1-methyl-1H-1,3-benzazaphosphole | 84759-25-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1-methyl-1H-1,3-benzazaphosphole
• 英文别名: 1-methyl-1,3-benzazaphosphole；N-methyl-1,3-benzazaphosphole；1-methyl-1,3-benzazaphosphol
• CAS: 84759-25-1
• 化学式: C₈H₈NP
• 分子量: 149.132
• InChiKey: OPWAGKVVDAXDHR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  4.9
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-methyl-1H-1,3-benzazaphosphole 在 水 、 叔丁基锂 作用下， 以 乙醚 为溶剂， 生成 1-Methyl-1H-benzo[1,3]azaphosphole-2-carboxylic acid
  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：

  N-甲基氨基苯膦酸二乙酯 在 lithium aluminium tetrahydride 作用下， 生成 1-methyl-1H-1,3-benzazaphosphole
  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

文献信息

• Sterically and Polarity-Controlled Reactions oftBuLi with PCH-NR Heterocycles: Novel Heterocyclic P- and P,O-Ligands and Preliminary Tests in Transition-Metal Catalysis
  作者：Bhaskar R. Aluri、Markus K. Kindermann、Peter G. Jones、Joachim Heinicke

  DOI：10.1002/chem.200702016

  日期：2008.5.9

  reactivity towards addition at the P=C bond. The preferred regioselectivity is tert-butylation at phosphorus, occurring with excellent diastereoselectivity for trans-adducts 3 b and 3 c, but the inverse tert-butylation at C2 to 5 b was also observed. N-Neopentyl groups, with intermediate steric demand, give rise to formation of mixtures in ethers but allow switching either to selective CH lithiation in

  （1R）-1,3-Benzazaphospholes 1 ac（吲哚类型的P = CH-NR杂环）与tBuLi发生两种反应，具体取决于N取代基的空间需求和介质的极性。小的N-烷基基团的存在会在2-位诱导CH去质子化，生成杂芳基锂试剂2a和2b，而大体积的N-取代基和非极性溶剂会改变在P = C键处的加成反应性。优选的区域选择性是在磷处的叔丁基化，其对反式加合物3b和3c具有优异的非对映选择性，但是在C2至5b处也观察到了叔丁基化。具有中等空间需求的N-新戊基基团导致在醚中形成混合物，但允许切换为在THF / KOtBu中进行选择性CH锂化或在戊烷中进行加成。更大的N-金刚烷基总是引起优选的加成。使用质子化，甲硅烷基化和羧化将P = CLi-NR，（E）-tBuP-CHLi-NR和LiP-CH（tBu）-NR物种转换为相应的sigma（2）-P或sigma（3） ）-P化合物4b和6a，b，
• 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。
• Solvent-controlled lithiation of PC–N-heterocycles: Synthesis of mono- and bis(trimethylsilyl)-tert-butyl-dihydrobenzazaphospholes – A new type of highly bulky and basic phosphine ligands
  作者：Mohammed Ghalib、Peter G. Jones、Joachim W. Heinicke

  DOI：10.1016/j.jorganchem.2014.04.014

  日期：2014.8

  The influence of solvents on the lithiation of N-methyl-1,3-benzazaphospholes is reported; these are accessible via catalytic phosphonylation of 2-bromoanilines, subsequent reduction to 2-phosphinoanilines and acid-catalysed disproportionative ring closure with excess paraformaldehyde. Reactions with tBuLi in polar solvents (THF, Et2O), particularly in the presence of tBuOK, lead to 2-lithiobenzazaphospholes (CH-lithiation) whereas hydrocarbons favour "normal" (hexane) or "inverse" (toluene) addition at the P=C bond. Reactive Li-species were trapped by ClSiMe3, present during the lithiation in hydrocarbons, and give rise to 2- and 3-trimethylsilyl-dihydro-1,3-benzazaphospholes, respectively. In hexane, via preferred lithiation of the primary adduct, the 2,2'-bis(trimethylsilyl)-dihydro-1,3-benzazaphosphole is the main product. 5-Methyl-1,3-benzazaphosphole, with NH function, reacts in toluene in the "normal" mode to 3-tert-butyl-1,2-bis(trimethylsilyl)-5-methyl-dihydrobenzazaphosphole. The sterically demanding tert-butyl and trimethylsilyl groups are arranged in anti-position as shown by crystal structure analyses, the second 2-SiMe3 group in gauche position. The P-tert-butyl-2,2'-bis(trimethylsilyl)-dihydrobenzazaphospholes represent a new type of sterically congested dialkylaryl phosphine ligands with increased basicity by the +I-effect of the silyl groups and +M-effect of the basic nitrogen in o-position. (C) 2014 Elsevier B.V. All rights reserved.
• π‐Excess σ ² P=C–N–Heterocycles: Catalytic <i>P</i> ‐Arylation and Alkylation of <i>N</i> ‐Alkyl‐1,3‐benzazaphospholes and Isolation of <i>P</i> , <i>N</i> ‐Disubstituted Dihydrobenzaza­phosphole <i>P</i> ‐Oxides
  作者：Basit Niaz、Bhaskar R. Aluri、Peter G. Jones、Joachim W. Heinicke

  DOI：10.1002/ejic.201500532

  日期：2015.8

  Abstract2‐Unsubstituted N‐alkyl‐1,3‐benzazaphospholes, diagonally P–C related to 2,3‐unsubstituted indoles, were successfully arylated by aryl iodides and bromides or alkylated by neopentyl iodide by heating in DMF in the presence of a catalytic amount of PdCl2 or H2PtCl6 and a suitable base. In contrast to the known 2‐arylations of indoles under these conditions, the reactions led to arylation in the 3‐position and proceeded via highly moisture‐sensitive intermediates to P‐substituted 1,3‐benzazaphosphole P‐oxides. Thus, we present a novel route for the direct P‐substitution of aromatic σ2P‐heterocycles with electrophilic aryl/alkyl halides. Characteristic NMR spectroscopic data of the intermediates are consistent with –P(aryl)–C(Br/Cl)–N– species formed by metal‐mediated addition of the aryl halides at the P=C bond rather than by oxidative addition to ylidic intermediates. Benzazaphospholium salts, accessible by using triethyloxonium tetrafluoroborate at room temperature and also very sensitive to hydrolysis, display distinct NMR spectroscopic data. The structures of the products were elucidated by conclusive NMR spectroscopy and HRMS data and crystal‐structure analysis. Minor amounts of a bis(arylation) product could likewise be identified by crystal‐structure analysis.
• Lithium-1,3-Benzazaphospholides: Structure and Reactivity
  作者：J. Heinicke、N. Peulecke、A. Surana、S. Singh、N. Gupta、K. Steinhauser、R. K. Bansal、A. Spannenberg

  DOI：10.1080/10426500212258

  日期：2002.6.1

  The formation, structure and electrophilic substitution reactions at phosphorus or nitrogen of N-lithium-1,3-benzazaphospholides is reported.