diethyl cyclohexylethynylphosphonate | 30238-20-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl cyclohexylethynylphosphonate
• 英文别名: (2-cyclohexyl-etynyl)-phosphonic acid diethyl ester；Diaethylcyclohexylaethinylphosphonat；2-diethoxyphosphorylethynylcyclohexane
• CAS: 30238-20-1
• 化学式: C₁₂H₂₁O₃P
• 分子量: 244.271
• InChiKey: IDZTVWYOVZUXTO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  diethyl cyclohexylethynylphosphonate 在 四(三苯基膦)钯 作用下， 以 1,4-二氧六环 为溶剂， 反应 5.0h， 以45%的产率得到(E)-diethyl cyclohex-2-enylidenemethylphosphonate
  参考文献：
  名称：

  Isomerization of Diethyl 1-Alkynylphosphonates to 1,3-Dienylphosphonates Followed by Diels-Alder Reaction with Dead, Maleic Anhydride and Maleimide

  摘要：

  Isomerization of diethyl 1-alkynylphosphonates, 1, with Pd[(PPh)(3)](4) in refluxing 1,4-dioxane provides 1,3-dienylphosphonates, 2, in satisfactory to excellent isolated yield (45-83%). The reaction is tolerant of chlorides and cyclic substituents. Cycloaddition reaction of 2 with DEAD provided the corresponding diethyl 3-(diethoxyphosphoryl)-6-alkyl-3,6-dihydropyridazine-1,2-dicarboxylates, 3, in 85% isolated yield. The cycloaddition products can be obtained in a one-pot reaction directly from the isomerized 1-alkynylphosphonates with no loss in yields. Similarly, 1,3-dioxo-1,3,3a,4,7,7a-hexahydroisobenzofuran-4-ylphosphonate, and 1,3-dioxo-2,3,3a,4,7,7a-hexahydro-1H-isoindo1-4-ylphosphonate 4 were obtained by reacting 1,3-dienylphosphonates with maleic anhydride and maleimide respectively.

  DOI：

  10.3987/com-10-s(e)12
• 作为产物：
  描述：

  (cyclohexylethynyl)magnesium bromide 、 氯磷酸二乙酯 以 四氢呋喃 为溶剂， 以12.7%的产率得到diethyl cyclohexylethynylphosphonate
  参考文献：
  名称：

  Substituted ethynylphosphonates and their anticholinesterase activity

  摘要：

  DOI：

  10.1007/bf00962510

文献信息

• Ruthenium-Catalyzed [2 + 2] Cycloadditions of Bicyclic Alkenes with Alkynyl Phosphonates
  作者：Neil Cockburn、Elham Karimi、William Tam

  DOI：10.1021/jo9010206

  日期：2009.8.7

  Ruthenium-catalyzed [2 + 2] cycloadditions of bicyclic alkenes with alkynyl phosphonates were investigated. The phosphonate moieties were found to be compatible with the Ru-catalyzed cycloadditions giving the corresponding cyclobutene cycloadducts in low to excellent yield (up to 96%). Alkynyl phosphonates showed lower reactivity than other heteroatom-substituted alkynes such as alkynyl halides, ynamides

  研究了钌催化的双环烯烃与炔基膦酸酯的[2 + 2]环加成反应。发现膦酸酯部分与Ru催化的环加成物相容，从而以低至优异的产率（高达96％）给出相应的环丁烯环加合物。炔基膦酸酯的反应性比其他杂原子取代的炔烃（如炔基卤化物，乙酰胺，炔基硫醚和炔基砜）低，并且需要更高的反应温度和更长的反应时间。
• Ruthenium-Catalyzed Homo Diels–Alder [2 + 2 + 2] Cycloadditions of Alkynyl Phosphonates with Bicyclo[2.2.1]hepta-2,5-diene
  作者：Tanner J. Kettles、Neil Cockburn、William Tam

  DOI：10.1021/jo2010928

  日期：2011.8.19

  Ruthenium-catalyzed homo Diels–Alder [2 + 2 + 2] cycloadditions between alkynyl phosphonates and bicyclo[2.2.1]hepta-2,5-diene were studied. The observed reactivity was found to be dependent on the presence of the phosphonate moiety. The Ru-catalyzed cycloaddition was compatible with a variety of aromatic and aliphatic substituted alkynyl phosphonates, providing the corresponding phosphonate substituted

  研究了炔基膦酸酯与双环[2.2.1]庚-2,5-二烯之间钌催化的均Diels-Alder [2 + 2 + 2]环加成反应。发现观察到的反应性取决于膦酸酯部分的存在。Ru催化的环加成反应可与多种芳族和脂族取代的炔基膦酸酯相容，从而以低至良好的收率（高达88％）提供相应的膦酸酯取代的δ-环戊烯。
• Gold(I)-Catalyzed Hydration of Alkynylphosphonates: Efficient Access to β-Ketophosphonates
  作者：Longyong Xie、Rui Yuan、Ruijia Wang、Zhihong Peng、Jiannan Xiang、Weimin He

  DOI：10.1002/ejoc.201400066

  日期：2014.5

  A general, efficient, and highly regioselective protocol with the use of a gold(I) complex catalytic system for the transformation of alkynylphosphonates into the corresponding β-ketophosphonates has been successfully developed. This method produces a variety of β-ketophosphonates with the advantages of mild reaction conditions, high functional-group tolerance, and excellent yields.

  已成功开发了一种通用、高效且高度区域选择性的方案，该方案使用金 (I) 络合物催化系统将炔基膦酸酯转化为相应的 β-酮膦酸酯。该方法可生产多种β-酮膦酸酯，具有反应条件温和、官能团耐受性高、收率高等优点。
• Regio- and stereoselective preparation of dienylcarboxylic acids and dienylphosphonic esters using a (Z)-alkenyl sulfone–titanocene(II) system
  作者：Akitoshi Ogata、Masami Nemoto、Yoshitaka Takano、Akira Tsubouchi、Takeshi Takeda

  DOI：10.1016/j.tetlet.2008.03.055

  日期：2008.5

  Titanocene(II)-promoted alkenylation of functionalized alkynes with (Z)-alkenyl sulfones proceeded with high regio- and stereoselectivity to produce functionalized dienes. Conjugated dienylcarboxylic acids and dienylphosphonic esters were obtained using acetylenic lithium carboxylates and dialkyl phosphonates as starting materials.

  钛茂茂（II）促进的功能化炔烃与（Z）-烯基砜的烯基化反应具有很高的区域选择性和立体选择性，从而可以生成功能化的二烯。以炔属羧酸锂和膦酸二烷基酯为起始原料，得到共轭二烯基羧酸和二烯基膦酸酯。
• Transformation of alkynyl sulfones into alkynylphosphonates with trialkyl phosphites
  作者：Yasutaka Yatsumonji、Akitoshi Ogata、Akira Tsubouchi、Takeshi Takeda

  DOI：10.1016/j.tetlet.2008.02.013

  日期：2008.3

  1-Alkynylphosphonates were obtained in good to high yields by simple heating of 1-alkynyl sulfones with trialkyl phosphites.

  通过简单地将1-炔基砜与亚磷酸三烷基酯一起加热，可以以高至高产率获得1-炔基膦酸酯。