1-Methyl-1H-benzo[1,3]azaphosphole-2-carboxylic acid | 84759-32-0

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1-Methyl-1H-benzo[1,3]azaphosphole-2-carboxylic acid
• 英文别名: 1-Methyl-1,3-benzazaphosphole-2-carboxylic acid
• CAS: 84759-32-0
• 化学式: C₉H₈NO₂P
• 分子量: 193.142
• InChiKey: ADOAVASKPAZESA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  42.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tungsten pentacarbonyl tetrahydrofuran 、 1-Methyl-1H-benzo[1,3]azaphosphole-2-carboxylic acid 反应 24.0h， 以68%的产率得到pentacarbonyl-η1P-(1-methyl-1H-1,3-benzazaphosphole-2-carboxylic acid)tungsten
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/j.jorganchem.2014.04.014
• 作为产物：
  描述：

  N-甲基氨基苯膦酸二乙酯 在 lithium aluminium tetrahydride 、 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

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，
• Ambident Reactivity of P˭CH‒N‒Heterocycles: Lithiation and Substitution Sites
  作者：Joachim Heinicke、Bhaskar R. Aluri、Basit Niaz、Sebastian Burck、Dietrich Gudat、Mark Niemeyer、Oldamur Holloczki、Laszlo Nyulaszi、Peter G. Jones

  DOI：10.1080/10426507.2010.514486

  日期：2011.3.31

  Benzofused 1H-1,3-azaphospholes are lithiated at the N-atom by tBuLi but phosphinylation takes place at either the N- or the P-atom. Smaller chlorophosphines react at nitrogen, bulkier react at phosphorus. Substituents at C2 promote the latter mode. N- Substituted 2H-1,3-benzazaphospholes undergo CH-metalation or addition at the P=C bond, depending on the conditions, and allow access to 2-functionally substituted benzazaphospholes or their 2,3-dihydro derivatives, new sigma P-2,X or sigma P-3,X hybrid ligands (X=O,P).