3-<(diethoxyphosphoryl)methyl>cyclohex-2-enone | 134891-99-9

• 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: 3-<(diethoxyphosphoryl)methyl>cyclohex-2-enone
• 英文别名: diethyl <(3-oxo-1-cyclohexen-1-yl)methyl>phosphonate；3-[(diethoxyphosphoryl)methyl]cyclohex-2-enone；diethyl (3-oxocyclohex-1-enyl)methylphosphonate；Phosphonic acid, [(3-oxo-1-cyclohexen-1-yl)methyl]-, diethyl ester；3-(diethoxyphosphorylmethyl)cyclohex-2-en-1-one
• CAS: 134891-99-9
• 化学式: C₁₁H₁₉O₄P
• 分子量: 246.243
• InChiKey: JTHDOWLUEUXYNO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  3-<(diethoxyphosphoryl)methyl>cyclohex-2-enone 在 盐酸羟胺 、 sodium acetate 作用下， 以 乙醇 为溶剂， 反应 1.5h， 以85%的产率得到diethyl (3-oximinocyclohex-1-enyl)methylphosphonate
  参考文献：
  名称：

  环和侧链取代的 3-膦基甲基环己烯酮的 O-甲磺肟衍生物的 NEBER 重排

  摘要：

  摘要 环和侧链取代的 3-膦酰基甲基环己烯酮的 O-甲磺酰肟衍生物经过碱性氧化铝促进的 Neber 重排，区域选择性地得到相应的乙烯基氨基环己烯酮烷基膦酸酯。没有检测到预期的贝克曼重排产生的产物。

  DOI：

  10.1080/10426509708040503
• 作为产物：
  描述：

  diethyl <(1-hydroxy-3-chloro-2-cyclohexen-1-yl)methyl>phosphonate 在 硫酸 作用下， 以 氯仿 为溶剂， 反应 0.08h， 以80%的产率得到3-<(diethoxyphosphoryl)methyl>cyclohex-2-enone
  参考文献：
  名称：

  Reaction of Phosphonate-Stabilized Carbanions with Cyclic Enones Bearing a .beta.-Leaving Group

  摘要：

  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.

  DOI：

  10.1021/jo00130a024

文献信息

• Synthesis of 3-(Phosphorylmethyl)cycloalkenones by Forced Conjugate Addition of α-Phosphonate Carbanions to Cyclic Enones
  作者：Marian Mikolajczyk、Wieslawa Perlikowska

  DOI：10.1055/s-2007-965982

  日期：2007.4

  group giving 1,2-adducts. When complexes of cycloalkenones with aluminum tris(2,6-diphenylphenoxide) were used for this reaction, regioselective 1,4-addition was observed. Upon oxidation the thus-formed 1,4-adducts gave the corresponding 3-(phosphorylmethyl)cycloalk-2-enones. An alternative approach to the latter compounds involved 1,4-addition of diethyl lithiomethylphosphonate to 2-sulfinylcycloalk-2-enones

  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。
• Mphahlele, Malose J.; Pienaar, Andre; Modro, Tomasz A., Journal of the Chemical Society. Perkin Transactions 2 (2001), 1996, vol. 7, p. 1455 - 1460
  作者：Mphahlele, Malose J.、Pienaar, Andre、Modro, Tomasz A.

  DOI：——

  日期：——
• Structurally Simple Dipolar Organic Dyes Featuring 1,3-Cyclohexadiene Conjugated Unit for Dye-Sensitized Solar Cells
  作者：Kuan-Fu Chen、Ying-Chan Hsu、Qiongyou Wu、Ming-Chang P. Yeh、Shih-Sheng Sun

  DOI：10.1021/ol802630x

  日期：2009.1.15

  A series of structurally simple dipolar light-harvesting organic dyes featuring 1,3-cyclohexadiene in the aromatic pi framework for dye-sensitized solar cells has been synthesized and characterized. The highest conversion efficiency of the DSSCs based on these dyes can reach up to 4.4%.
• 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.