[chloro(difluoro)acetyl]phosphoramidic acid dichloride | 1063763-91-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: [chloro(difluoro)acetyl]phosphoramidic acid dichloride
• CAS: 1063763-91-6
• 化学式: C₂HCl₃F₂NO₂P
• 分子量: 246.365
• InChiKey: XUGUQNDFFRMNRB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.52
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.17
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  [chloro(difluoro)acetyl]phosphoramidic acid dichloride 、 乙烷,三氯氟- 在 三乙胺 作用下， 以 氯仿 为溶剂， 反应 6.0h， 生成 N-(2-chloro-2,2-difluoroacetyl)-N',N''-bis(4-methylphenyl)phosphoric triamide
  参考文献：
  名称：

  Different cyclic motifs in phosphoric triamides containing a C(O)NHP(O)(NH)₂skeleton and anR₂²(10) graph set in three new compounds: a database analysis of hydrogen-bond strengths based on motifs

  摘要：

  In the crystal networks of N, N'bis(2-chlorobenzyl)-N ''-(2,6-ifluorobenzoyl) phosphoric triamide, C21H18Cl2F2N3O2P, (I), N-(2,6-difluorobenzoyl)-N',N ''-bis(4-methoxybenzyl) phosphoric triamide, C23H24F2N3O4P, (II), and N-(2-chloro-,2-difluoroacetyl)-N',N ''-bis(4-methylphenyl) phosphoric triamide, C16H17ClF2N3O2P, (III), C=O center dot center dot center dot H-N-C(O)NHP(O) and P=O center dot center dot center dot H-N-amide hydrogen bonds are responsible for the aggregation of the molecules. This is the opposite result from that commonly observed for carbacylamidophosphates, which show a tendency for the phosphoryl group, rather than the carbonyl counterpart, to form hydrogen bonds with the NH group of the C(O) NHP(O) skeleton. This hydrogen-bond pattern leads to cyclic R-2(2)(10) motifs in (I)-(III), different from those found for all previously reported compounds of the general formula RC(O) NHP(O)[(NRR2)-R-1](2) with the syn orientation of P O versus NH [R-2(2)(8)], and also from those commonly observed for RC(O) NHP(O)[NHR1](2) [a sequence of alternate R-2(2)(8) and R-2(2)(12) motifs]. In these cases, the R-2(2)(8) and R-2(2)(12) graph sets are formed through similar kinds of hydrogen bond, i.e. a pair of P=O center dot center dot center dot H-N-C(O)NHP(O) hydrogen bonds for the former and two C=O center dot center dot center dot H-Namide hydrogen bonds for the latter. This article also reviews 102 similar structures deposited in the Cambridge Structural Database and with the International Union of Crystallography, with the aim of comparing hydrogen-bond strengths in the above-mentioned cyclic motifs. This analysis shows that the strongest N-H center dot center dot center dot O hydrogen bonds exist in the R22 (8) rings of some molecules. The phosphoryl and carbonyl groups in each of compounds (I)-(III) are anti with respect to each other and the P atoms are in a tetrahedral coordination environment. In the crystal structures, adjacent molecules are linked via the above-mentioned hydrogen bonds in a linear arrangement, parallel to [010] for (I) and (III) and parallel to [100] for (II). Formation of the NC(O)NHP(O)-H center dot center dot center dot O=C instead of the NC(O) NHP(O)-H center dot center dot center dot O P hydrogen bond is reflected in the higher NC(O) NHP(O)-Hvibrational frequencies for these molecules compared with previously reported analogous compounds.

  DOI：

  10.1107/s0108270111019755
• 作为产物：
  描述：

  氯二氟乙酰胺 在 五氯化磷 、 甲酸 作用下， 以 四氯化碳 为溶剂， 反应 3.0h， 生成 [chloro(difluoro)acetyl]phosphoramidic acid dichloride
  参考文献：
  名称：

  Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂phosphoric triamides (X= CClF₂, 3-F-C₆H₄and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]₂core

  摘要：

  在磷酸三酰胺N,N,N′,N′-四苄基-N′′-(2-氯-2,2-二氟乙酰基)磷酸三酰胺中、(I)、N,N,N′,N′-四苄基-N′′-(3-氟苯甲酰基)磷酸三酰胺，C35H33FN3O2P、(II)和 N,N,N′,N′-四苄基-N′′-(3,5-二氟苯甲酰基)磷酸三酰胺 C35H32F2N3O2P,(III)，二苄基氨基的三级 N 原子的平面偏离最小。(I)-(III)中关于 N 原子的三个键角之和与 360°的平面值偏差小于 8°。对剑桥结构数据库[CSD; Allen (2002).Acta Cryst.B58, 380-388]中所有具有 C(O)NHP(O)[N]2 骨架的磷酸三酰胺中三级 N 原子的几何形状进行了研究，并考虑了两个三级 N 原子（SUM1 和 SUM2）上的键角总和以及参数 ΔSUM (= SUM1 - SUM2)。研究发现，在具有较大 ΔSUM 值的化合物中，较多金字塔形 N 原子的取向通常使相应的孤电子对与 P=O 基团成反方向。在(I)、(II)和(III)中，被一个 N 原子隔开的磷酰基和羰基相互反向。在(I)-(III)的 C(O)NHP(O)片段中，与分子中的其他两个 P-N 键和 O-P-N 角相比，P-N 键较长，O-P-N 角收缩。这些效应在沉积在 CSD 中的类似化合物中也可以看到。这里没有考虑[C(O)NH]P(O)[N]X(X≠N)的化合物，例如具有[C(O)NH]P(O)[N][O]骨架的化合物。此外，含有 [C(O)NH]2P(O)[N] 片段的化合物至今也未见报道。在所有这三种标题化合物的晶体结构中，相邻分子都以 P=O...H-N 氢键成对连接，形成具有对称性的二聚体。

  DOI：

  10.1107/s0108270112036396

文献信息

• [Chloro(difluoro)acetyl]phosphoramidic acid dichloride ClF2CC(O)NHP(O)Cl2, synthesis, vibrational and NMR spectra and theoretical calculations
  作者：Ana G. Iriarte、Mauricio F. Erben、Khodayar Gholivand、Jorge L. Jios、Sonia E. Ulic、Carlos O. Della Védova

  DOI：10.1016/j.molstruc.2007.10.036

  日期：2008.8

  The synthesis of a new carbacylamidophosphate compound, [chloro(difluoro)acetyl]phosphoramidic acid dichloride (ClF2CC(O)NHP(O)Cl-2), is reported along with its FTIR, Raman and mass spectra. The theoretical vibrational spectra were used to perform a tentative assignment of the observed bands. Quantum chemical calculations were realized with ab initio and density functional theory (DFT) methods using different levels of approximation. The title compound was analyzed as a dimer with C-i symmetry (C=O double bond in anti position with respect to the P=O double bond). The simulation of the potential energy surface was performed varying the dihedral angles phi(Cl-C-C-N) and omega(C-C-N-P) using HF and B3LYP methods. The harmonic vibrations obtained by all theoretical methods are in good agreement with the experimental results. H-1, C-13 and P-31 NMR are also reported. (C) 2007 Elsevier B.V. All rights reserved.