p-Chlorphenyl-trimethylsilylethinylketon | 37166-46-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: p-Chlorphenyl-trimethylsilylethinylketon
• 英文别名: p-Chlorphenyltrimethylsilylaethinylketon；1-(4-Chlorophenyl)-3-trimethylsilylprop-2-yn-1-one
• CAS: 37166-46-4
• 化学式: C₁₂H₁₃ClOSi
• 分子量: 236.773
• InChiKey: VMTYDZCTSOSCFT-UHFFFAOYSA-N

物化性质

• 沸点：
  107 °C(Press: 0.1 Torr)
• 密度：
  1.086±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  p-Chlorphenyl-trimethylsilylethinylketon 在 sodium tetraborate decahydrate 作用下， 以 甲醇 、 水 为溶剂， 以26 %的产率得到1-(4-氯苯基)丙-2-炔-1-酮
  参考文献：
  名称：

  1,1,1,3,3,3-六氟异丙醇和PPh3为助催化剂通过醇与炔酮的α-加成选择性合成α-烷氧基烯酮

  摘要：

  证明了醇与炔酮的 α-加成。一系列α-烷氧基烯酮可以在温和条件下以中等到高产率直接合成。通过各种方式进行了机理研究。

  DOI：

  10.1002/ejoc.202201163
• 作为产物：
  描述：

  1-(4-chlorophenyl)-3-(trimethylsilyl)prop-2-yn-1-ol 在 重铬酸吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 p-Chlorphenyl-trimethylsilylethinylketon
  参考文献：
  名称：

  Cascade and Effective Syntheses of Functionalized Tellurophenes

  摘要：

  A one-pot and transition-metal-catalyst-free synthetic strategy to construct functionalized tellurophenes has been developed. Substituted 1,1-dibromo-l-en-3-ynes are smoothly converted to tellurophenes with telluride salts in high yield via a series of cascade reactions through reductive debromination, hydrotelluration, nucleophilic cyclization, and aromatization. Close inspection of the results clearly showed that the reactivity of in situ prepared telluride salts are significantly influenced by the polarity of the solvent system and the electronic nature of the substituent on the enyne substrate. This method reports the first direct synthesis of 3-aryltellurophenes in high yields at room temperature. This novel reaction strategy is also found to be a promising synthetic method for multisubstituted tellurophenes and selenophenes.

  DOI：

  10.1021/acs.orglett.8b00279

文献信息

• Kinetic resolution of donor-functionalised tertiary alcohols by Cu–H-catalysed stereoselective silylation using a strained silicon-stereogenic silane
  作者：Betül Karatas、Sebastian Rendler、Roland Fröhlich、Martin Oestreich

  DOI：10.1039/b802186d

  日期：——

  A series of propargylic tertiary alcohols decorated with an sp2-hybridised nitrogen donor were kinetically resolved by reagent-controlled dehydrogenative Si–O coupling with a strained, highly reactive silicon-stereogenic cyclic silane.

  一系列由sp2杂化氮供体修饰的炔丙基叔醇通过反应物控制的脱氢硅氧偶联反应，实现了动力学拆分，该反应使用了一种具有高度反应性且硅立体中心固定的受限环硅烷。
• A phosphine-free, atom-efficient cross-coupling reaction of triorganoindiums with acyl chlorides catalyzed by immobilization of palladium(0) in MCM-41
  作者：Jiankang Miao、Bin Huang、Haiyi Liu、Mingzhong Cai

  DOI：10.1039/c7ra08355f

  日期：——

  first phosphine-free heterogeneous palladium(0)-catalyzed cross-coupling of triorganoindiums with acyl chlorides has been developed that proceeds smoothly in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable aryl ketones and α,β-acetylenic ketones with high atom-economy and high yield. This phosphine-free heterogeneous palladium(0) catalyst can be easily prepared

  已开发出首个无膦的异质钯（0）催化三有机铟与酰氯的交叉偶联反应，可在68°C的THF中顺利进行，并为合成各种有价值的芳基酮和α提供了通用而强大的工具，具有高原子经济性和高收率的β-炔酮。这种无膦的非均相钯（0）催化剂可以很容易地从市售试剂中制备，并可以通过简单过滤反应溶液进行回收，并至少进行10次连续试验而活性没有降低。我们的系统不仅避免使用膦配体，而且解决了钯催化剂回收和再利用的基本问题。
• Consecutive three- and four-component coupling-Bagley-Bohlmann-Rahtz syntheses of tri- and tetrasubstituted pyridines
  作者：Janis Dohe、Thomas J.J. Müller

  DOI：10.1515/znb-2016-0046

  日期：2016.6.1

  The concatenation of the modified Sonogashira alkynone synthesis and the Bagley-Bohlmann-Rahtz pyridine synthesis gives novel consecutive three- and four-component coupling-Bagley-Bohlmann-Rahtz (cBBR) syntheses of tri- and tetrasubstituted pyridines in a one-pot fashion. With these processes 15 differently substituted 3-ethoxycarbonyl 2-methylpyridines can be readily obtained in modest to moderate yields.

  修改后的Sonogashira炔酮合成与Bagley-Bohlmann-Rahtz吡啶合成的串联反应，以一锅法给出了新颖的连续三元和四元组分偶联-Bagley-Bohlmann-Rahtz (cBBR)合成方法，用于合成三取代和四取代吡啶。通过这些过程，可以轻松地以适度到中等产率获得15种不同取代的3-乙氧羰基-2-甲基吡啶。

• Friedel-crafts reactions of bis(trimethylsilyl)polyynes with acyl chlorides; a useful route to terminal-alkynyl ketones
  作者：D.R.M. Walton、F. Waugh

  DOI：10.1016/s0022-328x(00)89260-8

  日期：1972.4

  chloride-aluminium chloride complexes, XC6H4 COCl·AlCl3 in methylene chloride at 0–20° to form the corresponding ketones XC6H4CO(CC)nSiMe3 in excellent (n = 1) or moderate (n = 2, 4) yield. Treatment of the products with aqueous methanolic borax results in virtually quantitative liberation of the terminal alkynyl ketones XC6H4CO(CC)nH. The method provides the first practical route to the ketotetraynes (n = 4) and

  双（三甲基甲硅烷基）乙炔Me 3 Si（CC）n SiMe 3与酰氯-氯化铝络合物XC 6 H 4 COCl·AlCl 3在二氯甲烷中于0-20°反应形成相应的酮XC 6 H 4 CO（CC）n SiMe 3具有极好（n = 1）或中等（n = 2，4）的产率。用含水甲醇硼砂处理产品实际上可定量释放末端炔基酮XC 6 H 4 CO（CC）nH.该方法提供了通向酮四炔的第一种实用途径（n＝ 4），并有用地补充了现有的用于酮-单炔和-二炔合成的氧化方法。与我草酰氯氯化-铝复合发生反应3 SiCCSiMe 3，得到新的甲硅烷基取代的杂环（I）：
• Elemental Iodine-CatalyzedCoupling of Alkynylsilanes with Acid Chlorides: A Facile Synthesisof α,β-Acetylenic Ketones
  作者：J. S. Yadav、B. V. Reddy、M. Sridhar Reddy

  DOI：10.1055/s-2003-41014

  日期：——

  Alkynylsilanes undergo coupling smoothly with acid chloridesin the presence of molecular iodine under mild reaction conditionsto afford the corresponding α,β-acetylenic ketonesin excellent yields in a short reaction time with high selectivity.

  烷基硅烷在温和反应条件下，与酸氯化物在分子碘存在下顺利耦合，生成相应的α,β-炔烃酮，产率优秀，反应时间短且选择性高。