methyl 9-(R,S)-hydroperoxy-10-trans,12-cis-octadecadienoate | 60900-57-4

• 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: methyl 9-(R,S)-hydroperoxy-10-trans,12-cis-octadecadienoate
• 英文别名: (10E,12Z)-9-hydroperoxyoctadecadienoic acid methyl ester；methyl 9-hydroperoxy-10-trans-12-cis-octadecadienoate；methyl 9-hydroperoxy-trans-10,cis-12-octadecadienoate；9-hydroperoxy-trans-10, cis-12-octadecadienoate；methyl 10E,12Z-9-hydroperoxyoctadecadienoate；Methyl 9-Hydroperoxy-trans-10,cis-12-octadecadienoat；10,12-Octadecadienoic acid, 9-hydroperoxy-, methyl ester, (E,Z)-；methyl (10E,12Z)-9-hydroperoxyoctadeca-10,12-dienoate
• CAS: 60900-57-4
• 化学式: C₁₉H₃₄O₄
• 分子量: 326.477
• InChiKey: NAIVAZYIMZYEHW-BSZOFBHHSA-N

物化性质

• 沸点：
  444.7±38.0 °C(Predicted)
• 密度：
  0.968±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  23
• 可旋转键数：
  16
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 9-(R,S)-hydroperoxy-10-trans,12-cis-octadecadienoate 在 氢氧化钾 、 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.25h， 生成 (10E,12Z)-9-hydroxy-10,12-octadecadienoic acid
  参考文献：
  名称：

  Auto-Growth Inhibitory Substance from the Fresh-Water Cyanobacterium Phormidium tenue.

  摘要：

  蓝藻 P. tenue 的提取物对其自身生长表现出显著的抑制作用。生物测定导向的分级分离已导致对自我生长抑制物质的鉴定为一种脂肪酸混合物。亚油酸和亚麻酸等不饱和脂肪酸似乎主要负责自我生长抑制效应。

  DOI：

  10.1248/cpb.41.1863
• 作为产物：
  描述：

  (Z,Z)-9,12-十八烷二烯酸二聚物 、 重氮甲烷 生成 methyl 9-(R,S)-hydroperoxy-10-trans,12-cis-octadecadienoate
  参考文献：
  名称：

  NAGATA, RYU;MORIMOTO, SHINJI;SAITO, ISAO, TETRAHEDRON LETT., 31,(1990) N1, C. 4185-4188

  摘要：

  DOI：

文献信息

• Singlet-oxygen reactions sensitized on solid surfaces of lignin or titanium dioxide: Product studies from hindered secondary amines and from lipid peroxidation
  作者：L RC Barclay、M -C Basque、M R Vinqvist

  DOI：10.1139/v02-199

  日期：2003.6.1

  oxidation, whereas 5 or lignin coated with methyl linoleate acted as singlet-oxygen sensitizers, according to both prod- uct studies (method B) and the kinetic order in oxygen consumption during UV photolysis. Photolysis of phase- separated sensitizer (TiO2 or lignin) and substrate (methyl linoleate) resulted in typical singlet-oxygen products. These results indicate that singlet oxygen plays a significant

  产物分析和动力学方法用于确定单线态氧在木质素催化的有机底物氧化中的作用。方法 A 使用单线态氧（II 型）在 2,2,6,6-四甲基哌啶 1 或四甲基哌啶酮 2 上形成的硝基氧自由基的 ESR 分析。方法 B 使用 9- 和 13-亚油酸酯链氢过氧化物的 HPLC 分析基于亚油酸甲酯的氧化形成，根据不同的顺式、反式（动力学）与反式、反式（热力学）产物比率区分自由基过氧化（I 型）和单线态氧氧化（II 型）。方法 A 应用于木质素或二氧化钛（TiO 2，一种已知的单线态氧敏化剂）的固体分散体表明单线态氧反应。除了氮氧三联体，木质素的辐照在固体中产生持久的宽信号，这归因于苯氧基自由基。二苯甲酮和 3,5-二叔丁基邻苯醌 5 涂在硅胶上被用作模型来比较辐照这些化合物对亚油酸甲酯氧化产物和动力学的影响。根据产品研究（方法 B）和紫外线光解过程中耗氧量的动力学顺序，二苯甲酮作为引发剂，产生自由基过氧化，而
• Peroxyl Radical Clocks
  作者：Bill Roschek、Keri A. Tallman、Christopher L. Rector、Jason G. Gillmore、Derek A. Pratt、Carlo Punta、Ned A. Porter

  DOI：10.1021/jo0601462

  日期：2006.4.1

  A series of peroxyl radical clocks has been developed and calibrated based on the competition between the unimolecular β-fragmentation (kβ) of a peroxyl radical and its bimolecular reaction with a hydrogen atom donor (kH). These clocks are based on either methyl linoleate or allylbenzene and were calibrated directly with α-tocopherol or methyl linoleate, which have well-established rate constants for

  一系列过氧化自由基的时钟已经被开发以及基于所述单分子β -断裂（之间的竞争校准ķ β一个过氧化氢自由基及其与氢原子供体（双分子反应的）ķ ħ）。这些时钟是基于任一亚油酸甲酯或烯丙基苯和用α生育酚或亚油酸甲酯，已公认的速率常数与过氧自由基反应（直接校准ķ ħ -生育酚= 3.5×10 6中号- 1个小号- 1，ķ ħ -亚油酸= 62男- 1个小号- 1）。这种过氧自由基时钟方法已成功应用于确定抑制和传播速率常数，范围从10 0到10 7 M - 1 s - 1。
• Functionalization of Cyclodextrins with N-Hydroxyphthalimide Moiety: A New Class of Supramolecular Pro-Oxidant Organocatalysts
  作者：Lucio Melone、Manuel Petroselli、Nadia Pastori、Carlo Punta

  DOI：10.3390/molecules200915881

  日期：——

  N-hydroxyphthalimide (NHPI) is an organocatalyst for free-radical processes able to promote the aerobic oxidation of a wide range of organic substrates. In particular, NHPI can catalyze the hydroperoxidation of polyunsaturated fatty acids (PUFA). This property could be of interest for biological applications. This work reports the synthesis of two β-cyclodextrin derivatives (CD5 and CD6) having a different

  N-羟基邻苯二甲酰亚胺（NHPI）是用于自由基过程的有机催化剂，能够促进多种有机底物的需氧氧化。尤其是，NHPI可以催化多不饱和脂肪酸（PUFA）的加氢过氧化反应。该特性可能对生物学应用感兴趣。这项工作报告了两个甲基化程度不同并带有NHPI部分的β-环糊精衍生物（CD5和CD6）的合成。这些化合物在水中的溶解度不同，已成功测试了被选为PUFA模型分子的亚油酸甲酯的氢过氧化作用。
• 1992 Syntex Award Lecture Model biomembranes: quantitative studies of peroxidation, antioxidant action, partitioning, and oxidative stress
  作者：L. R. C. Barclay

  DOI：10.1139/v93-001

  日期：1993.1.1

  This review outlines a decade of research that employs quantitative kinetic methods of autooxidation to phospholipids aggregated into membranes. The classical rate law for autoxidation:[Formula: see text]was found to apply to heterogeneous systems of bilayers and micelles, where k_p and 2k_t. are the rate constants for chain propagation and termination, respectively, and R_i, the rate of chain initiation, is controlled by thermal initiators. The oxidizability of a typical lipid chain, linoleate 18:2, at 30 °C was similar (0.02–0.04 M^−1/2 s^−1/2) in different media (solution, micelles, bilayers) and for different procedures using water-soluble or lipid-soluble initiators and inhibitors. A reduction in the absolute rate constant for termination, 2k_t by a hundredfold in bilayers of dilinoleoylphosphatidyl choline (DLPC) compared to that in tert-butyl alcohol solution, and a drop in the k_p by a factor of five are interpreted in terms of diffusion of polarized peroxyl radicals from the hydrophobic bilayer phase to the aqueous surface, where peroxyls are strongly solvated by water. Such phenomena may also account for significant changes as observed by ³¹P NMR spectra in bilayer lamellar structure accompanying extensive peroxidation. Analysis of the hydroperoxides formed by peroxidation of mixed bilayers of DLPC + DPPC (16:0) initiated by a water-soluble initiator, azobis(2-amidinopropane•HCl) (ABAP), showed a linear trend between the ratio of cis, trans to trans, trans geometrical isomeric hydroperoxides and [DPLC] consistent with a peroxidation mechanism proposed in homogeneous solution.The antioxidant activities, k_inh, of three classes of antioxidants: (a) polyalkyl-6-hydroxychromans (e.g., vitamin E), (b) polyalkyl-4-methoxyphenols, and (c) trialkylphenols, were measured in DLPC membranes. The results show an overall leveling and depression of k_inh values in DLPC membranes in the series (a) (by several orders of magnitude), (b), and (c) compared to known values in solution in chlorobenzene. In aqueous bilayers it is proposed that k_inh values are attenuated by hydrogen bonding by water at both the para ether oxygen and phenolic groups. Restricted diffusion (e.g., of α-tocopherol) may also reduce antioxidant activities in membranes. A synergistic effect between ascorbic acid and α-tocopherol was discovered under conditions of inhibited peroxidation of linoleate in SDS micelles. The natural peptide glutathione, GSH, however, acts as a co-antioxidant with vitamin E by trapping peroxyls in the aqueous phase.Solid cholesterol was found to partition directly into PC lipsomes by shaking, above or below the phase transition temperature, and membrane-bound cholesterol, unlike the solid, undergoes facile peroxidation. A water-soluble form of α-tocopherol complexed with bovine serum albumin (α-toc:BSA) is an effective antioxidant for autoxidations of linoleate in SDS micelles. In contrast, α-toc:BSA required a long equilibration time (e.g., 12 h) with liposomes (DLPC) before the α-tocopherol was transferred to the liposomes to provide effective antioxidant action.

  这篇评论概述了十年来使用定量动力学方法研究将磷脂聚集成膜的自氧化过程。自氧化的经典速率定律如下：[公式：见文本] 发现适用于双分子层和胶束等异质系统，其中k_p和2k_t是链传播和终止的速率常数，R_i是由热引发剂控制的链起始速率。在不同介质（溶液、胶束、双分子层）以及使用水溶性或脂溶性引发剂和抑制剂的不同程序中，30°C时典型脂肪链亚油酸18:2的氧化性相似（0.02-0.04 M^−1/2 s^−1/2）。在二亚油酰磷脂醯胆碱（DLPC）双分子层中，终止的绝对速率常数2k_t相对于叔丁醇溶液降低了一百倍，而传播速率常数k_p降低了五倍，这被解释为极性过氧基自烷基双分子层相向水相表面扩散，过氧基在水中强烈溶解。这种现象也可能解释了通过³¹P NMR光谱观察到的伴随广泛过氧化的双分子层层状结构的显着变化。通过水溶性引发剂azobis(2-amidinopropane•HCl) (ABAP)引发DLPC + DPPC (16:0)混合双分子层的过氧化形成的过氧化物的分析显示了顺式、反式与反式、反式几何异构过氧化物比例与[DPLC]之间的线性趋势，与在均相溶液中提出的过氧化机制一致。三类抗氧化剂：(a)聚烷基-6-羟基色酮（例如，维生素E）、(b)聚烷基-4-甲氧基苯酚和(c)三烷基酚的抗氧化活性k_inh在DLPC膜中进行了测量。结果显示在DLPC膜中，与氯苯溶液中已知值相比，(a)（几个数量级）、(b)和(c)系列的k_inh值整体水平和降低。在水相双分子层中，提议k_inh值受到水分子在对位醚氧和酚基处的氢键作用的衰减。受限扩散（例如α-生育酚）也可能降低膜中的抗氧化活性。在SDS胶束中发现了抗坏血酸和α-生育酚之间的协同效应，可抑制亚油酸的过氧化。然而，天然肽谷胱甘肽GSH通过在水相中捕获过氧基作为维生素E的辅助抗氧化剂。实验证明，固体胆固醇通过摇动可以直接分配到PC脂质体中，在相变温度之上或之下，与固体不同，膜结合的胆固醇容易发生过氧化。与SDS胶束中亚油酸的自氧化相比，与牛血清白蛋白（BSA）形成的水溶性α-生育酚复合物（α-生育酚：BSA）对SDS胶束中亚油酸的自氧化具有有效的抗氧化作用。相反，与脂质体（DLPC）相比，α-生育酚：BSA在脂质体中提供有效的抗氧化作用前需要较长的平衡时间（例如12小时）。
• Autoxidation of polyunsaturated fatty acids, an expanded mechanistic study
  作者：Ned A. Porter、Dennis G. Wujek

  DOI：10.1021/ja00321a022

  日期：1984.5

  Etude de l'autooxydation des quatre octadecadiene-9,12oates de methyle isomeres dans le benzene/cyclohexadiene-1,4

  Etude de l'autooxydation des quatre十八二烯-9,12oates demethyle isomeres dans le benzo/cyclohexadiene-1,4