1,3-dichloro-2-propyl pivaloate | 220499-01-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1,3-dichloro-2-propyl pivaloate
• 英文别名: 1,3-dichloropropyl pivaloate；2,2-dimethyl-propionic acid 2-chloro-1-chloromethyl-ethyl ester；1,3-Dichloropropan-2-yl 2,2-dimethylpropanoate；1,3-dichloropropan-2-yl 2,2-dimethylpropanoate
• CAS: 220499-01-4
• 化学式: C₈H₁₄Cl₂O₂
• 分子量: 213.104
• InChiKey: YSTPCLGTRMHREN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3-dichloro-2-propyl pivaloate 在 sodium iodide 作用下， 以 丁酮 为溶剂， 反应 48.0h， 以84%的产率得到allyl t-butyl carbonate
  参考文献：
  名称：

  串联的Finkelstein重排消除反应：烯丙基酯的直接合成路线

  摘要：

  烯丙基酯可以通过NaI诱导的2-氯-1-（氯甲基）乙基酯的Finkelstein重排消除反应获得。碘化钠可以在还原当量以下使用还原剂作为硫代硫酸钠使用。使用大多数已研究的各种酯均可获得高收率。所描述的方法避免了使用烯丙醇作为试剂。2-氯-1-（氯甲基）乙酯是由甘油制成的，甘油是生物柴油工业的主要副产品。还证实了碘作为水解烯丙基酯的试剂的有效性。

  DOI：

  10.1016/j.tet.2009.04.042
• 作为产物：
  描述：

  甘油 、 三甲基乙酸 在 三甲基氯硅烷 作用下， 反应 48.0h， 以95%的产率得到1,3-dichloro-2-propyl pivaloate
  参考文献：
  名称：

  串联的Finkelstein重排消除反应：烯丙基酯的直接合成路线

  摘要：

  烯丙基酯可以通过NaI诱导的2-氯-1-（氯甲基）乙基酯的Finkelstein重排消除反应获得。碘化钠可以在还原当量以下使用还原剂作为硫代硫酸钠使用。使用大多数已研究的各种酯均可获得高收率。所描述的方法避免了使用烯丙醇作为试剂。2-氯-1-（氯甲基）乙酯是由甘油制成的，甘油是生物柴油工业的主要副产品。还证实了碘作为水解烯丙基酯的试剂的有效性。

  DOI：

  10.1016/j.tet.2009.04.042

文献信息

• Protective opening of epoxide using pivaloyl halides under catalyst-free conditions
  作者：Chitturi Bhujanga Rao、Dasireddi Chandra Rao、Mallem Venkateswara、Yenamandra Venkateswarlu

  DOI：10.1039/c1gc15506g

  日期：——

  An efficient and environmentally benign protocol for protective opening of epoxide (POE) with pivaloyl halides in solvent-free conditions and in aqueous media under catalyst-free conditions has been developed. The green reaction conditions, simple work-up procedures, high yields and broad scope of the reaction illustrate the good synthetic utility of this method. The key advantages of the reaction are regioselectivity and reconvertability of products into their prior epoxides in the presence of mild reaction conditions.

  在无溶剂条件下和无催化剂条件下的水介质中，开发出了一种高效且对环境无害的环氧化物（POE）与特戊酰卤保护性开环方法。绿色的反应条件、简单的操作步骤、高产率和广泛的反应范围说明了这种方法的良好合成用途。该反应的主要优点是具有区域选择性，而且在温和的反应条件下，产物可重新转化为其先前的环氧化物。
• Applying a continuous capillary-based process to the synthesis of 3-chloro-2-hydroxypropyl pivaloate
  作者：Marc Escribà、Volker Hessel、Sonja Rothstock、Jordi Eras、Ramon Canela、Patrick Löb

  DOI：10.1039/c0gc00655f

  日期：——

  Nowadays, continuous chemical processes (‘flow chemistry’) using micro process technology are becoming highly competitive, both for cost (better selectivity, higher productivity) and sustainability (low environmental impact) reasons. The first needs true process intensification and the second, among others, new eco-efficient starting and product materials. In this context, a new application for glycerol is reported with increasing industrial interest and tested here under highly intensified conditions. Starting from prior batch processing experience, it is reported about the transfer to a continuous process to transform dichloropropyl pivaloate, prepared from glycerol, into 3-chloro-2-hydroxypropyl ester. The continuous microreactor based process has up to three orders-of-magnitude reduced reaction times (5760×) by virtue of exploiting unusual experimental conditions in organic chemistry (Novel Process Windows), i.e. superheated pressurised processing much above the boiling point. The yields are fully comparable with the ones obtained under batch conditions, but with (expected) loss in selectivity through enhanced diproduct formation. This principally enables the new continuous process to target much higher productivities; however this also results in a more complex reaction mixture therefore the ease of separation and commercial value of the second product will decide its exploitation. Beyond such benefits for the individual reaction under investigation, this is among the very first reports about a superheated reaction with a distinct selectivity issue with two known byproduct pathways, and thus provides the first respective generic information after an upheavalled reporting on capillary- or microreactor-based superheated processing, so far mostly done for less complex reactions.

  如今，出于成本（更好的选择性、更高的生产率）和可持续性（低环境影响）的原因，使用微加工技术的连续化学工艺（“流动化学”）正变得极具竞争力。第一个需要真正的工艺强化，第二个需要新的生态高效的起始材料和产品材料。在此背景下，甘油的一种新应用被报道，引起了越来越多的工业兴趣，并在高强度条件下进行了测试。据报道，从以前的间歇加工经验开始，将由甘油制备的新戊酸二氯丙酯转化为3-氯-2-羟丙酯，转而采用连续工艺。通过利用有机化学中不寻常的实验条件（新颖的工艺窗口），即远高于沸点的过热加压处理，基于连续微反应器的工艺可将反应时间缩短三个数量级（5760×）。产率与在间歇条件下获得的产率完全可比，但由于二产物形成的增强而导致选择性（预期）损失。这主要使新的连续工艺能够实现更高的生产率；然而，这也会导致更复杂的反应混合物，因此第二种产品的分离容易程度和商业价值将决定其利用。除了对所研究的单个反应的这些好处之外，这是关于具有两种已知副产物途径的明显选择性问题的过热反应的最早的报告之一，因此在毛细管或微反应器的剧烈报告之后提供了第一个相应的通用信息。基于过热的处理，到目前为止主要用于不太复杂的反应。
• From glycerol to chlorohydrin esters using a solvent-free system. Microwave irradiation versus conventional heating
  作者：Marc Escribà、Jordi Eras、Miquel Duran、Sílvia Simon、Cristina Butchosa、Gemma Villorbina、Mercè Balcells、Ramon Canela

  DOI：10.1016/j.tet.2009.10.048

  日期：2009.12

  Esterification-chlorination of glycerol provides chlorohydrin esters in high yields. A ratio of reagents close to equivalence can be used, so that atom economy of the reaction is optimized. The reaction can be carried out using either classical or microwave heating, and no solvent is required. 2-Chloro-1-(chloromethyl)ethyl esters can be obtained in high regioisomeric relationship when either low or moderate temperature is used. In contrast, microwave irradiation allows the use of higher reaction temperatures that render mixtures of both regioisomers in variable relationships. Kinetic control of the process is proposed for classical heating, and experimental results are analyzed with the aid of ab initio calculated values. Non-thermal phenomena can be used to explain the high efficiency of microwave irradiation at low temperature. (C) 2009 Elsevier Ltd. All rights reserved.