Ethyl (5-ethyl-2-oxo-1,3-dioxan-5-yl)methyl carbonate | 282098-17-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: Ethyl (5-ethyl-2-oxo-1,3-dioxan-5-yl)methyl carbonate
• CAS: 282098-17-3
• 化学式: C₁₀H₁₆O₆
• 分子量: 232.233
• InChiKey: FFCDXXMFFZKYBA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1,1,1-三(羟甲基)乙烷 、 碳酸二乙酯 在 Novozym 435 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 115.0h， 生成 5-乙基-5-(羟基甲基)-1,3-二恶烷-2-酮 、 Ethyl (5-ethyl-2-oxo-1,3-dioxan-5-yl)methyl carbonate 、 、
  参考文献：
  名称：

  Lipase-mediated synthesis of six-membered cyclic carbonates from trimethylolpropane and dialkyl carbonates: Influence of medium engineering on reaction selectivity

  摘要：

  Six-membered cyclic carbonates are potential monomers for aliphatic polycarbonates and polyurethanes in a process without using toxic phosgene and isocyanate. Lipase catalyzed transesterification of the polyol, trimethylolpropane (TMP) with dimethyl carbonate (DMC) or diethyl carbonate (DEC) followed by thermal cyclization was used for synthesis of six-membered cyclic carbonates with pendant hydroxyl and alkoxycarbonyloxyl groups. Immobilized lipase B from Candida antarctica (Novozym (R) 435) was used as the catalyst. Mixture of a hydrophilic solvent such as THF for high solubility of TMP, and a hydrophobic solvent such as toluene, were selected as the best solvent system for achieving high substrate conversion and selectivity. A relationship between polyol conversion and solvent hydrophobicity (log P) and solvent type, respectively, was established. THF:toluene system at a ratio of 0.5:1.0 (v/v) provided high degree of TMP conversion to product with high proportion of cyclic carbonates (>80%). The cyclic carbonate with pendant hydroxyl group was obtained with almost 85% selectivity at TMP conversion of 68.6% using 10% (w/w)Novozym (R) 435 at TMP:DMC ratio of 1:1. However, at TMP:DMC ratio of 1:5 and the same biocatalyst concentration, the TMP conversion was 100% with 72% selectivity for the cyclic carbonate with pendant alkoxycarbonyloxyl group. The product formed was without or with less content of linear carbonates, bis and tris(methoxycarbonyloxy)-TMP, as compared to that in a solvent-free system. The reactivity of DEC was lower than that of DMC. The reaction pathway leading to the formation of cyclic carbonate in this process comprised enzymatic carbonation of TMP with alkylcarbonates and thermal cyclization of linear carbonates. The process affords high degree of conversion of polyol to cyclic carbonates and provides a potentially attractive synthetic route for monomers of polycarbonates and polyurethanes. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2011.07.019

文献信息

• [EN] METHOD FOR PRODUCING CYCLIC CARBONATES<br/>[FR] PROCÉDÉ POUR PRODUIRE DES CARBONATES CYCLIQUES
  申请人：HATTI-KAUL RAJNI

  公开号：WO2012158107A1

  公开（公告）日：2012-11-22

  Linear or cyclic carbonates as potential monomers for isocyanate-free polyurethanes and polycarbonates were prepared from polyols and dialkylcarbonatesor diphenyl carbonates. This invention was developed to produce linear or cyclic carbonates with or without using catalysts. Polyol compounds were reacted with carbonates such as dimethylcarbonate and diethylcarbonate to produce thecorresponding linear and/or cyclic carbonate.

  线性或环状碳酸酯作为异氰酸酯自由聚氨酯和聚碳酸酯的潜在单体，是由多元醇和二烷基碳酸酯或二苯碳酸酯制备的。这项发明旨在生产带有或不带有催化剂的线性或环状碳酸酯。多元醇化合物与碳酸酯（如二甲基碳酸酯和二乙基碳酸酯）反应，以产生相应的线性和/或环状碳酸酯。
• Solvent-free lipase-mediated synthesis of six-membered cyclic carbonates from trimethylolpropane and dialkyl carbonates
  作者：Sang-Hyun Pyo、Per Persson、Stefan Lundmark、Rajni Hatti-Kaul

  DOI：10.1039/c0gc00783h

  日期：——

  heating at 60–80 °C without any catalyst. The total yield of cyclic carbonates was about 85% after thermal treatment at 80 °C. This process, consisting of lipase-catalyzed transesterification and thermal disproportionation, provides a novel and more environmentally friendly approach for the synthesis of cyclic carbonates without using toxic organic solvents, phosgene or isocyanate.

  六元循环 碳酸盐 和 羟 和/或烷氧基羰氧基作为聚氨酯和聚碳酸酯的潜在单体，是通过 三羟甲基丙烷 （TMP）与碳酸二甲酯（DMC）或 碳酸二乙酯（DEC）通过固定化介导的南极假丝酵母脂肪酶B，诺维信®在435溶剂-无介质。碳酸二烷基酯用作溶剂反应。TMP在50°C下的溶解度在DMC中为565 mg mL -1，在DEC中为64.8 mg mL -1。使用浓度为10％，20％和40％（TMP的w / w）的生物催化剂的反应显示出相似的特征，TMP的转化率在24小时内线性增加至90％，并在48小时内完全转化。在2.5和5％的生物催化剂的浓度（w / w的TMP的），主要产物单碳酸TMP（3）和/或环状碳酸酯（4），而二和三碳酸TMP（5，7）获得在脂肪酶浓度为20％和40％的情况下。DEC的反应性低于DMC，但导致3或4的生产具有更高的选择性。线性的很大一部分碳酸盐 混合后的产物通过歧化环化，
• [EN] SOLVENT-FREE SYNTHESIS OF CYCLIC CARBONATES<br/>[FR] SYNTHÈSE DE CARBONATES CYCLIQUES SANS SOLVANT
  申请人：PERSTORP AB

  公开号：WO2011159219A1

  公开（公告）日：2011-12-22

  Disclosed is a process for production of a cycloaliphatic carbonate from a diol, triol or polyol and a carbon dioxide source, such as a dialkyl carbonate. Said process is performed in a solvent-free medium using a N-heterocyclic carbene or N-heterocyclic carbene complex as catalyst. Said N-heterocyclic carbene or carbene complex is preferably attached to a lipase. Said process comprises preferably a transesterification step and a thermal disproportionation step and yielded cycloaliphatic carbonate is in preferred embodiments a monocyclic carbonate having a five-membered or a six-membered ring.

  本发明揭示了一种从二元醇、三元醇或多元醇和碳酸二酯等二氧化碳源生产环状脂肪族碳酸酯的方法。该方法在无溶剂介质中使用N-杂环卡宾或N-杂环卡宾配合物作为催化剂。所述N-杂环卡宾或卡宾配合物优选附着于脂肪酶上。该方法优选包括酯交换步骤和热不均化步骤，所得的环状脂肪族碳酸酯在优选实施例中是具有五元环或六元环的单环碳酸酯。
• METHOD FOR PRODUCING CYCLIC CARBONATES
  申请人：Hatti-Kaul, Rajni

  公开号：EP2709995A1

  公开（公告）日：2014-03-26
• US9546147B2
  申请人：——

  公开号：US9546147B2

  公开（公告）日：2017-01-17