(Z)-1-acetyl-3-ethylidene-2,5-piperazinedione | 53736-76-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (Z)-1-acetyl-3-ethylidene-2,5-piperazinedione
• 英文别名: (Z)-1-acetyl-3-ethylidenepiperazine-2,5-dione；1-acetyl-3-ethylidene-piperazine-2,5-dione；1-Acetyl-3-ethylidinpiperazin-2,5-dion；1-Acetyl-3-eth-(Z)-ylidene-piperazine-2,5-dione；(3Z)-1-acetyl-3-ethylidenepiperazine-2,5-dione
• CAS: 53736-76-8
• 化学式: C₈H₁₀N₂O₃
• 分子量: 182.179
• InChiKey: QHGJYSHFKBLXAJ-UTCJRWHESA-N

物化性质

• 熔点：
  145 °C
• 沸点：
  475.3±45.0 °C(Predicted)
• 密度：
  1.349±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  66.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-1-acetyl-3-ethylidene-2,5-piperazinedione 在 potassium acetate 、 溶剂黄146 作用下， 以 溶剂黄146 为溶剂， 反应 36.0h， 生成 1-acetyl-3-methoxy-3-(1-(phenylselenyl)ethyl)-2,5-piperazinedione
  参考文献：
  名称：

  Comparative studies on the reactivity of 4-methylene-1-oxa-6,9-diazaspiro[4.5]decane-7,10-dione, 1-acetyl-3-hydroxy-3-vinyl-2,5-piperazinedione, and bicyclomycin. Examination of a key structural element necessary for bicyclomycin-mediated transformations

  摘要：

  Two select mimics, 4-methylene-1-oxa-6,9-diazaspiro[4.5]decane-7,10-dione (8) and 1-acetyl-3-hydroxy-3-vinyl-2, 5-piperazinedione (7) of the structurally novel antibiotic, bicyclomycin (1), have been prepared. Comparison of the chemical reactivity of 7 versus 1 both in the presence and absence of added nucleophiles at various "pH" values has provided important new information concerning the role of key structural elements present in bicyclomycin. The product profiles determined for 7 indicated that modification of the terminal double bond proceeded through an alpha,beta-unsaturated ring imine intermediate (i.e., 43). Correspondingly, activation of the exo-methylene group in bicyclomycin is believed to occur through initial hemiaminal bond scission to give a ring-opened alpha,beta-unsaturated carbonyl species (i.e., 2). Functionalization of the terminal double bond in 7 has been shown to proceed under milder conditions than that required for 1. These results demonstrated that incorporation of the exo-methylene group within the O(2)-C(3)-C(4)-C(5) bridge in 1 required that the terminal double bond activation pathway proceed by an alternative, energetically more-demanding pathway than that observed for 7. Ramifications of the decreased reactivity noted for 1 are to allow other functional groups (i.e., the C(1)-triol moiety) in the antibiotic to have important catalytic roles in the drug modification processes and to permit thiolate species (the proposed biological targets?) to effectively compete with other nucleophiles for 2.

  DOI：

  10.1021/jo00039a028
• 作为产物：
  描述：

  1,2,4-triacetylpiperazine-2,5-dione 在 lithium tri-t-butoxyaluminum hydride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以83%的产率得到(Z)-1-acetyl-3-ethylidene-2,5-piperazinedione
  参考文献：
  名称：

  活化的2，5-二酮哌嗪的跨瓣环重排：原始支架的关键途径。

  摘要：

  从活化的2，5-二酮哌嗪开始的有效且原始的立体控制的跨环重排已被开发，这对于药物化学领域来说是一个机会，该领域要求获得新型的生物支架。这种强力的环收缩可能与Chan重排的立体选择性氮杂相关，例如可以一步合成各种四酸，获得2-二取代他汀类药物，或合成相关的内酰胺约束的二肽模拟物。使用TRAL-RCM序列。

  DOI：

  10.1039/b810352f

文献信息

• Directed 1,3-dipolar cycloadditions of ylidene piperazine-2,5-diones
  作者：Christina L.L Chai、Alison J Edwards、Bronwyn A Wilkes、Ruth C.J Woodgate

  DOI：10.1016/j.tet.2003.09.040

  日期：2003.10

  The reactivities and selectivities of 1,3-dipolar cycloaddition reactions of ylidene piperazine-2,5-diones with mesitonitrile oxide are reported. The stereoselectivities of reactions with chiral ylidene piperazine-2,5-diones can be directed by judicious choice of substituents on the N- and/or C-substituents of the piperazinedione ring. (C) 2003 Elsevier Ltd. All rights reserved.
• Transannular rearrangement of activated 2,5-diketopiperazines: a key route to original scaffolds
  作者：Daniel Farran、Isabelle Parrot、Loïc Toupet、Jean Martinez、Georges Dewynter

  DOI：10.1039/b810352f

  日期：——

  original stereocontrolled transannular rearrangement starting from activated 2,5-diketopiperazines has been developed, an opportunity for the medicinal chemistry field, which requests access to novel biological scaffolds. This powerful ring contraction, which can be related to a stereoselective aza-version of the Chan rearrangement, allows for example the one-step synthesis of various tetramic acids, access

  从活化的2，5-二酮哌嗪开始的有效且原始的立体控制的跨环重排已被开发，这对于药物化学领域来说是一个机会，该领域要求获得新型的生物支架。这种强力的环收缩可能与Chan重排的立体选择性氮杂相关，例如可以一步合成各种四酸，获得2-二取代他汀类药物，或合成相关的内酰胺约束的二肽模拟物。使用TRAL-RCM序列。
• Comparative studies on the reactivity of 4-methylene-1-oxa-6,9-diazaspiro[4.5]decane-7,10-dione, 1-acetyl-3-hydroxy-3-vinyl-2,5-piperazinedione, and bicyclomycin. Examination of a key structural element necessary for bicyclomycin-mediated transformations
  作者：Yeong Soo Oh、Harold Kohn

  DOI：10.1021/jo00039a028

  日期：1992.6

  Two select mimics, 4-methylene-1-oxa-6,9-diazaspiro[4.5]decane-7,10-dione (8) and 1-acetyl-3-hydroxy-3-vinyl-2, 5-piperazinedione (7) of the structurally novel antibiotic, bicyclomycin (1), have been prepared. Comparison of the chemical reactivity of 7 versus 1 both in the presence and absence of added nucleophiles at various "pH" values has provided important new information concerning the role of key structural elements present in bicyclomycin. The product profiles determined for 7 indicated that modification of the terminal double bond proceeded through an alpha,beta-unsaturated ring imine intermediate (i.e., 43). Correspondingly, activation of the exo-methylene group in bicyclomycin is believed to occur through initial hemiaminal bond scission to give a ring-opened alpha,beta-unsaturated carbonyl species (i.e., 2). Functionalization of the terminal double bond in 7 has been shown to proceed under milder conditions than that required for 1. These results demonstrated that incorporation of the exo-methylene group within the O(2)-C(3)-C(4)-C(5) bridge in 1 required that the terminal double bond activation pathway proceed by an alternative, energetically more-demanding pathway than that observed for 7. Ramifications of the decreased reactivity noted for 1 are to allow other functional groups (i.e., the C(1)-triol moiety) in the antibiotic to have important catalytic roles in the drug modification processes and to permit thiolate species (the proposed biological targets?) to effectively compete with other nucleophiles for 2.