octa-4t,6t-dien-1-yn-3-ol | 135958-18-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: octa-4t,6t-dien-1-yn-3-ol
• 英文别名: (4E,6E)-octa-4,6-dien-1-yn-3-ol；octa-4t,6t-dien-1-yn-3-ol；Octa-4t,6t-dien-1-in-3-ol
• CAS: 135958-18-8
• 化学式: C₈H₁₀O
• 分子量: 122.167
• InChiKey: RLLKIJNPVVBTQZ-TWTPFVCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.11
• 重原子数：
  9.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  octa-4t,6t-dien-1-yn-3-ol 在 四氢呋喃 、 lithium aluminium tetrahydride 、 乙基溴化镁 作用下， 生成 hexadeca-2ξ,4ξ,6ξ,8ξ,10ξ,12ξ,14ξ-heptaene
  参考文献：
  名称：

  Investigation of a Mechanism for Accelerated Breakdown of Immune Tolerance to the Primary Biliary Cirrhosis–Associated Autoantigen, Pyruvate Dehydrogenase Complex

  摘要：

  Primary biliary cirrhosis (PBC) is an autoimmune liver disease characterized by autoreactive T- and B-cell responses to the highly conserved enzyme pyruvate dehydrogenase complex (PDC). In this study we have examined the breakdown of T-cell tolerance to self-PDC using a mouse model. Female SJL/J mice were sensitized intraperitoneally with foreign-PDC (bovine) and/or self-PDC (murine) in complete Freund's adjuvant, and serum, spleen, and liver tissue was taken 8 weeks later. Animals sensitized with foreign-PDC produced IgG antibodies that were reactive with both foreign and self-PDC, but splenic T cells from these animals only responded to stimulation with foreign PDC. Sensitization with self-PDC elicited neither antibodies nor reactive T cells. Significantly, cosensitization with mixed self-PDC and foreign-PDC resulted in a full breakdown of self-tolerance, with generation of both antibody and T-cell responses to self-PDC of the type seen exclusively in human PBC patients. Mild bile duct lesions deficient in CD8(+) T cells were seen 8 weeks after sensitization with either foreign or self-PDC. However, after sensitization with mixed self-PDC and foreign-PDC, these lesions were significantly larger and heavily infiltrated by CD8(+) T cells. Liver-infiltrating T cells derived from the self-PDC and foreign-PDC cosensitized but not from control animals showed reactivity with self-PDC, suggesting a possible role for autoreactive PDC-specific T-cell responses in the pathogenesis of the observed histologic changes. It is likely that B-cell cross-reactivity between foreign and self-PDC enhances the potential for breakdown of T-cell self-tolerance by allowing efficient presentation of self-antigens in the inoculum. This model may provide a useful system for investigating the etiology and treatment of PBC.

  DOI：

  10.1038/labinvest.3780413
• 作为产物：
  描述：

  (E,E)-2,4-己二烯醛 在 四丁基氟化铵 、 甲基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 3.0h， 生成 octa-4t,6t-dien-1-yn-3-ol
  参考文献：
  名称：

  脱水亚乙基–Co2（CO）6离子：生成，反应性和阳离子稳定性评估

  摘要：

  所述dehydrotropylium钴2（CO）6，通过HBF的作用产生的离子4或BF 3 ⋅ OET 2上的相应cycloheptadienynol复杂，这反过来又在四个步骤制备从一个已知diacetoxycycloheptenyne复杂。环庚二烯炔诺醇络合物通过脱氢tropylium-Co 2（CO）6离子与几个亲核试剂的反应导致与反应性亲核试剂的取代反应（N> 1），并在反应性较低的亲核试剂存在下进行自由基二聚化反应。环庚二烯醇复合物与无环三烯醇复合物的竞争性反应显示，与无环阳离子相比，偏氢萘乙酰-Co 2（CO）6离子的生成没有偏爱。DFT研究了脱氢吡啶鎓-Co 2（CO）6离子，特别是对其芳香族（HOMA）值（+0.95）的谐波振荡器模型，基于同链反应的稳定能（≈2.8kcal mol -1）及其NICS（1）值（-2.9），连同实验研究一起表明，脱氢吡啶鎓-Co 2（CO）6离子是弱芳香族的。

  DOI：

  10.1002/chem.201002685

文献信息

• Gold-Catalyzed Oxidative Cyclization Involving Nucleophilic Attack to the Keto Group of α,α′-Dioxo Gold Carbene and 1,2-Alkynyl Migration: Synthesis of Furan-3-carboxylates
  作者：Ali Wang、Mingduo Lu、Yuanhong Liu

  DOI：10.1021/acs.orglett.1c02389

  日期：2021.9.3

  for the synthesis of functionalized furan-3-carboxylates based on gold-catalyzed oxidative cyclization of diynones with alcohols or water has been developed. Mechanistic studies revealed that a rare nucleophilic attack to the carbonyl group of the α,α′-dioxo gold carbene instead of the carbene center and 1,2-alkynyl group migration were involved in this transformation. This method offers several advantages

  基于金催化二炔酮与醇或水的氧化环化，开发了一种用于合成功能化呋喃-3-羧酸酯的多组分策略。机理研究表明，对 α,α'-二氧代金卡宾的羰基的罕见亲核攻击而不是卡宾中心和 1,2-炔基迁移参与了这种转变。该方法具有多种优势，例如条件温和、区域选择性和化学选择性高以及官能团兼容性广。
• Investigation of a Mechanism for Accelerated Breakdown of Immune Tolerance to the Primary Biliary Cirrhosis–Associated Autoantigen, Pyruvate Dehydrogenase Complex
  作者：David E J Jones、Jeremy M Palmer、Kate Bennett、Amanda J Robe、Stephen J Yeaman、Helen Robertson、Margaret F Bassendine、Alastair D Burt、John A Kirby

  DOI：10.1038/labinvest.3780413

  日期：2002.2

  Primary biliary cirrhosis (PBC) is an autoimmune liver disease characterized by autoreactive T- and B-cell responses to the highly conserved enzyme pyruvate dehydrogenase complex (PDC). In this study we have examined the breakdown of T-cell tolerance to self-PDC using a mouse model. Female SJL/J mice were sensitized intraperitoneally with foreign-PDC (bovine) and/or self-PDC (murine) in complete Freund's adjuvant, and serum, spleen, and liver tissue was taken 8 weeks later. Animals sensitized with foreign-PDC produced IgG antibodies that were reactive with both foreign and self-PDC, but splenic T cells from these animals only responded to stimulation with foreign PDC. Sensitization with self-PDC elicited neither antibodies nor reactive T cells. Significantly, cosensitization with mixed self-PDC and foreign-PDC resulted in a full breakdown of self-tolerance, with generation of both antibody and T-cell responses to self-PDC of the type seen exclusively in human PBC patients. Mild bile duct lesions deficient in CD8(+) T cells were seen 8 weeks after sensitization with either foreign or self-PDC. However, after sensitization with mixed self-PDC and foreign-PDC, these lesions were significantly larger and heavily infiltrated by CD8(+) T cells. Liver-infiltrating T cells derived from the self-PDC and foreign-PDC cosensitized but not from control animals showed reactivity with self-PDC, suggesting a possible role for autoreactive PDC-specific T-cell responses in the pathogenesis of the observed histologic changes. It is likely that B-cell cross-reactivity between foreign and self-PDC enhances the potential for breakdown of T-cell self-tolerance by allowing efficient presentation of self-antigens in the inoculum. This model may provide a useful system for investigating the etiology and treatment of PBC.
• Dehydrotropylium-Co2(CO)6 Ion: Generation, Reactivity and Evaluation of Cation Stability
  作者：Sheida Amiralaei、James Gauld、James R. Green

  DOI：10.1002/chem.201002685

  日期：2011.4.4

  conditions, and a radical dimerisation reaction in the presence of less reactive nucleophiles. Competitive reactions of the cycloheptadienynol complex with an acyclic trienynol complex show no preference for generation of the dehydrotropylium–Co2(CO)6 ion over an acyclic cation. DFT studies on the dehydrotropylium–Co2(CO)6 ion, specifically evaluation of its harmonic oscillator model of aromaticity

  所述dehydrotropylium钴2（CO）6，通过HBF的作用产生的离子4或BF 3 ⋅ OET 2上的相应cycloheptadienynol复杂，这反过来又在四个步骤制备从一个已知diacetoxycycloheptenyne复杂。环庚二烯炔诺醇络合物通过脱氢tropylium-Co 2（CO）6离子与几个亲核试剂的反应导致与反应性亲核试剂的取代反应（N> 1），并在反应性较低的亲核试剂存在下进行自由基二聚化反应。环庚二烯醇复合物与无环三烯醇复合物的竞争性反应显示，与无环阳离子相比，偏氢萘乙酰-Co 2（CO）6离子的生成没有偏爱。DFT研究了脱氢吡啶鎓-Co 2（CO）6离子，特别是对其芳香族（HOMA）值（+0.95）的谐波振荡器模型，基于同链反应的稳定能（≈2.8kcal mol -1）及其NICS（1）值（-2.9），连同实验研究一起表明，脱氢吡啶鎓-Co 2（CO）6离子是弱芳香族的。