diethyl <(3-oxo-1-cyclopenten-1-yl)methyl>phosphonate | 134891-98-8

• 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 <(3-oxo-1-cyclopenten-1-yl)methyl>phosphonate
• 英文别名: 3-<(diethoxyphosphoryl)methyl>cyclopent-2-enone；3-[(diethoxyphosphoryl)methyl]cyclopent-2-enone；3-(Diethoxyphosphorylmethyl)cyclopent-2-en-1-one
• CAS: 134891-98-8
• 化学式: C₁₀H₁₇O₄P
• 分子量: 232.216
• InChiKey: MXLFKYNWYYIIIP-UHFFFAOYSA-N

物化性质

• 沸点：
  344.4±31.0 °C(Predicted)
• 密度：
  1.158±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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 <(3-oxo-1-cyclopenten-1-yl)methyl>phosphonate 在 咪唑 、 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 21.0h， 生成 diethyl 2-[3-(tert-butyldiphenylsiloxy)-1-cyclopenten-1-yl]methylphosphonate
  参考文献：
  名称：

  通过7-氧代-2,8-链二烯基酯的还原环化反应构建取代的环己酮。

  摘要：

  [反应：见正文]与三苯基膦铜氢化物六聚物立体反应时，对7-氧代-2,8-链二烯基酯的环化反应选择性地产生了取代的环己酮，其在C2和C3处具有碳侧链的顺式关系。这种环己酮结构对于制备4-烷氧基-或4-甲硅烷氧基-2,3-二取代的环己酮特别有用，在这种情况下立体选择为>或= 20：1。

  DOI：

  10.1021/ol0169325
• 作为产物：
  描述：

  diethyl (phenylselanyl)methylphosphonate 在 正丁基锂 、 双氧水 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 diethyl <(3-oxo-1-cyclopenten-1-yl)methyl>phosphonate
  参考文献：
  名称：

  α-膦酸碳负离子与环烯酮的强制共轭加成合成 3-(磷酰甲基)环烯酮

  摘要：

  发现环烯酮与 α-锂化二乙基（苯基硒基）甲基膦酸酯优先或仅在羰基处反应，产生 1,2-加合物。当环烯酮与三(2,6-二苯基苯氧基)铝的配合物用于该反应时，观察到区域选择性1,4-加成。如此形成的1，4-加合物在氧化后得到相应的3-（磷酰基甲基）环烷-2-烯酮。后一种化合物的另一种方法涉及将锂硫甲基膦酸二乙酯 1,4-加成到 2-亚磺酰基环烷-2-烯酮上，然后消除亚砜。

  DOI：

  10.1055/s-2007-965982

文献信息

• Reaction of Phosphonate-Stabilized Carbanions with Cyclic Enones Bearing a .beta.-Leaving Group
  作者：Malose J. Mphahlele、Tomasz A. Modro

  DOI：10.1021/jo00130a024

  日期：1995.12

  Reaction between alpha-lithiated alkylphosphonic esters and alpha,beta-unsaturated cyclopentenones and cyclohexenones carrying a heteroatom substituent Y in the beta-position was studied. Complete chemoselectivity was observed as a function of substituent Y. For Y = OMe exclusive addition-elimination at the beta-carbon was observed, yielding alpha,beta-unsaturated delta-ketophosphonates. The beta-chloro-substituted substrates (Y = Cl) derived from cyclohexenone reacted exclusively at the carbonyl carbon, yielding (2-hydroxyalkyl)phosphonates with the retained chlorovinyl function. The alcohols, depending on the conditions, could be dehydrated to two different products. The reaction of 3-chlorocyclopent-2-en-1-one with diethyl (lithiomethyl)phosphonate occurred at the beta-carbon, but the ketophosphonate product was isolated in a stable enolic form.
• Mikina, Maciej; Mikolajczyk, Marian, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 75, # 1-4, p. 39 - 42
  作者：Mikina, Maciej、Mikolajczyk, Marian

  DOI：——

  日期：——
• A general approach to 3-phosphorylmethyl cycloalkenones by intramolecular Horner-Wittig reaction of bis-.beta.-ketophosphonates
  作者：Marian Mikolajczk、Maciej Mikina

  DOI：10.1021/jo00101a041

  日期：1994.11

  The reaction of dicarboxylic acid diesters with lithiomethylphosphonates was found to give bis-beta-keto phosphonates 1 [(RO)(2)P(O)CH2C(O)](2)(CH2)(n) (n = 2, 3, 4), a new class of compounds. Their cyclization under basic conditions provides an easy access to five-, six- and seven-membered 3-phosphorylmethyl cycloalkenones 2. The cyclization of 1,6-bis(dialkoxyphosphoryl)hexan-2,5-dione (1a,d) was found to be bidirectional in course and a competition between the intramolecular Horner-Wittig and Knoevenagel reaction was observed. It was demonstrated that the latter reaction is reversible which allows conversion of the Knoevenagel reaction product into the Horner-Wittig reaction product (for example 5b into 2d). Two efficient methods for the synthesis of 2- and 3-functionalized cycloalkenones 6 and 7 involving alkylation and olefination of the cycloalkenones 2 anion were devised.
• Ohler; Zbiral, Synthesis, 1991, # 5, p. 357 - 361
  作者：Ohler、Zbiral

  DOI：——

  日期：——
• Mikolajczyk Marian, Mikina Maciej, J. Org. Chem., 59 (1994) N 22, S 6760-6765
  作者：Mikolajczyk Marian, Mikina Maciej

  DOI：——

  日期：——