2,5-dimethyl-3H-1,3-benzazaphosphole | 404578-27-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 2,5-dimethyl-3H-1,3-benzazaphosphole
• 英文别名: 2,5-dimethyl-1H-1,3-benzazaphosphole
• CAS: 404578-27-4
• 化学式: C₉H₁₀NP
• 分子量: 163.159
• InChiKey: XYYBWJHEDVSAIG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  11.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  15.79
• 氢给体数：
  1.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  2,5-dimethyl-3H-1,3-benzazaphosphole 在 叔丁基锂 作用下， 以 乙醚 、 正戊烷 为溶剂， 生成 lithium-2,5-dimethyl-1,3-benzazaphospholide
  参考文献：
  名称：

  金属化的1,3-氮杂磷腈：1,3-苯并氮杂磷酸锂的合成及其对有机元素和有机金属卤化物的反应性

  摘要：

  苯并氮杂磷1a - e与t -BuLi的金属化提供了高选择性的阴离子1a - e Li。1b Li ·3THF的晶体结构分析显示，单体和锂在氮原子上的配位。如2a和2d与t- BuLi的反应所示，五羰基钨络合物还优选在氮下反应。在2a的情况下，在PC键处加成是一个较小的过程。化合物1a，c Li和2d Li与卤代烷在磷处反应，得到3-烷基-1,3-苯并氮杂唑3a和3d或相应的W（CO）5络合物4d。甚至乙酰基和新戊酰氯也能攻击磷的1e Li，从而得到P-酰基衍生物5e和6e。甲硅烷基化可以在氮或磷发生，得到7和/或8根据由取代基在位置2 2-的不同效果施加空间和电子效应吨丁基是由图示在上N和P中的空间位阻基团1d的分子几何通过晶体结构分析确定。软有机金属卤化物，诸如Me 3的SnCl，CpFe的量（CO）2 I和CPW（CO）3 Cl可反应1李优选在磷得到的甲锡烷基或单体有机-过渡金属衍生物9

  DOI：

  10.1016/s0022-328x(01)01035-x
• 作为产物：
  描述：

  2'-溴-4'-甲基乙酰苯胺 在 lithium aluminium tetrahydride 、 nickel dichloride 作用下， 以 乙醚 为溶剂， 反应 24.0h， 生成 2,5-dimethyl-3H-1,3-benzazaphosphole
  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

• Ambident PCN Heterocycles: N- and P-Phosphanylation of Lithium 1,3-Benzazaphospholides
  作者：Bhaskar���R. Aluri、Sebastian Burck、Dietrich Gudat、Mark Niemeyer、Oldamur Holloczki、Laszlo Nyulaszi、Peter���G. Jones、Joachim Heinicke

  DOI：10.1002/chem.200901753

  日期：2009.11.16

  Synthetic and structural aspects of the phosphanylation of 1,3‐benzazaphospholides 1Li, ambident benzofused azaphosphacyclopentadienides, are presented. The unusual properties of phospholyl‐1,3,2‐diazaphospholes inspired us to study the coupling of 1Li with chlorodiazaphospholene 2, which led to the N‐substituted product 3. Reaction of 1Li with chlorodiphenyl‐ and chlorodicyclohexylphosphane likewise

  介绍了1,3-苯并氮杂膦酸酯1 Li的环烷基苯并稠合的azaphosphacyclopentadienides的膦酰化的合成和结构方面。磷酸1,3,2-二氮杂唑的非同寻常的性质激发了我们研究1 Li与氯二氮杂磷腈2的偶合的方法，从而导致了N-取代的产物3的产生。的反应1李与chlorodiphenyl-和chlorodicyclohexylphosphane同样得到Ñ -phosphanylbenzazaphospholes 4和5，而用更笨重二-叔丁基-和二-1- adamantylchlorophosphanes，所述diphosphanes 6和7获得; 在7的情况下，它们被分离为二聚LiCl（THF）加合物。结构信息由单晶X射线衍射和溶液NMR光谱实验提供。2D交换光谱法证实在室温下存在两个氨基膦5的旋转异构体。对6个样品的变温NMR光谱研究显示了两个动力学过程，即环磷的低温反演（ΔH
• Cycloadditions of <i>1H</i> ‐1,3‐Benzazaphospholes with <i>o</i> ‐Chloranil
  作者：Joachim W. Heinicke、Nidhi Gupta、Peter Mayer、Konstantin Karaghiosoff

  DOI：10.1002/zaac.202000067

  日期：2020.7.15

  NH‐Functional 1H‐1,3‐benzazaphospholes 1a–1c and o‐chloranil (tetrachloro‐o‐benzoquinone ‐ TCBQ) undergo rapid [1+4]‐cycloaddition in a 1:2 molar ratio to give 2a–2c as high‐melting zwitterionic σ6λ5‐phosphorus compounds. In the case of 2a the yield is high (rel. to TCBQ) even if the reactants were used in a 1:0.5 molar ratio. For the 2‐tert‐butyl‐substituted compounds 2b and 2c the yields were significantly

  NH功能性1H -1,3-苯并氮杂唑1a-1c和邻氯苯甲腈（四氯邻苯醌TCBQ）以1：2摩尔比快速[1 + 4]环加成，得到2a - 2c为高熔化两性离子σ 6 λ 5 -磷化合物。在2a的情况下，即使以1：0.5的摩尔比使用反应物，收率也很高（相对于TCBQ）。对于2-叔丁基取代的化合物2b和2c，产率显着降低，部分原因是未鉴定的副产物。在原油2c中添加过量的TCBQ包含未转化的1c的含量没有增加，但大大降低了2c的含量。结晶和XRD分析导致检测到次要的副产物或连续产物3c，形式上对应于P = C键断裂和三个等价TCBQ的[1 + 4]环加成，两个在次膦基上，一个在卡宾末端。的NMR光谱数据2a中-图2c包括确凿13为C数据2a中的新化合物的结构的提供证据。
• Coplanar Tetracyclic π‐Excess σ ² P Ligands
  作者：Basit Niaz、Fatima Iftikhar、Markus K. Kindermann、Peter G. Jones、Joachim Heinicke

  DOI：10.1002/ejic.201300342

  日期：2013.8.12

  AbstractThe acid‐catalyzed reactions of 5‐methyl‐2‐phosphanylaniline (1) with dialdehydes were studied. Whereas the reaction with glyoxal provides a mixture of two 1H‐1,3‐benzazaphospholes, 2 and 3, by concomitant reduction of a CHO group and C–C bond cleavage, respectively, the reaction with o‐phthalic dicarbaldehyde provided in excellent yield the tetracyclic planar benzazaphosphole 4, which was characterized by crystal structure analysis. The active hydrogen atoms, delivered by aromatization of a dihydrobenzazaphosphole intermediate, forms an N–CH2 bridge by reductive N‐alkylation. Pyridine‐2,6‐dicarbaldehyde reacts analogously but not chemoselectively and, thus, gives two isomers 5 and 6. Condensation with pyridine‐2,6‐dicarbaldehyde afforded the bis(benzazaphosphole)pyridine pincer ligand 7, but along with 2‐(benzazaphospholyl)‐6‐tolylpyridine (8) by partial P–C bond cleavage. The high upfield 31P NMR chemical shift of 4 compared to those of normal benzazaphospholes indicates it to be a particularly π‐rich σ2P ligand.
• ——
  作者：Joachim Heinicke、Nidhi Gupta、Shreeyukta Singh、Anushka Surana、Olaf Kühl、Raj K. Bansal、Konstantin Karaghiosoff、Martin Vogt

  DOI：10.1002/1521-3749(200213)628:13<2869::aid-zaac2869>3.0.co;2-3

  日期：——

  1H-1,3-Benzazaphospholes react with M(CO)(5)(THF) (M = Cr, Mo, W) to give thermally and relatively air stable eta(1)-(1H-1,3-Benzazaphosphole-P)M(CO)(5) complexes. The H-1- and C-13-NMR-data are in accordance with the preservation of the phosphaaromatic pi-system of the ligand. The strong upfield P-31 coordination shift, particularly of the Mo and W complexes, forms a contrast to the downfield-shifts of phosphine-M(CO)(5) complexes and classifies benzazaphospholes as weak donor but efficient acceptor ligands. Nickelocene reacts as organometallic species with metalation of the NH-function. The resulting ambident 1,3-benzazaphospholide anions prefer a mu(2)-coordination of the eta(5)-CpNi-fragment at phosphorus to coordination at nitrogen or a eta(3)-heteroallyl-eta(5)-CpNi-semisandwich structure. This is shown by characteristic NMR data and the crystal structure analysis of a eta(5)-CpNi-benzazaphospholide. The latter is a P-bridging dimer with a planar Ni2P2 ring and trans-configuration of the two planar heterocyclic phosphido ligands arranged perpendicular to the four-membered ring.

表征谱图