diethyl(2,2-dimethyl-1-(tert-butyl-(1-(pyridine-4-yl)ethoxy)amino)propyl)phosphonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diethyl(2,2-dimethyl-1-(tert-butyl-(1-(pyridine-4-yl)ethoxy)amino)propyl)phosphonate
• 英文别名: diethyl (1-(tert-butyl(1-(pyridin-4-yl)ethoxy)amino)-2,2-dimethylpropyl)phosphonate；Diethyl(1-(tert-butyl(1-(pyridin-4-yl)ethoxy)amino)-2,2-dimethylpropyl)phosphonate；N-tert-butyl-1-diethoxyphosphoryl-2,2-dimethyl-N-(1-pyridin-4-ylethoxy)propan-1-amine
• 化学式: C₂₀H₃₇N₂O₄P
• 分子量: 400.499
• InChiKey: HPBKDHJVTHGBGP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  60.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diethyl(2,2-dimethyl-1-(tert-butyl-(1-(pyridine-4-yl)ethoxy)amino)propyl)phosphonate 在 盐酸 作用下， 以 甲醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  Chemically Triggered C–ON Bond Homolysis in Alkoxyamines. 6. Effect of the Counteranion

  摘要：

  We showed (J. Org. Chem. 2012, 77, 9634) that the activation by methylation of pyridyl-based alkoxyamine 1 increased with the hydrogen bond donor properties of solvents. In this paper, activation of 1 by protonation with acids, CF3COOH and CSA, in tert-butylbenzene (t-BuPh) and in H2O/MeOH afforded, with CF3COOH, k(d) 28-fold larger in H2O/MeOH than in t-BuPh, whereas it was only 4-fold larger when CSA was used. This puzzling observation was ascribed to the dissociation of the intimate ion pair.

  DOI：

  10.1021/jo401227a

文献信息

• First proton triggered C–ON bond homolysis in alkoxyamines
  作者：Paul Brémond、Sylvain R. A. Marque

  DOI：10.1039/c0cc05637e

  日期：——

  Rate constants kd of the C–ON bond homolysis in a new type of alkoxyamines (initiator/controller for Nitroxide Mediated Polymerization) carrying alkyl fragments capable of protonation were measured. A 20-fold increase was reported for the protonated alkoxyamine compared to the non-protonated homologue as predicted (Chem. Soc. Rev., 2011).

  测量了新型烷氧基胺（硝基氧化聚合的引发剂/控制剂）中C-ON键断裂的速率常数kd，该烷氧基胺带有能够质子的烷基片段。与预测值相比，质子化的烷氧基胺比非质子化的同系物增加了20倍（Chem. Soc. Rev.，2011）。
• ALKOXYAMINES FOR THE TREATMENT OF CANCERS
  申请人：CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE

  公开号：US20160115130A1

  公开（公告）日：2016-04-28

  The present invention relates to alkoxyamines of general formula (I), and to compounds of general formula (IIa), (IIb), (IIc), (IId), IIe), (IIf) or (IIg), as such and for the treatment of cancers.

  本发明涉及一般式(I)的烷氧胺化合物，以及一般式(IIa)、(IIb)、(IIc)、(IId)、(IIe)、(IIf)或(IIg)的化合物，作为治疗癌症的药物。
• Chemically Triggered C–ON Bond Homolysis of Alkoxyamines. Quaternization of the Alkyl Fragment
  作者：Paul Brémond、Abdoulaye Koïta、Sylvain R. A. Marque、Vincent Pesce、Valérie Roubaud、Didier Siri

  DOI：10.1021/ol2031075

  日期：2012.1.6

  15-fold increase in kd (Chem. Commun. 2011, 47, 4291–4293) was investigated experimentally and theoretically by quaternization of the pyridyl moiety using methylating (MeOTs), acylating (AcCl), and benzylating (PhCH2Br) agents as well as by oxidation of the pyridyl moiety into N-oxide and by the formation of a dative bond with BH3 as a Lewis acid.

  4-吡啶基烷基片段的质子化可以化学触发烷氧基胺2a中的C-ON键均裂。在所得到的15倍增加ķ d（化学式COMMUN。2011，47，4291-4293）中的实验和理论上通过该吡啶基部分的季铵化的甲基化使用（MeOTs）研究，酰化（ACCL），和苄基化（物理信道2溴剂，以及通过将吡啶基部分氧化成N-氧化物以及通过与BH 3形成路易斯酸的键合来实现的。
• Alkoxyamines for the treatment of cancers
  申请人：Centre National De La Recherche Scientifique

  公开号：US10421725B2

  公开（公告）日：2019-09-24

  The present invention relates to alkoxyamines of general formula (I), and to compounds of general formula (IIa), (IIb), (IIc), (IId), IIe), (IIf) or (IIg), as such and for the treatment of cancers.

  本发明涉及通式(I)的烷氧基胺和通式(IIa)、(IIb)、(IIc)、(IId)、(IIe)、(IIf)或(IIg)的化合物，并用于治疗癌症。
• Chemically Triggered C–ON Bond Homolysis in Alkoxyamines. 6. Effect of the Counteranion
  作者：Gérard Audran、Paul Brémond、Sylvain R. A. Marque、Germain Obame

  DOI：10.1021/jo401227a

  日期：2013.8.2

  We showed (J. Org. Chem. 2012, 77, 9634) that the activation by methylation of pyridyl-based alkoxyamine 1 increased with the hydrogen bond donor properties of solvents. In this paper, activation of 1 by protonation with acids, CF3COOH and CSA, in tert-butylbenzene (t-BuPh) and in H2O/MeOH afforded, with CF3COOH, k(d) 28-fold larger in H2O/MeOH than in t-BuPh, whereas it was only 4-fold larger when CSA was used. This puzzling observation was ascribed to the dissociation of the intimate ion pair.