N,N-dimethylamino-P-phenyl-C-methylmethylenephosphine | 75589-83-2

• 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-dimethylamino-P-phenyl-C-methylmethylenephosphine
• 英文别名: Ethanamine, N,N-dimethyl-1-(phenylphosphinidene)-；N,N-dimethyl-1-phenylphosphanylideneethanamine
• CAS: 75589-83-2
• 化学式: C₁₀H₁₄NP
• 分子量: 179.202
• InChiKey: FOJMFINSAQJHLP-UHFFFAOYSA-N

物化性质

• 沸点：
  118-123 °C(Press: 1 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N-dimethylamino-P-phenyl-C-methylmethylenephosphine 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 13.0h， 生成 tert-butyl (E)-3-[1-[bis(trimethylsilyl)methylidene]-3-(dimethylamino)-2-phenyl-1lambda5,2-diphosphet-1-yl]prop-2-enoate
  参考文献：
  名称：

  Phosphaalkenes as Building Blocks in Ene Reactions:  Synthesis and Reactivity of 3-Amino-1,2-dihydro-1,2-diphosphetes

  摘要：

  Phospha-ene reactions of the type II between methylidenephosphanes as enophiles and C-aminophosphaalkenes possessing allylic hydrogen atoms proceed by P-P bond formation to furnish the corresponding functionalized diphosphanes. Thus, the reaction of the methylidenephosphane 1 with the C-amino-substituted ethylidenephosphane 3a runs smoothly at room temperature to afford the unsymmetrical 1,2-diphosphane 4 as a 60:40 mixture of two diastereomers in 64% yield. Rotation about the P-N bond in 4 is hindered at room temperature, but free enthalpies of activation of Delta G(double dagger)(PN) = 16.3 kcal.mol(-1) (major diastereomer) and 15.2 kcal . mol(-1) (minor diastereomer) were determined by variable temperature H-1 NMR spectroscopy; In contrast, reactions of the ethylidenephosphanes 3a-c with the chlorophosphane 2 as enophile follow an unusual course involving a regiospecific ene reaction of the type II and a subsequent intramolecular ring closure reaction to furnish the 3-amino-1,2-dihydro-1,2-diphosphetes 7a-e in good yields (53-79%). The reactivity of this new class of heterocyclic compounds has been studied exemplarily for product 7a. The trans form of 7a obtained by synthesis can be converted to the corresponding cis form photochemically. Complexation of both phosphorus centers in 7a is possible by reaction with 2 equiv of diiron nonacarbonyl and gives rise to complex 8, the constitution of which has been confirmed by X-ray crystallography. Unexpectedly, hydrolysis of ?a does not proceed by attack at the endocyclic enamine unit but rather by way of P-P bond cleavage to afford the functionalized phosphaalkene 9. On the other hand, oxidation of 7a by bis(trimethylsilyl) peroxide takes place with retention of the P2C2 skeleton: a selective increase in coordination at P-1 results in the formation of the 1-oxo-1,2-dihydrodiphosphete 10, the structure of which was confirmed by X-ray crystallography. The reactions of 7a with the electron-poor acetylenes 11a-d also follow an unusual course. Nucleophilic attack of P-1 at the C=C triple bond and proton shift lead stereospecifically to the 1-methylene-1,2-dihydro-1,2-diphosphetes 12a-d as thermolabile addition products. The constitution and configuration of 12c were unambiguously confirmed by X-ray crystallography.

  DOI：

  10.1021/jo9707186
• 作为产物：
  描述：

  (1-Methoxy-1-phenylphosphanyl-ethyl)-dimethyl-amine 生成 N,N-dimethylamino-P-phenyl-C-methylmethylenephosphine
  参考文献：
  名称：

  MERIEM, A.;MAJORAL, J. -P.;REVEL, M.;NAVECH, J., TETRAHEDRON LETT., 1983, 24, N 19, 1975-1978

  摘要：

  DOI：

文献信息

• Photochemical reactions of phosphaalkenes
  作者：Abdekader Meriem、Jean-Pierre Majoral、Monique Revel、Jacques Navech

  DOI：10.1016/s0040-4039(00)81820-1

  日期：——

  Photolysis of phosphaalkenes leads to an inversion of polarity of the phosphorus carbon double bond and to a cleavage into transient phosphinidene and carbene ; unexpected alcoholysis of a PIII-C bond and the [4+2] cycloaddition of a linear phosphaalkine on a diene are also reported.

  磷烯烃的光解导致磷碳双键的极性反转，并裂解为瞬时的亚膦烯和卡宾; 还报道了P III -C键的意外醇解和线性磷酸链烷烃在二烯上的[4 + 2]环加成反应。
• Réaction de P-phényl C-aminophosphaalcénes avec l'oxyde de parachlorobenzonitrile, évolution thermique des adduits
  作者：Mustapha Rahmouni、Yeung Yat Cheng Yeung Lam Ko、Robert Carrié、François Tonnard

  DOI：10.1016/s0040-4020(01)89395-9

  日期：1994.1

  P-phenyl C-aminophosphaalkenes 1 react with p-chlorobenzonitrile oxides at -20 degrees C leading to 1,2,4-oxazaphospholines 2, which are characterized by NMR and decompose slowly at room temperature. An experimental and theoretical study of their thermal evolution shows that the most probable mechanism involves the formation of an azaphospholine such as 10 which is unstable generating a phenyl phosphinidene. The latter polymerize quickly.
• Navech, J.; Majoral, J. P.; Meriem, A., Phosphorus and Sulfur and the Related Elements, 1983, vol. 18, p. 27 - 30
  作者：Navech, J.、Majoral, J. P.、Meriem, A.、Kraemer, R.

  DOI：——

  日期：——
• Synthese von aryl-dialkylaminoalkylidenphosphinen - ein neuer zugang zu derivaten des zweifach-koordinierten dreibindigen phosphors
  作者：H. Oehme、E. Leissring、H. Meyer

  DOI：10.1016/s0040-4039(01)83934-4

  日期：——
• Reaction of phenyl azide with N,N-dimethyl-aminomethylenephenylphosphines
  作者：B. A. Arbuzov、A. S. Ionkin、S. N. Ignat'eva、Yu. Ya. Efremov、V. M. Nekhoroshkov

  DOI：10.1007/bf00962146

  日期：1989.10