3-allyl-5,5-dimethyl-4-methyleneoxazolidin-2-one | 128457-24-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 3-allyl-5,5-dimethyl-4-methyleneoxazolidin-2-one
• 英文别名: 5,5-Dimethyl-4-methylidene-3-prop-2-enyl-1,3-oxazolidin-2-one
• CAS: 128457-24-9
• 化学式: C₉H₁₃NO₂
• 分子量: 167.208
• InChiKey: WKYHZNIQCYUWOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4,4-二甲基-5-亚甲基-1,3-二氧戊环-2-酮 、 丙烯胺 在 四(三苯基膦)钯 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以61%的产率得到3-allyl-5,5-dimethyl-4-methyleneoxazolidin-2-one
  参考文献：
  名称：

  Reactions of 5,5-Dimethyl-4-methylene-1,3-dioxolan-2-one with Amines in the Presence of Palladium Catalyst

  摘要：

  In the reaction of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with primary amines in the presence of Pd(0) catalyst, the 3-alkyl-4-hydroxy-4,5,5-trimethyloxazolidin-2-ones (1) are obtained as the major products, along with the fort-nation of ring opened products at room temperature. On the other hand, 3-alkyl-5,5-dimethyl-4-methyloxazolidin-2-ones (2) are obtained as reaction products in high yields at high temperature. But in the absence of Pd(0) catalyst, the ring opened compounds alkylcarbamic acid 1,1-dimethyl-2-oxopropyl esters (3) are formed exclusively. In addition, in the reaction of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with secondary amines, the ring opened compounds were obtained as the sole prod-acts. A plausible mechanism for the formation of 1 and 2 is proposed.

  DOI：

  10.3987/com-01-9379

文献信息

• Effective Guanidine-Catalyzed Synthesis of Carbonate and Carbamate Derivatives from Propargyl Alcohols in Supercritical Carbon Dioxide
  作者：Nicola Della Ca'、Bartolo Gabriele、Giuseppe Ruffolo、Lucia Veltri、Tito Zanetta、Mirco Costa

  DOI：10.1002/adsc.201000607

  日期：2011.1.10

  The reactions of propargyl alcohols with carbon dioxide in supercritical carbon dioxide or in acetonitrile with gaseous carbon dioxide in the presence of organic bases as catalysts have been examined. Bicyclic guanidines are effective catalysts for the formation of α‐methylene cyclic carbonates under mild reaction conditions. Oxoalkyl carbonates, oxoalkyl carbamates or α‐methyleneoxazolidinones are

  在有机碱作为催化剂存在下，研究了炔丙醇与二氧化碳在超临界二氧化碳中或在乙腈与气态二氧化碳中的反应。双环胍是在温和的反应条件下形成α-亚甲基环状碳酸酯的有效催化剂。碳酸氧烷基酯，氨基甲酸氧代烷基酯或α-亚甲基恶唑烷酮可从炔丙基醇和外部亲核试剂（醇或胺）开始，一步一步获得高收率和良好的选择性，其中双环胍作为催化剂在超临界二氧化碳中使用。在相同反应条件下，丙炔二醇经过重排过程，而不是二氧化碳的插入，而在存在外部亲核试剂的情况下，形成了碳酸氧根，
• Efficient and eco-friendly process for the synthesis of N-substituted 4-methylene-2-oxazolidinones in ionic liquids
  作者：Qinghua Zhang、Feng Shi、Yanlong Gu、Jing Yang、Youquan Deng

  DOI：10.1016/j.tetlet.2005.06.116

  日期：2005.8

  The carbonylation of amines with propargylic alcohol using CO2 as carbonyl source to yield N-substituted 4-methylene-2-oxazolidinones could efficiently proceed in ionic liquids, and various 4-methylene oxazolidinones with high yields could be obtained under relatively mild conditions. This result showed that ionic liquid might be an effective catalyst and reaction medium for the activation of CO2,

  以CO 2为羰基源，用炔丙醇对胺进行羰基化反应，可在离子液体中有效地进行N-取代的4-亚甲基-2-恶唑烷酮，在相对温和的条件下可获得高产率的各种4-亚甲基恶唑烷酮。结果表明，离子液体可能是CO 2活化的有效催化剂和反应介质，也为CO 2的化学固定提供了新的途径。
• An Efficient and Eco-friendly Process for the Conversion of Carbon Dioxide into Oxazolones and Oxazolidinones under Supercritical Conditions
  作者：Huanfeng Jiang、Jinwu Zhao、Azhong Wang

  DOI：10.1055/s-2008-1032166

  日期：2008.3

  The cycloaddition reactions of carbon dioxide with propargylic alcohols and amines under supercritical conditions produce 4-methyleneoxazolidin-2-ones or 4-methyloxazol-2-ones. The optimized conditions consist of the use of an alcohol (2 mmol), an amine (2 mmol), copper(I) iodide (0.1 mmol), carbon dioxide (8 MPa), and a temperature of 60 °C. The regiochemical control is dependent on the substituents of the propargylic alcohols. Tertiary propargylic alcohols give 4-methyleneoxazolidin-2-ones, while primary and secondary ones generate 4-methyloxazol-2-ones. The effects of various parameters such as temperature, pressure, and time have also been investigated.

  在超临界条件下，二氧化碳与炔丙醇和胺的环加成反应生成4-甲亚胺基噁唑烷-2-酮或4-甲基噁唑-2-酮。优化的条件包括使用醇（2 mmol）、胺（2 mmol）、碘化亚铜（0.1 mmol）、二氧化碳（8 MPa）和60 °C的温度。区域化学控制取决于炔丙醇的取代基。三级炔丙醇产生4-甲亚胺基噁唑烷-2-酮，而一级和二级炔丙醇生成4-甲基噁唑-2-酮。还研究了温度、压力和时间等各种参数的影响。
• Efficient catalyst-free chemical fixation of carbon dioxide into 2-oxazolidinones under supercritical condition
  作者：Jing Xiu Xu、Jin Wu Zhao、Zhen Bin Jia

  DOI：10.1016/j.cclet.2011.04.004

  日期：2011.9

  Abstract 4-Methylene-1,3-oxazolidin-2-ones can be synthesized from propargylic alcohols, primary amines and carbon dioxide under supercritical condition in the absence of any additional catalyst and solvent. Various propargylic alcohols and primary amines were examined.

  摘要在不存在任何其他催化剂和溶剂的情况下，可以在超临界条件下，由炔丙醇，伯胺和二氧化碳合成4-亚甲基-1,3-恶唑烷-2-酮。检查了各种炔丙醇和伯胺。
• Facile and Mild Process for Chemical Fixation of CO₂to 4-Methylene-1,3-oxazolidin-2-ones Under Solvent-Free Conditions
  作者：Jingxiu Xu、Jinwu Zhao、Zhenbin Jia、Jianhe Zhang

  DOI：10.1080/00397911003707014

  日期：2011.2.28

  [image omitted] 4-Methylene-1,3-oxazolidin-2-ones were prepared via the cycloadditon reaction of propargylic alcohols with primary amines and CO2 under atmospheric pressure at 60 degrees C in the absence of any additional solvent. This methodology affords an ecofriendly, mild, and easy approach to chemical fixation of CO2.