trans-9-oxa-bicyclo[6.2.0]decan-10-one

• 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: trans-9-oxa-bicyclo[6.2.0]decan-10-one
• 英文别名: trans-9-oxabicyclo[6.2.0]decan-10-one；(1S,8S)-9-oxabicyclo[6.2.0]decan-10-one
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: LPYWUOKFXMGVJU-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  trans-9-oxa-bicyclo[6.2.0]decan-10-one 生成 反式环辛烯
  参考文献：
  名称：

  A Readily Synthesized and Highly Active Epoxide Carbonylation Catalyst Based on a Chromium Porphyrin Framework:  Expanding the Range of Available β-Lactones

  摘要：

  Catalytic carbonylation of epoxides to beta-lactones was effected by a highly active and selective bimetallic catalyst comprised of a chromium(III) porphyrin cation and a cobalt tetracarbonyl anion. The complex is readily synthesized from commercially available compounds in high yield. Carbonylation of numerous linear epoxides, as well as bicyclic epoxides derived from 8- and 12-membered hydrocarbons, proceeded with high activity, selectivity, and yield.

  DOI：

  10.1021/ol036244g
• 作为产物：
  描述：

  一氧化碳 、 cis-1,2-epoxycyclooctane 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trans-9-oxa-bicyclo[6.2.0]decan-10-one
  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

• 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。
• PROCESSES FOR PRODUCING BETA-LACTONE AND BETA-LACTONE DERIVATIVES WITH HETEROGENOUS CATALYSTS
  申请人：Novomer, Inc.

  公开号：US20190047972A1

  公开（公告）日：2019-02-14

  The present invention is directed to processes from producing beta-lactone and beta-lactone derivatives using heterogenous catalysts. In preferred embodiments of the present invention, the processes comprise the steps: passing a feed stream comprising an epoxide reagent and a carbon monoxide reagent to a reaction zone; contacting the epoxide reagent and the carbon monoxide reagent with a heterogenous catalyst to produce a beta-lactone product in the reaction zone; and removing the beta-lactone product from the reaction zone. In preferred embodiments, the heterogenous catalyst comprises a solid support containing a cationic Lewis acid functional group and a metal carbonyl compound comprising at least one of anionic metal carbonyl compound or a neutral metal carbonyl compound. In certain preferred embodiments, the epoxide reagent and carbon monoxide reagent have a biobased content.

  本发明涉及使用异质催化剂生产β-内酯和β-内酯衍生物的过程。在本发明的首选实施例中，该过程包括以下步骤：将包含环氧试剂和一氧化碳试剂的进料流通入反应区；将环氧试剂和一氧化碳试剂与异质催化剂接触，在反应区内产生β-内酯产物；并从反应区中移除β-内酯产物。在首选实施例中，异质催化剂包括固体支撑体，其中包含阳离子路易斯酸功能团和金属羰基化合物，其中至少包括一种阴离子金属羰基化合物或中性金属羰基化合物。在某些首选实施例中，环氧试剂和一氧化碳试剂具有生物基含量。
• The first asymmetric ring-expansion carbonylation of meso-epoxides
  作者：Prasad Ganji、Hasim Ibrahim

  DOI：10.1039/c2cc35596e

  日期：——

  The first asymmetric ring-expansion carbonylation of meso-epoxides to β-lactones is reported. Two structurally diverse chiral Cr(III) chloro complexes in conjunction with Co2(CO)8 were shown to be competent catalytic systems for this transformation, displaying significant levels of asymmetric induction of up to 56% ee.

  首次报道了介环氧化物与 β-内酯的不对称扩环羰基化反应。研究表明，两种结构不同的手性铬(III)氯配合物与 Co2(CO)8 共同组成的催化体系能够胜任这一转化过程，并显示出高达 56% ee 的显著不对称诱导水平。
• 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。
• Processes for producing beta-lactone with heterogenous catalysts
  申请人：Novomer, Inc.

  公开号：US10590099B1

  公开（公告）日：2020-03-17

  The present invention is directed to processes from producing beta-lactone and beta-lactone derivatives using heterogenous catalysts. In preferred embodiments of the present invention, the processes comprise the steps: passing a feed stream comprising an epoxide reagent and a carbon monoxide reagent to a reaction zone; contacting the epoxide reagent and the carbon monoxide reagent with a heterogenous catalyst to produce a beta-lactone product in the reaction zone; and removing the beta-lactone product from the reaction zone. In preferred embodiments, the heterogenous catalyst comprises a solid support containing a cationic Lewis acid functional group and a metal carbonyl compound comprising at least one of anionic metal carbonyl compound or a neutral metal carbonyl compound. In certain preferred embodiments, the epoxide reagent and carbon monoxide reagent have a biobased content.

  本发明涉及使用异质催化剂生产β-内酯和β-内酯衍生物的工艺。在本发明的优选实施方案中，该工艺包括以下步骤：将包含环氧化物试剂和一氧化碳试剂的进料流通入反应区；使环氧化物试剂和一氧化碳试剂与异质催化剂接触，在反应区生成β-内酯产物；从反应区除去β-内酯产物。在优选的实施方案中，异质催化剂包括含有阳离子路易斯酸官能团和金属羰基化合物的固体载体，金属羰基化合物包括阴离子金属羰基化合物或中性金属羰基化合物中的至少一种。在某些优选的实施方案中，环氧化物试剂和一氧化碳试剂具有生物基含量。