2-(Diethoxyphosphinyl)cycloheptanone | 136213-60-0

• 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: 2-(Diethoxyphosphinyl)cycloheptanone
• 英文别名: 2-Diethoxyphosphorylcycloheptan-1-one
• CAS: 136213-60-0
• 化学式: C₁₁H₂₁O₄P
• 分子量: 248.259
• InChiKey: AMFRWGIORSCYJR-UHFFFAOYSA-N

物化性质

• 沸点：
  357.0±31.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 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：

  2-(Diethoxyphosphinyl)cycloheptanone 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 2-((2SR,6SR)-6-hexyltetrahydropyran-2-yl)cycloheptanone
  参考文献：
  名称：

  测量在吡喃和相邻环之间形成碳-碳键的方法。

  摘要：

  我们已经研究了在立体中心已经存在的连续环之间立体选择性地形成碳-碳键的几种方法。所研究的方法是：环状乙烯基乙缩醛的[1,3]氧至碳重排，在原位生成的氧碳鎓离子中添加分子间烯醇硅烷，拴系的烷氧基烯酮的分子内共轭物添加以及几种α-吡喃基环烷酮的差向异构化。已经发现这些途径在几种情况下是互补的，并且使得能够以优异的产率和优异的非对映选择性形成反式：反式和顺式：反式立体异构体。我们已经通过化学相关性证明了C2-C2'的相对立体化学为1-2。

  DOI：

  10.1016/j.tet.2006.02.042
• 作为产物：
  描述：

  二乙基亚磷酰氯 、 环庚酮 生成 2-(Diethoxyphosphinyl)cycloheptanone
  参考文献：
  名称：

  Reaction of diethyl phosphorochloridite with enolates: a general method for synthesis of .beta.-keto phosphonates and .alpha.-phosphono esters through carbon-phosphorus bond formation

  摘要：

  The reaction of ketone enolates with diethyl phosphorochloridite, followed by air oxidation of the immediate reaction products, has proven to be a general and convenient method for preparation of beta-keto phosphonates. Fourteen beta-keto phosphonates have been prepared by this method, in an average yield greater than 60%. This procedure also appears to be applicable to preparation of both alpha-phosphono aldehydes and alpha-phosphono esters. Although special precautions may be necessary to avoid aldol condensation during formation of aldehyde enolates, in two cases it was shown that the resulting enolates react readily with diethyl chlorophosphite. Finally, a set of five ethyl esters was converted to alpha-phosphono esters by this method. Yields of the alpha-phosphono esters are influenced by steric hindrance at the enolate carbon, but the average yield for this series was ca. 70%. Because this synthetic method relies upon an electrophilic phosphorus reagent for formation of the C-P bond, it is complementary to the traditional Arbuzov synthesis. On the basis of the 21 examples presented here, it appears to be more widely applicable.

  DOI：

  10.1021/jo00019a016

文献信息

• Synthesis of Multisubstituted 1,2,3-Triazoles: Regioselective Formation and Reaction Mechanism
  作者：Tzu-Ching Chi、Po-Chun Yang、Shao-Kung Hung、Hui-Wen Wu、Hong-Chi Wang、Hsin-Kuan Liu、Li-Wen Liu、Ho-Hsuan Chou

  DOI：10.1021/acs.joc.3c02836

  日期：2024.4.19

  synthetically useful approach to functionalized triazoles is described via the reaction of β-carbonyl phosphonates and azides. 1,4- and 1,5-disubstituted and 1,4,5-trisubstituted triazoles can be regio- and chemoselectively accessed under mild conditions in good to excellent yields (31 examples, up to 99%). A mechanism is proposed that rationalizes the avoidance of the 4-phosphonate byproducts, which

  通过β-羰基膦酸酯和叠氮化物的反应描述了一种合成功能化三唑的有用方法。 1,4-和1,5-二取代和1,4,5-三取代三唑可以在温和条件下以区域选择性和化学选择性获得，产率良好至优异（31个例子，高达99%）。提出了一种合理避免 4-膦酸酯副产物的机制，该机制与晶体学和实验证据一致。
• Ring Expansion Reactions of Cyclic .beta.-Keto Phosphonates
  作者：Suzanne M. Ruder、Vithalanand R. Kulkarni

  DOI：10.1021/jo00115a024

  日期：1995.5

  Phosphonate stabilized anions derived from a variety of cyclic beta-keto phosphonates were shown to react with dimethyl acetylenedicarboxylate to afford [n + 2] ring expansion products. Highly substituted medium sized rings containing phosphonate functionality were thus obtained in reasonable yields. The reaction was found to proceed via a tandem Michael-aldol-fragmentation mechanism to give the ring enlarged products. An alternate competing pathway involving an ''abnormal Michael'' reaction was also shown to exist, resulting in a net 1,3-phosphorus migration, without ring expansion. Furthermore, the electronic and steric character of the carbonyl moiety of the cyclic beta-keto phosphonates were shown to be very crucial in determining the course of the reaction.
• Preparation of spirocyclic cyclopropyl ketones through condensation of epoxides with .beta.-keto phosphonates
  作者：Thomas E. Jacks、Heidi Nibbe、David F. Wiemer

  DOI：10.1021/jo00069a018

  日期：1993.8

  The beta-keto phosphonate derivatives of several cyclic ketones have been shown to undergo condensation with epoxides upon treatment with base, affording spirocyclic cyclopropyl ketones. Moderate to reasonable yields were obtained under sealed tube conditions with ethylene oxide, propylene oxide, and styrene oxide, and the substituted epoxides gave a single diastereomer in each case. The process can be viewed as an example of regiospecific geminal dialkylation, and cleavage of the cyclopropyl ring allows access to additional alpha,alpha-dialkylated ketones.
• Surveying approaches to the formation of carbon–carbon bonds between a pyran and an adjacent ring
  作者：Jeffrey D. Frein、Tomislav Rovis

  DOI：10.1016/j.tet.2006.02.042

  日期：2006.5

  We have examined several methods for the stereoselective formation of carbon-carbon bonds between contiguous rings where a stereogenic center is already present. The approaches investigated were a [1,3] oxygen to carbon rearrangement of cyclic vinyl acetals, an intermolecular enolsilane addition into an in situ generated oxocarbenium ion, an intramolecular conjugate addition of tethered alkoxy enones

  我们已经研究了在立体中心已经存在的连续环之间立体选择性地形成碳-碳键的几种方法。所研究的方法是：环状乙烯基乙缩醛的[1,3]氧至碳重排，在原位生成的氧碳鎓离子中添加分子间烯醇硅烷，拴系的烷氧基烯酮的分子内共轭物添加以及几种α-吡喃基环烷酮的差向异构化。已经发现这些途径在几种情况下是互补的，并且使得能够以优异的产率和优异的非对映选择性形成反式：反式和顺式：反式立体异构体。我们已经通过化学相关性证明了C2-C2'的相对立体化学为1-2。
• Reaction of diethyl phosphorochloridite with enolates: a general method for synthesis of .beta.-keto phosphonates and .alpha.-phosphono esters through carbon-phosphorus bond formation
  作者：Koo Lee、David F. Wiemer

  DOI：10.1021/jo00019a016

  日期：1991.9

  The reaction of ketone enolates with diethyl phosphorochloridite, followed by air oxidation of the immediate reaction products, has proven to be a general and convenient method for preparation of beta-keto phosphonates. Fourteen beta-keto phosphonates have been prepared by this method, in an average yield greater than 60%. This procedure also appears to be applicable to preparation of both alpha-phosphono aldehydes and alpha-phosphono esters. Although special precautions may be necessary to avoid aldol condensation during formation of aldehyde enolates, in two cases it was shown that the resulting enolates react readily with diethyl chlorophosphite. Finally, a set of five ethyl esters was converted to alpha-phosphono esters by this method. Yields of the alpha-phosphono esters are influenced by steric hindrance at the enolate carbon, but the average yield for this series was ca. 70%. Because this synthetic method relies upon an electrophilic phosphorus reagent for formation of the C-P bond, it is complementary to the traditional Arbuzov synthesis. On the basis of the 21 examples presented here, it appears to be more widely applicable.