二乙基二氯膦酰胺 | 1498-54-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 中文名称: 二乙基二氯膦酰胺
• 英文名称: N,N-diethylphosphoramidous dichloride
• 英文别名: diethylphosphoramidous dichloride；Diethylphosphoramidic dichloride；N-dichlorophosphoryl-N-ethylethanamine
• CAS: 1498-54-0
• 化学式: C₄H₁₀Cl₂NOP
• mdl: MFCD00013897
• 分子量: 190.009
• InChiKey: FXKRFCBTXGJQPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 储存条件：
  室温

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  二乙基二氯磷	diethylphosphoramidous dichloride	1069-08-5	C4H10Cl2NP	174.01

反应信息

• 作为反应物：
  描述：

  二乙基二氯膦酰胺 在 溴苯 、 乙醚 、 sodium 作用下， 生成 N,N-diethyl P,P-diphenylphosphinamide
  参考文献：
  名称：

  Michaelis; Schall, Justus Liebigs Annalen der Chemie, 1903, vol. 326, p. 183

  摘要：

  DOI：
• 作为产物：
  描述：

  N-chlorodiethylamine 在 二氧化硫 、 三氯化磷 作用下， 以 四氯化碳 为溶剂， 生成 二乙基二氯膦酰胺
  参考文献：
  名称：

  Petrov,K.A. et al., Journal of general chemistry of the USSR, 1961, vol. 31, p. 1265 - 1269

  摘要：

  DOI：
• 作为试剂：
  描述：

  3,5-二甲基溴苯 在 二乙基二氯膦酰胺 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 以76%的产率得到bis(3,5-dimethylphenyl)phosphinic acid
  参考文献：
  名称：

  Cationic BINAP-Ru(II) Halide Complexes: Highly Efficient Catalysts for Stereoselective Asymmetric Hydrogenation of .alpha.- and .beta.-Functionalized Ketones

  摘要：

  Cationic ruthenium-BINAP complexes 5, 7, and 10 of the formula [RuX((S)-BINAP) (arene)]Y, where X = Cl, Br, I; Y = Cl, Br, I, BF4, B(C6H5)(4); arene = benzene, p-cymene, ethyl benzoate, and their enantiomers have been prepared by the reaction of arene-ruthenium halide complexes 4, 6, and 9 with (S)-BINAP or (R)-BINAP. Structures of the complexes were established by spectroscopy, conductivity, and a single-crystal X-ray analysis (5d: orthorhombic, P2(1)2(1)2; a 20.141(2) Angstrom, b = 18.504(1) Angstrom, c 12.241(1) Angstrom V = 4562.0(7) Angstrom(3), Z = 4, R = 0.078 for unique 4177 reflections). BINAP derivatives with various substituents at the para and meta positions of four phenyl rings on phosphorus atoms and their cationic Ru(II) complexes have also been synthesized. These BINAP-Ru(II) complexes have been used as catalysts for the asymmetric hydrogenation of various unsaturated organic compounds such as alpha- and beta-keto esters, allylic alcohols, and alpha,beta-unsaturated carboxylic acids in excellent diastereo- and/or enantioselectivities. Catalytic activities and stereoselectivities depend highly on reaction conditions such as solvent, temperature, and additives. Variation of halogen ligands bound to ruthenium atom and substituents on four phenyl rings of BINAP also have exerted remarkable effects on the efficiency of the catalysis. Asymmetric hydrogenation of methyl (+/-)-2-(benzamidomethyl)-3-oxobutanoate catalyzed by the species derived from 9c and 3,5((t)Bu)(2)-BINAP afforded the corresponding syn-(2S,3R)-17 in 98% de and 99% ee.

  DOI：

  10.1021/jo00090a026

文献信息

• Hydrolysis of cyclic phosphoramides. Evidence for syn lone pair catalysis
  作者：Andrés Núñez、Dyanna Berroterán、Oswaldo Núñez

  DOI：10.1039/b300916e

  日期：——

  Hydrolysis between 1.5 < pH < 4 of five and six membered cyclic phosphoramides has been followed by UV and 31PNMR spectroscopy. The observed rates fit the equation: kobs = kH2O [H+]/([H+] + Ka) + k′H2O, where kH2O and k′H2O are the pseudo first-order rate constants of water attack on the protonated phosphoramide and its unprotonated form, respectively, and Ka is the phosphoramide acidity equilibrium constant. Although, faster hydrolysis rates on the five membered ring are expected due to the energy released in going from a strained cyclic to a “strained free” trigonal-bipyramidal-pentacoordinated intermediate, with one of the cyclic nitrogens occupying the apical position, these compounds react slightly faster (kH2O values) but slower regarding the k′H2O values than the six membered analogs. The balance in reactivity is attributed to the additional stability obtained in the six membered cyclic compounds by a syn orientation of the two lone pairs of the cyclic nitrogen to the water attack. This stabilization does not exist in the five membered phospholidines since the water attack is perpendicular to the electron pairs of the cyclic nitrogen. In agreement with the incoming water orientation, the product ratios from the hydrolysis show that in the five membered rings the main product is the one produced by endocyclic cleavage; meanwhile, in the six membered cyclic phospholines the kinetic product is the one produced by exocyclic cleavage. The syn orientation of two electron pairs on nitrogen stabilizes the transition state of water approach to the phosphoramides by ca. 3 kcal mol−1 when compared to the orthogonal attack.

  在1.5 < pH < 4的条件下，五元环和六元环磷酰胺的水解过程通过紫外光谱和31P核磁共振波谱进行了研究。观察到的反应速率符合以下方程：kobs = kH2O [H+]/([H+] + Ka) + k′H2O，其中kH2O和k′H2O分别是水分子攻击质子化磷酰胺和非质子化磷酰胺的假一级速率常数，Ka是磷酰胺酸度平衡常数。虽然预计五元环的水解速率会更快，因为从受限环状结构转变为“无受限”三角双锥五配位中间态时释放能量，其中一个环状氮原子占据顶端位置，但这些化合物的反应速率（kH2O值）略快，而关于k′H2O值则较慢于六元环的类似物。反应活性的平衡归因于六元环状化合物在水攻击时通过syn取向使环状氮的两个孤对电子与水攻击方向一致所获得的额外稳定性。这种稳定化在五元环磷酯中不存在，因为水攻击方向垂直于环状氮的电子对。与进来的水取向一致，水解产物的比例表明，在五元环中主要产物是由环内断裂产生的；而在六元环磷脂中，动力学产物是由环外断裂产生的。氮原子上两个电子对的syn取向通过与正交攻击相比，大约稳定了磷酰胺水接近过渡态的3 kcal mol−1。
• CHEMISTRY OF N-PHOSPHORYLATED NITROGEN MUSTARDS: THE EFFECT OF A SECOND NITROGEN SUBSTITUENT AT PHOSPHORUS ON THE STABILITY OF THE SYSTEM
  作者：Huijie Wan、Tomasz A. Modro

  DOI：10.1080/10426509608029648

  日期：1996.1.1

  Abstract Methyl N,N-diethyl-N'N'-bis(2-chloroethyl)phosphoramidate was prepared as a precursor for the corresponding phosphordiamidate anion, a model for the phosphoramidate mustard, biologically active degradation product of cyclophosphamide drug. Demethylation of the precursor led to a highly unstable ion which underwent spontaneous fragmentation. In the absence of an external nucleophile, the ion

  摘要 制备了 N,N-二乙基-N'N'-双（2-氯乙基）磷酰胺酸甲酯作为相应的二酰胺磷阴离子的前体，氨基磷酸芥的模型，环磷酰胺药物的生物活性降解产物。前体的去甲基化导致高度不稳定的离子发生自发分裂。在没有外部亲核试剂的情况下，离子分解产生偏氨基磷酸酯和 N-取代的乙烯亚胺作为主要中间体。在吡啶的存在下，两个吡啶发生双烷基化，产生双 [2-(N-吡啶并)乙基]胺二甲基化，此外还有一些 1,3,2-氧氮杂膦衍生物，通过竞争性 1,5-去甲基化阴离子的环化。在苯硫酚/三乙胺存在下孵育前体导致两个平行的亲核置换：(i) O-去甲基化，然后是两个苯硫酚分子的双烷基化，以及一些 1,5-环化；(ii) 初始直接分配...
• Synthesis, activation, and cytotoxicity of aldophosphamide analogs
  作者：Richard F. Borch、Ronald R. Valente

  DOI：10.1021/jm00114a014

  日期：1991.10

  tautomerization to an enamine intermediate might provide a mechanistic alternative to the beta-elimination reaction for release of phosphoramide mustard. The 4,4,6-trimethyltetrahydro-1,3-oxazine moiety was selected on the basis of its rapid rate of iminium ion generation and relatively slow rate of hydrolysis. These analogues underwent phosphorodiamidate release by three distinct mechanisms: hydrolysis to aldophosphamide

  制备了一系列醛磷酰胺的全氢恶嗪类似物，并对其31P NMR动力学和体外细胞毒性进行了评估。这些化合物是基于这样的想法而开发的，即开环和互变异构化为烯胺中间体可能为释放磷酰胺芥菜的β-消除反应提供一种机械替代方法。选择4,4,6-三甲基四氢-1,3-恶嗪部分是基于其亚胺离子生成速度快和水解速度相对慢的原因。这些类似物通过三种不同的机制释放二氨基磷酸酯：水解为醛基磷酸酰胺和随后的β-消除；环化生成4-羟基环磷酰胺，该环磷酰胺通过开环和消除作用释放二氨基磷酸酯；并通过快速排出二氨基氨基磷酸酯而互变为烯胺。动力学研究表明，水解成醛对整个活化过程的贡献最小，烯胺途径代表了活化的主要途径。对于那些可能经历环化的类似物，该途径与烯胺释放有效竞争，并且这些类似物在细胞毒性上基本上等同于它们的4-羟基环磷酰胺。制备了一系列不能进行环化的四-N-取代的磷酸二氨基甲酸酯，以探索环化对这些类似物的细胞毒性的影响。
• Kinetic Resolution of Hydroperoxides with Enantiopure Phosphines:  Preparation of Enantioenriched Tertiary Hydroperoxides
  作者：Tom G. Driver、Jason R. Harris、K. A. Woerpel

  DOI：10.1021/ja070482f

  日期：2007.4.1

  kinetic resolution strategy capable of accessing optically active tertiary hydroperoxides is reported. Readily accessible tertiary hydroperoxides are resolved with commercially available (R)- or (S)-xylyl-PHANEPHOS with selectivity factors as large as 37. The resulting bis(phosphine oxide) can be recycled in high yields. The isolated mono(phosphine oxide) intermediate resolved hydroperoxides with the

  报告了一种能够访问光学活性叔氢过氧化物的有效还原动力学拆分策略。容易获得的叔氢过氧化物用市售的 (R)- 或 (S)-二甲苯基-PHANEPHOS 拆分，选择性因子高达 37。得到的双（氧化膦）可以高产率回收。分离的单（氧化膦）中间体以与母体双膦相同的选择性拆分氢过氧化物。
• Imide-Amide Rearrangement of Cyclic Phosphorimidates: A Mechanistic Study
  作者：Eurico J. Cabrita、Carlos A. M. Afonso、António Gil de Oliveira Santos

  DOI：10.1002/1521-3765(20010401)7:7<1455::aid-chem1455>3.0.co;2-u

  日期：2001.4.1

  imide -amide rearrangement of cyclic phosphorimidates. As a result of this work new types of oligomeric organophosphorus compounds, formed by a novel 1,4-addition type ring opening polymerisation, were identified. These compounds are the stable intermediates of the imide-amide rearrangement, which upon heating yield the previously reported rearranged product. A detailed study of the mechanism of the Lewis

  旨在开发适用于不对称化学的手性环状草酰氮和二氮杂磷酰胺的制备的新合成途径的研究使我们对环状亚磷酸酯的酰亚胺-酰胺重排进行了研究。作为这项工作的结果，鉴定了通过新型的1，4-加成型开环聚合反应形成的新型低聚有机磷化合物。这些化合物是酰亚胺-酰胺重排的稳定中间体，加热时可得到先前报道的重排产物。报道了对路易斯酸催化的酰亚胺-酰胺重排机理和最终产物的立体化学控制的详细研究。结果，阐明了完整的机理，并提出了在重新排列的碳原子处保留构型的证据。