2,6-哌嗪二酮,3-甲基-,(3S)- | 4225-51-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2,6-哌嗪二酮,3-甲基-,(3S)-
• 英文名称: 4-nitrophenyl dichlorothiophosphate
• 英文别名: phosphorodichloridothioic acid O-para-nitrophenyl ester；[14N]-p-nitrophenyl thiophosphorodichloridate；O-(4-nitrophenyl) phosphorodichloridothioate；p-nitrophenyl phosphorodichloridothioate；4-nitrophenyl phosphorothiodichloridate；p-nitrophenyl dichlorothiophosphonate；(4-Nitrophenoxy)phosphonothioyl dichloride；dichloro-(4-nitrophenoxy)-sulfanylidene-λ5-phosphane
• CAS: 4225-51-8
• 化学式: C₆H₄Cl₂NO₃PS
• 分子量: 272.048
• InChiKey: RJALBHUNPRJDIE-UHFFFAOYSA-N

物化性质

• 熔点：
  54 °C
• 沸点：
  130-135 °C(Press: 0.15 Torr)
• 密度：
  1.663±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  87.1
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  2,6-哌嗪二酮,3-甲基-,(3S)- 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 36.0h， 生成 methyl 2-[[[(2S,3S,5R)-3-azido-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-(4-nitrophenoxy)phosphinothioyl]amino]propanoate
  参考文献：
  名称：

  ONE POT SYNTHESIS OF ARYL THIOPHOSPHORAMIDATE DERIVATIVES OF AZT

  摘要：

  Novel aryl thiophosphoramidate derivatives of the anti-HIV nucleoside analogue 3'-azido-3'-deoxythymidine (AZT) have been prepared by the thiophosphorochloridate chemistry. These materials were designed to act as membrane-soluble prodrugs of the bioactive free nucleotides.

  DOI：

  10.1081/scc-120014036
• 作为产物：
  描述：

  对硝基苯酚 在 三乙胺 、 三氯氧磷 作用下， 以 苯 为溶剂， 生成 2,6-哌嗪二酮,3-甲基-,(3S)-
  参考文献：
  名称：

  In Search of new Organophosphorus Pesticides and Insecticides. Part III: Synthesis and Anticholinesterase Studies of 3-(Subs)-Quinoxy/Pyridinoxy/Cyclica Mino-2,3- Dihydro-2-(4-Chlorophenyl)-1H-Naphth [1,2-E][1,3,2] Oxazaphosphorine 3-Sulfides

  摘要：

  In situ treatment of (cyclic) amino derivatives with the product obtained from the cyclocondensation of 1-p-chloroanilinomethyl naphthol-2 and thiophosphoryl chloride in dry benzene-THF afforded the titled oxazaphosphorine sulfides in good yield. Subsequently, the reaction of pyridinoky/quioxythiophosphorodi chloridates and 1-p-chloro anilino methyl naphthol-2 in dry benzene-THF mixture gave the corresponding pyridinoxy/quinoxy oxaza phosphorine 3-sulfides in quantitative yield. All the condensations proceeded smoothly by employing triethylamine to scavenge the liberated hydrogen chloride gas. Anticholinestease studies of these compounds indicated very high degree of inhibition several times higher than the reference standard-methyl parathion.

  DOI：

  10.1080/10426500008082383

文献信息

• Synthesis and physiological activity of new organophosphorus pesticides of 1,3,2-oxazaphosphorinane series
  作者：A. E. Shipov、G. K. Genkina、O. I. Artyushin、Z. O. Mndzhoyan、B. E. Gushchin、E. I. Chumakova、S. A. Roslavtseva、O. Yu. Eremina、E. I. Bakanova、Yu. S. Kagan、E. A. Ershova、T. A. Mastryukova、M. I. Kabachnik

  DOI：10.1007/bf00696722

  日期：1995.11

  Methods for the synthesis of 2-aryloxy(arylthio)- and 2-alkoxy(alkylthio)-2-thio(oxo)-1,3,2-oxazaphosphorinanes and theirN-substituted derivatives based on the reactions of the corresponding dichlorophosphates, dichlorothio-, and dithiophosphates with 3-aminopropan-1-ol or its substituted derivatives in the presence of Et3N or aqueous alkali under phase transfer catalysis conditions, as well as by

  基于相应的二氯磷酸盐、二氯硫代-和 2-芳氧基（烷硫基）-2-硫代（氧代）-1,3,2-氧氮杂膦烷及其 N-取代衍生物的合成方法，以及二硫代磷酸盐与 3-氨基丙-1-醇或其取代衍生物在 Et3N 或碱水溶液存在下，在相转移催化条件下，以及通过 2-羟基-2-硫代-1 的四甲基铵盐的反应， 3,2-oxazaphosphorinane 与烷基-和酰基卤化物，2-chloro-2-thio-1,3,2-oxazaphosphorinane 与硫醇钠，以及通过其他方法，被开发出来。获得的化合物表现出高杀线虫活性，但对哺乳动物的毒性低。在这些化合物中发现了一些氯菊酯的活性增效剂。
• Comparisons of Phosphorothioate with Phosphate Transfer Reactions for a Monoester, Diester, and Triester:  Isotope Effect Studies
  作者：Irina E. Catrina、Alvan C. Hengge

  DOI：10.1021/ja0340026

  日期：2003.6.1

  Phosphorothioate esters are sometimes used as surrogates for phosphate ester substrates in studies of enzymatic phosphoryl transfer reactions. To gain better understanding of the comparative inherent chemistry of the two types of esters, we have measured equilibrium and kinetic isotope effects for several phosphorothioate esters of p-nitrophenol (pNPPT) and compared the results with data from phosphate esters

  在酶促磷酰基转移反应的研究中，硫代磷酸酯有时用作磷酸酯底物的替代物。为了更好地了解两种酯类的比较固有化学，我们测量了对硝基苯酚的几种硫代磷酸酯 (pNPPT) 的平衡和动力学同位素效应，并将结果与​​磷酸酯的数据进行了比较。酚基（（18）k（桥））的初级（18）O同位素效应，硝基中的二级氮 - 15同位素效应（（15）k），以及（对于单酯和二酯）二级测量了磷酰氧中的氧 18 同位素效应 ((18)k(nonbridge))。pNPPT 单阴离子去质子化的平衡同位素效应 (EIE) (18)k（非桥）为 1.015 +/- 0.002，与先前报道的磷酸单酯值非常相似。Zn(2+) 和 Cd(2+) 与二价阴离子 pNPPT(2-) 络合的 EIEs 都是统一的。使用重原子动力学同位素效应探讨了 pNPPT、二酯乙基 pNPPT 和三酯二甲基 pNPPT 的单阴离子和二阴离子的水溶液水解机理。
• A reappraisal of the role of the E1cB mechanism of hydrolysis of phosphoramidic derivatives
  作者：Neil K. Hamer、Robert D. Tack

  DOI：10.1039/p29740001184

  日期：——

  lead to the conclusion that, despite considerable differences in rate with varying degree of N-substitution, there is no important contribution from an E1cB process such as operates for related phosphoramidic halides and acyl carbamates. On the basis of the results of studies on the relative rates and direction of cleavage in the basic solvolysis of some OS-dimethyl phosphoramidothioates and phosphoramidodithioates

  已测量了一系列芳基氨基氨基磷酸酯和硫代氨基磷酸酯的碱溶剂分解速率；结果得出的结论是，尽管速率随N取代程度的不同而有很大差异，但E 1cB工艺（例如对相关的磷酰胺卤化物和酰基氨基甲酸酯的操作）并没有重要的贡献。根据对某些OS-二甲基磷酰胺基硫代酸酯和磷酰胺基二硫代酸酯的基本溶剂分解中相对裂解速率和裂解方向的研究结果，与较早的建议相反，有人提出P-O和P-S裂解均主要发生亲核攻击引起的，尽管对后者的某些贡献可能是由消除机制引起的。
• Unusual resistance of cobalt bis dicarbollide phosphate and phosphorothioate bridged esters towards alkaline hydrolysis: The “metallacarborane effect”
  作者：Carla Sardo、Sławomir Janczak、Zbigniew J. Leśnikowski

  DOI：10.1016/j.jorganchem.2019.06.001

  日期：2019.9

  phosphate [3]- esters under alkali conditions was discovered. The hydrolysis of metallacarborane esters [2]- and [3]- was studied, and the kinetic and thermodynamic parameters were measured and compared with those of their organic counterparts, parathion and paraoxon. The extreme differences between the hydrolytic properties of alkyl- and metallacarborane phosphate and phosphorothioate esters are attributed

  发现在碱性条件下，桥连的O，O- [双（二碳二钴）钴] O-（4-硝基苯基）硫代磷酸酯[2] -和磷酸酯[3] -酯的非凡稳定性。金属碳碳烷酸酯[2] -和[3] -的水解进行了研究，测量了动力学和热力学参数，并与有机对硫磷和对氧磷进行了比较。烷基和金属碳硼烷磷酸盐和硫代磷酸酯的水解性能之间的极端差异归因于金属碳硼烷非离去基团的电子和空间效应（“金属碳硼烷效应”）。已知的“硫代效应”有助于在较小程度上对的电阻[2] -的基本条件。
• The P-Stereocontrolled Synthesis of PO/PS-Chimeric Oligonucleotides by Incorporation of Dinucleoside Phosphorothioates Bearing anO-4-Nitrophenyl Phosphorothioate Protecting Group
  作者：Lucyna A. Wozniak、Marcin Góra、Małgorzata Bukowiecka-Matusiak、Sophie Mourgues、Geneviève Pratviel、Bernard Meunier、Wojciech J. Stec

  DOI：10.1002/ejoc.200400910

  日期：2005.7

  The synthesis of protected model dinucleoside (3',5')-O-aryl phosphorothioates, their separation into pure diastereomers, and their successful incorporation into oligonucleotides followed by stereospecific deprotection of the O-aryl phosphorothioate function with oximate ion (inversion) enables the preparation of chimeric PO/PS-oligonucleotides with a predetermined sense of P-chirality at each internucleotide

  受保护的模型二核苷 (3',5')-O-芳基硫代磷酸酯的合成，将它们分离成纯的非对映异构体，并成功掺入寡核苷酸，然后用肟酸离子（反转）立体特异性脱保护 O-芳基硫代磷酸酯功能，使制备在每个核苷酸间硫代磷酸酯位置具有预定的 P-手性意义的嵌合 PO/PS-寡核苷酸。已经指定了“二聚体结构单元”中核苷酸间 O-芳基硫代磷酸酯的磷的绝对构型。3'-末端 SP-硫代磷酸酯键有效地保护此类嵌合构建体免于被人血浆外切核酸酶降解（© Wiley-VCH Verlag GmbH & Co. KGaA，69451 Weinheim，德国，2005）