N,N,N',N'-tetramethyldiamide of phenylmethanephosphonic acid | 14655-73-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N,N,N',N'-tetramethyldiamide of phenylmethanephosphonic acid
• 英文别名: N,N,N',N'-tetramethylbenzylphosphondiamide；P-benzyltetramethylphosphonic diamide；Benzylphosphonic bis(dimethylamide)；Toluol-ω-phosphonsaeure-N,N,N',N'-tetramethyl-diamid；Bis-dimethylamino-benzyl-phosphonat；Phosphonic diamide, N,N,N',N'-tetramethyl-P-(phenylmethyl)-；N-[benzyl(dimethylamino)phosphoryl]-N-methylmethanamine
• CAS: 14655-73-3
• 化学式: C₁₁H₁₉N₂OP
• 分子量: 226.258
• InChiKey: SFOKRXGUVAFIIW-UHFFFAOYSA-N

物化性质

• 沸点：
  311.7±35.0 °C(Predicted)
• 密度：
  1.075±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N,N,N',N'-tetramethyldiamide of phenylmethanephosphonic acid 在 正丁基锂 、 silica gel 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 10.0h， 生成 2-甲基-1-苯基丙烯
  参考文献：
  名称：

  Momchilova, Snejana; Petrova, Jordanka; Kirilov, Marko, Phosphorus and Sulfur and the Related Elements, 1988, vol. 35, p. 319 - 328

  摘要：

  DOI：
• 作为产物：
  描述：

  benzyltris(dimethylamino)phosphonium chloride 在 氢氧化钾 作用下， 以79%的产率得到N,N,N',N'-tetramethyldiamide of phenylmethanephosphonic acid
  参考文献：
  名称：

  Mizrakh, L. I.; Polonskaya, L. Yu., Journal of general chemistry of the USSR, 1989, vol. 59, p. 1299

  摘要：

  DOI：

文献信息

• Nucleophilic substitution reactions of benzyl- and diphenylmethyl-phosphonamidic chlorides with amines: competition between the usual SN2(P) mechanism and elimination–addition with an alkylideneoxophosphorane (phosphene) intermediate
  作者：Martin J. P. Harger

  DOI：10.1039/b007288p

  日期：——

  The substitution reaction of PhCH2P(O)(NMe2)Cl with Me2NH or Et2NH in CHCl3 is very sensitive to the bulk of the nucleophile (200 times slower with Et2NH), affords only the product derived from Me2NH in competition experiments, and gives largely undeuterated product with Et2ND; these features are in accord with an SN2(P) mechanism. The corresponding reaction of Ph2CHP(O)(NMe2)Cl is relatively insensitive to the bulk of the nucleophile (5 times slower with Et2NH), gives some of the product derived from Et2NH in competition experiments, and gives extensively deuterated product with Et2ND; these features point to an elimination–addition (EA) mechanism with an alkylideneoxophosphorane intermediate [Ph2CP(O)NMe2]. There is only a modest (13–19 fold) increase in the rate of substitution on going to ArPhCHP(O)(NMe2)Cl (Ar = 4-NO2C6H4) but with R2ND there is now very rapid H/D exchange at the α carbon atom. This suggests that the elimination stage of the EA mechanism comprises rapid reversible formation of the conjugate base followed by rate-limiting expulsion of chloride ion.

  PhCH2P(O)(NMe2)Cl 与 CHCl3 中的 Me2NH 或 Et2NH 的取代反应对大量亲核试剂非常敏感（Et2NH 慢 200 倍），在竞争实验中仅产生源自 Me2NH 的产物，并且得到大部分未氘化的产物含有 Et2ND 的产品；这些特征符合SN2(P)机制。 Ph2CHP(O)(NMe2)Cl 的相应反应对大部分亲核试剂相对不敏感（与 Et2NH 反应慢 5 倍），在竞争实验中给出了一些源自 Et2NH 的产物，并与 Et2ND 给出了广泛的氘化产物；这些特征表明亚烷基氧代正膦中间体 [Ph2CP(O)NMe2] 存在消除-加成 (EA) 机制。转向 ArPhCHP(O)(NMe2)Cl (Ar = 4-NO2C6H4) 时，取代率仅略有增加（13-19 倍），但使用 R2ND 现在，H/D 交换速度非常快α碳原子。这表明 EA 机制的消除阶段包括共轭碱的快速可逆形成，随后是氯离子的限速排出。
• ——
  作者：N. V. Lukashev、E. A. Tarasenko、I. P. Beletskaya

  DOI：10.1023/a:1012326700328

  日期：——

  Copper derivatives of methylphosphonic amides are sufficiently stable thermally and can be used in palladium-catalyzed arylation reactions resulting in synthesis of previously unknown aryl- and hetaryl-methylphosphonic tetramethyldiamides in high yields.
• Palladium-catalyzed copper(I) salt-mediated arylation of a bis(dimethylamino)phosphonyl-stabilized carbanion
  作者：Elena A Tarasenko、Nikolai V Lukashev、Irina P Beletskaya

  DOI：10.1016/s0040-4039(99)02341-2

  日期：2000.3

  The synthesis of new arylmethylphosphonic acid tetramethyl diamides by a palladium-catalyzed cross-coupling reaction of a bis(dimethylamino)phosphonylmethylcopper(I) reagent with aryl iodides is described. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Lukashev; Tarasenko; Beletskaya, Russian Journal of Organic Chemistry, 2000, vol. 36, # 8, p. 1150 - 1156
  作者：Lukashev、Tarasenko、Beletskaya

  DOI：——

  日期：——
• Collignon,N., Bulletin de la Societe Chimique de France, 1977, p. 120 - 124
  作者：Collignon,N.

  DOI：——

  日期：——