5-乙基-5-(羟基甲基)-1,3-二恶烷-2-酮 | 38802-97-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 中文名称: 5-乙基-5-(羟基甲基)-1,3-二恶烷-2-酮
• 英文名称: trimethylolpropane cyclic monocarbonate
• 英文别名: 5-Ethyl-5-(hydroxymethyl)-1,3-dioxan-2-one
• CAS: 38802-97-0
• 化学式: C₇H₁₂O₄
• 分子量: 160.17
• InChiKey: ULLQSQVSYJHWHX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-乙基-5-(羟基甲基)-1,3-二恶烷-2-酮 、 N,N’-二异丙基乙二胺 反应 6.0h， 生成
  参考文献：
  名称：

  환식 탄산염으로부터의 우레탄, 이의 중합체, 코팅 조성물과 그 제조

  摘要：

  本发明涉及功能化碳酸酯、聚氨酯和聚氨酯，以及它们的制备方法和应用。

  公开号：

  KR20160032019A
• 作为产物：
  描述：

  1,1,1-三(羟甲基)乙烷 、 碳酸二甲酯 在 Novozym 435 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 72.0h， 生成 5-乙基-5-(羟基甲基)-1,3-二恶烷-2-酮
  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

• Fast Monomers:  Factors Affecting the Inherent Reactivity of Acrylate Monomers in Photoinitiated Acrylate Polymerization
  作者：Johan F. G. A. Jansen、Aylvin A. Dias、Marko Dorschu、Betty Coussens

  DOI：10.1021/ma021785r

  日期：2003.6.1

  study on the effect of molecular structure on the photoinitiated polymerization of acrylates was undertaken. Initially, the research was focused on the effect of hydrogen bonding, and it was found that preorganization via hydrogen bonding enhances the maximum rate of polymerization (Rp). This hydrogen bonding facilitated preorganization also affected the tacticity of the resultant polymer. Next, the

  对分子结构对丙烯酸酯光引发聚合反应的影响进行了系统的研究。最初，研究的重点是氢键的作用，发现通过氢键进行的预组织可提高最大聚合速率（R p）。这种氢键促进的预组织也影响了所得聚合物的立构规整度。接下来，研究了由给定单体的计算偶极矩（μcalc）表示的极性影响。观察到R p与计算的玻尔兹曼平均偶极矩（μcalc）之间存在直接的线性关系。的[R p -μ计算值相关性适用于纯单体，单体混合物，甚至单体与惰性溶剂的混合物。这种相关性使得能够合理设计具有所需反应性的单体。另外，这些研究表明，聚合的传播步骤受氢键的影响，而偶极矩则影响终止速率常数。可以将这两种机理解释视为影响丙烯酸酯聚合速度的互补因素。
• [EN] PROCESS FOR PRODUCING CARBAMOYLOXY (METH)ACRYLATES AND NEW CARBAMOYLOXY (METH)ACRYLATES<br/>[FR] PROCESSUS DE PRODUCTION DE (METH)ACRYLATES CARBAMOYLOXY ET DE NOUVEAUX (METH)ACRYLATES CARBAMOYLOXY
  申请人：UCB SA

  公开号：WO2004052843A1

  公开（公告）日：2004-06-24

  The invention relates to a process for producing carbamoyloxy (meth)acrylates which comprises transesterification of hydroxyalkyl carbamates with an (meth)acrylate of formula CH2=CR29-COOR30 wherein R29 is hydrogen or methyl and R30 represents an alkyl group comprising from 1 to 8 carbon atoms, in the presence of an organotitanate, an organozirconate catalyst or an organotin catalyst, the carbamoyloxy (meth)acrylates thereby obtained and their use in radiation curable compositions.

  该发明涉及一种生产羰酰氧基（甲基）丙烯酸酯的方法，包括将羟基烷基氨基甲酸酯与具有化学式CH2=CR29-COOR30的（甲基）丙烯酸酯进行酯交换反应，其中R29为氢或甲基，R30代表含有1至8个碳原子的烷基基团，在有机钛、有机锆或有机锡催化剂的存在下进行，从而得到羰酰氧基（甲基）丙烯酸酯，并将其用于辐射固化组合物中。
• [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。
• [EN] PROCESS FOR PRODUCING URETHANE (METH)ACRYLATES AND NEW URETHANE (METH)ACRYLATES<br/>[FR] PROCÉDÉ POUR LA FABRICATION DE (MÉTH)ACRYLATES D'URÉTHANE ET NOUVEAUX (MÉTH)ACRYLATES D'URÉTHANE
  申请人：SURFACE SPECIALTIES SA

  公开号：WO2005110978A1

  公开（公告）日：2005-11-24

  The invention relates to urethane(meth)acrylates and to a process for their production which comprises transesterification of hydroxyalkyl carbamates with an (meth)acrylate of formula [CH2=CR29-CO-O-]t-R30 wherein R29 is hydrogen or methyl, and R30 represents an alkyl, optionally substituted by hydroxy, which may contain from 1 to 10 ether bridges group, from 1 to 10 -CO- bridges and/or from 1 to 5 -O-CO- bridges, and at least one carbonate of formula (IX) and/or a diester of formula (X) wherein each R31, each R32, each R33, each R34 is, independently, chosen from the group of alkyl and aryl, and R35 is alkylene, alkenylene or arylene.

  该发明涉及氨基甲酸酯（甲基）丙烯酸酯以及它们的生产方法，该方法包括将羟基烷基氨基甲酸酯与具有以下结构的（甲基）丙烯酸酯进行酯交换反应：[CH2=CR29-CO-O-]t-R30，其中R29为氢或甲基，R30代表一种烷基，该烷基可以选择性地被羟基取代，可能含有1到10个醚桥基团，1到10个-CO-桥基和/或1到5个-O-CO-桥基，并且至少含有一个具有以下结构的碳酸酯（IX）和/或一个具有以下结构的二酯（X），其中每个R31、每个R32、每个R33、每个R34独立地选择自烷基和芳基群，而R35为烷基、烯基或芳基。
• 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，