(E)-3,4-di-O-acetylcaffeoyl chloride

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-3,4-di-O-acetylcaffeoyl chloride
• 英文别名: 3,4-di-O-acetylcaffeoyl chloride；3,4-diacetoxycinnamoyl chloride；3,4-diacetylcaffeoyl chloride；(E)-3-(3,4-diacetoxyphenyl)acryloyl chloride；(E)-4-(3-chloro-3-oxoprop-1-en-1-yl)-1,2-phenylene diacetate；[2-acetyloxy-4-[(E)-3-chloro-3-oxoprop-1-enyl]phenyl] acetate
• 化学式: C₁₃H₁₁ClO₅
• 分子量: 282.68
• InChiKey: YXWAVXQOQBBLQZ-GQCTYLIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-3,4-di-O-acetylcaffeoyl chloride 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 (-)-5-咖啡酰奎宁酸
  参考文献：
  名称：

  First Efficient Synthesis of Chlorogenic Acid

  摘要：

  The first efficient synthesis of chlorogenic acid (1) was achieved in four steps (three purifications) from quinic acid (2). The overall yield was 65%. The key intermediate was quinic acid bisacetonide (6), selectively prepared by a modified kinetic acetalization protocol. Esterification of 6 with caffeic acid chloride (3) afforded ester 12. Cleavage of all the protecting groups of 12 was accomplished in one step under acidic conditions. The progress of the hydrolysis was monitored by MALDI-MS.

  DOI：

  10.1002/1099-0690(200103)2001:6<1137::aid-ejoc1137>3.0.co;2-2
• 作为产物：
  描述：

  TRANS-咖啡酸 在 吡啶 、 4-二甲氨基吡啶 、 氯化亚砜 作用下， 反应 1.0h， 生成 (E)-3,4-di-O-acetylcaffeoyl chloride
  参考文献：
  名称：

  借助稳定的同位素稀释测定法对烘焙过的咖啡和可可粉中的N-苯基丙烯酰基-L-氨基酸进行定量分析。

  摘要：

  自从最近有报道称N-苯基丙烯酰基-L-氨基酸作为强力抗氧化剂和可可豆粒涩味的主要贡献者以来，人们对植物性食品中这些植物化学物质的浓度越来越感兴趣。开发了一种通用的分析方法，该方法可通过HPLC-MS / MS和合成的稳定同位素标记的N-苯基丙烯酰基-L-氨基酸作为内标物，对植物衍生食品中的N-苯基丙烯酰基-L-氨基酸进行准确定量分析。通过开发的稳定同位素稀释法（SIDA），回收率达到95-102％，首次对可可和咖啡样品中的14种N-苯基丙烯酰基-L-氨基酸进行了定量。根据LC-MS / MS实验结果以及使用合成参考化合物N- [3'，4'进行共色谱法

  DOI：

  10.1021/jf053207q

文献信息

• A simple approach to pyrazol-3-ones via diazenes
  作者：Bojan Burja、Marijan Kočevar、Slovenko Polanc

  DOI：10.1016/j.tet.2009.08.047

  日期：2009.10

  An efficient entry into pyrazol-3-ones is described starting from propenoic acids that were first transformed into the corresponding hydrazides. Oxidation of the hydrazides gave the diazenes and the latter cyclized to pyrazol-3-ones on treatment with ZrCl4. The methoxycarbonyl protection of the N-1 of the pyrazolone derivatives was easily removed under mild reaction conditions.

  描述了从首先被转化成相应的酰肼的丙烯酸开始有效地进入吡唑-3-酮。酰肼的氧化产生了二氮烯，并且在用ZrCl 4处理时将其环化成吡唑-3-酮。在温和的反应条件下，容易除去吡唑啉酮衍生物的N-1的甲氧基羰基保护基。
• Antimycobacterial Activity of Cinnamate-Based Esters of the Triterpenes Betulinic, Oleanolic and Ursolic Acids
  作者：Tanud Tanachatchairatana、John Barnard Bremner、Ratchanaporn Chokchaisiri、Apichart Suksamrarn

  DOI：10.1248/cpb.56.194

  日期：——

  Betulinic acid, oleanolic acid and ursolic acid have been modified at the C-3 position to cinnamate-based esters and in vitro antimycobacterial activity against Mycobacterium tuberculosis H(37)Ra has been determined. The results indicated that modification of the parent structures of betulinic acid, oleanolic acid and ursolic acid to the p-coumarate and, in the case of the latter two triterpenes, the ferulate

  在C-3位置将贝丁酸，齐墩果酸和熊果酸修饰为基于肉桂酸酯的酯，并且已确定了针对结核分枝杆菌H（37）Ra的体外抗分枝杆菌活性。结果表明，将桦木酸，齐墩果酸和熊果酸的母体结构修饰为对香豆酸酯，在后两个三萜烯的情况下，阿魏酸酯类似物导致较高的抗分枝杆菌活性。讨论了在三聚戊二烯，齐墩果烷和烷类似物中以及这些三萜之间的结构-活性关系。
• Antioxidant activity of olive phenols: mechanistic investigation and characterization of oxidation products by mass spectrometry
  作者：Marjolaine Roche、Claire Dufour、Nathalie Mora、Olivier Dangles

  DOI：10.1039/b416101g

  日期：——

  In this work, the antioxidant activity of olive phenols is first characterized by their stoichiometries ntot (number of radicals trapped per antioxidant molecule) and their rate constants for the first H-atom abstraction k1 by the stable radical DPPH. It appears that oleuropein, hydroxytyrosol and caffeic acid have the largest k1 values, whereas dihydrocaffeic acid, an intestinal metabolite of caffeic acid, is the best antioxidant in terms of ntot. For phenols with a catechol moiety ntot is higher than two, implying an antioxidant effect of their primarily formed oxidation products. A HPLC–MS analysis of the main products formed in the AAPH-induced oxidation of olive phenols reveals the presence of dimers and trimers. With hydroxytyrosol and dihydrocaffeic acid, oligomerization can take place with the addition of water molecules. The antioxidant activity of olive phenols is then evaluated by their ability to inhibit the AAPH-induced peroxidation of linoleic acid in SDS micelles. It is shown that olive phenols and quercetin act as retardants rather than chain breakers like α-tocopherol. From a detailed mechanistic investigation, it appears that the inhibition of lipid peroxidation by olive phenols can be satisfactorily interpreted by assuming that they essentially reduce the AAPH-derived initiating radicals. Overall, olive phenols prove to be efficient scavengers of hydrophilic peroxyl radicals with a long lasting antioxidant effect owing to the residual activity of some of their oxidation products.

  在本研究中，首先通过它们的化学计量学ntot（每个抗氧化剂分子捕获的自由基数量）和稳定自由基DPPH的第一个H原子抽提反应速率常数k1，来表征橄榄多酚的抗氧化活性。结果显示，橄榄苦苷、羟基酪醇和咖啡酸具有最大的k1值，而咖啡酸的肠道代谢物二羟基咖啡酸在ntot方面是最优秀的抗氧化剂。对于含有邻苯二酚基团的多酚，ntot值高于二，这意味着它们初始形成的氧化产物具有抗氧化效果。通过高效液相色谱-质谱（HPLC-MS）分析，在AAPH诱导的橄榄多酚氧化过程中形成的主要产物显示出二聚体和三聚体的存在。在羟基酪醇和二羟基咖啡酸的情况下，聚合反应伴随着水分子的加入。 然后，通过它们抑制AAPH诱导SDS胶束中亚油酸过氧化的能力来评估橄榄多酚的抗氧化活性。结果表明，橄榄多酚和槲皮素作为延缓剂而非链断裂剂如α-生育酚。通过详细的机理研究，发现橄榄多酚抑制脂质过氧化的作用可以通过假设它们基本减少AAPH衍生出的引发自由基来满意地解释。总体而言，橄榄多酚证明是有效的亲水性过氧自由基清除剂，由于其氧化产物中一些残余的活性，具有持久的抗氧化效果。
• An expeditious route to the synthesis of kelampayosides A and B
  作者：Howard I. Duynstee、Martijn C. de Koning、Gijs A. van der Marel、Jacques H. van Boom

  DOI：10.1016/s0040-4020(99)00527-x

  日期：1999.8

  Chemoselective NIS/ cat. TfOH-mediated glycosylation of ethyl2,3,4-tri-O-benzoyl-1-thio-β-d-glucopyranoside (13) with ethyl2,3-di-O-acetyl-5-O-benzyl-1-thio-αβ-d-erythro-apiofuranoside (4a) gave dimer14 in an excellent yield. BF3•Et2O-catalysed condensation of the α-trichloroacetimidate31, accessible in two steps from14, with 3,4,5-trimethoxyphenol gave β-linked derivative32 followed by deprotection

  化学选择性NIS /猫。TfOH介导的乙基2,3,4-三-O-苯甲酰基-1-硫代-β-d-吡喃葡萄糖苷（13）与乙基2,3-二-O-乙酰基-5-O-苄基-1-硫代-的糖基化作用αβ-d-赤型-呋喃呋喃糖苷（4a）以优异的产率得到二聚体14。BF 3 •Et 2 O催化的α-三氯乙酰亚胺酸酯31的缩合反应（从14步可分两个步骤进行）与3,4,5-三甲氧基苯酚生成β-连接的衍生物32，然后脱保护得到KelampayosideA。保护基的操作为32和所得的后续caffeoylation 36接着进行脱保护，得到Kelampayoside B.图选项
• Synthesis of Selenium-Containing Polyphenolic Acid Esters and Evaluation of Their Effects on Antioxidation and 5-Lipoxygenase Inhibition
  作者：Chi-Fu Lin、Tsu-Chung Chang、Chih-Chia Chiang、Hou-Jen Tsai、Ling-Yih Hsu

  DOI：10.1248/cpb.53.1402

  日期：——

  Six novel selenium-containing polyphenolic acid esters were synthesized and evaluated as antioxidants and 5-lipoxygenase inhibitors. Synthesis of the title compounds involved the Mitsunobu reaction of polyphenolic acids (4—8, 14) with 2-phenylselenoethanol (3). Compounds 22, 23, and 25 were found to be very effective antioxidants and 5-lipoxygenase inhibitors with activity comparable to or better than caffeic acid (3,4-dihydroxycinnamic acid) phenethyl ester (CAPE).

  合成了6种新型的含硒多酚酸酯，并评价了它们的抗氧化活性和5-脂氧合酶抑制活性。标题化合物的合成涉及多酚酸（4-8, 14）与2-苯硒基乙醇（3）的 Mitsunobu 反应。化合物 22、23 和 25 被发现是非常有效的抗氧化剂和 5-脂氧合酶抑制剂，其活性与或优于咖啡酸（3,4-二羟基肉桂酸）苯乙酯（CAPE）。