N-cyclopentylidenemethanamine N-oxide | 72552-74-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-cyclopentylidenemethanamine N-oxide
• 英文别名: N-methylcyclopentylideneamine N-oxide；C,C-tetramethylene-N-methyl nitrone；cyclopentylidenemethylamine N-oxide；cyclopentanone-(N-methyl oxime )；Cyclopentanon-(N-methyl-oxim)；N-Methylcyclopentanimine N-oxide；N-methylcyclopentanimine oxide
• CAS: 72552-74-0
• 化学式: C₆H₁₁NO
• 分子量: 113.159
• InChiKey: FBMIBZYVHZLIIM-UHFFFAOYSA-N

物化性质

• 沸点：
  72 °C(Press: 0.1 Torr)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-cyclopentylidenemethanamine N-oxide 以 苯 为溶剂， 反应 24.0h， 生成 6-methyl-6-azaspiro<4.5>decan-9-one
  参考文献：
  名称：

  Rearrangement of isoxazoline-5-spiro derivatives. 8. Selective formation of tetrahydropyridones from C,C-disubstituted nitrones

  摘要：

  The thermal rearrangement of isoxazolidines 3, 7, 9, 17, and 19 obtained by 1,3-dipolar cycloaddition of C,C-disubstituted nitrones and methylenecyclopropanes 1 and 6 has been studied. The lack of hydrogen at the C-3 position of the isoxazolidine ring leads selectively to azaheterocyclic ketones, structurally differentiated according to the stating dipoles and dipolarophiles. The process allows the "one-pot" synthesis of valuable perhydro pyridone, indolizinone, and pyrrolo[1,2-a]quinolinone ring systems with excellent overall yield and atom economy. A new entry to the functionalized 1-azaspiro[5.5]undecane 22 framework found in alkaloids of the histrionicotoxin family is also presented.

  DOI：

  10.1021/jo00047a019
• 作为产物：
  描述：

  N-甲基羟胺 、 环戊酮 生成 N-cyclopentylidenemethanamine N-oxide
  参考文献：
  名称：

  Exner, Collection of Czechoslovak Chemical Communications, 1951, vol. 16/17, p. 258,264

  摘要：

  DOI：

文献信息

• One-Pot Sequential [3 + 3] Dipolar Cycloaddition of Aldehyde or Ketone and Hydroxylamine with Spirocyclopropyl Oxindole
  作者：Peng-Wei Xu、Chen Chen、Jia-Kuan Liu、Yu-Ting Song、Feng Zhou、Jun Yan、Jian Zhou

  DOI：10.1021/acs.joc.8b02208

  日期：2018.10.19

  A Sc(OTf)3-catalyzed highly diastereoselective one-pot sequential [3 + 3] dipolar cycloaddition reaction of aldehyde or ketone, N-alkyl hydroxylamine, and spirocyclopropyl oxindole is developed, allowing facile construction of spirocyclic oxindole-tetrahydro-1,2-oxazines with sufficient structural diversity. The corresponding catalytic enantioselective one-pot protocol of aldehydes is also reported

  开发了Sc（OTf）3催化的醛或酮，N-烷基羟胺和螺环丙基氧吲哚的高非对映选择性一锅顺序[3 + 3]双极环加成反应，从而可以轻松地构建螺环氧吲哚-四氢-1,2 -恶嗪具有足够的结构多样性。还报道了相应的醛催化对映选择性一锅操作方案，可提供高达97％ee的所需加合物。对选定的基于吲哚的螺环四氢-1，2-恶嗪的生物学评估表明，它们对人前列腺癌细胞具有细胞毒性作用，并具有抑制前列腺癌细胞中NFκB信号传导的能力。
• Fast Method for Synthesis of Alkyl and Aryl-N-Methylnitrones
  作者：Serkan Yavuz、Hamdi Ozkan、Naki Colak、Yilmaz Yildirir

  DOI：10.3390/molecules16086677

  日期：——

  A simple, fast, efficient and eco-friendly procedure was developed for the synthesis of alkyl and aryl-N-methylnitrones. The corresponding nitrones of aromatic aldehydes, aliphatic aldehydes and alicyclic carbonyl compounds were prepared from N-methylhydroxylamine hydrochloride and Na2CO3-Na2SO4 by simply grinding at room temperature without using solvent.

  开发了一种简单、快速、高效且环保的合成烷基和芳基-N-甲基硝酮的方法。以N-甲基羟胺盐酸盐和Na2CO3-Na2SO4为原料，在室温下简单研磨，不使用溶剂，制备了相应的芳香醛、脂肪醛和脂环族羰基化合物硝酮。
• Control of regiochemistry in nitrone cycloadditions. Regioselectivity of the reactions of trisubstituted nitrones with electron-deficient and conjugated dipolarophiles
  作者：Marina Burdisso、Remo Gandolfi、Paolo Grünanger

  DOI：10.1016/s0040-4020(01)89503-x

  日期：1989.1

  temperatures. Under these latter conditions the 5-substituted isoxazolidine was clearly prevalent owing to its being sterically less congested than the 4-substituted derivative. Evaluation of relative cycloaddition rates for 1a showed that the activating effect of formyl (rel. rate = 1.5) and acetyl groups (1.00) is about five times higher than that of cyano (0.18) and methoxycarbonyl groups (0.22) whilst

  三苯基硝酮1a和C，C-二苯基-N-甲基硝酮1b在室温下与带有电子吸引基团（即甲酰基，乙酰基，氰基，甲氧羰基，磺酰基和硝基）的单取代烯烃反应，得到两种区域异构体的动力学控制混合物。通常，由于对区域化学的电子控制，所以4-取代的异恶唑烷比5-区域异构体占优势（仅4-硝基异构体由硝基乙烯获得）。由于这些反应易于逆转，因此可以在较高温度下实现热力学控制。在这些后面的条件下，由于5-取代的异恶唑烷在空间上比4-取代的衍生物少拥塞，因此显然是普遍的。估算相对环加成率图1a显示甲酰基（相对比率＝ 1.5）和乙酰基（1.00）的活化作用比氰基（0.18）和甲氧羰基（0.22）的活化作用高约五倍，而硝基的作用显着高。 （1,155）尤其是与磺酰基（0.03）的效果相当低相比。在1a和1b与苯乙烯和1,1-二取代衍生物（例如，甲基丙烯醛）的反应中仅获得5-取代的衍生物，而在相同硝酮与单取代乙炔（例如，甲基）
• Synthesis of 1,2-Oxazinanes via Hydrogen Bond Mediated [3 + 3] Cycloaddition Reactions of Oxyallyl Cations with Nitrones
  作者：Lingbowei Hu、Michael Rombola、Viresh H. Rawal

  DOI：10.1021/acs.orglett.8b02301

  日期：2018.9.7

  the development of [3 + 3] cycloaddition reactions between oxyallyl cations and nitrones to yield 1,2-oxazinane heterocycles. Oxyallyl cation intermediates, generated in situ from α-tosyloxy ketones in the presence of hexafluoro-2-propanol (HFIP), a cosolvent, and a base, are found to react with a range of nitrones to afford 1,2-oxazinanes in good to high yields. The reactions are catalyzed by hydrogen-bond

  本文报道了在氧烯丙基阳离子和硝酮之间[3 + 3]环加成反应的发展，以产生1,2-恶嗪烷杂环。发现在六氟-2-丙醇（HFIP），助溶剂和碱的存在下，由α-甲苯磺酰氧基酮原位生成的草酸烯丙基阳离子中间体可与多种硝酮反应，从而提供良好的1,2-恶嗪二酮高产。该反应由氢键供体（例如苯酚和方酸酰胺）催化，观察到4-硝基苯酚的非对映选择性大大提高。
• Rhodium‐Catalyzed Asymmetric Hydrogenation and Transfer Hydrogenation of 1,3‐Dipolar Nitrones
  作者：Liren Xu、Tilong Yang、Hao Sun、Jingwen Zeng、Shuo Mu、Xumu Zhang、Gen‐Qiang Chen

  DOI：10.1002/anie.202319662

  日期：2024.4.2

  The enantioselective reduction of 1,3-dipolar nitrones to hydroxylamines was achieved by Rh(III)-catalyzed asymmetric hydrogenation and transfer hydrogenation. A wide range of chiral N,N-disubstituted hydroxylamines were synthesized with up to 99 % yield and >99 % ee. Mechanistic investigations and DFT calculations were conducted to elucidate the origin of reactivity and enantioselectivity.

  通过 Rh(III) 催化的不对称氢化和转移氢化实现了 1,3-偶极硝酮对映选择性还原为羟胺。合成了多种手性N , N-二取代羟胺，产率高达 99%，ee >99%。进行了机理研究和 DFT 计算，以阐明反应性和对映选择性的起源。