diethyl (2,2-dimethylpropylidene)malonate | 17085-89-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl (2,2-dimethylpropylidene)malonate
• 英文别名: Diethyl(2,2-dimethylpropylidene)propanedioate；diethyl 2-(2,2-dimethylpropylidene)propanedioate
• CAS: 17085-89-1
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: WBXLTCRTGYJWFQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl (2,2-dimethylpropylidene)malonate 在 氢氧化钾 作用下， 生成 β-tert-butylacrylic acid
  参考文献：
  名称：

  The Reaction of Organic Halides with Piperidine. V. Negatively Substituted Ethyl Bromides

  摘要：

  DOI：

  10.1021/ja01863a029
• 作为产物：
  描述：

  特戊醛 、 丙二酸二乙酯 在 乙酸酐 、 zinc(II) chloride 作用下， 反应 72.0h， 以65%的产率得到diethyl (2,2-dimethylpropylidene)malonate
  参考文献：
  名称：

  乙烯基环丙烷向重排二烯和环戊烯的发散重排：机理，范围和局限性

  摘要：

  来自一个中间体的两个目标：报道了乙烯基环丙烷向跳过的二烯的新重排。通过组合的实验和计算研究，对它的机理有了基本的了解，从而以高度选择性和可控的方式向环戊烯或跳过的二烯发展了不同的方法。

  DOI：

  10.1002/ejoc.202100430

文献信息

• [EN] CATALYSTS<br/>[FR] CATALYSEURS
  申请人：BOREALIS AG

  公开号：WO2018091684A1

  公开（公告）日：2018-05-24

  A complex of formula (I) wherein M is zirconium or hafnium; each X independently is a sigma ligand; L is a divalent bridge selected from -R'2C-, -R'2C-CR'2-, -R'2Si-, -R'2Si-SiR'2-, -R'2Ge-, wherein each R' is independently a hydrogen atom or a C1-C20-hydrocarbyl group optionally containing one or more silicon atoms or heteroatoms of Group 14-16 of the periodic table or fluorine atoms, and optionally two R' groups taken together can form a ring; R2 and R2' are each independently a C1-C20 hydrocarbyl group, -OC1- hydrocarbyl group or -SC1-20 hydrocarbyl group; R5 is a -OC1-20 hydrocarbyl group or -SC1-20 hydrocarbyl group, said R5 group being optionally substituted by one or more halo groups; R5' is hydrogen or a C1-20 hydrocarbyl group; -OC1-20 hydrocarbyl group or -SC1-20 hydrocarbyl group; said C1-20 hydrocarbyl group being optionally substituted by one or more halo groups; R6 and R6' are each independently a C1-20 hydrocarbyl group; -OC1-20 hydrocarbyl group or -SC1-20 hydrocarbyl group; each R1 and R1' are independently -CH2Rx wherein Rx are each independently H, or a C1-20 hydrocarbyl group, optionally containing heteroatoms.

  式中M为锆或铪；每个X独立地是一个σ配体；L是一个二价桥，选自-R'2C-、-R'2C-CR'2-、-R'2Si-、-R'2Si-SiR'2-、-R'2Ge-，其中每个R'独立地是一个氢原子或一个C1-C20的烃基团，可选地包含一个或多个硅原子或周期表中第14-16族的杂原子或氟原子，并且可选地两个R'基团一起可以形成一个环；R2和R2'各自独立地是一个C1-C20烃基团、-OC1-烃基团或-SC1-20烃基团；R5是一个-OC1-20烃基团或-SC1-20烃基团，所述R5基团可被一个或多个卤素取代；R5'是氢或一个C1-20烃基团；-OC1-20烃基团或-SC1-20烃基团；所述C1-20烃基团可被一个或多个卤素取代；R6和R6'各自独立地是一个C1-20烃基团；-OC1-20烃基团或-SC1-20烃基团；每个R1和R1'各自独立地为-CH2Rx，其中Rx各自独立地为H，或一个C1-20烃基团，可选地含有杂原子。
• Active Base Hybrid Organosilica Materials based on Pyrrolidine Builder Units for Fine Chemicals Production
  作者：Sebastián Llopis、Alexandra Velty、Urbano Díaz

  DOI：10.1002/cctc.202101031

  日期：2021.12.7

  high catalytic activity performance, stability and recyclability of “pyrrolidine type” fragments included in mesoporous silica for the preparation of α,β-unsaturated compounds through base-catalyzed reactions such as Knoevenagel, Claisen-Schmidt and Henry reactions under microwave irradiation, contributing to the development of sustainable process, was reported.

  混合催化剂：介孔二氧化硅中包含的“吡咯烷型”片段的高催化活性、稳定性和可回收性，用于在微波辐射下通过碱催化反应（如 Knoevenagel、Claisen-Schmidt 和 Henry 反应）制备 α,β-不饱和化合物，有助于可持续过程的发展，被报道。
• Bridged metallocene catalysts
  申请人：Resconi Luigi

  公开号：US09079985B2

  公开（公告）日：2015-07-14

  A solid, particulate catalyst comprising: (i) a complex of formula (I) wherein M is zirconium or hafnium; each X is a sigma ligand; L is a divalent bridge selected from —R′2C—, —R′2C—CR′2—, —R′2Si—, —R′2Si—SiR′2—, —R′2Ge—, wherein each R′ is independently a hydrogen atom, C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl; each R1 is a C4-C20 hydrocarbyl radical branched at the β-atom to the cyclopentadienyl ring, optionally containing one or more heteroatoms belonging to groups 14-16, or is a C3-C20 hydrocarbyl radical branched at the β-atom to the cyclopentadienyl ring where the β-atom is an Si-atom; each R18 is a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16; each R4 is a hydrogen atom or a C1-6-hydrocarbyl radical; each W is a 5 or 6 membered aryl or heteroaryl ring wherein each atom of said ring is optionally substituted with at least one R5 group; each R5 is the same or different and is a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16; and optionally two adjacent R5 groups taken together can form a further mono or multicyclic ring condensed to W optionally substituted by one or two groups R5; and each R7 is a C1-C20 hydrocarbyl radical; and (ii) a cocatalyst, preferably comprising an organometallic compound of a Group 13 metal.

  一种固体颗粒催化剂，包括：（i）具有式（I）的配合物，其中M为锆或铪；每个X为σ配体；L为从—R′2C—、—R′2C—CR′2—、—R′2Si—、—R′2Si—SiR′2—、—R′2Ge—中选择的二价桥，其中每个R′独立地为氢原子、C1-C20-烃基、三(C1-C20-烷基)硅基、C6-C20-芳基、C7-C20-芳基烷基或C7-C20-烷基芳基；每个R1为在β-原子处分支到环戊二烯基环的C4-C20烃基基团，可选地含有属于14-16族的一个或多个杂原子，或者是在β-原子处分支到环戊二烯基环的C3-C20烃基基团，其中β-原子为Si原子；每个R18为可选地含有一个或多个属于14-16族的杂原子的C1-C20烃基基团；每个R4为氢原子或C1-6-烃基基团；每个W为5或6成员芳基或杂芳基环，其中所述环的每个原子可选择地用至少一个R5基团取代；每个R5相同或不同，为可选地含有一个或多个属于14-16族的杂原子的C1-C20烃基基团；并且可选地，两个相邻的R5基团一起可以形成一个进一步的单环或多环环，与W形成共轭，可选择地由一个或两个R5基团取代；每个R7为C1-C20烃基基团；以及（ii）一个共催化剂，优选包括第13族金属的有机金属化合物。
• SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, CATALYST FOR OLEFIN POLYMERIZATION, AND METHOD FOR PRODUCING OLEFIN POLYMER
  申请人：Uozumi Toshiya

  公开号：US20140221583A1

  公开（公告）日：2014-08-07

  An olefin polymer that is obtained using an olefin polymerization catalyst that includes a solid catalyst component for olefin polymerization that includes titanium, magnesium, a halogen, and an ester compound (A) represented by the following formula (1): R 1 R 2 C═C(COOR 3 )(COOR 4 ), an organoaluminum compound, and an optional external electron donor compound, exhibits primary properties (e.g., molecular weight distribution and stereoregularity) similar to those of an olefin polymer obtained using a solid catalyst component that includes a phthalic ester as an electron donor.

  使用一种包括钛、镁、卤素和酯化合物(A)的固体催化剂组分（式子1：R1R2C═C(COOR3)(COOR4)）进行烯烃聚合得到的烯烃聚合物，加上有机铝化合物和可选的外部电子给体化合物，表现出与包括邻苯二甲酸酯作为电子给体的固体催化剂组分得到的烯烃聚合物相似的主要性质（如分子量分布和立构规则性）。
• BRIDGED METALLOCENE CATALYSTS
  申请人：Resconi Luigi

  公开号：US20140018506A1

  公开（公告）日：2014-01-16

  A solid, particulate catalyst comprising: (i) a complex of formula (I) wherein M is zirconium or hafnium; each X is a sigma ligand; L is a divalent bridge selected from —R ′2 C—, —R′ 2 C—CR′ 2 —, —R′ 2 Si—, —R′ 2 Si—SiR′ 2 —, —R′ 2 Ge—, wherein each R′ is independently a hydrogen atom, C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl; each R 1 is a C4-C20 hydrocarbyl radical branched at the β-atom to the cyclopentadienyl ring, optionally containing one or more heteroatoms belonging to groups 14-16, or is a C3-C20 hydrocarbyl radical branched at the β-atom to the cyclopentadienyl ring where the β-atom is an Si-atom; each R 18 is a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16; each R 4 is a hydrogen atom or a C 1-6 -hydrocarbyl radical; each W is a 5 or 6 membered aryl or heteroaryl ring wherein each atom of said ring is optionally substituted with at least one R 5 group; each R 5 is the same or different and is a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms belonging to groups 14-16; and optionally two adjacent R 5 groups taken together can form a further mono or multicyclic ring condensed to W optionally substituted by one or two groups R 5 ; and each R 7 is a C1-C20 hydrocarbyl radical; and (ii) a cocatalyst, preferably comprising an organometallic compound of a Group 13 metal.

  一种固体颗粒催化剂，包括：(i)公式(I)的复合物，其中M为锆或铪；每个X为σ配体；L为二价桥，选自-R'2C-、-R'2C-CR'2-、-R'2Si-、-R'2Si-SiR'2-、-R'2Ge-，其中每个R'独立地为氢原子、C1-C20烃基、三(C1-C20-烷基)硅基、C6-C20芳基、C7-C20芳基烷基或C7-C20烷基芳基；每个R1为分支在环戊二烯基环的β原子处的C4-C20烃基基团，可选地包含属于14-16族的一个或多个杂原子，或者为分支在环戊二烯基环的β原子处的C3-C20烃基基团，其中β原子为Si原子；每个R18为可选地含有属于14-16族的一个或多个杂原子的C1-C20烃基基团；每个R4为氢原子或C1-6烃基基团；每个W为5或6元芳基或杂芳基环，其中该环的每个原子可选择地被至少一个R5基团取代；每个R5相同或不同，为可选地含有属于14-16族的一个或多个杂原子的C1-C20烃基基团；并且可选地，相邻的两个R5基团组成进一步的单环或多环环，与可选择地被一个或两个R5基团取代的W相接；每个R7为C1-C20烃基基团；以及(ii)辅助催化剂，优选地包括第13族金属的有机金属化合物。