Diethyl 2-(4-pentynyl)malonate | 66980-43-6

• 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-(4-pentynyl)malonate
• 英文别名: 2-(1-methylbut-3-ynyl)malonic acid diethyl ester；Diethyl 2-pent-4-yn-2-ylpropanedioate
• CAS: 66980-43-6
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: BADYXSQYQOQUGF-UHFFFAOYSA-N

物化性质

• 沸点：
  130-132 °C(Press: 14 Torr)
• 密度：
  1.037±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  8
• 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-(4-pentynyl)malonate 在 氢氧化钾 、 N-溴代丁二酰亚胺(NBS) 、 碳酸氢钠 作用下， 以 甲醇 、 二氯甲烷 、 水 、 间二甲苯 为溶剂， 反应 14.0h， 生成 6-[1-Bromo-meth-(E)-ylidene]-4-methyl-tetrahydro-pyran-2-one
  参考文献：
  名称：

  New approaches to the synthesis of alkyl-substituted enol lactone systems, inhibitors of the serine protease elastase

  摘要：

  We have synthesized a series of alkyl-substituted enol lactones designed to act as mechanism-based inhibitors of human neutrophil elastase (HLE). General methods were developed for the preparation of alpha- and beta-alkyl-substituted 5-hexynoic acids by the bromoform reaction on the corresponding alkynoic methyl ketone, prepared by an Eschenmoser-Tanabe fragmentation sequence from a suitably substituted cyclohexenone. By this method, beta-methyl- and beta,beta-dimethyl-5-hexynoic acids were synthesized from commercially available isophorone and 3,5-dimethyl-2-cyclohexen-1-one, respectively. Alpha-Substituted 5-hexynoic acids were prepared from 3-ethoxy-2-cyclohexen-1-one, using a novel ZnCl2-mediated alkylation that we developed; this method gives high yields of alpha'-alkylation products, even with secondary halides. The most efficient method for the preparation of alpha-substituted 5-hexynoic acids involved a four-reaction sequence-alkylation of the alpha-substituted ester with 1,4-dibromobutane, elimination, bromination and bisdehydrobromination-that proceeded in high overall yield. Protio enol lactonizations were performed with mercury(II) catalysis in CH2Cl2 or CH2Cl2-H2O. Stereo-selective Z-bromo enol lactonization was carried out by Br+-induced lactonization in the presence of Ag+. E-Bromo enol lactonization with N-bromosuccinimide in CH2Cl2 in the presence of a small amount of water gave better yields and shorter reaction times than the traditional anhydrous conditions. In studies of the inhibitory activity of these lactones toward several proteases (reported in full elsewhere), we found that the alpha-alkyl-substituted protio and bromo enol lactones 1-3 were very good inhibitors of HLE, with k(a)/K(i) values ranging from 14 500 to 37 500 M-1 s-1; the beta-alkyl-substituted enol lactones 5-8 showed only moderate inhibition of HLE.

  DOI：

  10.1021/jo00059a049
• 作为产物：
  描述：

  4-戊炔-2-醇 在 吡啶 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 paraffin oil 为溶剂， 反应 1.0h， 生成 Diethyl 2-(4-pentynyl)malonate
  参考文献：
  名称：

  [EN] 1,4-DICARBONYL-PIPERIDYL DERIVATIVES
  [FR] DÉRIVÉS DE 1,4-DICARBONYLE-PIPÉRIDYLE

  摘要：

  式I中Z、W、Q、R和Y具有权利要求1中指示的含义的化合物是坦克酶的抑制剂，可用于治疗癌症、心血管疾病、中枢神经系统损伤和不同形式的炎症等疾病。

  公开号：

  WO2017076484A1

文献信息

• 1,4-dicarbonyl-piperidyl derivatives
  申请人：Merck Patent GmbH

  公开号：US10570116B2

  公开（公告）日：2020-02-25

  Compounds of the formula I in which Z, W, Q, R and Y have the meanings indicated in claim 1, are inhibitors of Tankyrase, and can be employed, inter alia, for the treatment of diseases such as cancer, cardiovascular diseases, central nervous system injury and different forms of inflammation.

  式 I 的化合物 其中 Z、W、Q、R 和 Y 的含义如权利要求 1 所示，是 Tankyrase 的抑制剂，可用于治疗癌症、心血管疾病、中枢神经系统损伤和不同形式的炎症等疾病。
• A New, Convenient Synthesis of Cyclopentene Derivatives
  作者：M. BELLASSOUED、Y. FRANGIN、M. GAUDEMAR

  DOI：10.1055/s-1978-24698

  日期：——
• BELLASSOUED M.; FRANGIN Y.; GAUDEMAR M., SYNTHESIS, 1978, NO 2, 150-152
  作者：BELLASSOUED M.、 FRANGIN Y.、 GAUDEMAR M.

  DOI：——

  日期：——
• 1,4-DICARBONYL-PIPERIDYL DERIVATIVES
  申请人：Merck Patent GmbH

  公开号：EP3371166A1

  公开（公告）日：2018-09-12