试剂2-(4-Morpholino)ethyl2-bromoisobutyrate | 627106-74-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 中文名称: 试剂2-(4-Morpholino)ethyl2-bromoisobutyrate
• 英文名称: 2-(4-morpholino)ethyl 2-bromoisobutyrate
• 英文别名: Propanoic acid, 2-bromo-2-methyl-, 2-(4-morpholinyl)ethyl ester；2-morpholin-4-ylethyl 2-bromo-2-methylpropanoate
• CAS: 627106-74-5
• 化学式: C₁₀H₁₈BrNO₃
• 分子量: 280.162
• InChiKey: XEXMMWOKORAPHR-UHFFFAOYSA-N

物化性质

• 密度：
  1.258 at 25 °C
• 闪点：
  >110°C

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• WGK Germany：
  3
• 储存条件：
  2-8°C

反应信息

• 作为反应物：
  描述：

  4-乙酰基苯甲酸叔丁酯 、 试剂2-(4-Morpholino)ethyl2-bromoisobutyrate 在 四氢吡咯 、 三乙烯二胺 、 copper(l) iodide 、 N,N,N',N'',N''-pentaethyldiethylenetriamine 、 对羟基苯甲酸甲酯 作用下， 以 正己烷 为溶剂， 反应 20.0h， 以74%的产率得到tert-butyl 4-(3,3-dimethyl-4-(2-morpholinoethoxy)-4-oxobutanoyl)benzoate
  参考文献：
  名称：

  铜-有机催化剂组合体系中酮的直接α-叔烷基化

  摘要：

  在本文中，我们报告了一种有效的方法，通过在复合有机铜催化剂体系中使用α-溴羰基化合物作为叔烷基源，可以使酮进行叔烷基化。这种双重催化剂体系能够将叔烷基加成到烯胺上。机理研究表明，催化生成的烯胺是催化循环中的关键中间体。所开发的方法可用于合成取代的1,4-二羰基化合物，这些化合物包含带有各种烷基链的季碳。

  DOI：

  10.1002/anie.202016051
• 作为产物：
  描述：

  2-吗啉乙醇 、 2-溴-2-甲基丙酰溴 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以77%的产率得到试剂2-(4-Morpholino)ethyl2-bromoisobutyrate
  参考文献：
  名称：

  丁二酸酐在温和条件下由羟基化甲基丙烯酸共聚物合成近单分散酸性均聚物和嵌段共聚物

  摘要：

  据报道，一条新的简便途径可以得到定义明确的低多分散性多元酸，而该方法不需要保护基化学。首先，通过ATRP合成甲基丙烯酸2-羟乙酯，甲基丙烯酸2-羟丙酯或甘油一甲基丙烯酸酯的近单分散羟基化聚合物，然后在温和条件下使用过量的酸酐进行酯化。例如，使用吡啶中的琥珀酸酐/羟基摩尔比为2时，在20°C下48 h内，聚甲基丙烯酸2-羟乙酯中的羟基基本上完全酯化。而且，改变该摩尔比可以容易地控制最终的酯化度。THF被作为替代溶剂进行了研究，但是在这些条件下，需要叔胺催化剂才能实现高度酯化。根据1 H NMR研究表明，琥珀酸酯键在pH等于或高于12时易于水解，但在pH 2时相对稳定。最后，合成了一种新的基于聚环氧乙烷的二嵌段共聚物，该分子在中性pH下可溶解但会发生胶束化在低pH下自组装。

  DOI：

  10.1021/ma048726t

文献信息

• Controlling Cyclic Dienamine Reactivity in Radical tert‐Alkylation for Molecular Diversity to Synthesize Multicyclic Compounds Possessing a Quaternary Carbon
  作者：Shinjiro Kusano、Takashi Nishikata

  DOI：10.1002/chem.202304215

  日期：2024.3.20

  Selective formation of the desired dienamines from β-methylcyclohexenone and their reaction with tertiary alkyl radicals generated from α-bromoesters led to the synthesis of γ-oxoalkyl substituted cyclohexenone derivatives (OAC) with a quaternary carbon have been successfully synthesized. This OAC can be used as a common synthetic intermediate for fused [5,6] rings and spirocycles.

  由β-甲基环己烯酮选择性形成所需的二烯胺，并与α-溴酯产生的叔烷基自由基反应，成功合成了具有季碳的γ-氧代烷基取代的环己烯酮衍生物（OAC）。该OAC可用作稠合[5,6]环和螺环的常见合成中间体。
• Diagnostic methods for the detection and quantification of blood-related diseases
  申请人：ADOLPHE MERKLE INSTITUTE, UNIVERSITY OF FRIBOURG

  公开号：US10983122B2

  公开（公告）日：2021-04-20

  A diagnostic method suitable for detection and quantification of blood-related diseases or conditions. The methods utilize biomarkers, such as hemoglobin and hemozoin as catalysts in an atom transfer radical polymerization (ATRP) reaction performed above a lower critical solution temperature (LCST) of a polymer which allows the polymerization to be tracked by rate of turbidity formation. The rate of turbidity formation is correlated to the concentration of the biomarker, making the tests useful quantitative techniques which can be utilized as point-of-care tests in the field.

  一种适用于检测和量化与血液有关的疾病或病症的诊断方法。这些方法利用生物标记物，如血红蛋白和安息香酸作为催化剂，在聚合物的较低临界溶液温度（LCST）以上进行原子转移自由基聚合（ATRP）反应，从而通过浊度形成的速率跟踪聚合反应。浊度形成的速率与生物标记物的浓度相关联，使测试成为有用的定量技术，可用作现场护理点测试。
• Nanoscale multiple emulsions and nanoparticles
  申请人：The Regents of the University of California

  公开号：US11254773B2

  公开（公告）日：2022-02-22

  Nanoscale multiple emulsions, nanoparticles resulting therefrom and methods of making and using thereof are described. The nanoscale multiple emulsions are typically double nanoemulsions, such as oil-in-water-in-oil (O1/W/O2) nanoemulsions, in which nanodroplets of the first oil (O1) phase are suspended in the aqueous (W) phase and together are dispersed in the second oil (O2) phase. The double nanoemulsions are stable with high encapsulation efficiency allowing templating to form multiphase nanoparticles. The multiphase nanoparticles include nanodroplets of O1 phase dispersed in a continuous matrix that can be a liquid, a gel, or a solid at room temperature and pressure. Methods of making the double nanoemulsions include high-energy forces and serial nanoemulsifications.

  本文描述了纳米级多重乳液、由此产生的纳米颗粒及其制造和使用方法。纳米级多重乳液通常是双纳米乳液，如油包水（O1/W/O2）纳米乳液，其中第一油相（O1）的纳米微滴悬浮在水相（W）中，并一起分散在第二油相（O2）中。双纳米乳液稳定，封装效率高，可模板化形成多相纳米粒子。多相纳米颗粒包括分散在连续基质中的 O1 相纳米微滴，该基质在室温和压力下可以是液体、凝胶或固体。制造双纳米乳剂的方法包括高能量力和连续纳米乳化。
• Stimulus-Responsive Water-Soluble Polymers Based on 2-Hydroxyethyl Methacrylate
  作者：J. V. M. Weaver、I. Bannister、K. L. Robinson、X. Bories-Azeau、S. P. Armes、M. Smallridge、P. McKenna

  DOI：10.1021/ma0356358

  日期：2004.4.1

  The homopolymerization and block/statistical copolymerization of 2-hydroxyethyl methacrylate (HEMA) using atom transfer radical polymerization (ATRP) in methanol at 20 degreesC has been investigated. For the homopolymerizations, both high conversions and low polydispersities (M-w/M-n < 1.25) were obtained over a wide range of target degrees of polymerization. According to the literature, HEMA homopolymer is usually described as only water-swellable, but in this work low molecular weight HEMA oligomers (target degrees of polymerization, DPn, less than 20) exhibited water solubility over a wide temperature range (no cloud point behavior). Furthermore, for actual DPn's between 20 and 45, HEMA homopolymers exhibited inverse temperature solubility in dilute aqueous solution at pH 6.5, and their cloud points increased systematically as the DPn was reduced. Gravimetric studies indicated that "water-insoluble" HEMA homopolymers with DPn's higher than 50 were actually partially soluble: GPC studies confirmed that fractionation occurred due to preferential dissolution of the shorter chains. Furthermore, HEMA homopolymers with DPn's up to 50 are water-soluble at pH 2.2 and do not exhibit cloud points. This is attributed to protonation of the terminal morpholine groups derived from the ATRP initiator. Thus, depending on the mean DPn and the solution pH, water can be a good solvent, a marginal solvent or a nonsolvent for HEMA homopolymer. Chain extension (self-blocking) experiments conducted for the ATRP of HEMA in methanol at 20 degreesC using a Cu(I)Cl catalyst and bpy ligand indicated reasonable living character. Statistical copolymerizations of HEMA with other comonomers such as glycerol monomethacrylate (GMA) and 2-hydroxypropyl methacrylate (HPMA) allowed the cloud point behavior to be manipulated. Finally, a range of novel HEMA-based block copolymers were synthesized in which the HEMA block was either thermoresponsive or permanently hydrophilic, depending on its DPn and the nature of the second block. Thus, diblock copolymer micelles with either hydroxylated cores or coronas could be prepared.
• Development of Branching in Living Radical Copolymerization of Vinyl and Divinyl Monomers
  作者：Iveta Bannister、Norman C. Billingham、Steven P. Armes、Steven P. Rannard、Paul Findlay

  DOI：10.1021/ma061811b

  日期：2006.10.1

  The branching copolymerization of 2-hydroxypropyl methacrylate ( HPMA) with either ethylene glycol dimethacrylate (EGDMA) or bisphenol A dimethacrylate (BPDMA) as the branching agent has been carried out using atom transfer radical polymerization (ATRP) in methanol at 20 C. With EGDMA, soluble branched copolymers were obtained provided that less than one branching agent was incorporated per primary chain: higher levels of EGDMA led to gelation, as expected. Analysis of the changes in the molecular weight and polydispersity of the polymers shows that the formation of highly branched chains occurs only at high (> 90%) conversions. Chain coupling is close to the ideal behavior predicted by the Flory-Stockmayer theory, suggesting that all double bonds are equally reactive and that there is no significant cyclization, in contrast to conventional free radical polymerization. This analysis is confirmed by comparison of the consumption of the EGDMA branching agent with predictions from both theory and simulation. With BPDMA as the branching agent, similar results are obtained although branching is slightly less efficient.