N-methyl-2-phosphanylaniline | 84759-23-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-methyl-2-phosphanylaniline
• 英文别名: N-methyl-o-phosphanylaniline；o-Phospholino-N-methylanilin；N-methyl-2-phosphinoaniline
• CAS: 84759-23-9
• 化学式: C₇H₁₀NP
• 分子量: 139.137
• InChiKey: LWYSGKKUZKMDBC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-methyl-2-phosphanylaniline 在 叔丁基锂 作用下， 以 乙醚 为溶剂， 生成 1-methyl-1,3-benzazaphosphol-2-yl-lithium
  参考文献：
  名称：

  C-metallierung an phosphaaromaten - 2-lithio-1-methyl-1,3-benzazaphosphol

  摘要：

  DOI：

  10.1016/s0040-4039(00)88646-3
• 作为产物：
  描述：

  o-Brom-N-methylformanilid 在 lithium aluminium tetrahydride 、 potassium tert-butylate 、 palladium dichloride 作用下， 以 乙醚 为溶剂， 生成 N-methyl-2-phosphanylaniline
  参考文献：
  名称：

  Synthesis of 1H-1,3-benzazaphospholes: substituent influence and mechanistical aspects

  摘要：

  Various substituted carboxylic acid 2-chloro- and 2-bromoanilides 1a-j react with triethylphosphite in the presence of anhydrous NiCl2 or NiBr2 to give o-acylamido-benzenephosphonic acid esters 2a-g and 2j. Yields depend strongly on the substituents. 2-Fluoro-4,6-dibromoacetanilide 1g reacts only at 6-position, indicating an o-directed process. Based on substituent effects, we infer a mechanism via Ni(0) intermediates that insert into the carbon-halogen bond. The N-tertiary 2-bromoformanilide 4 does not undergo phosphonylation to 5 in the presence of the Ni-catalyst but reacts in the presence of Pd-catalysts. The subsequent reduction of the N-secondary o-acylamido-benzenephosphonic acid esters 2 with excess LiAlH4 is coupled with an intramolecular cyclisation to the 1H-1,3-benzazaphospholes 6 whereas the N-tertiary derivative 5 does not undergo cyclisation upon reduction. NMR data and the crystal structure of 6d are reported. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)01019-5

文献信息

• 1H-1,3-Benzazaphospholes: The Organometallic Route and a New Three-Step Synthesis with Reductive Ring Closure
  作者：Raj K. Bansal、Neelima Gupta、Joachim Heinicke、George N. Nikonov、Farida Saguitova、Dinesh C. Sharma

  DOI：10.1055/s-1999-3394

  日期：1999.2

  Primary and N-secondary 2-phosphanylanilines were synthesized via metallation of 2-bromoanilines, coupling with ClP(NMe2)2, alcoholysis and reduction with LiAlH4, and subsequently reacted with formimidoester hydrochloride to give 1,3-benzazaphospholes. For 1H-1,3-benzazaphospholes, a shorter alternative three-step synthesis was developed, based on N-acylation of 2-bromoaniline, NiCl2-catalyzed arylation of triethyl phosphite and a new reductive cyclization of amidophosphonic acid este with excess LiAlH4.

  主要和N-次级2-磷胺基苯胺通过2-溴苯胺的金属化反应、与ClP(NMe2)2偶联、醇解以及用LiAlH4还原合成，并随后与甲酰亚胺酯盐酸盐反应生成1,3-苯并氮杂膦。对于1H-1,3-苯并氮杂膦，开发了一种更短的替代三步合成方法，基于2-溴苯胺的N-酰化、NiCl2催化的三乙基磷酸酯芳基化，以及用过量LiAlH4进行的新型还原环化反应。
• π-Excess σ2P ligands: synthesis of biaryl-type 1,3-benzazaphosphole hybrid ligands and formation of P^P′–M(CO)4 chelate complexes
  作者：Basit Niaz、Mohammed Ghalib、Peter G. Jones、Joachim W. Heinicke

  DOI：10.1039/c3dt50981h

  日期：——

  aldehyde. N-Secondary 2-phosphanylanilines 5 also react with aldehydes to form the corresponding N-substituted benzazaphospholes 6. The formation of (P^P′)M(CO)4-chelate complexes 8a (M = Cr) and 9a,b (M = Mo) was demonstrated by reaction with M(CO)4(norbornadiene). The crystal structure of 9a, determined in addition to the solution structure elucidation by multinuclear NMR spectra, confirms the chelate

  2- phosphanylanilines酸催化cyclocondensations 1与取代的苯甲醛或杂芳基醛打开到新的联芳基型1一个方便的途径ħ -1,3- benzazaphosphole混合配体2A-F与ö -phosphanylphenyl，吡啶基，咪唑基，噻吩基或ö -甲氧基苯基供体基团（除σ 2 P供体）和对溴苯基取代的benzazaphospholes 2克，H。过量的醛导致伴随的还原性N-烷基化，如2h以外的3h的形成所示。反应通过二氢苯并氮杂唑4进行，可以在温和的条件下检测到。芳香性驱动的脱氢作用不会释放出二氢，而是通过转移加氢（主要是通过还原某些醛）来完成的。N-仲2-膦基苯胺5也与醛反应形成相应的N-取代的苯并氮杂磷6。通过与M（CO）4（降冰片二烯）反应证明了（P ^ P'）M（CO）4螯合物8a（M = Cr）和9a，b（M = Mo ）的形成。9a的晶体结构，
• Syntheses of 2-Unsubstituted 1<i>H</i>-1,3-Benzazaphospholes from<i>N</i>-Formyl-2-bromoanilides
  作者：Mohammed Ghalib、Basit Niaz、Peter G. Jones、Joachim W. Heinicke

  DOI：10.1002/hc.21111

  日期：2013.11

  The phosphonylation of 2-bromo-formylanilides 1 with triethyl phosphite in the presence of preformed Pd(0)(triethyl phosphite)n catalyst furnished 2-phosphono-formanilides 2 in good yields. Reduction with excess LiAlH4 provided mainly N-methyl-2-phosphinoanilines 3 and minor amounts of 1,2-unsubstituted benzazaphospholes 4. N-Methyl-1,3-benzazaphospholes 5 were synthesized by the cyclocondensation

  在预先形成的 Pd(0)(亚磷酸三乙酯)n 催化剂存在下，2-溴-甲酰苯胺 1 与亚磷酸三乙酯的膦酰化以良好的产率提供了 2-膦酰-甲酰苯胺 2。用过量的 LiAlH4 还原主要提供 N-甲基-2-膦基苯胺 3 和少量 1,2-未取代的苯并氮杂磷 4。N-甲基-1,3-苯扎磷 5 是通过 3 与二甲基甲酰胺二甲基缩醛 (DMFA) 的环缩合反应合成的。避免 4 的色谱分离，更方便的 5 路线是将 1 还原为 2-溴-N-甲基苯胺 6，然后进行膦酰化为 7，LiAlH4 还原，然后用 DMFA 环化。苯扎磷光体在 σ2P 处的配位特性由 (5b)W(CO)5 的晶体结构分析获得的结构数据表征。
• Benzazaphospholine-2-carboxylic acids: Synthesis, structure and properties of heterocyclic phosphanyl amino acids
  作者：Mohammed Ghalib、Joanna Lach、Olga S. Fomina、Dmitry G. Yakhvarov、Peter G. Jones、Joachim Heinicke

  DOI：10.1016/j.poly.2014.03.046

  日期：2014.7

  1,3-Dialkyl-1,3-benzazaphospholine-2-carboxylic acids 2a,b can be conveniently prepared by metalation and alkylation of N-methyl- and N-neopentyl-o-phosphanylaniline in liquid ammonia and cyclocondensation of the resulting N,P-disecondary phosphanylanilines 1a,b with glyoxylic acid hydrate (GAH) in ether. The primary neopentylphosphanylaniline reacts with two equivalents of GAH and forms a phosphanyl-bis(amino acid) 3 with toluidine. alpha-Branched P-substituents induce strongly preferred formation of trans-diastereoisomers with R,R- and S,S-configuration at P and C2, as shown by a crystal structure analysis of 2a, whereas a P-neopentyl (P-Np) group gives rise to trans/cis-diastereoisomeric mixtures. The trans-configuration exhibits the P lone-pair in cis-position to the COOH group, suitable for formation of five-membered chelate rings, as in diphenylphosphanylacetate nickel catalysts for ethylene oligomerization. Screening of 2a,b/Ni(COD)(2) solutions in THF by a batch procedure indeed showed formation of catalysts for conversion of ethylene to linear oligomers and waxy low-molecular weight polymers. The conversion depends strongly on the size of the N-alkyl group, being slow and limited for the N-Me catalyst 2a/Ni and much faster and more complete for the N-Np-substituted catalysts 2b/Ni and 2c/Ni (N-Np, P-tBu). Comparison of 2b/Ni with 2c/Ni shows that the more bulky P-substituent further increases the catalyst activity. (C) 2014 Elsevier Ltd. All rights reserved.
• Hydroformylation process using a rhodium complex catalyst with triarylphosphine and biphosphine monoxide ligands
  申请人：UNION CARBIDE CORPORATION

  公开号：EP0073398B1

  公开（公告）日：1984-12-19