3,4-methylenedioxybenzylidenebutylamine | 717-24-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 3,4-methylenedioxybenzylidenebutylamine
• 英文别名: N-[1,3-benzodioxol-5-ylmethylene]butylamine；1-(1,3-benzodioxol-5-yl)-N-butylmethanimine
• CAS: 717-24-8
• 化学式: C₁₂H₁₅NO₂
• 分子量: 205.257
• InChiKey: AYERMVWJDQQQPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  30.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,4-methylenedioxybenzylidenebutylamine 在 氯化亚砜 作用下， 以 氯仿 为溶剂， 反应 12.75h， 生成 6-(1-Butyl)-5,6-dihydro-5,11-diketo-2,3-dimethoxy-8,9-methylenedioxy11H-indeno[1,2-c]isoquinoline
  参考文献：
  名称：

  Synthesis of Cytotoxic Indenoisoquinoline Topoisomerase I Poisons

  摘要：

  A number of indenoisoquinolines were prepared and evaluated for cytotoxicity in human cancer cell cultures and for activity vs topoisomerase 1 (top1). The two most cytotoxic indenoisoquinolines proved to be cis-6-ethyl-5,6,12,13-tetrahydro-2,3-dimethoxy-8,9-(methylenedioxy)-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (21) and cis-6-allyl-5,6,12,13-tetrahydro-2,3-dimethoxy-6,9-(methylenedioxy)-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (22), both of which displayed submicromolar mean graph midpoints when tested in 55 human cancer cell cultures. Two of the most potent top1 inhibitors were 6-(3-carboxy-1-propyl)-5,6-dihydro-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (26) and 6-ethyl-2,3-dimethoxy-8,9-(methylenedioxy)-11H-indeno[1,2-c]isoquinolinium chloride (27), both of which also inhibited top2, unwound DNA, and are assumed to be DNA intercalators. However, two additional potent top1 inhibitors, 6-allyl-5,6-dihydro-2,3-dimethoxy-8,9-(methylenedioxy)-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (13c) and 5,6-dihydro-6-(4-hydroxybut-1-yl)-2,3-dimethoxy-8,9-methylenedioxy-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (19a), did not unwind DNA and did not affect top2, Some of the DNA cleavage sites detected in the presence of the indenoisoquinolines were different from those seen with the camptothecins. The cleavage sites induced by the indenoisoquinolines were reversed by salt treatment, which is consistent with the reversible trapping of top1 cleavable complexes by the indenoisoquinolines. In general, the potencies of the indenoisoquinolines as top1 inhibitors did not correlate with their potencies as cytotoxic agents, as some of the most cytotoxic agents had little if any effect on top1. On the other hand, the most potent of the indenoisoquinolines vs top1 were not the most-cytotoxic. In several cases, moderate activity was observed for both cytotoxicity and activity vs top1.

  DOI：

  10.1021/jm9803323
• 作为产物：
  描述：

  N-butyl-1,3-benzodioxole-5-carboxamide 在 二氯二茂锆 、 甲基二甲氧基硅烷 、 二乙胺 作用下， 以 甲苯 为溶剂， 以69.0 mg的产率得到3,4-methylenedioxybenzylidenebutylamine
  参考文献：
  名称：

  通过茂锆氢化物催化仲酰胺和叔酰胺的轻度发散半还原转化

  摘要：

  酰胺温和催化部分还原为亚胺已被证明是一种具有挑战性的合成转化，许多过渡金属直接将这些底物还原为胺。在此，我们报告了一种通过二茂氢化物催化半还原仲酰胺和叔酰胺的温和催化方法。仅使用 5 mol% 的 Cp 2 ZrCl 2 ，仲酰胺的还原脱氧即可提供多种亚胺，产率高达 94%，具有优异的化学选择性，且无需手套箱操作。此外，当催化方案在伯胺存在下于室温下进行时，也可以实现叔酰胺的新型还原氨基转移，从而以高达 98% 的收率获得更多的亚胺。通过轻微的程序调整，酰胺到亚胺、醛、胺或烯胺的单烧瓶转化是可行的，包括多组分合成。

  DOI：

  10.1021/jacs.2c11786

文献信息

• An integrated electrocatalytic nESI-MS platform for quantification of fatty acid isomers directly from untreated biofluids
  作者：Kavyasree Chintalapudi、Abraham K. Badu-Tawiah

  DOI：10.1039/d0sc03403g

  日期：——

  Positional isomers of alkenes are frequently transparent to the mass spectrometer and it is difficult to provide convincing data to support their presence. This work focuses on the development of a new reactive nano-electrospray ionization (nESI) platform that utilizes non-inert metal electrodes (e.g., Ir and Ru) for rapid detection of fatty acids by mass spectrometry (MS), with concomitant localization

  烯烃的位置异构体通常对质谱仪是透明的，并且很难提供令人信服的数据来支持它们的存在。这项工作的重点是开发新的反应性纳米电喷雾电离（nESI）平台，该平台利用非惰性金属电极（例如Ir和Ru）通过质谱（MS）快速检测脂肪酸，并同时定位C C键可区分脂肪酸异构体。在电喷雾过程中，利用电能（直流电压）通过电氧化在电极表面上原位形成氧化物。发现形成的表面氧化物有助于在C温度下原位形成环氧化物MS实时分析C键位置和产物。这种现象已应用于分析复杂血清样品中不饱和脂肪酸的异构体，而无需进行预处理。
• Chemical Reactivity and Skin Sensitization Potential for Benzaldehydes: Can Schiff Base Formation Explain Everything?
  作者：Andreas Natsch、Hans Gfeller、Tina Haupt、Gerhard Brunner

  DOI：10.1021/tx300278t

  日期：2012.10.15

  conditions, Schiff base formation was only observable for the strong sensitizers atranol and chloratranol and for salicylaldehyde. Trapping experiments with NaBH3CN showed that Schiff base formation occurred under these conditions also for some less sensitizing aldehydes, but the reaction is not favored in the absence of in situ reduction. Surprisingly, the Schiff bases of some weaker sensitizers apparently

  皮肤敏化剂化学修饰皮肤蛋白，使其具有免疫原性。敏化化学品已根据其可疑的反应机理分为适用范围。广泛接受的席夫碱适用范围涵盖醛和酮，并给出了该化学基团的详细结构-活性模型。尽管席夫碱的形成是这些化学物质的明显反应途径，但硅有限的实验工作跟进了这项工作。尚不清楚水解不稳定的席夫碱能否形成足够稳定的表位，从而在存在过量水的情况下在活生物体中引发免疫反应。在这里，我们对皮肤致敏性差异很大的苯甲醛进行了实验研究。在乙腈中评估了对丁胺的席夫碱形成，并进行了详细的SAR研究。邻羟基苯甲醛（如水杨醛）和橡苔过敏原中的阿特拉醇和氯三醇具有很高的形成席夫碱的倾向。在对羟基苯甲醛（如非敏化香兰素）中，其反应性大大降低，对对烷基和对苯二酚的反应性中等-甲氧基苯甲醛。在含肽赖氨酸的七肽的肽反应性测定中，在更多生理条件下对该工作进行了跟踪。在这些条件下，仅对于强敏剂阿特拉诺尔和氯他诺尔以及水杨醛而言，可观察到席夫碱的形成。用NaBH
• A Combined Experimental and Theoretical Study of the Polar [3 + 2] Cycloaddition of Electrophilically Activated Carbonyl Ylides with Aldehydes and Imines
  作者：Ghenia Bentabed-Ababsa、Aicha Derdour、Thierry Roisnel、Jose A. Sáez、Patricia Pérez、Eduardo Chamorro、Luis R. Domingo、Florence Mongin

  DOI：10.1021/jo8027104

  日期：2009.3.6

  nzylamine) proceed diastereoselectively. The effect of microwave irradiation on the outcome of the reaction was studied. The mechanism of these [3 + 2] cycloaddition reactions has been theoretically investigated using DFT methods. These cycloadditions, which have one-step mechanisms, consist of the nucleophilic attack of the aldehyde oxygen or imine nitrogen on the carbonyl ylide. For the reaction

  通过羰基内酯之间的[3 + 2]环加成反应合成了许多2,5-二芳基-1,3-二氧戊环-4,4-二腈和2,4-二苯基-1,3-恶唑烷-5,5-二腈由环氧化物，醛或亚胺生成。与此相反的使用醛类（3,4,5-三甲氧基苯，胡椒醛，1-萘甲醛，吲哚-3-甲醛，呋喃-2-甲醛，和噻吩-2-甲醛）的，反应与亚胺进行（ñ - （苯基亚甲基）甲胺，N-（1,3-苯并二恶唑-5-基亚甲基）丙胺，N-（1,3-苯并二恶唑-5-基亚甲基）丁胺和N-（1，3-苯并二恶唑-5-基亚甲基）苄胺）非对映选择性地进行。研究了微波辐射对反应结果的影响。这些[3 + 2]环加成反应的机理已使用DFT方法进行了理论研究。这些具有一步机制的环加成包括醛氧或亚胺氮对羰基内酯的亲核攻击。对于与醛的反应，在过渡结构处发现了不可预期的反向电荷转移，这归因于背电荷作用。反应性指标的分析表明，羰基乙炔的大亲电特性可诱导它们在这些极性的[3 +
• 1,3‐Dipolar Cycloadditions of Aldehydes or Imines with Carbonyl Ylides Generated from Epoxides: Classical Heating and Microwave Irradiation
  作者：Ghenia Bentabed、Mustapha Rahmouni、Florence Mongin、Aicha Derdour、Jack Hamelin、Jean Pierre Bazureau

  DOI：10.1080/07370650701471699

  日期：2007.8.1

  Cycloadditions of aldehydes with carbonyl ylides to give dioxolanes have been carried out without solvent under microwave irradiation. The reactions proceeded in similar yields and stereoselectivities, but in shorter reaction times, than those obtained in toluene at reflux using an oil bath. Cycloadditions conducted between imines and carbonyl ylides using the same protocol were less efficient because the oxazolidines formed proved unstable under the reaction conditions.
• Synthesis of Cytotoxic Indenoisoquinoline Topoisomerase I Poisons
  作者：Dirk Strumberg、Yves Pommier、Kenneth Paull、Muthusamy Jayaraman、Pamela Nagafuji、Mark Cushman

  DOI：10.1021/jm9803323

  日期：1999.2.1

  A number of indenoisoquinolines were prepared and evaluated for cytotoxicity in human cancer cell cultures and for activity vs topoisomerase 1 (top1). The two most cytotoxic indenoisoquinolines proved to be cis-6-ethyl-5,6,12,13-tetrahydro-2,3-dimethoxy-8,9-(methylenedioxy)-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (21) and cis-6-allyl-5,6,12,13-tetrahydro-2,3-dimethoxy-6,9-(methylenedioxy)-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (22), both of which displayed submicromolar mean graph midpoints when tested in 55 human cancer cell cultures. Two of the most potent top1 inhibitors were 6-(3-carboxy-1-propyl)-5,6-dihydro-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (26) and 6-ethyl-2,3-dimethoxy-8,9-(methylenedioxy)-11H-indeno[1,2-c]isoquinolinium chloride (27), both of which also inhibited top2, unwound DNA, and are assumed to be DNA intercalators. However, two additional potent top1 inhibitors, 6-allyl-5,6-dihydro-2,3-dimethoxy-8,9-(methylenedioxy)-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (13c) and 5,6-dihydro-6-(4-hydroxybut-1-yl)-2,3-dimethoxy-8,9-methylenedioxy-5,11-dioxo-11H-indeno[1,2-c]isoquinoline (19a), did not unwind DNA and did not affect top2, Some of the DNA cleavage sites detected in the presence of the indenoisoquinolines were different from those seen with the camptothecins. The cleavage sites induced by the indenoisoquinolines were reversed by salt treatment, which is consistent with the reversible trapping of top1 cleavable complexes by the indenoisoquinolines. In general, the potencies of the indenoisoquinolines as top1 inhibitors did not correlate with their potencies as cytotoxic agents, as some of the most cytotoxic agents had little if any effect on top1. On the other hand, the most potent of the indenoisoquinolines vs top1 were not the most-cytotoxic. In several cases, moderate activity was observed for both cytotoxicity and activity vs top1.