4-(n-butyloxymethyl)-2-propiolactone | 666234-89-5

• 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-(n-butyloxymethyl)-2-propiolactone
• 英文别名: 4-(Butoxymethyl)oxetan-2-one
• CAS: 666234-89-5
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: TVKAZUMAUBFYLC-UHFFFAOYSA-N

物化性质

• 沸点：
  230.5±13.0 °C(Predicted)
• 密度：
  1.040±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  一氧化碳 、 4-(n-butyloxymethyl)-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-butoxymethyldihydrofuran-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：

  正丁基缩水甘油醚 、 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-(n-butyloxymethyl)-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。
• A New Multicomponent Reaction Catalyzed by a [Lewis Acid]⁺[Co(CO)₄]^- Catalyst:  Stereospecific Synthesis of 1,3-Oxazinane-2,4-diones from Epoxides, Isocyanates, and CO
  作者：Tamara L. Church、Christopher M. Byrne、Emil B. Lobkovsky、Geoffrey W. Coates

  DOI：10.1021/ja069065d

  日期：2007.7.1

  catalytic multicomponent reaction is described. The complex [(salph)Al(THF)2]+[Co(CO)4]- (1, salph = N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneimine), THF = tetrahydrofuran), which is known to carbonylate epoxides, aziridines, and beta-lactones, was used to catalyze the synthesis of 1,3-oxazinane-2,4-diones from epoxides, isocyanates, and CO. Under optimized conditions, the reaction was both selective

  描述了使用机械信息开发新的催化多组分反应。络合物[(salph)Al(THF)2]+[Co(CO)4]- (1,salph = N,N'-o-亚苯基双(3,5-二叔丁基水杨亚胺),THF = 四氢呋喃)已知可将环氧化物、氮丙啶和 β-内酯羰基化，用于催化由环氧化物、异氰酸酯和 CO 合成 1,3-恶嗪烷-2,4-二酮。在优化条件下，该反应具有选择性和高产。1,3-氧嗪烷-2,4-二酮由多种环氧化物和异氰酸酯合成，包括一些不进行简单扩环羰基化的环氧化物。最好的结果是使用高度亲电子的异氰酸酯获得的。使用标记和立体化学研究了多组分反应的机理，
• Beta-propiolactone based copolymers containing biogenic carbon, methods for their production and uses thereof
  申请人：Novomer, Inc.

  公开号：US10144802B2

  公开（公告）日：2018-12-04

  Provided herein are methods and systems for producing biodegradable beta-propoiolacone-based polyester polymers from renewable EO and CO on an industrial scale.

  本文提供了在工业规模上利用可再生环氧乙烷和一氧化碳生产可生物降解的β-丙烯酰丙酮基聚酯聚合物的方法和系统。
• Systems and processes for thermolysis of polylactones to produce organic acids
  申请人：Novomer, Inc.

  公开号：US10457624B2

  公开（公告）日：2019-10-29

  Reactor systems and processes produce organic acids through thermolysis of polylactones. The reactor systems and processes introduce at least one epoxide reagent and carbon monoxide reagent to at least one reaction vessel through at least one feed stream inlet. The epoxide reagent and carbon monoxide reagent contact at least one carbonylation catalyst to produce at least one beta-lactone intermediate. The beta-lactone intermediate is polymerized with at least one initiator in the presence of a metal cation to produce at least one polylactone product. The polylactone product is heated under thermolysis conditions to produce at least one organic acid product. The processes control the presence of contaminates, impurities, catalytic materials, and/or reagents to provide for highly pure organic acid products.

  反应器系统和工艺通过热分解聚内酯生产有机酸。反应器系统和工艺通过至少一个进料流入口将至少一种环氧试剂和一氧化碳试剂引入至少一个反应容器。环氧化物试剂和一氧化碳试剂与至少一种羰基化催化剂接触，生成至少一种β-内酯中间体。在金属阳离子存在下，β-内酯中间体与至少一种引发剂聚合，生成至少一种聚内酯产品。聚内酯产品在热分解条件下加热，生成至少一种有机酸产品。这些工艺可控制污染物、杂质、催化材料和/或试剂的存在，以提供高纯度的有机酸产品。