4-(but-3-enyl)-2-propiolactone | 360565-74-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 4-(but-3-enyl)-2-propiolactone
• 英文别名: 4-But-3-enyloxetan-2-one
• CAS: 360565-74-8
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: AAIKVJNVKVXSKJ-UHFFFAOYSA-N

物化性质

• 沸点：
  189.8±9.0 °C(Predicted)
• 密度：
  1.015±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  一氧化碳 、 4-(but-3-enyl)-2-propiolactone 在 ({1,2-di[(2-OH-3,5-di-tBu)PhCH=N]Ph}Al[THF]2)⁺[Co(CO)4]^- 作用下， 以 甲苯 为溶剂， 80.0 ℃ 、1.38 MPa 条件下， 反应 24.0h， 以90%的产率得到3-but-3-enyldihydrofuran-2,5-dione
  参考文献：
  名称：

  Catalytic Carbonylation of β-Lactones to Succinic Anhydrides

  摘要：

  A well-defined, highly active and selective catalyst for the synthesis of succinic anhydrides from CO and beta-lactones is reported. At 200 psi of CO, the catalyst [(N,N'-bis(3,5-di-tert-butylsalicylidene)phenylenediamino)Al(THF)2][Co(CO)4] carbonylates beta-propiolactones to succinic anhydrides in high yield. (R)-beta-Butyrolactone is carbonylated to (S)-methylsuccinic anhydride with clean inversion of stereochemistry, while cis-2,3-dimethyl-beta-propiolactone yields exclusively trans-2,3-dimethylsuccinic anhydride. These data are consistent with a mechanism involving nucleophilic attack by [Co(CO)4]- on the beta carbon of the lactone, followed by CO insertion and anhydride formation.

  DOI：

  10.1021/ja048946m
• 作为产物：
  描述：

  1,2-环氧基-5-己烯 、 一氧化碳 在 chromium(III) octaethylporphyrinato tetracarbonylcobaltate 作用下， 60.0 ℃ 、6.21 MPa 条件下， 反应 6.0h， 以100%的产率得到4-(but-3-enyl)-2-propiolactone
  参考文献：
  名称：

  Chromium (III) Octaethylporphyrinato Tetracarbonylcobaltate：一种用于环氧化物羰基化的高活性、选择性和多功能催化剂

  摘要：

  详细介绍了高活性和选择性的基于卟啉的环氧化物羰基化催化剂 [(OEP)Cr(THF)2][Co(CO)4]（1；OEP = 八乙基卟啉；THF = 四氢呋喃）的开发。配合物 1 是一个分离的离子对，由四羰基钴酸根阴离子和八面体铬卟啉配合物通过两个 THF 配体轴向连接而成。关于环氧化物羰基化为 β-内酯，催化剂 1 表现出优异的周转数（高达 10,000）和周转频率（高达 1670 h(-1)），在氧和空间位阻较小的碳之间发生区域选择性羰基插入环氧底物。配合物 1 对非质子官能团具有高度耐受性，可将一系列脂肪族和脂环族环氧化物以及带有侧链醚、酯和酰胺的环氧化物羰基化。通过对缩水甘油酯羰基化反应条件的仔细控制，实现了β-或γ-内酯异构体的独家生产。通过反应立体化学分析，提出了γ-内酯产物的形成机制。总体而言，已经通过使用 [(OEP)Cr(THF)2][Co(CO)4] 的催化羰基化以快速和

  DOI：

  10.1021/ja051874u

文献信息

• Acrylonitrile Derivatives from Epoxide and Carbon Monoxide Reagents
  申请人：Novomer, Inc.

  公开号：US20190002400A1

  公开（公告）日：2019-01-03

  The present invention is directed to reactor systems and processes for producing acrylonitrile and acrylonitrile derivatives. In preferred embodiments of the present invention, the processes comprise the following steps: introducing an epoxide reagent and carbon monoxide reagent to at least one reaction vessel through at least one feed stream inlet; contacting the epoxide reagent and carbon monoxide reagent with a carbonylation catalyst to produce a beta-lactone intermediate; polymerizing the beta-lactone intermediate with an initiator in the presence of a metal cation to produce a polylactone product; heating the polylactone product under thermolysis conditions to produce an organic acid product; optionally esterifying the organic acid product to produce one or more ester products; and reacting the organic acid product and/or ester product with an ammonia reagent under ammoxidation conditions to produce an acrylonitrile product.

  本发明涉及反应器系统和生产丙烯腈及丙烯腈衍生物的工艺。在本发明的优选实施例中，该工艺包括以下步骤：将环氧试剂和一氧化碳试剂通过至少一个进料流入口引入至至少一个反应釜中；将环氧试剂和一氧化碳试剂与羰基化催化剂接触以产生β-内酯中间体；在金属阳离子存在下，将β-内酯中间体与引发剂聚合以产生聚内酯产品；在热解条件下加热聚内酯产品以产生有机酸产品；可选择酯化有机酸产品以产生一个或多个酯产品；并将有机酸产品和/或酯产品与氨试剂在氨氧化条件下反应以产生丙烯腈产品。
• Practical β-Lactone Synthesis:  Epoxide Carbonylation at 1 atm
  作者：John W. Kramer、Emil B. Lobkovsky、Geoffrey W. Coates

  DOI：10.1021/ol061292x

  日期：2006.8.1

  text] A readily prepared bimetallic catalyst is capable of effecting epoxide carbonylation to produce beta-lactones at substantially lower CO pressures than previously reported catalyst systems. A functionally diverse array of beta-lactones is produced in excellent yields at CO pressures as low as 1 atm. This procedure allows for epoxide carbonylation on a multigram scale without the requirement of specialized

  [反应：见正文]易于制备的双金属催化剂能够在比以前报道的催化剂体系低得多的CO压力下进行环氧化物羰基化反应以生成β-内酯。在低至1 atm的CO压力下，以优异的收率生产出功能多样的β-内酯。该方法允许在数克规模上进行环氧羰基化，而无需专门的高压设备。
• Synthesis of β-Lactones by the Regioselective, Cobalt and Lewis Acid Catalyzed Carbonylation of Simple and Functionalized Epoxides
  作者：Jong Tae Lee、P. J. Thomas、Howard Alper

  DOI：10.1021/jo010295e

  日期：2001.8.1

  The PPNCo(CO)(4) and BF(3) x Et(2)O catalyzed carbonylation of simple and functionalized epoxides in DME gives the corresponding beta-lactones regioselectively in good to high yields. The carbonylation occurred selectively at the unsubstituted C-O bond of the epoxide ring, and this reaction tolerates various functional groups such as alkenyl, halide, hydroxy, and alkyl ether.

  在DME中PPNCo（CO）（4）和BF（3）x Et（2）O催化的简单和功能化环氧化物的羰基化反应以良好或高收率选择性地产生相应的β-内酯。羰基化选择性地发生在环氧环的未取代的CO键上，该反应可耐受各种官能团，例如烯基，卤化物，羟基和烷基醚。
• [EN] MONONUCLEAR SALEN INDIUM CATALYSTS AND METHODS OF MANUFACTURE AND USE THEREOF<br/>[FR] CATALYSEURS MONONUCLÉAIRES D'INDIUM DE SALEN ET LEURS MÉTHODES DE PRODUCTION
  申请人：UNIV BRITISH COLUMBIA

  公开号：WO2016000071A1

  公开（公告）日：2016-01-07

  The present application provides salen indium catalysts of the following general structure wherein R is a coordinating alkoxide comprising at least one coordinating atom that forms a dative bond with In. The mononuclear salen indium catalysts are particularly useful in catalyzing ring-opening polymerizations of cyclic ester monomers, such as lactides. Also provided herein are methods of using the mononuclear salen indium complexes to catalyze polymerization of cyclic ester monomers. Of particular interest is the successful polymerization of lactides using the mononuclear salen indium catalysts to produce poly(lactic acid) having high isotacticity.

  本申请提供了以下一般结构的salen铟催化剂，其中R是一个包含至少一个与铟形成配位键的配位氧化物。这些单核salen铟催化剂在催化环酯单体的开环聚合中特别有用，例如内酯。本文还提供了使用单核salen铟配合物催化环酯单体聚合的方法。特别值得关注的是使用单核salen铟催化剂成功聚合内酯，生产具有高同构度的聚乳酸。
• COMPOSITIONS AND METHODS FOR SELECTIVE CARBONYLATION OF HETEROCYCLIC COMPOUNDS
  申请人：Massachusetts Institute of Technology

  公开号：US20200164353A1

  公开（公告）日：2020-05-28

  Compositions comprising metal organic frameworks and related methods and uses are generally provided, including use in selective carbonylation of heterocyclic compounds.

  通常提供了包含金属有机框架的组合物、相关方法和用途，包括在杂环化合物的选择性羰基化中使用。