3,4-diallyloxybenzaldehyde | 71186-67-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 3,4-diallyloxybenzaldehyde
• 英文别名: 3,4-bis(2-propenyloxy)benzaldehyde；O,O'-diallyl protocatechoaldehyde；3,4-bis(allyloxy)benzaldehyde；3,4-bisallyloxybenzaldehyde；3,4-Bis-(allyloxy)-benzaldehyd；3,4-Bis(prop-2-en-1-yloxy)benzaldehyde；3,4-bis(prop-2-enoxy)benzaldehyde
• CAS: 71186-67-9
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: RMPBVHBECFKPDB-UHFFFAOYSA-N

物化性质

• 沸点：
  124-127 °C(Press: 0.3 Torr)
• 密度：
  1.062±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,4-diallyloxybenzaldehyde 在 palladium 10% on activated carbon 、 potassium carbonate 作用下， 生成 3-(allyloxy)-4-hydroxybenzaldehyde
  参考文献：
  名称：

  海洋真菌新天然产物衍生物作为流感病毒神经氨酸酶抑制剂的合成及构效关系（SAR）研究。

  摘要：

  基于来自红树林真菌的天然异戊二烯苯基醚，合成了 32 种类似物并评估了其对流感 H1N1 神经氨酸酶的抑制活性。化合物 15 (3-(烯丙氧基)-4-羟基苯甲醛) 表现出最有效的抑制活性，A/GuangdongSB/01/2009 (H1N1) 的 IC(50) 值为 26.96 μM，A/Guangdong/03/ 为 27.73 μM 2009 (H1N1) 和 A/Guangdong/05/2009 (H1N1) 分别为 25.13 μM，比苯甲酸衍生物强（~mM 水平）。这是一种新型的非含氮芳香醚神经氨酸酶（NA）抑制剂。它们的结构简单，合成路线并不复杂。构效关系（SAR）分析表明芳醛和未取代的羟基对NA抑制活性很重要。

  DOI：

  10.3390/md9101887
• 作为产物：
  描述：

  3-溴丙烯 、 3,4-二羟基苯甲醛 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 6.0h， 以85%的产率得到3,4-diallyloxybenzaldehyde
  参考文献：
  名称：

  Reaction-based fluorescent silk probes with high sensitivity and selectivity to Hg²⁺ and Ag⁺ ions

  摘要：

  已制备出荧光功能化的丝绸。这些荧光丝绸探针仅对Hg²⁺或Ag⁺显示明显的荧光猝灭效应。

  DOI：

  10.1039/d0tc05429a

文献信息

• Aromatic hydroxylation of .beta.-adrenergic antagonists. Formation of 4'- and 5'-hydroxy-1-(isopropylamino)-3-[2'-(allyloxy)phenoxy]-2-propanol from oxprenolol
  作者：Wendel L. Nelson、Terrence R. Burke

  DOI：10.1021/jm00195a014

  日期：1979.9

  these standards was compared with urinary metabolites obtained from the rat, after methylation with diazomethane and derivatization with trifluoroacetic anhydride. Both 4'- and 5'-hydroxyoxprenolol (4a and 5a) were present in an approximate 4:1 ratio. No 3'- or 6'-hydroxyoxprenolol (3a and 6a) was detected. The metabolites obtained from a human urine treated in the same manner gave similar results with

  检查了大鼠中戊烯醇[1-（异丙基氨基）-3- [2'-（烯丙氧基）苯氧基] -2-丙醇]的代谢芳族羟基化。异构环甲氧基氧戊环醇（3b-6b）的合成是通过O-烯丙基化，然后进行Baeyer-Villiger氧化，由异构甲氧基水杨醛完成的。通过用环氧氯丙烷对Bayer-Villiger产物进行O-烷基化，然后用异丙胺将环氧乙烷开环，可以精制丙醇胺侧链。在用重氮甲烷甲基化并用三氟乙酸酐衍生化之后，将这些标准品的三氟乙酰基衍生物的气相色谱-质谱与从大鼠中获得的尿代谢物进行了比较。4′-和5′-羟基氧戊烯醇（4a和5a）均以约4∶1的比例存在。没有3'-或6' 检测到-羟基氧戊烯醇（3a和6a）。以相同方式处理的人尿液中获得的代谢物在存在4a和5a的情况下均得出相似的结果。
• Towards the development of a covalently tethered MALDI system — A study of allyl-modified MALDI matrixes
  作者：Sanela Martic、John D Brennan、Michael A Brook、Suzanne Ackloo、Noemi Nagy

  DOI：10.1139/v06-185

  日期：2007.1.1

  An emerging application of matrix-assisted laser desorption ionization (MALDI) mass spectrometry is the analysis of low molecular weight (LMW) compounds, often via coupled liquid chromatography — MALDI-MS methods. However, in many cases, the low molecular weight region of MALDI mass spectra is obscured by the presence of signals originating from the matrix, suggesting that the development of tethered MALDI matrixes may be required to optimize MS performance for such compounds. To gain insight into potential sites for covalent attachment of MALDI matrixes, we have systematically investigated the role played by a variety of functional group motifs in determining matrix efficiency for three common MALDI matrixes, as judged both by total signal intensity and background noise from matrix decomposition for a set of LMW compounds. A series of allyl derivatives of standard matrixes was prepared, and the efficiency of these materials in the MALDI experiment was measured. All modifications of established matrixes, e.g., 2,5-dihydroxybenzoic acid (DHB), α-cyano-4-hydroxycinnamic acid (CHCA), and caffeic acid (CA), or close analogues led to decreased absolute signal intensity and signal-to-background levels. Improved performance was generally observed with (i) the presence of a phenolic group (carboxylic acids were less effective) (ii) crystalline derivatives, and (iii) compounds that had high extinction coefficients at wavelengths near to that of the exciting laser (337 nm). The most interesting derivatives were the O-allyl ether (15) and N-allyl amide (16) of caffeic acid. These compounds did not facilitate signals from all four analytes tested. However, the observed spectra contained fewer signals from the matrix than from the parent compound CA. These compounds demonstrate that functionalization of MALDI matrixes, ultimately leading to tethered matrixes, is possible without jeopardizing signal intensity.Key words: MALDI, protected matrix, phenol, caffeic acid, allyl ether.

  基质辅助激光解吸电离（MALDI）质谱的一个新兴应用是分析低分子量（LMW）化合物，通常采用液相色谱-MALDI-MS 联用方法。然而，在许多情况下，MALDI 质谱的低分子量区域会因基质信号的存在而变得模糊不清，这表明可能需要开发系留 MALDI 基质，以优化此类化合物的质谱性能。为了深入了解共价附着 MALDI 基质的潜在位点，我们系统地研究了各种官能团基团在决定三种常见 MALDI 基质的基质效率方面所起的作用，这些作用是通过一组低分子量化合物的总信号强度和基质分解产生的背景噪声来判断的。我们制备了一系列标准基质的烯丙基衍生物，并测量了这些材料在 MALDI 实验中的效率。对 2,5-二羟基苯甲酸 (DHB)、α-氰基-4-羟基肉桂酸 (CHCA) 和咖啡酸 (CA) 等既定基质或近似物的所有改性都会导致绝对信号强度和信号-背景水平的降低。一般来说，(i) 含有酚基（羧酸的效果较差）(ii) 结晶衍生物，以及 (iii) 在接近激发激光波长（337 纳米）时消光系数较高的化合物，其性能会有所改善。最有趣的衍生物是咖啡酸的 O-烯丙基醚（15）和 N-烯丙基酰胺（16）。这些化合物并没有促进所有四种测试分析物发出信号。不过，观察到的光谱中来自基质的信号少于来自母体化合物 CA 的信号。这些化合物表明，在不影响信号强度的情况下，对 MALDI 基质进行功能化，最终形成系留基质是可能的：MALDI、保护基质、苯酚、咖啡酸、烯丙基醚。
• Bryophyte Constituents; 7: New Synthesis of (+)-Rosmarinic Acid and Related Compounds
  作者：Theophil Eicher、Markus Ott、Andreas Speicher

  DOI：10.1055/s-1996-4289

  日期：1996.6

  Efficient and expeditious syntheses are described for rosmarinic acid (1) and its derivatives 2-4, making extensive use of allyl protective groups for both carboxylic acids and phenolic building blocks. (+)-(R)-Rosmarinic acid was obtained by a chemoenzymatic resolution of its phenyl lactic acid precursors.

  描述了迷迭香酸（1）及其衍生物2-4的高效快捷合成方法，广泛采用了烯丙基保护基团用于羧酸和酚类构建单元。通过化学酶促拆分其苯基乳酸前体，获得了(+)-(R)-迷迭香酸。
• Synthesis of a Photo-Caged DOPA Derivative by Selective Alkylation of 3,4-Dihydroxybenzaldehyde
  作者：Tobias Schneider、Vladimir Kubyshkin、Nediljko Budisa

  DOI：10.1002/ejoc.201701749

  日期：2018.5.15

  A general route towards 3‐O‐alkylated DOPA derivatives has been developed. The regioselectivity of the synthesis was controlled by the number of base equivalents in the first alkylation step. In this way a photo‐caged DOPA was prepared that can readily be incorporated into recombinant protein sequences, thus enabling biosynthetic production of light‐activatable bioadhesives.

  已经开发了一种制备3-O-烷基化DOPA衍生物的一般方法。合成的区域选择性由第一烷基化步骤中碱当量的数量控制。这样，制备了光笼装的DOPA，可以将其轻松地掺入重组蛋白序列中，从而能够生物合成生产可光活化的生物粘合剂。
• Synthesis of Butein Analogues and their Anti-proliferative Activity Against Gefitinib-resistant Non-small Cell Lung Cancer (NSCLC) through Hsp90 Inhibition
  作者：Young Ho Seo、Ju Hui Jeong

  DOI：10.5012/bkcs.2014.35.5.1294

  日期：2014.5.20

  Non-small cell lung cancer (NSCLC) is the most common type of lung cancer representing 85% of lung cancer patients. Despite several EGFR-targeted drugs have been developed in the treatment of NSCLC, the clinical efficacy of these EGFR-targeted therapies is being challenged by the occurrence of drug resistance. In this regard, Hsp90 represents great promise as a therapeutic target of cancerous diseases due to its role in modulating and stabilizing numerous oncogenic proteins. Accordingly, inhibition of single Hsp90 protein simultaneously disables multiple signaling networks so as to overcome drug resistance in cancer. In this study, we synthesized a series of 11 butein analogues and evaluated their biological activities against gefitinibresistant NSCLC cells (H1975). Our study indicated that analogue 1h inhibited the proliferation of H1975 cells, down-regulated the expression of Hsp90 client proteins, including EGFR, Met, Her2, Akt and Cdk4, and upregulated the expression of Hsp70. The result suggested that compound 1h disrupted Hsp90 chaperoning function and could serve a potential lead compound to overcome the drug resistance in cancer chemotherapy.

  非小细胞肺癌（NSCLC）是最常见的肺癌类型，占肺癌患者的85%。尽管针对NSCLC开发了几种EGFR靶向药物，但这些EGFR靶向治疗的临床疗效正受到药物耐药性的挑战。在此背景下，由于Hsp90在调节和稳定多种致癌蛋白中的作用，它作为癌症疾病的潜在治疗靶点展现了巨大希望。相应地，通过抑制单个Hsp90蛋白，可以同时阻断多个信号网络，从而克服癌症中的药物耐药性。在本研究中，我们合成了一系列11个白杨素类似物，并评估了它们对吉非替尼耐药的NSCLC细胞（H1975）的生物活性。我们的研究表明，类似物1h抑制了H1975细胞的增殖，下调了Hsp90客户端蛋白的表达，包括EGFR、Met、Her2、Akt和Cdk4，并上调了Hsp70的表达。这些结果表明，化合物1h破坏了Hsp90的伴侣功能，并可能作为一种潜在的先导化合物，用于克服癌症化疗中的药物耐药性。