自由基形成，后者可以环化成二恶英，后者可以单价氧化丙二腈α-碳二酮以提供能够与胺亲核试剂反应的活化的酰基氰化物。
• The Selective<i>N</i>-Monoalkylation of Amides with Alkyl Halides in the Presence of Alumina and KOH
  作者：Kazuaki Sukata

  DOI：10.1246/bcsj.58.838

  日期：1985.3

  The effects of alumina impregnated with KOH (KOH/Al2O3) and a mixture of alumina and powdered KOH (KOH+Al2O3) have been examined using the alkylation of benzamide under various conditions. In each case, alkylation occurs exclusively in the pores of the alumina, the extent depending upon the alumina-pore size. For both yield and selectivity for N-monoalkylation, KOH+Al2O3 is superior to KOH/Al2O3. Dioxane is the best of the solvents employed. It is proposed that, in dioxane, an enolate-like species, (Remark: Graphics omitted.), exists as stable ion-pair aggregates, which are the true reactants in the pore. This method, using KOH/Al2O3 or KOH+Al2O3, has been applied to N-alkylation of the other amides, giving the N-monoalkylated products in substantial yields with extremely high selectivities. 2-Phenylacetamide is regioselectively N-monoalkylated in high yields. This regioselectivity is explained in terms of steric hindrance.

  使用KOH浸渍的氧化铝（KOH/Al2O3）和氧化铝与粉末状KOH的混合物（KOH+Al2O3），在不同条件下研究了苯甲酰胺的烷基化反应。在每种情况下，烷基化反应仅在氧化铝的孔隙中发生，其程度取决于氧化铝的孔径大小。对于N-单烷基化的产率和选择性，KOH+Al2O3优于KOH/Al2O3。二氧六环是所使用溶剂中最好的。研究表明，在二氧六环中，类似于烯醇盐的物种（注：图形省略）以稳定的离子对聚集形式存在，这些是孔隙中的真正反应物。这种方法使用KOH/Al2O3或KOH+Al2O3，已应用于其他酰胺的N-烷基化，以极高的选择性获得了大量的N-单烷基化产物。2-苯基乙酰胺以高产率选择性地进行N-单烷基化。这种区域选择性可通过空间位阻来解释。
• Metal-free, hydroacylation of CC and NN bonds via aerobic C–H activation of aldehydes, and reaction of the products thereof
  作者：Vijay Chudasama、Ahmed R. Akhbar、Karim A. Bahou、Richard J. Fitzmaurice、Stephen Caddick

  DOI：10.1039/c3ob41632a

  日期：——

  In this report, a thorough evaluation of the use of aerobically initiated, metal-free hydroacylation of various CC and NN acceptor molecules with a wide range of aldehydes is presented. The aerobic-activation conditions that have been developed are in sharp contrast to previous conditions for hydroacylation, which tend to use transition metals, peroxides that require thermal or photochemical degradation, or N-heterocyclic carbenes. The mildness of the conditions enables a number of reactions involving sensitive reaction partners and, perhaps most significantly, allows for α-functionalised chiral aldehydes to undergo radical-based hydroacylation with complete retention of optical purity. We also demonstrate how the resulting hydroacylation products can be transformed into other useful intermediates, such as γ-keto-sulfonamides, sultams, sultones, cyclic N-sulfonyl imines and amides.

  在本报告中，我们详细评估了使用需氧起始、不含金属的氢酰化方法，将多种CC和NN受体分子与广泛范围的醛进行反应的情况。我们所开发的有氧活化条件与之前的氢酰化条件形成鲜明对比，后者倾向于使用过渡金属、需要热或光化学分解的过氧化物，或者N-杂环卡宾。这些温和的条件使得许多涉及敏感反应物的反应得以进行，或许最为重要的是，能够让α-功能化的手性醛在基于自由基的氢酰化反应中完全保持光学纯度。我们还展示了所得氢酰化产物如何转化成其他有用的中间体，例如γ-酮-磺酰胺、磺内酰胺、磺内酯、环状N-磺酰亚胺和酰胺。
• Direct Regioselective Synthesis of Tetrazolium Salts by Activation of Secondary Amides under Mild Conditions
  作者：Veronica Tona、Boris Maryasin、Aurélien de la Torre、Josefine Sprachmann、Leticia González、Nuno Maulide

  DOI：10.1021/acs.orglett.7b01004

  日期：2017.5.19

  Tetrazolium salts are biologically active molecules that have found broad applications in biochemical assays. A regioselective synthesis of tetrazolium salts is described through a formal (3 + 2) cycloaddition. The possibility of employing simple amides and azides as starting material and the mild conditions allow a broad functional group tolerance.

  四唑盐是具有生物活性的分子，在生化分析中已发现了广泛的应用。通过正式的（3 + 2）环加成反应描述了四唑鎓盐的区域选择性合成。使用简单的酰胺和叠氮化物作为起始原料的可能性以及温和的条件允许宽泛的官能团耐受性。
• Functionalisation of aldehydes via aerobic hydroacylation of azodicarboxylates ‘on’ water
  作者：Vijay Chudasama、Jenna M. Ahern、Dipti V. Dhokia、Richard J. Fitzmaurice、Stephen Caddick

  DOI：10.1039/c0cc04520a

  日期：——

  Herein we report the functionalisation of aldehydesvia hydroacylation of azodicarboxylates. A range of functionalised aldehydes are employed as the limiting reagent including chiral non-racemic aldehydes bearing α-stereocentres which are functionalised giving access to enantiomerically pure products. The resultant hydrazides can be employed as acyl donors in the synthesis of amides.

  本文报道了通过叠氮羧酸酯的氢酰基化反应对醛进行功能化。使用一系列功能化的醛作为限制性试剂，其中包括具有α-立体中心的非外消旋手性醛，经过功能化反应后可以获得具有光学纯度的产物。生成的酰肼可以作为酰基供体，用于合成酧。