bis[3-(ethoxycarbonyl)propargyl] ether | 240493-22-5

• 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: bis[3-(ethoxycarbonyl)propargyl] ether
• 英文别名: Ethyl 4-(4-ethoxy-4-oxobut-2-ynoxy)but-2-ynoate
• CAS: 240493-22-5
• 化学式: C₁₂H₁₄O₅
• 分子量: 238.24
• InChiKey: YQDDVYHRIBSMJC-UHFFFAOYSA-N

物化性质

• 熔点：
  29-30 °C
• 沸点：
  366.5±27.0 °C(Predicted)
• 密度：
  1.153±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1H-全氟-1-辛炔 、 bis[3-(ethoxycarbonyl)propargyl] ether 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate C.I.酸性棕21 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 3.0h， 以75%的产率得到5-tridecafluorohexyl-1,3-dihydroisobenzofuran-4,7-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Synthesis of Perfluoroalkylated Benzenes and Pyridines through Cationic Rh(I)/Modified BINAP-Catalyzed Chemo- and Regioselective [2 + 2 + 2] Cycloaddition

  摘要：

  A convenient synthesis of perfluoroalkylated benzenes and pyridines has been achieved by a cationic Rh(I)/modified BINAP-complex-catalyzed chemo- and regioselective [2 + 2 + 2] cycloaddition of alkynes with a perfluoroalkylacetylene and a perfluoroalkylnitrile.

  DOI：

  10.1021/ol070456m
• 作为产物：
  描述：

  丙炔醚 、 氯甲酸乙酯 在 正丁基锂 作用下， 生成 bis[3-(ethoxycarbonyl)propargyl] ether
  参考文献：
  名称：

  A Convenient Method for the Synthesis of 2,5-Difunctionalized Phospholes Bearing Ester Groups

  摘要：

  Symmetrically and unsymmetrically 2,5-difunctionalized phospholes bearing ester groups were prepared in a one-pot procedure from the corresponding diynes and dichloro-(phenyl) phosphine via titanacyclopentadienes. The observed optical properties of the functionalized phospholes show that the pi-conjugative push-pull interaction between the 2- and 5-substituents plays an important role in controlling the light-emitting efficiency.

  DOI：

  10.1021/jo0605748

文献信息

• Rh-Catalyzed Synthesis of Helically Chiral and Ladder-Type Molecules via [2 + 2 + 2] and Formal [2 + 1 + 2 + 1] Cycloadditions Involving C−C Triple Bond Cleavage
  作者：Ken Tanaka、Akiyoshi Kamisawa、Takeshi Suda、Keiichi Noguchi、Masao Hirano

  DOI：10.1021/ja074914y

  日期：2007.10.1

  We have developed highly enantioselective synthesis of functionalized helically chiral molecules via a Rh-catalyzed [2 + 2 + 2] cycloaddition and synthesis of ladder-type molecules via an unprecedented Rh-catalyzed formal [2 + 1 + 2 + 1] cycloaddition involving C−C triple bond cleavage.

  我们已经开发了通过 Rh 催化的 [2 + 2 + 2] 环加成和梯形分子的高度对映选择性合成功能化螺旋手性分子，通过前所未有的 Rh 催化的形式 [2 + 1 + 2 + 1] 环加成，涉及 C -C 三键断裂。
• Commercially available liquid enol ethers and acetates as gaseous alkyne equivalents in cationic Rh(I)/BINAP-catalyzed chemo- and regioselective formal cross-alkyne cyclotrimerizations
  作者：Hiromi Hara、Masao Hirano、Ken Tanaka

  DOI：10.1016/j.tet.2009.02.047

  日期：2009.6

  A cationic rhodium(I)/BINAP complex catalyzes partial intramolecular [2+2+2] cycloadditions of 1,6- and 1,7-diynes with enol ethers or a ketene acetal giving substituted benzenes in good yields. The same catalyst also catalyzes complete intermolecular [2+2+2] cycloadditions of two different monoynes with enol acetates giving tri- and tetrasubstituted benzenes in good yields with complete regioselectivity

  阳离子铑（I）/ BINAP络合物可催化1,6-和1,7-二炔与烯醇醚或乙烯酮缩醛的部分分子内[2 + 2 + 2]环加成反应，从而以高收率得到取代的苯。相同的催化剂还催化两种不同的单炔与烯醇乙酸酯的完全分子间[2 + 2 + 2]环加成反应，从而以良好的收率和完全的区域选择性得到三和四取代的苯。在当前的铑催化的正式跨炔烃环三聚反应中，可商购的液体烯醇醚和乙酸酯可用作气态炔烃的通用等同物。
• Pd(0)-catalyzed selective [2 + 2 + 2] cycloaddition of dimethyl nona-2,7-diyne-1,9-dioate derivatives with dimethyl acetylenedicarboxylate
  作者：Yoshihiko Yamamoto、Asako Nagata、Kenji Itoh

  DOI：10.1016/s0040-4039(99)00927-2

  日期：1999.7

  In the presence of 2.5 mol % of Pd2(dba)3 and 5 mol % of PPh3, nearly equimolar amounts of dimethyl nona-2,7-diyne-1,9-dioate derivatives and dimethyl acetylenedicarboxylate (DMAD) were reacted in toluene at 110 °C to give indan, phthalin, and isoindoline derivatives selectively in moderate to good yields. The competing homo-couplings of both the diynediesters and DMAD were completely suppressed. The

  在2.5摩尔％的Pd 2（dba）3和5摩尔％的PPh 3的存在下，几乎等摩尔量的壬二-2,7-二炔-1,9-二酸二甲酯衍生物和乙酰二羧酸二甲酯（DMAD）发生反应。在110°C的温度下甲苯可选择性地以中等到良好的收率得到茚满，酞菁和异吲哚啉衍生物。二醛和DMAD的竞争同质偶合被完全抑制。炔烃末端的酯基起重要作用；相应的二炔二酮和二炔单酯的结果不令人满意。本Pd（0）催化的环三聚反应进一步扩展到三炔二酯的分子内[2 + 2 + 2]环加成反应。
• Palladium(0)-Catalyzed Intramolecular [2+2+2] Alkyne Cyclotrimerizations with Electron-Deficient Diynes and Triynes
  作者：Yoshihiko Yamamoto、Asako Nagata、Hitomi Nagata、Yoji Ando、Yasuhiro Arikawa、Kazuyuki Tatsumi、Kenji Itoh

  DOI：10.1002/chem.200204540

  日期：2003.6.6

  of these intramolecular alkyne cyclotrimerizations, stoichiometric reactions of [Pd(2)(dba)(3)] with a diyne diester and a triyne diester bearing ether tethers were conducted in acetone at room temperature to furnish an oligomeric bicyclopalladacyclopentadiene and a Pd(0) triyne complex, respectively. The structures of these novel complexes were unequivocally determined by Xray structure analysis.

  在存在2.5摩尔％的[Pd（2）（dba）（3）]（dba =二亚苄基丙酮）和5摩尔％的PPh（3）的情况下，几乎等摩尔的二甲基壬基2,7-二炔-1，使9-二酸酯衍生物（二炔二酯）和乙炔二羧酸二烷基酯在甲苯中于110摄氏度下反应，以中等至良好的收率得到[2 + 2 + 2]环加合物。同样，十三烷基二甲基-2,7,12-三炔-1,13-二酸酯衍生物（三炔二酯）以优异的产率催化转化为邻苯二甲酸酯类似物。为了深入了解这些分子内炔烃环三聚反应的机理，在室温下于丙酮中进行了[Pd（2）（dba）（3）]与二炔二酯和带有醚链的三炔二酯的化学计量反应，以提供低聚的双环戊四环戊二烯和一个Pd（0）三炔复合物。通过X射线结构分析明确地确定了这些新颖复合物的结构。将分离的三炔络合物在50℃下加热，或在室温下用PPh（3）在丙酮中的溶液处理，得到芳烃产物。此外，同一配合物催化有或没有PPh（3）的三炔环化反应。
• Rhodium-Catalyzed Highly Enantio- and Diastereoselective Cotrimerization of Alkenes and Dialkyl Acetylenedicarboxylates Leading to Furylcyclopropanes
  作者：Yu Shibata、Keiichi Noguchi、Masao Hirano、Ken Tanaka

  DOI：10.1021/ol800966f

  日期：2008.7.3

  A cationic rhodium(I)/Segphos or H-8-BINAP complex catalyzes the unprecedented cotrimerization of commercially available monoenes and dialkyl acetylenedicarboxylates, leading to functionalized furylcyclopropanes with excellent enantioselectivity and perfect diastereoselectivity.