bis(2-methylbut-3-en-2-yl) carbonate | 426827-36-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: bis(2-methylbut-3-en-2-yl) carbonate
• 英文别名: Bis(2-methylbut-3-en-2-yl) carbonate
• CAS: 426827-36-3
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: FYNBUGICXDEGIY-UHFFFAOYSA-N

物化性质

• 沸点：
  216.1±29.0 °C(Predicted)
• 密度：
  0.943±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.55
• 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：

  bis(2-methylbut-3-en-2-yl) carbonate 、 7,8-dihydroxy-2,2-dimethyl-4H-benzo[d][1,3]dioxin-4-one 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 生成 2,2-dimethyl-7,8-bis(2-methylbut-3-en-2-yloxy)-4H-benzo[d]-[1,3]dioxin-4-one
  参考文献：
  名称：

  Evaluation of the pharmacophoric motif of the caged Garcinia xanthones

  摘要：

  几种带有独特结构和强效生物活性的囊状（caged）Garciniaxanthone家族成员的结合，促使我们评估它们的药效团（pharmacophore）。我们开发了一种Pd(0)催化的方法，用于酚类化合物的反向普雷尼尔化（reverse prenylation），结合Claissen/Diels–Alder反应级联，实现了对各种囊状类似物的快速和高效获取。这些化合物的生长抑制活性评估得出结论，完整的ABC环系统及其C环囊状结构对生物活性至关重要。与克鲁文酮（cluvenone，每个7号的化合物）进行的研究还表明，这些化合物能够诱导细胞凋亡，并在多药耐药性白血病细胞中表现出显著的细胞毒性。因此，囊状Garciniaxanthone结构代表了一种新的强效药效团。

  DOI：

  10.1039/b913496d
• 作为产物：
  描述：

  2-甲基-3-丁烯-2-醇 、 2-methylbut-3-en-2-yl 1H-imidazole-1-carboxylate 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以7.7 g的产率得到bis(2-methylbut-3-en-2-yl) carbonate
  参考文献：
  名称：

  Evaluation of the pharmacophoric motif of the caged Garcinia xanthones

  摘要：

  几种带有独特结构和强效生物活性的囊状（caged）Garciniaxanthone家族成员的结合，促使我们评估它们的药效团（pharmacophore）。我们开发了一种Pd(0)催化的方法，用于酚类化合物的反向普雷尼尔化（reverse prenylation），结合Claissen/Diels–Alder反应级联，实现了对各种囊状类似物的快速和高效获取。这些化合物的生长抑制活性评估得出结论，完整的ABC环系统及其C环囊状结构对生物活性至关重要。与克鲁文酮（cluvenone，每个7号的化合物）进行的研究还表明，这些化合物能够诱导细胞凋亡，并在多药耐药性白血病细胞中表现出显著的细胞毒性。因此，囊状Garciniaxanthone结构代表了一种新的强效药效团。

  DOI：

  10.1039/b913496d

文献信息

• [EN] MACROCYCLIC PICOLINAMIDE COMPOUNDS WITH FUNGICIDAL ACTIVITY<br/>[FR] COMPOSÉS DE PICOLINAMIDE MACROCYCLIQUE PRÉSENTANT UNE ACTIVITÉ FONGICIDE
  申请人：DOW AGROSCIENCES LLC

  公开号：WO2016109290A1

  公开（公告）日：2016-07-07

  This disclosure relates to macrocyclic picolinamides of Formula (I) and their use as fungicides.

  本公开涉及式(I)的宏观环状吡啶酰胺及其作为杀菌剂的应用。
• A-ring oxygenation modulates the chemistry and bioactivity of caged Garcinia xanthones
  作者：Kristyna M. Elbel、Gianni Guizzunti、Maria A. Theodoraki、Jing Xu、Ayse Batova、Marianna Dakanali、Emmanuel A. Theodorakis

  DOI：10.1039/c3ob40395e

  日期：——

  Natural products of the caged Garcinia xanthones (CGX) family are characterized by a unique chemical structure, potent bioactivities and promising pharmacological profiles. We have developed a Claisen/Diels–Alder reaction cascade that, in combination with a Pd(0)-catalyzed reverse prenylation, provides rapid and efficient access to the CGX pharmacophore, represented by the structure of cluvenone. To further explore this pharmacophore, we have synthesized various A-ring oxygenated analogues of cluvenone and have evaluated their bioactivities in terms of growth inhibition, mitochondrial fragmentation, induction of mitochondrial-dependent cell death and Hsp90 client inhibition. We found that installation of an oxygen functionality at various positions of the A-ring influences significantly both the site-selectivity of the Claisen/Diels–Alder reaction and the bioactivity of these compounds, due to remote electronic effects.

  被笼罩的伽马林黄酮(CGX)家族的天然产物具有独特的化学结构、强大的生物活性和良好的药理特征。我们开发了一种Claisen/Diels–Alder反应级联反应，并结合Pd(0)催化的逆普瑞尼基反应，快速高效地获得了以cluvenone结构为代表的CGX药效基团。为进一步探索该药效基团，我们合成了多种cluvenone的A环氧化类衍生物，并评估了它们在生长抑制、线粒体碎片化、诱导线粒体依赖性细胞死亡和Hsp90底物抑制等方面的生物活性。我们发现，在A环不同位置引入氧功能团显著影响了Claisen/Diels–Alder反应的位点选择性以及这些化合物的生物活性，原因在于远程电子效应。
• Pyrocarbonic acid diesters and the preparation and use thereof
  申请人：Ciba Specialty Chemicals Corporation

  公开号：US06359122B1

  公开（公告）日：2002-03-19

  The invention relates to the preparation of pyrocarbonic acid diesters by an improved process and to the novel pyrocarbonic acid diesters prepared according to said process as well as to the use thereof. The core of the invention is a process for the preparation of a pyrocarbonic acid diester of formula (I) wherein R1 and R1′ are each independently of the other branched or straight-chain C1-C24alkyl, C3-C24alkenyl, C3-C24alkynyl, C4-C12cycloalkyl, C4-C12cycloalkenyl or C7-C24aralkyl, each of which is unsubstituted or substituted by one or more than one substituent which is inert under the reaction conditions, by reacting at least one ester carbonate of formula (II)  with 40-50 mol % of a sulfochloride of formula (IV)  in the presence of 0.8-5 mol % of a catalyst of formula (V) and with minor amounts of a heterocyclic aromatic amine in a nonpolar inert solvent, in which process the amount of heterocyclic aromatic amine is 1-3 mol % and the reaction is carried out in the temperature range from −10° C. to +25° C., all molar amounts being based on 100 mol % of ester carbonate of formula (II).

  该发明涉及通过改进的方法制备吡碳酸二酯以及根据该方法制备的新型吡碳酸二酯的用途。该发明的核心是一种制备式（I）的吡碳酸二酯的方法，其中R1和R1'各自独立地为分支或直链的C1-C24烷基，C3-C24烯基，C3-C24炔基，C4-C12环烷基，C4-C12环烯基或C7-C24芳基烷基，每种基团未被取代或被一个或多个在反应条件下是惰性的取代基取代，通过将至少一种式（II）的酯碳酸与40-50摩尔％的式（IV）的磺酰氯在0.8-5摩尔％的式（V）的催化剂存在下，以及微量的杂环芳香胺在非极性惰性溶剂中反应，其中杂环芳香胺的量为1-3摩尔％，反应在-10°C至+25°C的温度范围内进行，所有摩尔量均基于100摩尔％的酯碳酸的基础。
• Synthesis, structure-activity relationship and in vitro pharmacodynamics of A-ring modified caged xanthones in a preclinical model of inflammatory breast cancer
  作者：Oraphin Chantarasriwong、Andrew T. Milcarek、Theodore Habarth Morales、Aspen L. Settle、Celso O. Rezende、Bashayer D. Althufairi、Maria A. Theodoraki、Mary L. Alpaugh、Emmanuel A. Theodorakis

  DOI：10.1016/j.ejmech.2019.02.047

  日期：2019.4

  Inflammatory breast cancer (IBC) is a highly metastatic, lethal form of breast cancer that lacks targeted therapeutic strategies. Inspired by the promising cytotoxicity of gambogic acid and related caged xanthones in spheroids(MARY-X), an in vitro preclinical IBC model, we constructed a library of synthetic analogs and performed structure-activity relationship studies. The studies revealed that functionalizing the A-ring of the caged xanthone framework can significantly affect potency. Specifically, introduction of hydroxyl or fluorine groups at discrete positions of the A-ring leads to enhanced cytotoxicity at sub-micromolar concentrations. These compounds induce complete dissolution of spheroids(MARY-X) with subsequent apoptosis of both the peripherally- and centrally-located cells, proliferative and quiescent-prone (e.g. hypoxic), respectively. These results highlight the structural flexibility and pharmacological potential of the caged xanthone motif for the design of IBC-targeting therapeutics. (C) 2019 Elsevier Masson SAS. All rights reserved.
• Chiral resolution of a caged xanthone and evaluation across a broad spectrum of breast cancer subtypes
  作者：Oraphin Chantarasriwong、Tanis J. Dorwart、Theodore Habarth Morales、Stephanie F. Maggio、Aspen L. Settle、Andrew T. Milcarek、Mary L. Alpaugh、Maria A. Theodoraki、Emmanuel A. Theodorakis

  DOI：10.1016/j.bioorg.2019.103303

  日期：2019.12

  Racemic resolution of (+/-)-MAD28, a representative caged xanthone, was accomplished using (1S, 4R)-(-)-camphanic chloride as the chiral agent. Selective crystallization of the resulting diastereomers in acetonitrile produced, after hydrolysis, the pure enantiomers. Screening of racemic MAD28 and both enantiomers across a broad spectrum of breast cancer cell lines revealed that they: (a) are equipotent in each of the breast cancer subtypes examined; and (b) exhibit a higher degree of cytotoxicity against breast cancer cell lines of basal-like subtype and triple negative receptor status. The results support the notion that MAD28 and related caged xanthones are promising drug leads against chemoresistant and metastatic cancers.