4-methoxycarbonyl-N-hydroxyphthalimide | 214754-56-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 4-methoxycarbonyl-N-hydroxyphthalimide
• 英文别名: Methyl 2-hydroxy-1,3-dioxoisoindole-5-carboxylate
• CAS: 214754-56-0
• 化学式: C₁₀H₇NO₅
• 分子量: 221.169
• InChiKey: ASPKJEHYNZOPMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  83.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,3-二氢-1,3-二氧代异苯并呋喃-5-羧酸甲酯 在 盐酸羟胺 作用下， 反应 1.0h， 生成 4-methoxycarbonyl-N-hydroxyphthalimide
  参考文献：
  名称：

  萘酰亚胺介导的阳光诱导的N-羟基邻苯二甲酰亚胺的氧化光活化

  摘要：

  AbstractWe report the aerobic photoactivation of N‐hydroxyphthlimide (NHPI) to the phthalimido‐N‐oxyl (PINO) radical mediated by naphthalene monoimides (NI) for promoting the selective oxidation of alkylaromatics and allylic compounds to the corresponding hydroperoxides. In the absence of either NI or NHPI no oxidation was observed, meaning that the two molecules operate in a synergistic way. Sunlight as well as artificial UV‐light irradiation was necessary in order to perform the process at low temperature (30–35 °C). EPR spectroscopy confirmed the role of NI and oxygen in promoting the formation of the superoxide radicals O2.− which, in turn, increased the concentration of PINO radicals during the UV light irradiation of NI/NHPI mixtures in MeCN. The investigation was extended to NI bearing different substituents on the naphthalene moiety. Finally, the synthesis and application of a unique photocatalyst including the NI and NHPI moieties linked by a suitable spacer was also considered. In this case the photocatalyst showed a substrate‐dependent behaviour with some peculiarities in comparison to the system where NI and NHPI are independent units in the same reacting system. This photocatalytic system paves the way to a non‐thermal, metal‐free approach for CH bond activation towards aerobic oxidation under very mild conditions.magnified image

  DOI：

  10.1002/adsc.201300611
• 作为试剂：
  描述：

  1-(3,4-dimethoxyphenyl)-2,2-dimethylpropan-1-ol 在 4-methoxycarbonyl-N-hydroxyphthalimide 氧气 、 cobalt(II) acetate 、 3-氯苯甲酸 作用下， 以 1,4-二氧六环 、 乙酸乙酯 为溶剂， 反应 24.0h， 生成 1-(3,4-二甲氧基苯基)-2,2-二甲基丙烷-1-酮
  参考文献：
  名称：

  芳基取代的N-羟基邻苯二甲酰亚胺催化的苄醇的好氧氧化。电荷转移复合体的可能参与

  摘要：

  一系列含有吸电子基团（4-CH 3 OCO，3-F）或给电子基团（4-CH 3，4 -CH 3 O，3-的芳基取代的N-羟基邻苯二甲酰亚胺（X-NHPI）CH 3 O，3,6-（CH 3 O）2）已被用作伯苄醇和仲苄醇的有氧氧化的催化剂。在伯醇的氧化中观察到芳香醛的选择性形成。芳族酮是仲醇氧化的唯一产物。X-NHPI的O-H键离解焓（BDE）已使用EPR自由基平衡技术确定。BDEs随着芳基取代基吸电子性能的提高而增加。动力学同位素效应研究以及通过增加NHPI芳基取代基的吸电子能力来提高底物氧化速率表明，速率决定了从醇到芳基取代的邻苯二甲酰亚胺-N的苄基氢原子转移（HAT）-氧基自由基（X-PINO）。除焓效应外，极性效应还在HAT过程中起作用，如Hammett相关系数与σ +的负ρ值以及通过增加电子-而使ρ值减小（从-0.54到-0.70）所表明的。 NHPI芳基取代基的吸水性。3-CH 3

  DOI：

  10.1021/jo049887y

文献信息

• Metal-Free Synthesis of Adipic Acid via Organocatalytic Direct Oxidation of Cyclohexane under Ambient Temperature and Pressure
  作者：Yohei Matsumoto、Masami Kuriyama、Kosuke Yamamoto、Koyo Nishida、Osamu Onomura

  DOI：10.1021/acs.oprd.8b00196

  日期：2018.9.21

  A direct metal-free approach for the production of adipic acid from cyclohexane is reported. The use of N-hydroxyphthalimide (NHPI) as a catalyst in the presence of HNO3/TFA enables the direct oxidation of cyclohexane to yield adipic acid under ambient temperature and pressure via a simple procedure. This reaction proceeds through an initial oxidation of cyclohexane to cyclohexanone oxime and cyclohexanone

  据报道，由环己烷生产己二酸的直接无金属方法。在HNO 3 / TFA存在下使用N-羟基邻苯二甲酰亚胺（NHPI）作为催化剂能够通过简单的方法在环境温度和压力下将环己烷直接氧化以产生己二酸。该反应通过将环己烷最初氧化为环己酮肟和环己酮，然后将这些中间体第二次氧化为己二酸而进行。NHPI在两个氧化步骤中都起着至关重要的作用，以实现己二酸的高收率和选择性。
• Importance of π-Stacking Interactions in the Hydrogen Atom Transfer Reactions from Activated Phenols to Short-Lived<i>N</i>-Oxyl Radicals
  作者：Marco Mazzonna、Massimo Bietti、Gino A. DiLabio、Osvaldo Lanzalunga、Michela Salamone

  DOI：10.1021/jo500789v

  日期：2014.6.6

  A kinetic study of the hydrogen atom transfer from activated phenols (2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols, 2,2,5,7,8-pentamethylchroman-6-ol, caffeic acid, and (+)-cathechin) to a series of N-oxyl radical (4-substituted phthalimide-N-oxyl radicals (4-X-PINO), 6-substituted benzotriazole-N-oxyl radicals (6-Y-BTNO), 3-quinazolin-4-one-N-oxyl radical (QONO), and 3-benzotriazin-4-one-N-oxyl

  活化酚（2,6-二甲基-和2,6-二叔丁基-4-取代的酚，2,2,5,7,8-五甲基苯并吡喃-6-ol，咖啡酸和（+）-儿茶素）形成一系列N-氧基（4-取代的邻苯二甲酰亚胺-N-氧基（4-X-PINO），6-取代的苯并三唑-N-氧基（6-Y- BTNO），3-喹唑啉-4-酮-N-氧基（QONO）和3-苯并三嗪-4-酮-N-氧基（BONO））是通过激光闪光光解法在CH 3 CN中进行的。观察到N-氧基自由基结构对氢转移速率常数（k H）有显着影响。k H值随N-羟胺的NO–H键解离能（BDE NO-H）的增加而单调增加。对动力学数据的分析以及理论计算的结果表明，这些反应是通过氢原子转移（HAT）机理进行的，其中N-氧基和酚式芳环采用π堆积排列。理论计算还表明，N-氧基自由基对在π堆积构象中发生的电荷转移具有明显的结构作用。k H的比较在这项研究中测得的值与先前报道的氢原子转移至枯基过氧自由基的那些值表明，6-CH
• Process for the preparation of substituted phenols
  申请人：Daicel Chemical Industries, Ltd.

  公开号：EP1967505A1

  公开（公告）日：2008-09-10

  A substituted phenolic compound is prepared by oxidizing a substituted diarylethane compound with oxygen in the presence of a nitrogen-containing cyclic compound, and treating the oxidized product with an acid. The nitrogen-containing cyclic compound includes, as a constituent of its ring, a skeleton represented by following Formula (I): wherein X is oxygen atom or an -OR group, where R is hydrogen atom or a hydroxyl-protecting group. The substituted diarylethane compound is represented by following Formula (1): wherein each of Ring Ar1 and Ring Ar2 is independently a monocyclic or polycyclic aromatic carbocyclic ring; Y1 is an electron-donating group; Y2 is an electron-withdrawing group; "p" is an integer of 1 or more; and "q" is an integer of 0 or more. The substituted phenolic compound is represented by following Formula (2): wherein Ring Ar1, Y1, and "p" are as defined above.

  一种取代酚化合物是通过在含氮环化合物存在下氧化取代二芳乙烷化合物制备的，并且用酸处理氧化产物。含氮环化合物包括其环中的一个组分是由以下式（I）表示的骨架：其中X是氧原子或-OR基团，其中R是氢原子或羟基保护基团。取代二芳乙烷化合物由以下式（1）表示：其中Ar1环和Ar2环中的每一个独立地是单环或多环芳香碳环；Y1是电子给予基团；Y2是电子吸引基团；“p”是1或更多的整数；“q”是0或更多的整数。取代酚化合物由以下式（2）表示：其中Ar1环，Y1和“p”如上定义。
• METHOD FOR PRODUCING OXIDE
  申请人：DAICEL CORPORATION

  公开号：US20160159722A1

  公开（公告）日：2016-06-09

  Provided is a method of oxidizing a substrate with excellent oxidizing power to yield a corresponding oxide. The method can employ a commercially available imide compound as intact as a catalyst and can produce the oxide in a high yield under mild conditions. A method for producing an oxide according to the present invention includes performing oxidation of a substrate in the presence of oxygen and ozone under catalysis of an imide compound to yield a corresponding oxide. The imide compound has a cyclic imide skeleton represented by Formula (I). In the formula, n is selected from 0 and 1; and X is selected from an oxygen atom and an —OR group, where R is selected from hydrogen and a hydroxy-protecting group.

  提供了一种氧化底物以产生相应氧化物的方法，该方法可以利用商业可获得的亚酰胺化合物作为催化剂，并在温和条件下高产率地产生氧化物。根据本发明的一种制备氧化物的方法包括在氧气和臭氧的存在下，在亚酰胺化合物的催化下对底物进行氧化，以产生相应的氧化物。该亚酰胺化合物具有由式（I）表示的环状亚酰胺骨架。在该式中，n选择自0和1；X选择自氧原子和—OR基团，其中R选择自氢和羟基保护基团。
• Process for producing azine compounds and oxime compounds
  申请人：——

  公开号：US20030204084A1

  公开（公告）日：2003-10-30

  A process comprising allowing a peroxide compound represented by following Formula (2): 1 wherein R a , R b , R c and R d are the same or different and are each a hydrogen atom or a hydrocarbon group, and wherein R a and R b , R c and R d may be combined to form a ring together with the adjacent carbon atom, respectively, to react with ammonia and water to yield an azine compound represented by following Formula (3): 2 wherein R a , R b , R c and R d have the same meanings as defined above, or oxime compounds represented by following Formulae (4 a ) and/or (4 b ): 3 wherein R a , R b , R c and R d have the same meanings as defined above, in the presence of a nitrogen-containing cyclic compound constitutively having a skeleton represented by following Formula (A) in its ring: 4 wherein X is one of an oxygen atom and an —OR group, and wherein R is one of a hydrogen atom and a hydroxyl-protecting group. This process can produce an oxime compound or an azine compound useful as a material for oxime compounds from low-cost materials by easy and simple procedures.

  一种过程包括允许由以下式（2）表示的过氧化物化合物：其中Ra、Rb、Rc和Rd相同或不同，每个都是氢原子或烃基，且Ra和Rb、Rc和Rd可以分别与相邻的碳原子结合形成环，以与氨和水反应生成由以下式（3）表示的偶氮化合物：其中Ra、Rb、Rc和Rd的含义与上述定义相同，或者在具有以下式（A）中的环中具有骨架的含氮环化合物的存在下生成由以下式（4a）和/或（4b）表示的肟化合物：其中Ra、Rb、Rc和Rd的含义与上述定义相同，在X为氧原子和-OR基团之一，R为氢原子和羟基保护基团之一的情况下。该过程可以通过简单易行的步骤从低成本材料中产生用作肟化合物材料的肟化合物或偶氮化合物。