N-甲基丙烷-2-亚胺氧化物 | 72552-73-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: N-甲基丙烷-2-亚胺氧化物
• 英文名称: N-2-propylidenemethanamide N-oxide
• 英文别名: C,C-dimethyl-N-methylnitrone；N-methyl-C,C-dimethylnitrone；N-methyl dimethyl nitrone；acetone-(N-methyl oxime )；C,C,N-Trimethyl-nitron；Aceton-(N-methyl-oxim)；N-Methylpropan-2-imine N-oxide；N-methylpropan-2-imine oxide
• CAS: 72552-73-9
• 化学式: C₄H₉NO
• 分子量: 87.1216
• InChiKey: RZMUEDPRCNHRJF-UHFFFAOYSA-N

物化性质

• 沸点：
  132.2±23.0 °C(Predicted)
• 密度：
  0.842±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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-甲基丙烷-2-亚胺氧化物 、 <(2,4-dinitrophenyl)sulfinyl>-1,2-propadiene 以 二氯甲烷 为溶剂， 反应 4.0h， 以98%的产率得到5-<<(2,4-dinitrophenyl)sulfenyloxy>methyl>-2-methyl-3-phenyl-Δ⁴-isoxazoline
  参考文献：
  名称：

  (Nitroaryl)sulfinyl-substituted allenes. Novel and convenient propargyl alcohol synthons in 4 + 2 cycloaddition chemistry

  摘要：

  (Nitroaryl)sulfinyl-substituted allenes are conveniently prepared by treating propargyl alcohol or methyl 3-hydroxy-2-butynoate with a (nitroaryl)sulfenyl chloride and triethylamine. These activated allenes undergo 4 + 2 cycloaddition across the C1C2-pi-bond. The initially formed allylic sulfoxide readily undergoes a 2,3-sigmatropic rearrangement to produce a stable sulfenate ester that is easily cleaved with thiophilic reagents. The dienophilic reactivity of the (nitroary)sulfinyl-substituted allene is much greater than the corresponding propargyl alcohol, and the cycloaddition also proceeds with high regioselectivity. The Diels-Alder reaction of [(2-nitrophenyl)-sulfinyl]propadiene with Danishefsky's diene affords meta-substituted benzyl alcohols in high yield. Reaction of the more highly activated methyl 2-[(2-nitrophenyl)sulfinyl]-2,3-butadienoate with Danishefsky's diene followed by treatment of the resulting sulfenate ester with triethyl phosphite produces substituted phthalides in excellent yield. The (2,4-dinitrophenyl)sulfinyl-substituted allene was found to react smoothly with a variety of nitrones to give sulfenate esters of isoxazolidines. These allenyl sulfoxides correspond to formal equivalents of propargyl alcohol, which itself is too unreactive to undergo Diels-Alder chemistry or 1,3-dipolar cycloaddition with nitrones or nitrile oxides.

  DOI：

  10.1021/jo00013a033
• 作为产物：
  描述：

  碘甲烷 、 丙酮肟 在 乙醇 作用下， 生成 N-甲基丙烷-2-亚胺氧化物
  参考文献：
  名称：

  Dunstan; Goulding, Journal of the Chemical Society, 1897, vol. 71, p. 577

  摘要：

  DOI：

文献信息

• Regiochemistry of mercury(II) oxide oxidation of unsymmetrical N,N-disubstituted hydroxylamines
  作者：Sk.Asrof Ali、S.M. Azhar Hashmi、Mohammad N. Siddiqui、Mohammed I.M. Wazeer

  DOI：10.1016/0040-4020(96)00904-0

  日期：1996.11

  Mercury(II) oxide oxidation of N,N-disubstituted hydroxylamines with the α and α′ carbon atoms containing one and two hydrogen atoms, respectively, gave aldonitrones in a highly regioselective manner. Removal of the α proton is involved in the rate determining step as shown by primary kinetic isotope effect.

  N，N-二取代的羟胺分别被具有一个和两个氢原子的α和α'碳原子氧化的汞（II）氧化，以高度区域选择性的方式生成醛亚硝酮。如初生动力学同位素效应所示，速率确定步骤涉及α质子的去除。
• Tin-free radical alkylation of ketones viaN-silyloxy enamines
  作者：Hyun-Ji Song、Che Jo Lim、Sunggi Lee、Sunggak Kim

  DOI：10.1039/b606295d

  日期：——

  The radical alkylation of ketones is achieved by their conversion into corresponding N-silyloxy enamines, followed by a radical reaction with alkyl halides bearing electron-withdrawing groups.

  酮的自由基烷基化是通过将它们转化为相应的N-甲硅烷氧基烯胺，然后与带有吸电子基团的烷基卤进行自由基反应来实现的。
• Formation of cycloadducts with trans-configurated ester groups from nitrones and dimethyl maleate
  作者：Hans Günter Aurich、Gerlinde Frenzen、Markus G. Rohr

  DOI：10.1016/s0040-4020(01)90471-5

  日期：——

  there is no clue for either a non-concerted reaction course or a subsequent conversion of the cis-products to trans-product in general. Rather conversion of dimethyl maleate to dimethyl fumarate seems to be responsible for the formation of the trans-substituted cycloadducts. This conversion can be induced by small quantities of N-alkylhydroxylamine formed from slight decomposition of nitrones under the

  在1.3偶极环加成中，环状硝酮1c和非环状硝酮8a-h 12a b用马来酸二甲酯在回流的氯仿中，不仅形成了具有两个酯基的顺式构型的预期环加合物，而且还形成了具有反式构型的环加合物。该现象不仅限于氯仿，而且在极性溶剂如环己烷和正己烷中也观察到。但是，对于不确定的反应过程或随后的顺式产物向反式产物的转化，通常都没有任何线索。马来酸二甲酯向富马酸二甲酯的相反转化似乎是反式取代的环加合物形成的原因。在反应条件下，由硝酮的轻微分解形成的少量N-烷基羟胺，或由少量具有NOH部分的硝酮衍生物（如N-羟基烯胺互变异构体或硝酮二聚体）可以诱导这种转化。
• Synthesis of α-amidoketones. An application of the multi-hetero cope rearrangement
  作者：Ivan Lantos、wei-Yuan Zhang

  DOI：10.1016/0040-4039(94)88053-0

  日期：1994.8

  N-methylcarboximidoyl chloride affords after hydrolytic workup α-amidoketones. The results are interpreted in terms of the formation of an intermediate capable of undergoing a facile [3,3] sigmatropic rearrangement. Aldehyde derived nitrones form imides via a [3+2] cycloaddition reaction.

  水解后的α-酰胺酮使酮衍生的硝酮与N-甲基羧酰亚胺基氯缩合。结果的解释是根据中间体的形成，该中间体能够进行容易的[3,3]σ重排。醛衍生的硝酮通过[3 + 2]环加成反应形成酰亚胺。
• Tandem [3+2]-cycloaddition [2,3]-sigmatropic rearrangement reaction of allenyl sulfoxides with nitrones
  作者：Albert Padwa、Bryan H. Norman、John Perumattam

  DOI：10.1016/s0040-4039(01)80276-8

  日期：——